US 3007785 A
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3,h7,785 Patented Nov. 7, 1961 9 Claims. (Cl. 44-75) This invention relates to stabilized distillate fuel oils. More particularly, the invention is concerned with the stabilization of distillate fuel oils containing a m xture of straight run and catalytically cracked fuel oil distillates by incorporation therein of the herein disclosed 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 ant 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 o'ds contain predominantly parafiinc 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 considered 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. iSludging 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 furthensludge 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 paraifinic components contained in the oil, the reaction of acidic oxygenated products with metals contacted reaction may be carried out at any temperature between 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 parafiinic 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 adduots disclosed herein. The adducts whose use is 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 adducts disclosed herein 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
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 weight, 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.
The diaminopropanes that form reaction products whose use is included by this invention may be illustrated by the generic formula:
the'diamines in which the long-chain,'aliphatic N-substituent of the secondary amino grouping is an alkyl or alkenyl group containing at least 12, and preferably from 'lZ'to 18' straight chain carbon atoms are considered to form especially effective addition agents. Examples of 1,31'liaminopropanes which are considered to form cs pecially effective addition agents for the purposes of this invention are the 3-dodecyland the 3-hexadecylami-nopropylamines, and especially the 18 carbon 'alkyl-, all enyl-, and alkadienyl substituted 'l,3-diaminopropanes, such as the 3octadecyl-, 3-octadecenyl-(3-oleyl), and 3- octadecadienylaminopropylamines. Although aliphatic hydrocarbon N-substituted 1,3-diaminopropanes are preferred, 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- (chlorostearyl)aminopropylamine. Mixtures of 1,3-di-, aminopropanes, such as are formed when the long-chain, aliphatic N-substituent in the secondary amino grouping is derived from mixed fatty acids obtained from naturally occurring fats and oils, form highly effective phenolic adducts Within the scope of this invention. In such instances the aliphatic N-substituent in'the secondary amino groupi-ng will be a straight-chain, monov alent hydrocarbon radical containing from 8 to 20 carbon atoms. Examples of such mixtures of 1,3-diaminopropanes are 3-tallowaminopropylamine, 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 fatty acids, soybean (C C fatty acids, and coconut (Cg-C fatty acids.
The phenolic compounds that form adducts with the herein disclosed N-substituted 1,3-diaminopropanes include those which do not hinder the oil-solubility of the resulting reaction product. Thus, the invention includes, for example, reaction products of the discloseddiamines and monohydric, dihydric tor polyhydric phenolic compounds, such as phenol itself, catechol, resorcinol, and hydroquinone. Especially preferred phenols are'the hydrocarbon substituted phenols, e'.g., those having alkyl or aralkyl substitutents attached to the phenolic nucleus, specificexamples of which are iOI'thO-, meta-, and paracresol,
ortho-, meta-, and parabutylphenol, p-nonylphenol, 3,5-
diamylphenol, 3-methyl-5-propylphenol, 3-methyl-5-butylphenol, 3,5-diethylphenol, 3-et hyl-5-propylphenol, m-propylphenol, m-butylphenol, m-amylphenol, and p-octy-lphenol, bis-(2-hydroxy-3,S-diamylphenyl)sulfide, mono-, bis-, and tris-alpha-methylbenzylphenols, alpha-phenylethylcatechols, various bis-(hydroxyalkylphenyl)'-alkanes, representative of which are 2,2-bis-(4-hydroxy-5-methylpheny1)propane, 1,1-bis-(2-hydroxy3,S-dimethylphenyl)- isobutane, bis (2 hydroxy 3 t butyl 5-methylphen-' yl)-methane, and 1,1-bis-(2-hydroxy-3-t-butyl-5-methylm olecular weight) of mixed m-alkyl phenols were faddistillation or the like.
.At (a) is shown the probable formula for the reaction compounds in which the phenolic nucleus is substituted: with hydnocarbon substituents are preferred, the invention also includes the use of phenols containing non-hydrocarbon substituents such as nitro, chloro, bromo, amino and like groups, specific examples ofgsuch phenols being pnitro phenol, p amino phenol, and 'penta-chloro phenol. I
Commercial mixtures of phenols are also suitable for the purposes of this invention. Such mixtures may be those recoveredby treatmentof industrial wastes, by treatment of petroleum refinery process waters, or fromv coal tar Although the exact nature of thdadducts herein described has not been definitelyascertained, it is thought likely that these adducts partake of the nature of sub- 7 stituted ammonium'salts. Examples aregiven below of the formulae structure thought to beinvolved.
