US 3092475 A
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United States Patent 3,092,475 FUEL COMPOSITION Eldon B. Cole, Tulsa, and Phillip M. Niles, Sand Springs,
Okla., assignors, by mesne assignments, to Sinclair Research, Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed Dec. 22., 1958, Ser. No. 781,892
. 12 Claims. (Cl. 44-72) The present invention relates to fuel oil compositions stabilized against the harmful effects of oxidation or deterioration. More particularly the invention is concerned with distillate fuel oils containing certain additives adapted to stabilize the fuel oils against oxidative deterioration during storage or use.
Hydrocarbon fuels, for example, those distilling primarily in the range from about 300 to 750 F, tend to deteriorate and form sediment, insoluble gum, etc. which if not removed, plug filter screens, orifices and other parts of equipment used in burning the oils. The formation of sediment, insoluble gum, etc. inthese oils is attributable primarily to the oxidation of unstable constituents contained in the oils. This oxidation takes place under prolonged storage at atmospheric temperatures as well as underelevated temperatures during use.
'It has been found that certain oil-compatible, i.e. soluble, miscible ordispersible, oxyalkylated fatty diamines when added in relatively small amounts tovdistillate fuel oils effectively stabilize the oiltagainst deterioration. The oxyalkylated fatty diamines of the present invention are prepared by reacting about 5 to 80 weight percent, preferably about 30 to 70 Weight percent of a C -C alkylene oxide, for instance, ethylene oxide and propylene oxide or mixtures thereof with about 20 to 95 weight'percent, preferably about 70 to 30 Weight percent of certain fatty diarnines. These percentages are based on the total amount of diamine and alkylene oxide. The amount of alkylene oxide employed can be varied to obtain a product of maximum efficiency for the particular fuel oil utilized. Mixtures of alkylene oxides, as aforementioned, can also .be employed and in fact have been found to improve the solubility characteristics of the finished product. If utilized, mixtures of ethylene oxide and propylene oxide are preferred, generally in a ratio of about :5 to 5 parts ethylene oxide to 1 part propylene oxide.
The oxyalkylation reaction can in general be conducted at temperatures of about 250 F. to 400 F., preferably about 300 F. to 375 F. and, if desired, in the presence of an oxyalkylation catalyst in catalytic amounts. Ex!
amples of suitable oxyalkylation catalysts that may be employed are sodium methylate, sulfuric acid, sulfonic.
acids, etc. Prior to oxyalkylation, it is generally found desirable to dissolve the fatty diamines of the present invention in an aromatic hydrocarbon solvent such as xylene. Upon completion of the oxyalkylation the solvent can be removed and the finished product added as such to the fuel oils of the present invention or it can be added in its diluted form. -In the latter case, the oxyalkylated base will generally range from about 60 to 95 percent by weight depending on the amount of solvent employed. If desired, the oxyalkylated base-xylene product can be further diluted, as for example, to where it has or less of active ingredient.
. distillate stocks.
about 2 to 8 carbon atoms.
The fatty diamine contemplated by the present invention has the structural formula:
in which R is an aliphatic hydrocarbon radical of at least about 6 and preferably about 12 to 22 carbon atoms and R is a divalent aliphatic hydrocarbon radical containing The hydrocarbon radicals can be straight or branched chain and substituted or unsubstituted. Preferably, R is a polymethylene group of about 2 to 8 carbon atoms and advantageously about 2 to 4, carbon atoms; These diamines can be prepared by a variety of Well-known procedures, as for example, by reacting an aliphatic chloride containing the desired number of carbon atoms with a polymethylene diamine which contains from about 2 to 8 methylene groups. The aliphatic R group which is attached to the nitrogen atom is either saturated or unsaturated and is preferably an alkyl or alkylene residue radical obtained from fatty acids. Fatty acids which are suitable for providing residues containing the desired number of carbon atoms can be obtained from fats and oils such as soybean oil, lard oil, castor oil, corn oil, tallow, coconut oil, etc. or from resin acids such as those derived from tall oil which contains a mixture of fatty acids and resin acids.
' An example of a preferred fatty amine used in the preparation of the oxyalkylated products of this invention is a diamine designated as Duomeen T in which R in the above formula is trimethylene and R is the straight chain hydrocarbon residue derived from tallow fatty :acids containing 16 to 18 carbon atoms, both saturated and unsaturated. Similar fatty diamines can be used in which the hydrocarbon group is derived from monobasic acids such as, for example, lauric acid, myristic acid, palmitic acid, stearic acid, margaric acid, oleic acid, ricinoleic acid, linoleic acid, etc as Well as monobasic acids derived by oxidation of petroleum waxes.
