US3017360A - Hydrocarbon oil composition - Google Patents

Description

United States Patent Qfiflce 3,017,360 HY DROCARBON OIL COMPOSITION Henryk A. Cyba, Chicago, Ill., assignor, by mesne asslgnments, to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Filed May 23, 1958, Ser. No. 737,211 6 Claims. (Cl. 25234) This invention relates to a novel additive for hydrocarbon oil and more particularly to a novel method of improving hydrocarbon oil in a number of important properties.

During processing, transportation, storage and/or use, hydrocarbon oils generally deteriorate, particularly when subjected to elevated temperature. For example, hydrocarbon oil being subjected to fractionation or conversion is first heated to an elevated temperature. Such heating may be effected in an externally fired furnace or it may be accomplished by heat exchange with a hotter fluid. In the first case, the hydrocarbon fluid is passed through tubes during such heating and, in many cases, deposit formation occurs in the tubes and results in loss of etficien-t heating and/or plugging of the furnace tubes. In heat exchange systems the hydrocarbon oil is passed either through tubes disposed in a shell or through the shell surrounding the tubes. During heating of the oil, deposit formation occurs either within the tubes or in the hotter sections of the shell, with the result of decreased efi'iciency in heat transfer and even in plugging of the tubes. Another example in which hydrocarbon oil is passed in heat exchange is in the case of jet fuel, Where the jet fuel is passed in heat exchange with the hot exhaust gases, both to cool the exhaust gases and to heat the incoming fuel. Temperatures as high as 500 F. or more are encountered for at least short periods of time,

with the result that deposit formation occurs and either' plugs the heat exchanger or interferes with efficient heat transfer.

Other examples where instability of the hydrocarbon oil is a problem are hydrocarbon oils heavier than gasoline including diesel oil, heater oil-s, burner oils, range oils, fuel oils, transformer oils, hydraulic oils, slushing oils, etc. Deposit formation in these oils is objectionable because it results in plugging of filters, strainers, burner tips, injectors, etc., reduction in viscosity and accordingly in flowing properties, as well as the formation of varnish and sludge in the diesel engine. In addition to preventing these objectionable deposit formations, the novel additive of the present invention also functions to retard corrosion of metal surfaces in contact with hydrocarbon oil and water. It is well known that water generally is present in hydrocarbon oils and results in corrosion of piping, pumps, shells, fr-actionators, receivers, storage tanks, etc., as well as internal equipment such as baflie plates, bubble trays, bubble caps, etc.

In addition to serving the important functions hereinbefore set forth, the novel additive of the present invention also serves to lower the pour point of the hydrocarbon oil. This is of advantage in the case of heavier oils which are being pumped and also of particular advantage in the case of lubricating oils, gas turbine oils, steam turbine oils, jet turbine oils, marine oils, etc. in order that the oil retain its flowing properties at lower temperatures. In addition to reducing pour point and lowering the cold test, the additive also improves the viscosity index of lubricating oil.

The additive of the present invention also serves an important function in the case of gasoline or naphtha. As hereinbefore set forth, the additive serves as a corrosion inhibitor and therefore reduces corrosion problems during handling of the gasoline.

From the above description, it will be noted that the 3,017,360 Patented Jan. 16, 1962 novel additive to the present invention serves to improve hydrocarbon oil in a number of different ways. The hydrocarbon oil includes gasoline, naphtha, jet fuel, kerosene, burner oil, heater oil, range oil, gas oil, fuel oil, lubricating oil, residual oil, etc. As hereinbefore set forth, the additive may be incorporated in the oil prior to heating for further processing, or it may be incorporated in the oil after such treatment.

In one embodiment the present invention relates to a method of improving a hydrocarbon oil which comprises incorporating therein a stabilizing concentration of a carboxylic acid salt of the condensation product of an epihalohydrin compound with an amine compound having at least 12 carbon atoms.

In a specific embodiment the present invention relates to a method of preventing deposit formation in a heat exchanger through which two fluids at different temperatures are passed which comprises incorporating in at least one of said fluids, in an amount sufficient to prevent deposit formation, a salt of a dibasic carboxylic acid containing from about 6 to about 50 carbon atoms per molecule and the condensation product of epichlorohydrin with an amine compound having from about 12 to about 40 carbon atoms per molecule.

In still another embodiment the present invention relates to a method of improving burner oil which comprises incorporating therein a stabilizing concentration of an oleic acid salt of the condensation product of epichlorohydrin and tallow amine.

In still another embodiment the present invention relates to hydrocarbon oil containing a stabilizing concentration of the novel additive herein set forth.

The novel additives of the present invention also are new compositions of matter and are being so claimed in the present application.

