US2942028A - Addition agents for distillate fuel oils and stabilized distillate fuel oils containing the same - Google Patents

Description

United States Patent ADDITION AGENTS FOR DISTILLATE FUEL OILS AND STABILIZED DISTILLATE FUEL OILS CON- TAINING THE SAME Elizabeth L. Fareri, Pittsburgh, and John P. Pellegrini,

Jr., Blawnox, Pa., assignors to Gulf Research & Development Company, Pittsburgh, Pa., a corporation of Delaware N0 Drawing. Filed Aug. 12, 1954, Ser. No. 449,491

7 Claims. (Cl. 260-4675) This invention relates to addition agents for distillate fuel oils and stabilized distillate fuel oils containing the same. More particularly, the invention is concerned with the stabilization of distillate fuel oils containing a mixture of straight run and catalytically cracked fuel oil distillates by incorporation therein of the herein dis- 7 closed novel adducts.

Distillate fuel oil compositions containing mixed straight run and catalytically cracked fuel oil distillates have proved exceptionally. troublesome with regard to sludge deposition during storage at normal atmospheric temperatures. It has been found that the sludging characteristics of such mixed, or blended, fuel oil distillates are strikingly poor, much poorer than can be accounted for from the known sludging characteristics of the individual component fuel oil distillates alone. Although the exact cause for the unusual instability of mixed distillate fuel oils is not fully understood, the unusual character and the unexpectedly large volume of sludge formed by such mixed distillate fuel oils have led those skilled in the art to regard the problem of sludge deposition in mixed distillate fuel oils as separate and distinct from that of sludging or solids deposition in other oils.

More particularly, straight run distillate fuel oils contain predominantly paraifinic components. Sludge deposition in these oils, where such occurs, is considered to result from the presence of minor amounts of components that are not normally present and which impart instability to the otherwise stable oil, e.g., impurities picked up during refining, rather than from the inherent instability of the hydrocarbon components of the oil.

'The problem of sludge formation in such oils is con- :sidered essentially one involving oxidation and the formation of insoluble oxygenated products.

catalytically cracked fuel oil distillates on the other hand are rich in olefinic, aromatic and mixed olefinicaromatic compounds. Sludging in such oils is considered to involve primarily condensation and/or polymerization type reactions which result in the formation of insoluble reaction products of relatively high molecular weight.

Still further, sludge deposition in blends of straight run and catalytically cracked fuel oil distillates is an entirely distinct problem from that for either component oil. While the sludge formed in such blended fuel oils very probably contains some sludge of the type formed in each component oil, the sludge formed in blended fuel oils is consistently greatly in excess of the amount that can be accounted for from the known sludging tendencies of the individual component oils, thus indicating the existence of a special problem.

The problem of sludge deposition in mixed straight run and catalytically cracked fuel oil distillates is not only distinct from that of sludge deposition in individual fuel oil distillates, but also from that of sludge deposition in lubricating oils and from that of gum formation in gasolines. In the former instance sludge formation is attributed to the high temperature oxidation of the highly parafiinic components contained in the oil, the reaction of acidic oxygenated products with metals contacted therewith, and, in the case of crankcase lubricants, sludge formation'is additionally attributed to the presence of foreign materials such as water, dust particles, carbon, incompletely burned fuel and the like.

Gum formation in gasolines on the other hand is attributed primarily to the oxidation of olefinic linkages (as opposed to oxidation of paraflinic compounds); Moreover, the gums formed in gasoline are not normally insoluble in the gasoline as is the case with sludge; instead, deposition of gums from gasoline occurs upon vaporization of the latter, rather than during storage as is the case with blended fuel oils.

We have found that sludge deposition in mixed catalytically cracked and straight run fuel oil distillates can be substantially diminished by incorporation therein of small amounts of the novel adducts of this invention. The adducts included by this invention are the reaction products formed by the substantially spontaneous reaction of a phenolic compound and a 1,3-diaminopropane having the following general formula:

where R is an aliphatic radical containing from 8 to 30 carbon atoms, and where the mol ratio of reactants is from about 0.5 to about 1 mol of the 1,3-diaminopropane per equivalent weight of phenolic compound. The

invention not only includes, the novel adducts themselves but also stable distillate fuel oil compositions containing the same. i