Qfrnust be understood, however, that this term is not restricted to straight-run distillates. These fuels can be straight-run distillate fuel oils, catalytically or thermally cracked distillate fuel oils or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked The cracked materials will frequently be about 15 to volume percent of the fuel. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as, acid or caustic treatment, solvent refining, clay treatment, etc.
In order to effectively stabilize the distillate fuel oils 7 the condensation products of the present invention are added to the fuel oils in concentrations varying between about 5 pounds per thousand barrels of oil and about 250 pounds per thousand barrels of oil. Preferably the concentration varies between about 5 and 50 pounds per thousand barrels of oil.
Metal deactivators in relatively small amounts, i.e. up to about 2 pounds/1000 barrels of fuel oil, preferably about .5 to 1 pound per 1000 barrels of fuel oil, can be added along with the additives of the present invention to enhance the latters stabilizing effect on the fuel oils. Examples of suitable metal deactivators are N,N'-disalicylidene-1,2-propylene diamine, dimethyldithio oxamidc, condensated products of O-hydroxy aromatic aldehyde or O-hydroxy aromatic ketone and an aliphatic polyamine as disclosed by Downing et al. in Patents Nos. 2,181,121; 2,255,597 and 2,301,861. If desired, the fuel oil compositions of the present invention can contain other additives for the purpose of achieving other results. Thus, for example, there can be present foam inhibitors, anti-rust agents, and ignition and burning quality improvers.
The tests used to determine the stability of the fuel oil compositions of the present invention were the 100 F. cabinet storage test and the high temperature stability test. In the 100 F. cabinet storage test 400 milliliter samples of the fuel oil composition are placed in a cabinet maintained at 100 F., for periods of 2, 4 and 6 At the end of the test periods the sample is removed from the cabinet and cooled. The cooled sample is filtered to remove the insoluble matter. The weight of such matter in milligrams is reported as the amount of deposit or sediment per 100 milliliters.
In the high temperature stability test, samples of the fuel oil compositions are passed through a filter disc immediately after preparation week storage), and again after storage in cans at room temperature (12 weeks storage). In addition, the fuel compositions are similarly tested without heating to show deterioration at room temperature (before heating), and in the regular high temperature test at 300 F. for 90 minutes (after heating). The color of the filtered oil is recorded and the condition of each filter disc after the test is given a numerical scale rating, 0 representing no staining and representing heavy staining and deposits.
The following examples will serve to illustrate the compositions of the present invention but are not to be considered limiting.
EXAMPLE I 127 grams of Duomeen T were dissolved in 85 grams of xylene. This solution was oxyalkylated with 84 grams of ethylene oxide using 0.30 weight percent of sodium methylate as the catalyst at a reaction temperature of 300 to 350 F. The reaction was continued at least until the product is substantially completely dehydrated. This yielded a product which was 71.5% active and contained 40% ethylene oxide on an active ingredient basis. The oxyalkylatcd base was further diluted with xylene to 50% active ingredient content and designated as SS-1l02C. Using the above method, product SS-1102A containing 10% ethylene oxide and product SS-1102E containing 70% ethylene oxide were also prepared as shown on Table III.
The above oxyalkylated products were added in various concentrations to a distillate fuel oil composed of 50 volume percent Water white distillate having an end point of 565 and 50 volume percent light cycle oil derived by catalytic cracking of gas oil. The physical properties of the fuel oil and its constituents are shown in Table I.
Table l TESTS 0N NEAT FUEL Composition:
565 E.P. Water white distillate 50 Fluid light cycle oil 50 Physical tests:
Gravity, API 34.4 Flash, F 170 Cloud point, F --18 Pour Point, F -30 Distillation (200 ml.), F.:
20% 456 30% 464 40% 472 50% 480 488 498 508 524 536 E.P. 563 Recovery percent 99.5 Residue percent 0.5
The fuel compositions thus prepared were subjected to the F. cabinet storage test for periods of two and four months, respectively, to determine the effect of the additive contained therein for stabilizing heating oils. The fuel compositions were also subjected to the high temperature stability test to determine the effectiveness of the additives as stabilizers for diesel fuels. The neat fuel was similarly tested for purposes of comparison. The test results are shown in Table II.