As hereinbefore set forth, the novel additive of the present invention is a carboxylic acid salt of the condensation product of an epihalohydrin compound with an amine compound having at least 12 carbon atoms. The amine compound used in preparing the reaction product contains at least 12 carbon atoms and preferably at least 15 carbon atoms. Generally the total number of carbon atoms in the amine will not exceed about 40 carbon atoms per molecule. In a preferred embodiment the amine contains a straight chain of at least 3 carbon atoms attached to the nitrogen atom. In this preferred embodiment, the alkyl group attached to the nitrogen atom is of normal configuration and not secondary, tertiary or of cyclic configuration. However, the alkyl group may contain branching in the chain, provided such branching occurs on the fourth carbon atom from the nitrogen atom or further distant therefrom.

Any suitable alkyl amine meeting the requirements set forth herein may be used in preparing the additive of the present invention. In addition to the above requirements, it is essential that the alkyl amine is a primary or secondary amine; that is, only one or two of the hydrogen atoms attached to the nitrogen atom are substituted by alkyl groups. Tertiary amines (no hydrogen atom attached to the nitrogen atom) cannot be used in the present invention. It is understood that the term alkyl amine is used in the present specifications and claims to include primary alkyl amines, secondary alkyl amines, polyamines, N-alkyl polyamines, N,N'-dialkyl polyamines, etc., all of which meet the requirements hereinbefore set forth.

Illustrative examples of primary alkyl amines include dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine, heneicosyl amine, docosyl amine, tricosyl amine, tetracosyl amine,

pentacosyl amine, hexacosyl amine, heptacosyl amine, octacosyl amine, nonacosyl amine, triacontyl amine, hentriacontyl amine, dotriacontyl amine, tiitriacontyl amine, rtet ratriacontyl amine, pentatniacontyl amine, hexatriacontyl amine, heptatriacontyl. amine, octatriacontyl amine, nonatriacon-tyl amine, tetraco-ntyl amine, etc. Conveniently the long chain amines are prepared from fatty acids or more particularly from mixtures of fatty acids formed as products or by-products. Such mixtures are available commercially, generally at lower prices and, as another advantage of the present invention, the mixtures may be used without the necessity of separating individual amines in pure state.

An example of such a mixture is hydrogenated tallow amine which is available under various trade names including Alamine H26D and Armeen HTD. These products comprise mixtures predominating in alkyl amines containing 16 to 18 carbon atoms per alkyl group, although they contain a small amount of alkyl groups having 14 carbon atoms, and also meet the other requirements hereinbefore set forth.

Illustrative examples of secondary amines include di- (dodecyl) amine, di-(tridecyl) amine, di-(tetradecyl) amine, di-(pentadecyl) amine, di-(hexadecyl) amine, di- (heptadecyl) amine, di-(octadecyl) amine, di-(nonadecyl) amine, di-(eicosyl) amine, etc. In another embodiment, which is not necessarily equivalent, the secondary amine will contain one alkyl group having at least 12 carbon atoms and another alkyl group having less than 12 carbon atoms, both of the alkyl groups having a straight chain of at least 3 carbon atoms attached to the nitrogen atom. Illustrative examples of such compounds include N-propyl-dodecyl amine, N-butyl-dodecyl amine, N-amyldodecyl amine, N bu-tyl-tridecyl amine, N-amyl-tridecyl amine, etc. Here again, mixtures of secondary amines are available commercially, usually at a lower price, and such mixtures may be used in accordance with the present invention, provided that the amines meet the requirements hereiubefore set forth. An example of such a mixture available commercially is Armeen 2HT which consists primarily of dioctadecyl amine and dihexadecyl amine.

Preferred examples of N-alkyl polyamines com-prise N-alkyl 1,3-diaminopropanes which the alkyl group contains at least 12 carbon atoms. Illustrative examples include N-dodecyl 1,3 diaminopropane, -N-tn'decyl-1,3- diaminoprop-ane, N tetradecyl-l,3-diaminoprop-ane, N- pentadecyl 1,3 diaminopropane, N hexadecyl-l,3-diaminopropane, N-heptadecyl 1,3 diaminopropane, N- octadecyl-1,3 diaminopropane, N nonadecyl l,3-diammopropane, N- eicosyl-1,3-diaminopropane, N-heneicosyl-1,3 -diaminopropane, N doco-syl-1,3-diaminopropane, N-tricosyl-1,3-diaminopropane, N tetracosyl 1,3 diaminopropane, N -pentacosyl-1,3-diaminopropane, N- hexacosyl 1,3 diaminopropane, N -heptacosyl-l,3-diaminopropane, N-octacosyl 1,3 diaminopropane, N- nonacosyl 1,3 diaminopropane, N-triacontyl-1,3-diaminopropane, N-hentn'acontyl-l,3-diaminopropane, N- dotriacontyl 1,3 diaminopropane, N-tritriacontyl-1,3- diaminopropane, N tetratriacontyl-1,3-diaminopropane, N-pentatriacontyll ,3 -diaminopropane, N-hexatn'acontyl- 1,3-diaminopropane, N-heptatriacontyl 1,3 diaminopropane, N-octatriacontyl-1,3-diaminopropane, N-nonatriacontyl 1,3 diaminopropane, N -tetracontyl-l,3-diaminopropane, etc. As before, mixtures are available commercially, usually at lower prices, of suitable compounds in this class and advantageously are used for the purpose of the present invention. One such mixture is Duomeen T which is N-tallow-1,3-diaminopropane and predominates in alkyl groups containing 16 to 18 carbon atoms each, although the mixture contains a small amount of alkyl. groups containing 14 carbon atoms each. Another mixture available commercially is N-coco-l,3-diaminopropane which contains alkyl groups predominating in 12 to 14 carbon atoms each. Still another example is Nasoya 1,3 diaminopropane which predominates in alkyl groups containing 18 carbon atoms per group, although it contains a small amount of alkyl groups having 16 carbon atoms.