The adducts of this invention are prepared by reaction of a phenolic compound with a 1,3-diaminopropane that contains a long-chain aliphatic radical-substituted, secondary amino grouping. The aforesaid reaction takes place substantially spontaneously at room temperature. In most cases evolution of heat is observed, but in some cases the reaction has been observed to occur with the adsorption of heat. Although even the endothermic reactions take place spontaneously at room temperature, in the case of strongly endothermic reactions, or in the case .of highly viscous reactants, the reaction may be caused to take place substantially spontaneously with the application of moderate heat. The term substantially spontaneously as used herein is meant to include not only spontaneous reactions but also those in which moderate heating is utilized to accelerate and/or insure completion of the reaction. Subject to the foregoing qualification, and provided that the decomposition temperatures of the reactants and the reaction products are not exceeded, the reaction may be carried out at any temperature between about 10 and about C. In order to produce the desired reaction products, the ratio of the reactants in the reaction mixture should be from about 0.5 to about 1 mol of the 1,-3-diaminopropane per equivalent weight of phenolic compound. The terms mol and equivalent weight are used in their. conventional sense herein. Thus, the term mol is used to denote a gram-molecular weight, while the term equivalent weigh as applied to the phenolic compounds, is used to denote that amount that would furnish one gram-ionic weight of hydrogen ion, if the compound were completely ionized. By way of example, an equivalent weight of phenol is equal to the gram-molecular weight of phenol; an. equivalent weight of catechol is equal to one-half the gram-molecular weight of catechol.

'I'he diaminopropanes that form reaction products inwhere R is an aliphatic radical containing from 8 to 30 carbon atoms. Thus, the present invention includes, for example, phenolic adducts of long-chain alkyl-, alkeriyland alkadienylaminopropylamines. Specific examples of such diamino compounds are 3-octylaminopropylamine, 3 decylaminopropylamine, 3 tetradecylaminopropylamine, 3-tetradecenylaminopropylamine, 3-eicosylaminopropylarnine, 3-eicosenylaminopropylamine, 3-docosyla- 'ininopropylamine, 3 docosenylaminopropylamine, 3-docosodienylaminopropylamine, and 3-triacontanylaminopropylamine. Within the general class of 1,3-diaminopropanes capable of forming the adducts of this invention, 'the diamines in which the long-chain, aliphatic N-sub- 'sti-tuent of the secondary amino grouping is an alkyl or hlkfe nyl group containing at least 12, and preferably from 1-2 to 18 straight chain carbon atoms are considered to ram especially effective addition agents. Examples of l-,-3-diaminopropanes which are considered to form especially effective addition agents for the purposes of this invention are the 3-dodecyland the 3-hexadecylaminopropylamines, and especially the 18 carbon alkylalken- 3 1-, and alka-dienyl-substituted 1,3-diaminopropanes, such as the 3-octadecy1-, 3-octadeeenyl-(3-oleyl-), and 3-octadecadienylaminopropylamines. Although aliphatic hydrocarbon N-substituted 1,3-diaminopropanes are preterred, the invention includes phenolic reaction products "derived from diamines in which the N-substituent of the secondary amino grouping is itself substituted with one or more groups that contain elements such as oxygen, sulfur, nitrogen, phosphorus or halogen and that do not interfere with the oil-solubility of the adduct. Representative examples of 1,3-diaminopropanes containing such substituents are 3-ricinoleylaminopropylamine and 3- "(chlorostearyDaminopropylamine. Mixtures of 1,3-di- "'aminopropanes, such as are formed when thelong-chain,

aliphatic N-substituent in the secondary amino grouping is derived from mixed fatty acids obtained from naturallysoccurring fats and oils, form highly effective phenolic *adduct's Within the scope of this invention. In such instancesthe aliphatic N-substituent in the secondary amino :grouping will be a straight-chain, monovalent hydrocarbon radical containing from 8 to 20 carbon atoms. Ex- "amples of such mixtures of 1,3-diaminopropanm are 3-tallow'-aminopropylamine, 3 soya aminopropylamine, and 3-coco-aminopropylamine, where the respective'N-substituents are mixed alkyl and unsaturated alkyl groups derived from animal tallow (C -C fattyacids,

fsoybean (C -C fatty acids, and coconut (C -C iatty acids.