Table I1 100 F. CABIN ET STORAGE TEST Two months Four months Additive Dosage MDA Visual In- Visual In- #/MB #IMB Deposits Color spection for Deposits Color spection for mgs./100 ml. NPA precipitate mgs./100 ml. NPA precipitate in storage in storage tube tube Neat fuel 2. 2 3. 4 3 Heavy. (1) SSl102A (amine plus 10% ethylene oxide) 24 0. 5 0. 7 3%- None. (2) 88-11020 (amine plus 40% ethylene oxide) 30 0. 5 0.8 3% Do. (3) SS-1l02E (amine plus 70% ethylene oxide) 40 1.1 1.0 3% Trace. (4) SS-1102A (amine plus 10% ethylene oxide) 48 0.7 0.3 3%+ None. (5) 88-11020 (amine plus 40% ethylene oxide) 60 1. 4 1.2 3%- Medium. SS-1102E (amine plus 70% ethylene oxide).-. 80 1.0 0.9 3% None. (7) SS-1102A (amino plus 10% ethylene oxide)". 24 1 0. 4 0. 5 3%- D0 (8) SS-1102C (amine plus 40% ethylene oxide) 30 1 1.0 0. 8 3% D0 (9) SS1102E (amine plus 70% ethylene oxide) 40 0.8 0.9 3% Trace See footnote at end of table.
Table IlContinued HIGH TEMPERATURE STABILITY TEST week's storage 12 weeks storage Before heating Alter heating Before heating After heating Additive MDA #IMB Color Color Color Color Filter Filter Filter Filter disc 1 disc 1 disc 1 disc 1 NPA OD NPA OD NPA OD NPA OD Neat fuel 2 2+ 11 4 4+ 86 3 2- 19 4 4 /5 100 (1) SS-1102A (amine plus ethylene oxide 0 2 10 4 4+ 65 1 3- 3 4% 70 (2) SS-1102G (amine plus 40% ethylene ox 0 2 9 4 4+ 68 0 3- 18 3 4%i-. 88 (3) SS-1102E (amine plus 70% ethylene oxide 0 2 9 4 4% 68 0 3- 18 3-4 4 100 (4) 58-11024 (amine plus 10% ethylene Oxid 0 2- 10 2 4- 41 1 3- 20 2 4% 61 .(5) 83-11020 (amine plus 40% ethylene oxidel 0 2 9 2 4- 56 0 3- 18 1 4% 58 (6) SS-1102E (amine plus 70% ethylene oxide) 0 2 9 3 4+ 49 0 3- 18 2 4% 76 (7) SS-1102A (a one oxide). 0 2 9 0 3- 17 1 22 3 4% 76 (8) 88-11020 (amine plus ene oxi e 1 0 9 0 2%+ 18 0 22 1 4- 42 (9) SS-1102E (amine plus 70% ethylene oxide) 1 1 1+ 10 1 3- 19 2 3- 22 3 4% 75 1 Filter disc code: 0- no discoloration; 1light discoloration but no definite evidence of precipitate; 2-medium brown discoloration but not black,
indication of trace of precipitate; 3-black deposit showing definite evidence 5black deposit showing heavy precipitate.
The results .of the 100 F. cabinet storage test of Table 11 show that although the oxyalkylated product additives of the present invention did not improve color they eifechighest 1.4. In the majority of cases the amount of deposit formed in the additive compositions was below 1.0 milligram per 100 milliliters and as low as 0.5 milligram 6.
:per 100 milliliters. Visual inspection of the storage tubes after 4 months showed only trace amounts of deposit when using SS-l102E and none with the'other additivesas compared to a heavy precipitate in the neat fuel tube. Also .shown inTable II is the general enhancement of the additives of Example I as a fuel oil stabilizer by the incorporaof insolubles in fuel; 4-black deposit showing considerable precipitate;
tion of a metal deactivator. Thus, the results of the 100 F. cabinet storage test particularly illustrate the effectiveness of the additives of the present invention as stabilizers for home heating oils.
' Examination of the results of the high temperature tests shows that the additives of the present invention improve the stability of fuels under most of these conditions. It is preferred, however, when using the distillate fuels as diesel fuels, to incorporate in addition to the additives of the present invention minor amounts of a metal deactivator. As shown, the combination of a minor amount of metal deactivator with the additives of the present invention produces an excellent stabilizer for diesel fuels.
. EXAMPLE II A series of oxyalkylated products were prepared having the compositions shown in Table III.
Table III Composition Oxalkylated haseComposition Oxyalkyla- No. Percent Percent Fatty Ethylene Propylene Catalyst tion temp,
oxyalkylxylene diamine, oxide, Oxide, F.