While the N-alkyl-1,3-diaminopropanes are preferred compounds of this class, it is understood that suitable N-alkyl ethylene diamines, N-alkyl-1,3 diaminebutanes, N-alkyl 1,4 diaminobutanes, N-alkyl-1,3-diaminopentanes, N-alkyl 1,4 diaminopentanes, N-alkyl- 1,5-diaminopentanes, N alkyl-1,3-diaminohexanes, N- alkyl-1,4-diaminohexanes, N alkyl-1,5-diaminohexanes, N-alkyl-l,6-diammohexanes, etc. may be employed but not necessarily with equivalent results. Also, it is understood that polyamines containing 3 or more nitrogen atoms may be employed provided they meet the requirements hereinbefore set forth. Illustrative examples of such compounds include N-dodecyl-diethylene triamine, N tridecyl-diethylene triamine, N tetradecyl-diethylene triamine, etc., N-dodecyl-dipropylene triamine, N-tridecyldipropylene triamine, N-tetradecyl-dipropylene triamine, etc., N-dodecyl-diburtylene triamine, N-tridecyl-dibutylenc triamine, N-tetradecyl-dibutylene triamine, etc., N-dodecyl-triethylene tetramine, N-tridecyl-tniethylene tetramine, Natetradecyl-triethylene tetramine, etc., N-dodecyltripropylene tetramine, N-tridecyl-tripropylene tetramine, N-tetradecyl-tripropylene tetramine, etc., N-dodecyl-tributylene tetramine, N tridecyl-tributylene tetramine, N- tetradecyl-tri-butylene tetramine, etc., N-dodecyl-tetraethylene pentamine, N-tridecyl-tetraethylene pentamine, N- tetradecyl-tetraethylene pentamine, etc., N-dodecyl-tetrapropylene pentamine, N -tridecyl -tetrapropylene pentamine, N-tetradecyl-tetrapropylene pentamine, etc., N-dodecyl-tetrabutylene pentamine, N-tridecyl-tetrabutylene pentamine, N-tetradecyl-tetrabutylene pentamine, etc.

In another embodiment, polyaminoalkanes meeting the requirements hereiubefore set forth, may be employed but generally such materials are not available commercially and, therefore, generally are not preferred. Illustrative examples of such compounds include 1,12- diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, etc.

In general, it is preferred that the amine compound is a saturated compound and does not contain double bonds in the chain. However, in some cases, unsaturated compounds may be employed, provided they meet the other requirements hereinbefore set forth, although not necessarily with equivalent results. Such amine compounds may be prepared from unsaturated fatty acids and, therefore, may be available commercially at lower cost. Illustrative examples of such amine compounds include dodecylenic amine,'didodecylenic amine, N-dodecylinic ethylene diamine, N dodecylenic 1,3 diaminopropane, oleic amine, dioleic amine, N-oleic ethylene diamine, N- oleic-l,3-diaminopropane, linoleic amine, dilinoleic amine, N-linoleic ethylene diamine, N-linoleic-l,3-diaminopropane, etc. It is understood that these amine compounds are included in the present specifications and claims by reference to amine or amine compounds.

In another embodiment of the invention, two different amines may be reacted with the epihalohydrin compound. At least one of the amines must meet the qualifications hereinbefore set forth. The other amine may comprise any suitable compound containing primary and/0r secondary amine groups. Preferred compounds comprise ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, etc., similar propylene and polypropylene polyamines, butylene and polybutylene polyamines, etc. In still another embodiment, other suitable nitrogen-containing compounds may be used as, for example, urea, monoethanol amine, etc.