The phenolic compounds that form adducts with the -herein disclosed N-substituted 1,3-diaminopropanes in- "-butylphenol, 3,5-diethylphenol, 3-ethyl-5-propylphenol,

m propylph enol, m butylphenol, m amylphenol, and p-octy1phenol, bis-(2-hydroxy-3,5 diamylphenyl)sulfide, mono-, his, and tris-alpha-methylbenzylphenols, alphaphenylethylcatechols, various bis-(hydroxyalkylphenyl)- alkanes, representative of which are 2,2-bis-(4-hydroxy- S-meth'ylphenyDpropane, 1, 1-bis-(2-hydroxy-3,5 -dimethy1pheny1)isobutane, bis-.(2-hydroxy-3-t-butyl 5 methylphenyl)methane, and 1,1-bis-(2-hydroxy-3 t butyl-S- methylphenyl)ethane. Although phenolic compounds in which the phenolic nucleus is substituted with hydrocarbon substituents are preferred, the invention also includes the use of phenols containing non-hydrocarbon substituents-suchas nitro,-chloro, bromo, aminoand like groups, specific examples of such phenols being -pnitfo phenol, p-amino phenol, and pentachloro :phenol. Commercial mixtures of phenols are also suitable for the purposes of this invention. Such mixtures may be those recovered by treatment of'industrial wastes, by treatment of petroleum refinery process waters, or from coal tar distillation or the like. 7

Although the exact nature of the adducts herein described has not been definitely ascertained, it is thought likely that these adducts partake of the nature of substituted ammonium salts. Examples are given below of the formulae structure thought to be involved.

(c) H R At (a) is shown the probable formula for the reaction product of equimolar proportions of a diamine and a monohydric phenolic compound. At (b) is shown the probable formula for the reaction product of 0.5 mol diamine with 1 mol of mo'nohydric phenolic compound. At (c) is shown the probable formula for the reaction product of equimolar proportions of a diamine and a dihydric phenolic compound. In these formulae XO-- represents the negative ion 'of'a monohydric phenol,

EXAMPLE I Approximately 7.5 grams (0.05 combining gram-molecular weight) of mixed m-alkyl phenols were admixed and reacted with 20.0 grams (0.05 combining gram-molecular weight) of 3-tallow"-aminopropylamine. The reaction occurred spontaneously and was complete in less than about fifteen minutes. A temperature change in the reaction mixture of from 29 to 35 C. was noted during the course of thereaction. To insure completion of the reaction the mixture was heated to C., after no further spontaneous temperature rise was apparent. The

mixed m-alkyl phenols employed contained predominantly monoand di-m-alkyl phenols in which the alkyl substituents contained not more than 4'carbon atoms each, andi'n which the total alkyl-carbon atoms'was'between 3 and 5, together with substantial proportions of 4- and S-indanol. The mixture contained approximately 95'percent phenols. More particularly, in addition to indanols, the mixed phenols of this example contained m-alkyl phenols such as: 3-methyl-5-ethylpheno1, 3-methyl-5-propylphenol, 3-methyl-5-butylphenol, 3,5-diethylphenol, 3-ethyl-5-propylpheno1, m-propylphenol, m-butylphenol, and m-amylphenol. A sample of the mixed phenols had the following approximate make-up:

Percent by weight 4-indanol S-indanol 15 3-methyl-5-ethylphenol 10 n-Propylphenols (meta and para) 5-10 Mixed meta-substituted phenols of type indicated- 45-50 Apparent specific gravity at /20 C 1.03 Boiling range (ASTM D-850):

I.B.P 240 C.

D.P 280 C. Vapor pressure at 20 C 0.01 mm. Hg. Viscosity at 20 C Approx. 70 cps. Solubility in water at 20 C 0.08% by wt. Solubility of water in 20 C 5% by wt. Refractive index at C 1.543 Behavior on cooling, sets to glass or clouds below C. Average weight per gal. at 60 F 8.63 lb. Flash point (open cup) 250 F.

The 3-tallow"-aminopropylamine employed in this example contained approximately 80 percent diamines and was made up of a mixture of 3-fatty alkyland alkenylaminopropylamines. The mixture had a theoretical molecular weight of 320, a combining weight of approximately 400, and a melting range of approximately 44 to 48 C. The fatty alkyl and alkenyl substituents of the mixed diamines were derived from animal tallow fatty acids. Accordingly, the 3-"tallow"-aminopropylamine contained predominantly 3-oley1aminopropylamine (3- octadecenylaminopropylamine), together with lesser proportions of 3-hexadecyland 3-octadecylaminopropylamines, and small amounts of 3-myristyl-and 3-linoleylaminopropylamines.

The adduct prepared according to the foregoing procedure was a brown-colored liquid material having the fol lowing analysis: Nitrogen, percent, 5.64.