'xo-l Fonicnicnt-nn, V
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 monohydric phenolic compound. At (6) is shown the probable formula for the reaction prod uct of equimolar proportions of a'diamine and a'dihydric phenolic compound; In theseformulae XO- represents the negative ion of a monohydric phenol,
represents the negative ion of adihydric phenol, and R is as defined above.
' The preparation of the reaction products whose use is included by this invention, described in general, supra, is further illustrated by the following specific examples.
'EXAMPLEI Approximately 7.5 grams (0.05 combining grammixed and reacted with 20.0 grams (0.05 combining gram- 1 molecular weight) of 3-"tallow-aminopropylamine. The reaction occurred spontaneously and was completejin'less than about fifteen minutes. .A temperature change in the I a the course \of the reaction. To insure completion ofthe reaction mixture of from 2910 35C. was noted during 7 t stituents contained not more than 4 carbon atoms each,
and in which'the total alkyl carbon atoms was between 3" and 5, together with substantial proportions of;4-vand 5- indanol. The mixture contained approximately 95 percent phenyl)-ethane. Other phenols, the use of which is inf phenols. More particularly, in addition to indanols, the
mixed phenols of this example contained m-alkyl phenols such as: 3-methyl-5-ethylphenol, 3-methyl-5-propy1phe no], B-methyIeS-butyIphenOl, 3,5-diethy1phenol, 3,-ethyl-5- 4-indanol S-indanol 15 3-methy1-5-ethylphenol 10 n-Propylphenols (meta and para) 5-10 Mixed meta-substituted phenols of type indicatecL- 45-50 The physical properties of a typical sample of the mixed phenols were as follows:
Average molecular weight, approx 140450 Apparent specific gravity at /20 C 1.03 Boiling range (ASTM D-850):
-1.B.P C 240 1% C 242 5% C 245 50% C 250 95% C 270 DP C 280 Vapor pressure at 20 C mm. Hg 0.01 Viscosity at 20 C cps. approx 70 Solubility in water at 20 C percent by wt 0.08 Solubility of Water in 20 C do 5 Refractive index at C 1.543 Behavior on cooling-sets to glass or clouds below C Average weight per gal. at 60 F lb 8.63 Flash point (open cup) F 250 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-oleylarninopropylamine (3- octadecenylaminopropylamine), together with lesser proportions of 3-hexadecyland 3-octadecylaminopropylamines, and small amounts of S-rnyristyland 3-linoleylarninopropylamines.
The adduct prepared according to the foregoing procedure was a brown-colored liquid material having the following analysis: Nitrogen, percent, 5.64.
EXAMPLE II The adduct formed by reaction of mixed m-alkyl phenols and 3-tallow"-aminopropylamine in the ratio of 0.5 mol diarnine 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 definedin Example I. The reaction proceeded spontaneously, a temperature change from 29 to 41 C. being noted during the course of the reaction. After no further temperature change was noted, the mixture was heated to 110 C. in order to insure completion of the reaction. The product of this reaction was a brown-colored liquid material having the following analysis: Nitrogen, percent, 4.57.
EXAMPLE III The reaction product formed by reacting the 3-tallow-aminopropylamine of Example I with mixed alphamethylbenzylphenols in a ratio of 1 mol of diamine per equivalent weight of phenols (1:1 mol ratio) was prepared by admixing 11.6 grams (0.05 combining grammolecular weight) mixed alpha-methylbenzylphenols and 20.0 grams (0.05 combining gram-molecular weight) of 3-"tallow-aminopropylamine. Again the reaction pro ceeded 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 methylbenzyl)- 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 reaction 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 4.66 Sulfur, percent 2.92
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-tallowaminopropylamine of Example I were admixed with 4.13 grams (0.02 mol) 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 B-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 browncolored liquid material having the following analysis: Nitrogen, percent, 7.68.
EXAMPLE VII An additional adduct Was prepared by reacting 3-(2- ethylhexyl)aminopropylamine and mixed rn-alkyl phenols in a ratio of 1 mol of amine per equivalent weight of phenols (1:1 mol ratio). In this reaction 9.32 grams (0.05 mol) of 3-(2-ethylhexyl)aminopropylamine were admixed with 7.50 grams (0.05 combining gram-molecular weight) of the'mixed m-alkyl phenols referred to in Example I. The reaction proceeded spontaneously, a temperature change of from 26,to 48 (3. being noted, with heat to 100 C. being added thereafter. The product of this reaction was abrown-colored liquid material having the following analysis: Nitrogen, percent, 8.96.
EXAMPLE VIII trogen, percent, 6.32.