As hereinbefore set forth, the amine compound is reacted with an epihalohydrin compound. Epichlorohydrin is preferred. Other epichlorohydrin compounds include 1,2-epi-4-chlorobutane, 2,3-epi-4-chlorobutane, 1,2-epi-5- chloropentane, 2,3-epi--chloropentane, etc. In general, the chloro derivatives are preferred, although it is understood that the corresponding bromo and iodo compounds may be employed. In some cases epidihalohydrin compounds may be utilized. It is understood that the different epihalohydrin compounds are not necessarily equivalent in the same or different substrate and that, as hereinbefore set forth, epichlorohydrin is preferred.

In general, 1 or 2 mols of amine compound are reacted with 1 or 2 mols of epihalohydrin compound. It is understood that, in some cases, an excess of amine or of epihalohydrin may be supplied to the reaction zone in order to insure complete reaction, the excess being removed subsequently in any suitable manner. When 2 mols of amine are reacted per mol of epihalohydrin compound, the amine may comprise the same or different amine compound.

In a preferred embodiment of the invention, the reaction of 1 mol of amine compound with 1 mol of epihalohydrin compound proceeds to the formation of polymeric reaction product. In this embodiment of the invention, the reaction is first effected at a temperature Within the range hereinafter set forth, with only a portion of the reactants being present in the reaction mixture. After the initial reaction is completed, the remaining reactants are supplied to the reaction mixture and the reaction is completed at a higher temperature but within the same range set forth herein. For example, a portion of the amine may be first reacted With the epihalohydrin and then the remaining portion of the amine is reacted. These polymers may contain from about 3 to about 20 or more recurring units and preferably from about 5 to about recurring units.

The desired quantity of alkyl amine and epihalohydrin compounds may be supplied to the reaction zone and therein reacted, although generally it is preferred to supply one reactant to the reaction zone and then introduce the other reactant stepwise. Thus, usually it is preferred to supply the amine to the reaction zone and to add the epihalohydrin compound step-wise, with stirring. When it is desired to react two different alkyl amines With the epihalohydrin compound, the epihalohydrin compound is supplied to the reaction zone. One of the amines is added gradually, and the reaction completed, followed by the addition of the second alkyl amine. Generally, it is preferred to utilize a solvent and, in the preferred embodiment, a solution of the amine in a solvent and a separate solution of the epihalohydrin compound in a solvent are prepared, and these solutions then are commingled in the manner hereinbefore set forth. Any suitable solvent may be employed, a particularly suitable solvent comprising an alcohol including ethanol, propanol, butanol, etc., 2-propanol being particularly desirable.

The reaction is effected at any suitable temperature, which generally will be Within the range of from about 20 to about 100 C. and preferably is within the range of from about 50 to about 75 C. A higher temperature range of from about 30 to about 150 C. or more, and preferably of from about 50 to about 100 C., is specified when the reaction is effected at superatmospheric pressure to increase the reaction velocity. Conveniently, this reaction is effected by heating the amine solution in dilute alcohol at refluxing conditions, with stirring, gradually adding the epihalohydrin compound thereto, and continuing the heating until the reaction is completed.

Either before or after removal of the reaction product from the reaction zone, the product is treated to remove halogen, generally in the form of an inorganic halide salt as, for example, the hydrogen halide salt. This may be effected in any suitable manner and generally is accomplished by reacting the product with a strong inorganic base such as sodium hydroxide, potassium hydroxide, etc., to form the corresponding metal halide. The reaction to form the metal halide generally is effected under the same conditions as hereinbefore set forth. After this reaction is completed, the metal halide is removed in any suitable manner, including filtering, centrifugal separation, etc. It is understood that the reaction product also is heated sufficiently to remove alcohol and water and this may be effected either before or after the treatment to remove the inorganic halide.

In still another embodiment, after the reaction product of an alkyl amine and epihalohydrin is prepared, the reaction product may be reacted with other nitrogen-containing compounds including, for example, alkanol amines, urea, etc., instead of with the same or different alkyl amine as hereinbefore described. Illustrative alkanol amines include ethanol amine, propanol amine, butanol amine, pentanol amine, hexanol amine, etc. As hereinbefore set forth, a oarboxylic acid salt of the condensation product prepared in the above manner is used as an additive to hydrocarbon oil. Any suitable carboxylic acid may be utilized in forming the salt and preferably comprises a dibasic oarboxylic acid containing at least 6 and preferably at least l0 carbon atoms per molecule, and more particularly from about 20 to about 50 carbon atoms per molecule. The preferred acids are referred to herein as high molecular weight polybasic carboxylic acids and include adipic, pimelic, suberic, azelaic, sebacic, phthalic, etc., aconitic, citric, etc., hernimellitic, trimesic, prehnitic, mellophanic, pyromellitie, mellitic, etc., and higher molecular polybasic oarboxylic acids. It is understood that a mixture of acids may be employed.

A particularly preferred acid comprises a mixed byproduct acid being marketed commercially under the trade name of VR-l Acid. This acid is a mixture of polybasic acids, predominantly d-ib asic, has an average molecular weight by basic titration of about 750, an average molecular weight of about 1000, is a liquid at 77 F., has an acid number of about 150 and iodine of about 36, and contains about 37 carbon atoms per molecule.