EXAMPLE II The adduct formed by reaction of mxed malkyl phenols and 3-tallow-aminopropylamine in the ratio of 0.5 mol diamine per equivalent weight of phenols (1:2 mol ratio) was prepared by reacting 15.0 grams (0.1

combining gram-molecular weight) of the mixed m-alkyl phenols described in Example I with 20 grams (0.05 combining gram-molecular weight) of the 3-tallow-aminopropylamine defined in Example I.

analysis: Nitrogen, percent, 4.57.

EXAMPLE III The reaction product formed by reacting the 3-tallow- WTPQP Q P P pil i l with mbfed i admixing 11.6 grams (0.05 combining gram-molecular,

weight) mixed alpha-methylbenzylphenols and 20.0 grams (0.05 combining gram-molecular weight) of 3- tallow-aminopropylamine. Again the reaction proceeded spontaneously, the temperature changing during the course of the reaction (less than 15 minutes) from 27 to 35 C. The mixture was then heated to 110 C.

The mixed alpha-methylbenzylphenols employed in the reaction were an approximately percent pure mixture of substituted phenols containing predominantly ortho- (alpha-methylbenzyl)phenol, bis-(alpha-methylbenzyD- phenol, and tris(alpha-methylbenzyl)phenol in the respective approximate weight proportions of 12 percent, 2 percent and 36.7 percent, the balance of the over-all mixture being made up of higher substituted phenols.

The reaction product resulting from the foregoing re action was a brown-colored liquid material having the following analysis: Nitrogen, percent, 5.49.

EXAMPLE IV Another adduct was formed by reacting the 3-tallowaminopropylamine of Example I with bis-(2-hydroxy-3,5- diamylphenyl)sulfide in a ratio of 1 mol of diamine per equivalent weight of the bis-phenol sulfide (2:1 mol ratio). The reaction was carried out by admixing 20.0 grams (0.05 combining gram-molecular weight) of 3- tallow-aminopropylamine with 12.5 grams (0.025 combining gram-molecular weight) of the bis-phenol sulfide.

The materials reacted spontaneously, .a temperature change of 25 to 35 C. being observed. When no further temperature change occurred, the mixture was heated to C.

The product of the foregoing reaction was a viscous, brown-colored liquid material having the following analysis:

Nitrogen, percent Sulfur, percent EXAMPLE V Another adduct was prepared by reacting 3-tallowaminopropylamine and para-octylphenol in a ratio of 1 mol of diamine per equivalent Weight of phenol (1:1 mol ratio). According to this example 8.0 grams (0.02 combining gram-molecular weight) of the 3-"ta1low-aminopropylamine of Example I were admixed with 4.13 grams (0.02 mols) of p-octylphenol. The temperature of the reaction mixture changed from 25 to 29 C. during the reaction, which proceeded spontaneously. The mixture was heated to 110. C. after no further spontaneous temperature change was noted, in order to insure completion of the reaction. The product of the reaction was a tan-colored liquid material having the following analysis: Nitrogen, percent, 5.61.

EXAMPLE VI A further adduct was formed by reacting 3-laurylaminopropylamine and mixed m-alkyl phenols in a ratio of 1 mol of diamine per equivalent weight of m-alkyl phenols (1:1 mol ratio). In this example 6.06 grams (0.02 mol) of 3-laurylaminopropylamine were admixed with 3.00 grams 0.02 combining gram-molecular weight) of the mixed m-alkyl phenols of Example I. The materials reacted spontaneously, a temperature change of 28 to 20 C. being noted. At the conclusion of the spontaneous reaction period, the mixture was heated to 110 C. to insure driving the reaction to completion. The product of the foregoing reaction was a brown-colored liquid material having the following analysis: Nitrogen,

percent, 7.68.

EXAMPLE VH An additional adduct was prepared by reacting 3 -(2- ethylhexyDaminopropylamine and mixed m-alkyl phenols in matte of 1 n 'oier amine p'e'r equivalent weight or pheridls (1:1 e101 ratio). In 'this reaction 9.32 grams (0505 non of 3-"(2 ethylhexyl)amiriopropylarriine were admixed with "-7.50 grams (0.05 combining gram-molecu- Iar "weight') of the mixed -'m-alkyl phenols referred to in Example I. The reaction proceeded spontaneously, a tem'perature change of from 26 to 48C. being noted, with heat to 100 C. being added thereafter. The product of this reaction was a brown-colored liquid material having the following analysis: Nitrogen, percent, 8.96.