ated base percent percent percent percent Percent Type 62. 5 37. 5 90 10 Na methylate-.. 330-350 66. 7 33. 3 75 25 do 330-350 71. 5 28. 5 60 40 330-350 74. 9 25. 1 55 330-350 81. 8 18. 2 30 70 330-350 69. 1 30. 9 79. 5 10. 25 320-340 73. 3 26. 7 65 17. 5 230-340 78. 0 22. 0 25 320-340 81. 7 18. 3 40 30 320-340 67. 0 33. 0 75 25 310-330 70. 1 29. 9 65 35 310-330 73. 5 26. 5 45 310-330 77. 4 22. 6 45 55 310-330 79. 3 20. 7 40 310-330 81. 4 18. 6 35 310-330 83. 5 16. 5 30 310-330 80. 0 20. 0 25 300-320 83. 4 16. 6 60 40 300-320 87. 0 13. 0 45 55 300-320 91. 0 9. 0 30 70 300-320 83. 5 16. 5 60 40 300-320 80. 0 20. 0 75 25 300-320 83. 5 16. 5 60 40 300-320 80. 0 20.0 75 20 300-320 83. 5 16. 5 60 32 300-320 87. 0 13. 0 45 44 300-320 91. 0 9. 0 30 56 300-320 Norm-0n series 38-1147 and 88-1321 ethylene and propylene oxides were mixed prior to injection ito re- The fatty diamine in all instances was H R-fiI-Rr-NH] in which R is trimethylene and R is a straight chain hydrocarbon residue derived from tallow acids containing 16-18 carbon atoms, while the alkylene oxide and the proportions reacted as well as the reaction temperatures and catalyst employed are shown in Table 111.
Small amounts of the products thus prepared are added to the distillate fuel oil of Example I and tested as in Example I. All of the products show value as distillate fuel oil stabilizers.
1. A fuel oil composition consisting essentially of a distillate fuel oil and a small amount sufficient to efiectively stabilize said oil against deterioration of an oilcompatible reaction product of about 20 to 95 weight percent of a fatty diamine having the structural formula:
H R-I Q'R NHz in which R is an aliphatic hydrocarbon chain of at least about 6 carbon atoms and R is a divalent aliphatic hydrocarbon radical containing about 2 to 8 carbon atoms, and about to 80 weight percent of an alkylene oxide of 2 to 4 carbon atoms.
2. The fuel oil composition of claim 1 in which the distillate fuel contains cracked components.
3. The fuel oil composition of claim 1 wherein the fatty diamine is about 30 to 70 weight percent and the alkylene oxide is about 30 to 70 weight percent.
4. The fuel oil composition of claim 1 wherein R in the structural formula of the fatty diarnine is trimethylene and R is the straight chain hydrocarbon residue derived from tallow fatty acids containing 16 to 18 carbon atoms and the alkylene oxide is ethylene oxide.
5. The fuel oil composition of claim 1 wherein the oxyalkylated product is present in an amount ranging from about 5 pounds per 1000 barrels of fuel oil to 250 pounds per 1000 barrels of fuel oil.
6. The fuel oil composition of claim 4 wherein the oxyalkylated product is present in amounts of about 5 pounds per 1000 barrels of fuel oil to 100 pounds per 1000 barin which R is an aliphatic hydrocarbon chain of at least about 6 carbon atoms and R is a divalent aliphatic hydrocarbon radical containing about 2 to 8 carbon atoms, and about 5 to weight percent of an alkylene oxide of 2 to 4 carbon atoms, and about .25 to 2 pounds per 1000 barrels of said fuel of N,N'-disalicylidene-1,2-propylene diamine.
8. A fuel oil composition consisting essentially of a distillate diesel fuel and about 5 to 250 pounds per thousand barrels of said fuel of an oil-compatible reaction product of about 20 to weight percent of a fatty diamine having a structural formula:
in which R is trimethylene and R is a straight chain hydrocarbon residue derived from tallow fatty acids containing 16 to 18 carbon atoms, and about 5 to 80 weight percent of an alkylene oxide of 2 to 4 carbon atoms, and about .5 to 1 pound per thousand barrels of said fuel of N,N'-disalicylidene-1,2-propylenediamine.
9. The fuel oil composition of claim 1 in which the distillate fuel oil is a diesel fuel.
10. The fuel oil composition of claim 2 to which is added about .25 to 2 pounds per 1000 barrels of said fuel of N,N-disalicylidene-1,2-propylene diamine.
11. The fuel oil composition of claim 1 wherein R is an aliphatic hydrocarbon chain of about 12 to 22 carbon atoms.
12. The fuel oil'composition of claim 7 wherein R is an aliphatic hydrocarbon chain of 12 to 22 carbon atoms.
References Cited in the file of this patent UNITED STATES PATENTS 2,113,150 Wiezevich Apr. 5, 1938 2,684,893 Hughes et al July 27, 1954 2,690,426 Jefferson et al. Sept. 28, 1954 2,771,348 Meguerian Nov. 20, 1956 2,857,330 Hall Oct. 21, 1958 2,902,354 Giammaria Sept. 1, 1959 2,906,611 Schnaith et a1. Sept. 29, 1959 3,030,197 Godar et al Apr. 17, 1962 FOREIGN PATENTS 793,448 Great Britain Apr. 16, 1958 OTHER REFERENCES "Armour-Etho-Chemicals, Armour Chemical Div., copyright 1955 by Armour & Co., pages 1-4.