Another particularly preferred acid comprises a mixed acid being marketed commercially under the trade name of Empol 1022. This dimer acid is a dilinoleic acid and is represented by the following general formula:

This acid is a viscous liquid, having an apparent molecular Weight of approximately 600. It has an acid value of 180492, an iodine value of 80-95, a saponificatiorr value of 185-195, a neutralization equivalent of 2903l0, a refractive index at 250C. of 1.4919, a specific gravity at 15.5C./15.5C. of 0.95, a flash point of 530 F., a fire point of 600 F., and a viscosity at C. of 100 centistokes.

As hereinbefore set forth dibasic acids containing at least 6 carbon atoms per molecule are'preferred. However, it is understood that dibasic acids containing less than 6 carbon atoms also may be employed in some cases and thus include oxalic, malonic, succinic, glutar-ic, etc. Similarly monobasic oarboxylic acids may be used in forming the salt in some cases and thus include formic, acetic, propionic, butyric, valeric, trimethylacetic, but preferablycontains at least 6 carbon atoms including capnoic, caprylic, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric, cerotic, etc., decyleni'c, dodecylenic, palmito'leic, oleic, ricino leic, petroselinic, vaccenic, linoleic, linolenic, eleostearic, licanic, parinaric, gadoleic, arachidonic, cetoleic, erucic, selacholeic, etc.

It is understood that the various acids which may be used in preparing the salt are not neccesar-ily equivalent and also that mixtures of acids may be employed in preparing the salts.

.Thesalt of the carboxylic acid and epihalohydrinamine condensation product may be prepared in any suitable manner and may comprise the acid, neutral or basic salt. When utilizing a dibasic acid in forming the salt, the acid salt generally is preferred, although the neutral salt may be desirable in some cases. When using a monobasic carboxylic acid in forming the salt, the neutral or basic salt in general is preferred. The neutral salt is formed by using the reactants in a proportion to give an equivalent number of amine groups and an equivalent number of carboxylic acid groups. Thus, when using a monocarboxylic acid, one mol proportion of the carboxylic acid is used per each amine group in the condensation product. When using a dioarboxylic acid, one mol proportion of the acid per amine group in the condensation product produces an acid salt. Therefore, when using a dicarboxylic acid and a neutral salt is desired, one-half molproportion of the acid is used per each amine group in the condensation product. In some cases an excess of acid or condensation product may be present in the product but generally is not preferred.

The salt may be prepared in any suitable manner and, in general, is readily prepared by mixing the acid and condensation product at ambient temperature, preferably with vigorous stirring. While the salt is readily prepared at room temperature, in some cases it is of advantage to heat the mixture at slightly elevated temperature which generally will not exceed about 200 F. Excessive temperature must not be used in order not to cause formation of esters, amides or other undesired reaction products. Depending upon the particular condensation product and acid employed, it may be desirable to utilize a solvent, either in forming a more fluid mixture of the condensation product and/ or acid before mixing or during the mixing thereof. Any suitable solvent may be employed and preferably is an aromatic hydrocarbon including benzene, toluene, xylene, ethylbenzene, cumene, etc., or mixtures thereof. In other cases the solvent may be selected from alcohols, ethers, ketones, etc. In many cases it is desired to market the salt as a solution in a suitable solvent and conveniently the same solvent is used during manufacture of the salt as is desired in the final product.

It is understood that the different salts which may be prepared and used in accordance with the present invent-ion are not necessarily equivalent. For example, one salt may be effective for a certain purpose in one hydrocarbon oil, while another salt may be eifective in the same substrate for a different purpose or in different substrates for the same or different purposes.

The concentration of salt to be incorporated in the hydrocarbon oil will depend upon the particular use. For example, when utilized to prevent heat exchanger deposits, the salt generally is used in a concentration of from 1 to 1000 parts per million by weight of the hydrocarbon oil. When used for other purposes, the salt may be used in a concentration of from about 0.0001% to about 1% or more by weight of the hydrocarbon oil. It is understood that the salt is incorporated in the hydrocarbon oil in any suitable manner and generally is effected with stirring in order to obtain intimate mixing thereof. However, when introduced in a flowing stream of oil, mixing is accomplished by turbulence normally encountered therein.