EXAMPLE VIII "In'thisexainple 9.32 grams (0.05 mol) of 3-(2-ethylhexyDaminopropylamine were admixed with 15.00 grams (0.1 combining 'gfam rnolecular Weight) of the mixed 'r'n-alkyl phenols described in Example I. The ratio of reactant'was 0. 5 mol 'diamine 'per equivalent weight of phenols ('1:2 mol ratio). The materials reacted spont ane'oiisly, a temperature change of from 26 to 53 C. being noted.- The reaction mixture was then heated to 100 C. The product-of this reaction was a browncolored liquid material having the following analysis: "Nifiogil, percent, 6.32.

The foregoing examples indicate the manner and ease "of preparation of the adducts of'this invention, and also described specific embodiments of said adducts. Other adducts included by'th'e invention can be prepared similarly as "above by reaction in the indicated proportions "o'fother herein disclosed 1,3-diaminopropanes with the foregoing phenols, or with other members of the herein dis'closed class of phenols. V V

The addition of very small amounts of the reaction products of the above-described type to blended distillate fuel oils containing both straight run and catalytieauy cracked components has been found to provide a niarked improvement in the sludging tendencies of the oils. Naturally, the various adducts of the herein disclosed class do not possess exactly identical efiective- ;-ne s s, and the most advantageous concentration for each such adduct will depend to some extent upon the particular adduct used. Also, the minimum effective inhibitor concentration may vary somewhat according to the specific nature of the mixed fuel oil. In general, however, theherein disclosed reaction products are useful in concentrations of as little as about 0.005 percent to about 1.0 percent by weight of the composition. Major improvement of the sludging characteristics of mixed fuel oils 'is usually obtainable by incorporation therein of from about 0.01 to about 0.05 percent by weight of the heroin disclosed class of reaction products. Nevertheless, in some cases 'it'may be advantageous to add as much as about 0.1 percent by weight of the adducts. In veryunusual cases it'may be found desirable to add as much as about 1.0 percent by weight of the adducts.

The addition agents included by this invention may be incorporated in the mixed fuel oils in any suitable manner. Thus, the adducts may be formed in situ in the oil, they may be added, per se, directly to the mixed fuel oil, or they may be added in the form of concentrates, either immediately after formation of the mixture of distillate'fuel oils, or after the mixture has been stored'for a substantial period of time. Alternatively, the. sludge inhibiting addition agents of this invention may be-formed in situ in, or added per se or in the form of 'concentratedsolutions to, either the straight run or thecatalytically cracked fuel oil distillate, prior to blending of the components to form a mixed fuel oil. Suitable concentrates containing thesludge inhibiting adducts of this invention comprise, for example, 'mineral oil solutions or dispersions containing'from about to 75 percent, and'prefe'rably from about to 50 percent, active ingredient. Where the concentrate is in the form of a dispersion, it may be desirable to heat the dispersion and/or the oil that is to be inhibited, e.g., to a temperatiife' lbe'tween 100- F. -a'-nd140 '-F., in order to facilitate blending. alter-irate practice involves blending at storage temperatures, utilizing concentrated solutions of "the "additives in solvents that have a high solubility for 'the additives and that do "not adversely affect the stabilityo'f the oil. Examples of such concentrated solutions are 10 to Weight percent, e.g., 50 percent, solutions of the reaction product of equimolar propor- -tions of 3-tallow"-aminopropylamine and p-octylphenol in solvents such as kerosene, benzene, toluene, hexane, methyl isobutyl ketone, and methyl ethyl ketone.

As indicated, the class of distillate fuel oils to which this invention is applicable includes mixtures of straight -run and catalytically cracked distillate fuel oils such as are" used for domestic heating and for some industrial heating purposes, typical of which are the so-called No. 2 fuel oils, i.e., distillate oils boiling within the range of about 350 to 750 F. and having a minimum API gravity of about 26.

The problem of stabilization of such oils is unique and exists only when a catalytically cracked fuel oil distillate and a straight run fuel oil distillate are combined in suchproportions, as to cause a substantial deleterious effect of the kind previously described. The invention is important when the ratio of the volume of the catalytically cracked to the straight run oil-is 'within the range'of about 9:1 and about 1:9. It is especially advantageous when applied to mixed oils containing these oils in a volume ratio within the range of 4:1 and 1:4.