The foregoing examples indicate the manner and ease of preparation of the adducts whose use is included by this invention, and also described specific embodiments.
of said adducts. Other adducts whose use is included by the invention can be prepared similarly as above by reaction in the indicated proportions of other herein disclosed 1,3-diaminopropanes with the foregoing phenols, or with other members of the herein disclosed class of phenols.
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 catalytically cracked components has been found to provide a marked improvement in the sludging-tendencies of the oils. Naturally, the various adducts of the herein disclosed class do not possess'exactly identical effectiveness,'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, thehereinrdisclosed 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 at storage temperatures, utilizing concentrated solutions a of the. additivesrin solvents that have a high solubility. for the additives and that do not adversely affect the stability 'of the oil. Examples of such concentrated slu-, tions are to 75 weight percent, e.g., 50 percent, solutions offthe' "reaction .product' or equimolar proportions or 3-ftallow" aminopropylamine and p-octylphenol in solvents suchas kerosene, benzene, toluene, hexane, methyl isobutyl ketone, and methyl ethyl keton e. V v v i v 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 whichare the so-called No. 2 fuel oils, i.e., distillate oils boiling withinthe range of about 350. to 750 F. and having a minimum API.
gravity of about26. V a
'The problem of stabilization of such oilsis unique and exists, only when a catalytically,cracked'fueloil dis tillate and a straight run fuel oil distillate are combined in such proportions as'to cause a substantial, deleterious eifect of the kind previously described; .;The, invention is important when the ratio of thevolurne 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 tomixed oils containingthese 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 Va blendof catalytically cracked 1 and straight run fuel'oil distillates containing various concentrations of adducts representative of the class in cluded by the invention to'a standard accelerated sta-. bility test. The test samples Weremade up by adding the desired concentration of each addition agent to be tested directly to separate samples of the blendedffuel by incorporation therein of from about 0.01 to about 0.05
percent by weight of the herein 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 very unusual cases it may be found desirable to add as much as'about 1.0 percent by weight of the adducts.
The addition agents whose use is 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 afterthe mixture has been stored for a substantial period of time. Alterna tively, the sludge inhibiting addition agents of this invention may be formed in situ in, or added per se or in the form of'concentrated solutions to, either the straight run or the catalytically cracked fuel oil distillate, prior to blending of the components to form a mixed fuel oil. Suitable concentrates containing the sludge inhibiting adducts of this invention comprise, for example, mineral oil solutions or dispersions containing from about 10 to 75 percent, and preferably from about 25 to 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 temperature between 100 F. and 140 F., in orderrto facilitate blending. An alternate practice involves blending Gravity, API 33.5 Viscosity, SUS, 100 F. 34.5 Color, NPA 1.5+ Pour point, F. 15 Flash point, F. a 168 Carbon residue, Conradson, on 10% bottoms 0.38 Neutralization value, acid No. 0.12
7 Initial boiling point, F. 360
End boiling point, 7 F. 630 Bromine No. 11.7 Olefins, wt. percent 15.1 Aromatics, vol. percent 21.9 Aniline point F. 129 Ash, oxide, wt. percent 0.01,
oil whichhad the following physical properties:
' The stability test referred to was carried out on the 7 mixed fuel oil compositions by heating 600-grarn samples of the fuel oil compositions for periods ranging from 16 'to '64 hoursat 2l0 F. in loosely stoppcred, one quart clear glass bottles. Following the heating periods the test samples were cooled to room temperature and filteredby suction'thi'ough tared, medium porosity fritted glass 'Goooh-type crucibles. The sludge in each crucible. was washed with heptane.
sludge adhering to the inside of the bottles was obtained 1 Complete removal of the obtainable with the Examples I to V1, inclusive, are set forth in Table A below:
Table A Sludge, ing/600 g. Oil
After After After After After 16Hrs. 24H1's. 40 Hrs. 48Hrs. 64Hrs.