As hereinbefore set forth, the salt is particularly advantageous for use to prevent deposit formation in heat exchangers. Such heat exchange is utilized, for example, in a hydrotreating process in which oil is subjected to hydrogen treating in the presence of a catalyst comprising alumina-molybdenum oxide-cobalt oxide or alumina-molybdenum sulfide-cobalt sulfide. The oil, which may comprise gasoline, kerosene, gas oil or mixtures thereof, is introduced into the process at a temperature of from about ambient to 200 F. and is passed in heat exchange with reactor efliuent products being withdrawn at a temperature of from about 500 to about 800 F. The charge is heated by such heat exchange to a temperature of from about 300 to about 600 F., then is heated in a furnace or otherwise to a temperature of from about 625 to about 800 F. and passed with hydrogen in contact with the catalyst. This treatment serves to remove impurities and to hydrogenate unsaturates contained in the charge. Another illustration is a reforming process in which gasoline is contacted with hydrogen in the presence of a platinumcontaining catalyst at a temperature of from about 700 to about 1000 F. and the hot eflluent product from the reaction zone is passed in contact with the charge in order to cool the former and heat the latter.

An example in which oil is subjected to fractionation and the charge is passed in heat exchange with the hot eflluent products is in a crude column. In this column, crude oil is subjected to distillation at a temperature of from about 600 to about 700 F. in order toremove lighter components as overhead and/ or side streams. In some cases the charge first is passed in heat exchange with the overhead and/ or side streams from this column and then is passed in heat exchange with the hotter products withdrawn from the bottom of the crude column. In this way the charge is progressively heated and the hotter products are cooled.

The above examples are illustrative of typical uses of heat exchange to eflect economies in the process. However, difliculty is experienced in the heat exchange due to deposit formation, with the consequent necessity of interrupting plant operation as hereinbefore set forth. In accordance with the present invention, deposit formation in heat exchanger is reduced to an extent that normal plant operation need not be interrupted for this reason.

It is understood that the advantages of the present invention may be obtained in any suitable heat exchange equipment. In general, this equipment comprises a series of tubes or a tube coil positioned within a shell. One of the fluids is passed through the tubes, while the other fluid is passed through the shell. The heat exchange equipment generally is positioned externally to a fractionator or reactor. However, in some cases, the heat exchanger takes the form of a reboiler or condenser, and either a tube coil or a shell containing tubesis positioned within the lower or upper portion of the fractionator or reactor.

When the salt of the present invention is added to a finished product, it is incorporated therein with suitable mixing, and may be used along with other additives to be added to the oil for specific reasons as, for example, metal deactivator, antioxidant, synergist, cetane improver, etc. As hereinbefore set forth, the salt serves to improve the oil in many ways including preventing deposition of sediment, preventing formation of varnish or sludge, preventing corrosion of metal surfaces, depressing pour point, preventing icing, etc. It is understood that all of these improvements are not necessarily obtained in all substrates with the same additive. However, the different oils will be improved in one or more ways as hereinbefore set forth.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I The salt of this example is the VR-l acid salt of the condensation product of epichlorohydrin and tallow amine. The condensation product was prepared by the reaction of equal mol proportions of hydrogenated tallow amine (Armeen HTD) and epichlorohydrin. It will be noted that the tallow amine is a mixture of primary amines predominating in 16 to 18 carbon atoms per alkyl group. The reaction was effected by first forming a solution of 2 mols of epichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. of xylene and 200 cc. of 2-propanol. A separate solution of 2 mols of Armeen HTD was prepared in an equal volume of xylene. One mol of the latter solution was added gradually to the epichlorohydrin solution, with stirring and heating at 5560 C. for a period of 2.5 hours. Then another mol of Armeen HTD was added gradually to the reaction mixture, stirred and reacted at 80 C. for 2.5 hours. One mol of sodium hydroxide then was added with Stirring and heating at 85 90 C. for 3.5 hours, after which another mol of sodium hydroxide was added and the mixture stirred and reacted at 8590 C. for one hour. Following completion of the reaction, the mixture was cooled, filtered, and the filtrate then was distilled to remove the alcohol. The product was recovered as a 50% by weight solution of active ingredient in xylene.

10.04 grams of the 50% solution of the condensation product prepared in the manner described above was mixed with 11.6 grams of VR-l acid. As hercinbefore set forth, VR-l acid is a dibasic acid containing about 37 carbon atoms per molecule. 11.6 grams of xylene was added to the mixture so that a final solution of 0% active ingredient was prepared. The mixing was effected at room temperature with stirring, following which the mixture was heated at 140 F. for one hour on a water bath. The product was recovered as a viscous, dark brown liquid and is an acid salt because two equivalents of carboxylic acid groups were used per each amine group in the condensation product.

Example II A sal-t prepared in the manner described in Example I was evaluated as a corrosion inhibitor. In this evaluation, which is a modified MIL-1.25017 procedure, 300 cc. of depolarized isooctane, to which 30 cc. of synthetic sea water is added, is placed in a beaker open to the atmosphere. A steel strip of 95 thickness and A" wide is welded to a similar strip enclosed in a glass tube. The probe then is suspended in the mixed oil-water suspension, heated to and maintained at 100 F. for 20 hours. The extent of corrosion is determined by measuring the loss in conductivity which in turn is converted to loss of steel, reported as micro inches penetration. When a blank or control sample of the oil-water emulsion is evaluated in the above manner, the corrosion is reported as about 150 micro inches penetration. In contrast, in another evaluation in which 60 parts per million of the salt described in Example I was incorporated in the oil-water suspension, the corrosion was only 13 micro inches penetration.