The utility of the herein disclosed class of sludge 'inhibiting adducts of long-chain, aliphatic N-substituted 1,3-diaminopropanes and phenols has been demonstrated by. subjecting samples of a blend of catalytically cracked and straight run fuel oil distillates containing various -concentrations of adducts representative of the class included by the invention to astandard accelerated stability-test. The test samples were made up by adding the desired concentration of each addition agent to be tested directly to separate samples of the blended fuel oil which had the following physical properties:

Gravity, API... 33.5 Viscosity, SUS, 'F 34.5 Color, NPA 2 1.5+ Pour point, F --15 Flash point, F 168 Carbon residue, Conradson, on 10% bottoms---" 0.38 Neutralization value, acid No 0.12 Distillation Initial boiling point, F 360 End boiling point, F 630 Bromine No 11.7 Olefins, weight percent 15.1 Aromatics, volume percent 21.9 Aniline point, F 129 Ash, oxide, weight percent 0.01

The stability test referred to was carried out on the mixed fuel oil compositions by heating 600 gram samples of the fuel oil compositions for periods ranging from 16 to'64 hours at 210 F. in loosely stoppered, one-quart clear glass bottles. Following the heating periods the test samplesiwere cooled to room temperature and filtered by suction through tared, medium porosity fritted glass Goooh-type crucibles. The sludge in each crucible was washed with heptane, Complete removal of the sludge adhering to the inside of the bottles was obtained by means of a rubber policeman and heptane. The respec 'tive crucibles were dried in an oven maintained at 210 F. for 1 hour, cooled in a desiccator and reweighed. The increase in weight was recorded as milligrams of sludge per'600 grams of oil.

As illustrating the improvement obtainable with the class of addition agents included by this invention the specific results obtained by testing mixed fuel oil compositions containing the reaction products described in Examples I to V1, inclusive, are serfor'thinTable A.

Table A I Sludge, Mg./600 G. Oil

After After After Alter After 16 24 40 48 64 Hrs. Hrs. Hrs. Hrs. Hrs.

1. Blend A-lzlzl (Vol) Blend of West Texas Straight Run, South Louisiana Straight Run, and Fluid Oatalytically Cracked No. 2 Fuel Oil Distillate 8.3 30. 2 69. 6 81. 2 99. 6 2. Blend A plus 0.02 Wt Percent Reaction Product of Mixed Alkylpheno and low-aminopropylamine, 1:1 Mol Ratio (Example I Product) 2.3 0. 9 0. 4 0.7 0. 4 3. Blend A plus 0.05 Wt. Percent Reaction Product of Mixed Alkylphenols and B-Tallow"-aminopropylamine, 1:1 Mol Ratio (Example I Product) 2.0 4. Blend A plus 0.02 Wt. Percent Reaction Product of Mixed Alkylphenols and 3-Tallow-aminopropylamine, 2:1 M01 Ratio (Example II Product) 1. 7 1. 2 3. 1. 7 0. 2 l5. Blend A plus 0.05 Wt. Percent Reaction Product of Mixed Alkylphenols and 3-Tallow"-aminopropylamine, 2:1 Mol Ratio (Example II Product) 3. 2 6. Blend A plus 0.02 Wt. Percent Reaction Product of Mixed a-Methylbenzyl henols' and 8- Tallow"-aminopropylamine, 1:1 M01 Ratio (Example III Product 0. 6 7. Blend A plus 0.02 Wt. Percent Reaction Product of Bis-(Z-hydro -3,5-diamylhegybsulfide and 3-"Tallow"-aminopropylamine, 1:2 Mol Ratio Example IV 0 r0 uc 8. Blend A plus 0.02 Wt. Percent Reaction Product of p Octylphenol and lowaminopropylamine, 1:1 Moi Ratio (Example V Product) 3. 3 9 Blend A plus 0.02 Wt. Percent Reaction Product of Mixed Alkylphenols and 3-Laury1aminopropylamine, 1:1 Mol Ratio (Example VI Product). 0.4