1. Blend A1:1:1 (Vol) Blend of West Texas Straight Run,
South Louisiana Straight Run, and Fluid Catalytically Cracked N0. 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 Alkylphenols and 3-"'lollotWeminopropylamine, 1:1 Mel Ratio (Example I Product) 2.3 0. 9 0. 4 0.7 0. 4 3. Blend Aplus 0.05 ft. Percent Reaction Product of Mixed Al tvlphenols and 3-Tallow"-aminopropylan1ine, 1:1 M01 Ratio (Example I Product) 2.0 4. Blend A plus 0.02 Wt. Percent R Alkvlphcnols and 3-Tallow Ratio (Example If Product) 1. 7 1. 2 3. 1. 7 0- 2 5. Blend A plus 0.05 Wt. Percent Reaction Product of h xed Alkylphenols and S-Tallow-aminopropylamine, 2:1 Mol Ratio (Example II Product) 3. 2 6. Blend A plus 0.02 Wt. Percent Reaction Product of Mixed a-Methvlbenzylphenols and 3-"Tallow-aminopropylamine,
1:1 Mol Ratio (Example III Product) 0. 6 7. Blend A plus 0.02 Wt. Percent Reaction of Bis(2hydroxy-3,5-
diamylphenyl) sulfide and 3-"Tallow"-arninopropylaminc,
1:2 M01 Ratio (Example 1V Product) O. 8. Blend A plus 0.02 Wt. Percent Reaction Product of p-Octylphenol and 3-Tallo\v-eminopropylarnine, 1:1 Mol Ratio (Example V Product) 3. 3 9. Blend A plus 0.02 Wt. Percent Reaction Product of Mixed Alltylphenols and 3-Laurylarninopropylarnine, 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 from blank Compositions 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, 3-hcxadecy1aminopropylamine, 3-octadecylarninopropylamine, and 3 -octadecenylarninopropylamine with phenol, catechol, resorcinol, hydroquinone, cresol, bis-(2-hydroxy-3-t-butyl-5 methylphenyDmcthane, 1,1- bis-(2-hydroxy-3-t-butyl-5-methylphenyl)ethane, 3-methyl-S-propylphenol, 3-methyl-5-butylphenol, 3,5-diethylphenol, 3-ethyl-5-propylphenol, m-propylphenol, m-butylphenol, and m-arnylphenol, in ratios of 0.5 and 1 mol of diamine per equivalent weight of phenol. Other specific examples of addition agents Whose use is included by the invention are reaction products of the foregoing phenols in the ratios indicated with mixed fatty alkyland alkenylaminopropylamines such as 3-coco-arninopropylamine and 3-soya"-aminopropylamine. Other examples of fuel oil compositions included 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 herein disclosed class of 1,3-diaminopropanes in forming the reaction products disclosed herein, the results obtained by incorporating the reaction products of Example VII and VIII in the blended fuel oil have been prepared by reaction of a low molecular Weight alkyl-substituted aminopropylamine and a phenol.
Table B After 24 hrs. (1) Blend A (see Table A) 30.2 (2) Blend A plus 0.02 wt. percent reaction product of mixed alkylphenols and 3-(2-ethylhexyl) aminopropylamine, 1:1 mol ratio (Example VII)- 27.1 (3) Blend A plus 0.02 Wt. percent reaction product of mixed alkylphenols and 3-(2-cthylhexyl) aminopropylamine, 2:1 mol ratio (Example V-I'II) 27.8 (4) Blend A plus 0.02 wt. percent reaction product of bis-(2-hydroxy-3,S-dia-mylphenyl)sulfide and 3-isopropylaminopropylamine, 1:2 mol ratlo 64.8
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 aminopropylamines represent the threshold of utility insofar as sludge inhibition in mixed catalytically cracked and straight run distillate fuel oils is concerned.
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, filash 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 ther- '1 l mally 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 psi. The charged bomb is placed in a boiling Water bath and the gas pressure in V 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 psi. in minutes) occurs.
The results obtained by the foregoing test are indicated in Table C below:
' 12 reactants being from about 0.5 to about 1 mol of th 1,3-diaminopropane per equivalent weight of phenolic 1 compound, said small amount being sufficient to inhibit sludge deposition from said mixture of oils.
2. The fuel oil composition of claim l'wherein said small amount isbetween-about 0.005 andfabcut 1.0,percent by weight of said mixture of oils.
3. The fuel oil composition of claim .1 where the' phenolic compound is alkyl-substituted and monohydric and whereRis alkenyl;
V 4. A fuel oil composition comprising a major proper- 7 tion of a mixture of straight run and catalytically cracked distillate fuel 'oils tending to deposit sludge and a small amount or the reaction product formed by the substantially spontaneous reaction of (a) mixed m-alkyl phenols whose alkyl substituents contain not more than 4. carbon atoms each and whose total alkyl carbon atoms per molecule is from 3 to 5, and (b) mixed 3-alkyland 3-alkenylaminopropylamines whose alkyl and 'alkenyl substituents contain from 14 to 18 carbon atoms, the 11101 ratio of reactants being from about 1 to 2 mols of phenols per Comparison of the induction period for Compositions 3 and 4 of Table C with the induction period for Com-- position 2 (the blank gasoline plus a known commercial gum inhibitor) indicates the remarkable improvement obtainable with the reaction products 'of this invention.