From the above data it is seen that the salt of the present invention was very efiective in retarding corrosion.

Example III A salt prepared in the manner described in Example I also was evaluated as a corrosion inhibitor by a different method. This method is known as the Humidity Cabinet Test. In this test, a highly polished steel panel is dipped into a viscous naphthenic mineral oil, excess oil is drained, and the panel is placed in a humidity cabinet maintained at 120 F. in an atmosphere saturated with water. The panels are rotated slowly, and the days required for visible corrosion to appear on the panel is reported. A panel dipped in a control sample of the oil (not containing this additive) undergoes visible corrosion in 2-3 hours.

1% by weight of a salt prepared in the manner described in Example I was incorporated in another sample of the oil. The panel dipped in this oil and then placed in the humidity cabinet did not undergo visible corrosion until after 768 hours of exposure at 120 F. to the atmosphere saturated with water. Thus, it will be seen that this additive served to considerably reduce corrosion.

Example IV The salt of this example is the oleic acid salt of the condensation product of epichlorohydrin and tallow amine. This condensation was effected in substantially the same manner as described in Example I. The salt was prepared by mixing 100.2 grams of the 50% by weight solution of the condensation product in xylene with 41 grams of oleic acid and 41 grams of xylene. The mixture was stirred and heated at 124 F. for 30 minutes. The product was a neutral salt, was recovered as a 50% solution of active ingredient, and was a slightly viscous, reddish brown liquid.

Example V The salt prepared in the manner described in Example IV is used as a pour point depressant in lubricating oil. The lubricating oil is a commercial S.A.E. 20 Mid-Continent solvent extracted oil which, without additive, has an ASTM cold test of 5 F. and an ASTM pour point of 10 F. 1% by weight of the salt prepared as described in Example III is incorporated in a sample of this lubricatnig oil and serves to reduce the ASTM cold test and the ASTM pour point.

Example VI A salt prepared in substantially the same manner as described in Example I is evaluated in a method referred to as the Erdco Test. In this method, heated oil is passed through a filter, and the time required to develop a difierential pressure across the filter of 25 in. Hg is determined. It is apparent that the longer the time, the more efiective is the additive. However, with a very eifective additive, the time to reach a difierential pressure across the filter of 25 in. Hg is lengthened beyond reasonable limits that the test is stopped after about 300 minutes and the differential pressure at that time is reported.

The oil used in this example is a commercial J.P.-6 jet fuel. When evaluated for use as a jet fuel, which normally encounters higher temperature, the test is run at a higher temperature. The preheater is run at a temperature of 400 F. and the filter is run at a temperature of 500 F. The jet fuel, without additive, developed a differential pressure across the filter of 25 in. Hg in 60 minutes. The salt prepared in the manner described in Example I is added in a concentration of 0.005% by weight to another sample of the jet fuel and serves to considerably lengthen the time before a diiferential pressure of 25 in. Hg is reached.

Example VII A salt prepared in substantially the same manner as described in Example I is also evaluated according to the C.F.R. fuel coker thermal stability test. In this test, the oil heated to the specified temperature is passed through'the annular space surrounding a heated inside tube of 17" length and /2" diameter positioned within an outside tube of W inside diameter. The inside tube is heated by means of a heating coil positioned therein to a temperature of either 300 or 400 F. depending upon the particular fuel being evaluated. The test is conducted for 300 minutes, at a pressure of pounds per square inch, and a flow rate of 6 pounds of fuel per hour. Following the run the equipment is dismantled, 13" or less of the inner tube is marked off in l increments and the deposits on the outside surface of the heated inner tube are rated by visual comparison with standard metal coupons. In general the rating is substantially as follows:

clean and bright metal dulled but not discolored light yellow discoloration yellow to tan discoloration anything darker or heavier than 3 The ratings for the individual 1" increments are added together to give a final tube rating. Military specifications for jet fuels require that none of the 1" increments rates poorer than 3.

The fuel evaluated in this example is a J.P.6 commercial fuel and was tested at 400 F. A sample of the jet fuel evaluated in the above manner had a tube rating of 15. 50 parts per million by weight of the salt described above is incorporated in another sample of this fuel and, when evaluated in the above manner, willconsiderably lower the tube rating.