Compositions 2 to 9, inclusive, in the foregoing table are specific embodiments of the invention. Comparison of the results set forth in the table for these compositions with those obtained for blank composition 1 indicates the major improvement obtainable with the addition agents included by this invention. The foregoing results are considered typical of the preferred additives of this invention. Similar results are obtainable with other reaction products of the herein disclosed class, specific examples of which are the reaction products of 3-dodecylaminopropylamine, 3-tetradecylaminopropylamine, S-hexadecylaminopropylamine, 3-octadecylaminopropylam-ine, and 3-oct-adeceny-laminopropylamine with phenol, catechol, resorcinol, hydroquinone, cresol, bis (2 hydroxy 3 t butyl- S-methylphenyDmcthane, 1,1 bis (2 hydroxy 3 tbutyl 5 methylphenyl) ethane, 3 methyl 5 propylphenol, 3 methyl 5 butylphenol, 3,5 diethylphenol, S-ethyl-S-propylphenol, m-propylphenol, m-butylphenol, and m-amylphenol, in ratios of 0.5 and 1 mol of diamiue per equivalent weight of phenol. Other specific examples of addition agents included by the invention are reaction products of the foregoing phenols in the ratios indicated with mixed fatty alkyland alkenylaminopropylaminesa such as 3-coco"-aminopropylamine and 3-soya-am inopropylamine. Other examples of fuel oil compositions ineluded by the invention are mixtures of catalytically cracked and straight run No. 2 fuel oil distillates, where the volume ratio of cracked to straight run oil is from 9 1 to 1:9, e.g., 4:1, 2:1, 1:1, 1:2, 1:4, containing from 0.005 to 1.0 weight percent, e.g., 0.01, 0.02, 0.03, 0.04, 0.05 percent, of the above-named reaction products In order to demonstrate the importance of the use of the heroin disclosed class of 1,3-diaminopropanes in forming the reaction products of this invention, the results obtained by incorporating the reaction products of Examples VII and VIII in the blended fuel oil have been compared in Table B below with the results obtained by incorporation in the same fuel oil of a reaction product In the foregoing table, compositions 2 and 3 are specific embodiments of the invention. As indicated by the results obtained with these compositions and set forth in the foregoing table, reaction products involving the use of C aliphatic N-substituted aminoproplamines represent the threshold of utility insofar as sludge inhibition in mixed catalytically cracked and straight run distillate fuel oils is concerned. V

If desired, the stable fuel oil compositions of this invention may contain in addition to the additives disclosed herein other improvement agents, such as for example, oxidation inhibitors, flash point control agents, corrosion inhibitors, anti-foam agents, ignition quality improvers, combustion improvers and other additives adapted to improve the oils in one or more respects.

Although, as indicated in the preliminary discussion of the problem of sludging in blended fuel oils in relation to the problem of deterioration of other petroleum oils, the former is entirely distinct, the multifunctional reaction products of the herein disclosed invention have also been found to have utility in approximately the same concentrations that are used in fuel oils in inhibiting gum formation in gasolines. The utility of the herein disclosed reaction products in gasoline was determined by subjecting samples of a gasoline consisting of thermally cracked distillate to standard oxidation stability test ASTM D525-49. According to this test the gasoline sample is introduced into an oxidation bomb and oxygen is added to a pressure of about 100 p.s.i. The charged bomb is placed in a boiling water bath and the gas pressure in the bomb is recorded. The end of the induction period, i.e., the point at which rapid absorption of the oxygen by the gasoline takes place, is the time when a sharp drop in pressure (at least 2 p.s.i. in 15 minutes) occurs.

The results obtained by the foregoing test are indicated in Table C below:

prepared by reaction of a' low molecular weight alkyl- 60 Table 6 substituted aminopropylamine and a phenol. Addm C n T bl B tr a tiori Gen Induction After 24 hrs. Miimtes 1. Blend A (see Table A) 30.2 66 1 ia 2. Blend A plus 0.02 wt. percent reaction product of mixed alkylphenols and 3"(2'ethy1hexyl) 1 Blank Gasoline-Thermally Cracked aminopropylamine, 1:1 mol ratio, (Example Distillate 94 VII 27 2. Blank plus 2,4,6-Trl-tbutylphenol... 0.0525 0.0002 240 3. Blank plus Reaction Product of 3. Blend A plus 0.02 wt. percent reaction product of 70 Example I 0.1100 0. 0002 411 mixed alkylphenols and 3-(2-ethylhexyl) amifig gg Ream Pmdmt 0 1400 0 0002 479 nopropylamine, 2:1 mol ratio, (example VIII)- 28.1

4. Blend A plus 0.02 wt. percent reaction product of bis-(2-hydroxy-3,5-diamylphenyl)sulfide and 3- isopropylaminopropylaminc, 1:2 mol ratio 64.8

in blended fuel oils were demonstrated by subjecting an other sample of the above-identified gasoline and asample' of a 50/50 by volume blend of Eastern Venezuela straight run and fluid catalytically cracked No. 2 fuel oil distillates having a marked tendency to deposit sludge, respectively, to ASTM test 13525-49. instance a marked. drop in the oxygen pressure of the bomb was observed after only 97 minutes. stance of the blended fuel .oil no marked. drop in the oxygen pressure had occurred after 161.5 hours, at which time the test was discontinued.