Although applicants inhibitors have proved effective to inhibit both sludging in blended fueloilsand gum formation in gasoline, the problems involved in the respective instances are considered chemically and physically nonanalogous. For example, the dissimilar natures of the problems of inhibiting gum in gasolnes and sludging in blended fuel oils were demonstrated by subjecting another sample of the above-identified gasoline and a sample 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 D525-49. In
the former instance a marked drop in the oxygen pres-' sure of the bomb was observed after only '97 minutes. In the instance 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 apparent to those skilled in the art that many variations of the invention may be resorted to without departing from the spirit thereof. Accordingly, only such limitations should be imposed as are indicated in the claims appended hereto.
This application is a division of our copcnding application Serial No. 449,491, filed August 12, 1954, and now U.S. Patent 2,942,028.
1. A fuel oil composition comprising a major proportion of a mixture of straight run and catalytically cracked distillate fuel oils tending to deposit sludge and a small amount of 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 tri-substituted monoand dihydric phenols whose substituents are selected from the group consisting of alkyl and aryl-substituted alkyl radicals containing 1 to 9 carbon atoms,
and oil-soluble bis-phenolic sulfides and alkanes derived from such phenols, and a 1,3-diaminopropane of the general formula:
molofaminopropylamines, said small amount being suffi cient to inhibit sludge'deposition from saidimixture of oils. 1
-5. A fuel oil composition comprising a major proportion of a mixture of straight run and catalytically cracked distillate fuel oils tending to deposit sludge and a small amount of the reaction product formed by the substantially spontaneous reaction of about equirnolar proportions of mixed alpha-methylbenzylphenols and mixed 3-alkyland 3-alkenylaminopropylamines whose' alkyl and alkenyl substituents contain from 14 to 18 carbon atoms, said small amount being sufiicient to inhibit sludge deposition from said mixture of oils.
'6. A fuel oil composition comprising a major proportion of a mixture of straight run and catalytically cracked distillate fuel oils tending to deposit sludgefand a small amount of the reaction product formed by the I substantially spontaneous reaction of bis-(2-hydroxy-3,5-.
diamylphenyl)sulfide and mixed 3'-alkyland *3-alkenylaminopropylamines whose alkyl and alkenylsubstituents contain from 14 to 18 carbon atoms, the mol ratio of reactants being about 1:2, said small amount'being suffi- 'cient to inhibit sludge deposition from said mixture of oils. V r
7. A fuel oil'cornposition. comprising a major propor:
tion of a mixture of straight run and catalytically cracked distillate fuel oils tending to deposit sludge and a small] amount of the reaction product formed by the substan tially spontaneous reaction of about equimolar proportions of ,p-octylphenol and mixed 3-alkyland 3-alkenylaminopropylamines whose alkyl and alkenyl substituents contain from 14 to 18 carbon atoms, said small amount being sufficient to. inhibit sludge deposition from said mixture of oils.
-8. A fuel oil composition comprising a major proportion of 'a mixture of straight run and catalytically cracked distillate fueloils tending to depositsludge and j a small amount of the reaction product formed by the substantially spontaneous reaction of about .equimolar proportions of 3-laurylaminopropylamine' and mixed m-alkyl phenols whose alkyl substituents contain not more than 4 carbon atoms each and whose total alkyl carbon atoms per molecule is from 3 .105, said small amount being sufficient to inhibit sludge deposition fro said mixture of oils.
9. A fuel composition comprising major proportion I of a normally unstable liquid hydrocarbon fuel and a small amount, sufiicient to stabiilzesaidfueljof 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-, diand tri-substituted monoand dihydric phenols whose substituents are selected from the group consist-.
ing of alkyl and aryl-substituted alkyl radicals contains" 13 ing 1 to 9 carbon atoms, and oil-soluble bis-phenolic sulfidies and alkanes derived from such phenols, and a 1,3-diaminopropane of the general formula:
R HI1TCH2CH2-CH3-NH5; Where R is an aliphatic hydrocarbon radical selected from the group consisting of alkyl, alkenyl, and alkadienyl containing 8 to 30 carbon atoms, the ratio of reactants being in the range of about 0.5 to about 1 mol of the w 1,3-diaminopropane per equivalent weight of the phenolic compound.
References Cited in the file of this patent OTHER REFERENCES Sernon Aug. 7, 1934 Scheumann Sept. 23, 1941 Chenicek Dec. 22, 1942 Fareri et al. Aug. 11, 1959 Schnaith et al. Sept. 29, 1959 FOREIGN PATENTS Great Britain Sept. 2, 1933