Example VIII The salt prepared in the manner described in Example I is used in a commercial Unifining Unit to prevent heat exchanger deposits. In this unit gasoline is subjected to hydrotreating in the presence of an alumina-molybdenum oxide-cobalt oxide or alumina-molybdenum sulfide-cobalt sulfide catalyst. The gasoline charge is introduced at a temperature of 200 F. and is passed in heat exchange with reactor eflluent being withdrawn at a temperature of about 675 F. This serves to heat the charge to a temperature of about 550 F. and to cool the reactor effluent to a temperature of about 325 F. In this unit the charge is passed through the tubes of the exchanger and the reactor efliuent is passed through the shell. 25 parts per million by weight of the salt is incorporated in the gasoline before the same is passed into the exchanger and this serves to prevent heat exchanger deposits and to permit extended use of the heat exchanger without requiring shutting down the plant because of the plugging of the heat exchanger tubes.

I claim as my invention:

1. Hydrocarbon oil containing from about 0.000l% to about 1% by weight of a salt of a car-boxylic acid of from about 6 to about 50 carbon atoms per molecule and the condensation products of from 1 to 2 mols of an epihalohydrin compound with from 1 to 2 mols of an aliphatic amine of from about 12 to about 40 carbon atoms per molecule, said salt being the reaction product of from 1 to 2 mol proportions of acid per 1 to 2 mol proportions of amine group in the condensation product.

2. Hydrocarbon oil containing from about 0.0001% to about 1% by weight of a salt of a polybasic carboxylic acid containing from about 6 to about 50 carbon atoms per molecule and the condensation product of from 1 to 2 mols of epichlorohydrin with from 1 to 2 mols of an alkyl amine having from about 12 to about 40 carbon atoms per molecule, said salt being the reaction product of from 1 to 2 mol proportions of acid per 1 to 2 mol proportions of amine group in the condensation product.

3. Hydrocarbon oil containing from about 0.0001% to about 1% by weight of a salt of a dibasic carboxylic acid containing from about 6 to about 50 carbon atoms 12 per molecule and the condensation product of from 1 to 2 mols of epichlorohydrin with from 1 to 2 mols of an alkyl amine having about 12 to about 40 carbon atoms per molecule, said salt being the reaction product of from 1 to 2 mol proportions of acid per 1 to 2 mol proportions of amine group in the condensation product.

4. Hydrocarbon oil containing from about 0.000l% to about 1% by weight of an acid salt of a dibasic carboxylic acid containing from about 20 to about carbon atoms per molecule and the condensation product of from 1 to 2 mols of epichlorohydrin with from 1 to 2 mols of tallow amine, said salt being the reaction product of from 1 to 2 mol proportions of acid per 1 to 2 mol proportions of amine group in the condensation product.

5. Hydrocarbon oil containing from about 0.000l% to about 1% by weight of a salt of a monobasic carboxylic acid containing from about 6 to about 50 carbon atoms per molecule and the condensation product of from 1 to 2 mols of epichlorohydrin with from 1 to 2 mols of an alkyl amine having from about 1 2 to about 40 carbon atoms per molecule, said salt being the reaction product of from 1 to 2 mol proportions of acid per 1 to 2 mol proportions of amine group in the condensation product.

6. Hydrocarbon oil containing from about 0.0001% to about 1% by weight of an oleic acid salt of the condensation product of from 1 to 2 mols of epichlorohydrin with from 1 to 2 mols of tallows amine, said salt being the reaction product of from 1 to 2 mol proportions of acid per 1 to 2 mol proportions of amine group in the condensation product.

References Cited in the file of this patent UNITED STATES PATENTS 1,954,133 Jacobs Apr. 10, 1934 2,130,947 Carothers Sept. 20, 1938 2,143,388 Schlack Jan. 10, 1939 2,214,352 Schoeller et a1. Sept. 10, 1940 2,454,547 Bock et a1. Nov. 23, 1948 2,475,410 Smith et a1. July 5, 1949 2,479,480 Dudley Aug. 16, 1949 2,587,546 Matuszak Feb. 26, 1952 2,753,372 Lundberg July 3, 1956 2,908,640 Dougherty Oct. 13, 1959

Claims (1)

1. HYDROCARBON OIL CONTAINING FROM ABOUT 0.0001% TO ABOUT 1% BY WEIGHT OF A SALT OF A CARBOXYLIC ACID OF FROM ABOUT 6 TO ABOUT 50 CARBON ATOMS PER MOLECULE AND THE CONDENSATIO PRODUCTS OF FROM 1 TO 2 MOLS OF AN EPIHALOHYDRIN COMPOUND WITH FROM 1 TO 2 MOLS OF AN ALIPHATIC AMINE OF FROM ABOUT 12 TO ABOUT 40 CARBON ATOMS PER MOLECULE, SAID SALT BEING THE REACTION PRODUCT OF FROM 1 TO 2 MOL PROPORTIONS OF ACID PER 1 TO 2 MOL PROPORTIONS OF AMINE GROUP IN THE CONDENSATION PRODUCT.