It will be apparentto those skilled in the art that many variations of the invention'rnay be resorted to without departing from the spirit thereof. Accordingly, only suchlimitations should be imposed as are indicated in the claims appended hereto.

1.'The reaction product formed -by' the substantially "spontaneous reaction of a phenolic compound that will not hinder'the-oil-solubility of'said reaction'product and that is selected from the group consisting of unsubstituted and =mono-, 'di-, and trisubstituted monoand 'dihydric p h'enols whosesubstituents are selected 'fro'mthe group consisting of :alkyland 'aryl substituted radicals Icon- Ita-ini'n'g 1 -to 9carbon atoms, and 1 oil-soluble bisphenolic sulfides andaalkanesrlerived from such phenols, and a 1, 3 diaminopropaneiof the general formula:

where R is an "aliphatic hydrocarbon radical selected from the' group consisting of alkyl, alkenyl, and alkadienyl containing from 8 to 30 car-bon atoms, the "ratio of're- =actants-being'from'about 0.5 to.abo'ut-1 mol"of the 1,3- =dian1inopropane per equivalent weight of phenolic "compound.

In the former In the in- For example, the dissimilar natures of "3-alkyland 3-alkenylaminopropylamines Whose alkyl and alkenyl substituents contain from 14 to 18 carbon atoms, the mol ratio of reactants being from about 1 to 2 mols of phenols per mol of amino-propylamines.

4. The mixed homologous reaction products formed-by the substantially spontaneous reaction of about equimolar proportions of mixed alpha-methylbenzylphenols and mixed 3-alkyland 3-alkenylarninopropylamines whose alkyland alkenyl substituents contain from 14 to 18 carbon atoms. 7

5. The mixed homologous reaction products formed by the substantially spontaneous reaction of bis-('Z-hydtoxy- 3,5-diamylphenyl)sulfide and mixed 3-alky1- and 3-alkenylaminopropylamines Whose alkyl and alkenyl substitu- -'ents contain .from 14 to 18 carbon atoms, the-mol ratio of reactants being about 1:2.

6. Thetmixed homologous reaction'products.formediby .the substantially spontaneous. reaction .of about equimol-ar .proportions of :p-octylph'enol and mixed 3-'alkyland 3 alkenylaminopropylamines whose alkyl and alkenyl substituents contain from 14m 18 carbon atoms.

7. The mixed homologous reaction products .forrned by the substantially spontaneousreaction of about equimolar proportions of 3-laurylaminopropylamine and mixed m-alkyl'phenols whose alkyl substituents containnot more than 4-carbon atoms each and whose total alkyl .carbon atomssper molecule is from 3 to 5.

References Cited in the file of this patent UNITED STATES PATENTS 2,048,770 Ayres July 23, L936 2,053,466 Downing et al Sept. 8, .1936 2,256,753 Scheumann Sept..23, 194:1 2,362,464 Britton et a1 a- Nov. 14,119.44 2,385,848 :Smith et 'al Oct.'2, .1945 2,526,892 Minich Oct. .24, v.1950 .2 ,68'4,292 Caron .et .al. .July 2.0, .1954

Claims (1)

1. THE REACTION PRODUCT FORMED BY THE SUBSTANTIALLY SPONTANEOUS REACTION OF A PHENOLIC COMPOUND THAT WILL NOT HINDER THE OIL-SOLUBILITY OF SAID REACTION PRODUCT AND THAT IS SELECTED FROM THE GROUP CONSISTING OF UNSUBSTITUTED AND MONO-, DI-, AND TRISUBSTITUTED MONO- AND DIHYDRIC PHENOLS WHOSE SUBSTITUENTS ARE SELECTED FROM THE GROUP CONSISTING OF ALKYL AND ARYL-SUBSTITUTED RADICALS CONTAINING 1 TO 9 CARBON ATOMS, AND OIL-SOLUBLE BISPHENOLIC SULFIDES AND ALKANES DERIVED FROM SUCH PHENOLS, AND A 1,3-DIAMINOPROPANE OF THE GENERAL FORMULA: