COMPOSITION AND METHOD TO IMPROVE LUBRICITY IN FUELS

Abstract: It has been discovered that compositions which are blends or mixtures including a monomeric fatty acid component can serve as stable lubricity additives in distillate fuels, including gasoline. The compositions may include saturated or unsaturated, monomeric fatty acids having from 12 to 22 carbon atoms; a synthetic monomeric acid having from 12 to 40 carbon atoms; and saturated or unsaturated, oligomeric fatty acids having from 24 to 66 carbon atoms. Where a saturated monomeric fatty acid is used, a hindered and/or tertiary amine may be present as a stabilizer.

Description: COMPOSITION AND METHOD TO IMPROVE LUBRICITY IN FUELS Field pf the Invention The present invention relates to lubricity additives for distillate fuels, and more particularly relates, in one embodiment to lubricity additives for hydrocarbon fuels, where the additives comprise mixtures of monomeric and polymeric fatty acids. Backgrou d of the Invention It is well known that in many engines the fuel is the lubricant for the fuel system components, such as fuel pumps and injectors. Many studies of fuels with poor lubricity have been conducted in an effort to understand fuel compositions which have poor lubricity and to correlate lab test methods with actual field use. The problem is general to diesel fuels, kerosene and gasolines, however, most of the studies have concentrated on the first two hydrocarbons. Previous work has shown that saturated, monomeric and dimeric, fatty acids of from 12 to 54 carbon atoms used individually give excellent performance as fuel lubricity aids in diesel fuels. While these materials show excellent lubricity properties, they are often difficult to formulate into products due to their poor solubility in hydrocarbons and fatty acid mixtures. Commercial product TOLAD ® 9103 Fuel Lubricity Aid sold by Baker Petrolite Corporation only contains approximately 3.8 weight % stearic acid (a saturated monomeric fatty acid) in a specific and complex mixture of unsaturated monomeric and unsaturated oligomeric fatty acids and heavy aromatic solvent. It has performance characteristics better than products which do not contain the high levels of these saturated acids. However, levels of stearic acid higher than 3.8% tend to separate from the product on standing which limits their usefulness as additives. Simply increasing the stearic acid proportion in TOLAD 9103 Fuel Lubricity Aid above about 3.8% results in an unstable product. Summary of the Invention Accordingly, it is an object of the present invention to provide fuel lubπcity additives which improves lubricity over conventional additives. It is another object of the present invention to provide fuel lubricity additives which improves lubricity over conventional additives, and are stable. Another object of the invention is to provide fuel lubricity additives which improves lubricity in gasoline, which have not heretofore employed lubricity additives. In carrying out these and other objects of the invention, there is provided, in one form, a composition for improving the lubricity of distillate fuels which has (a) at least one monomeric fatty acid component which may be either a C 12 -C 22 saturated, monomeric fatty acid; an C 12 -C 22 unsaturated, monomeric fatty acid; or a C 12 -C 40 synthetic monomeric fatty acid; and (b) at least one oligomeric fatty acid component which may be either a C 24 -C 66 saturated, oligomeric fatty acid; and an C 24 -C 66 unsaturated, oligomeric fatty acid. Brief Description of the Drawings FIG. 1 is a chart of the results o£ wear scar testing of various lubricity aids at 100 ppm; FIG. 2 is a chart of the results of wear scar testing of various lubricity aids at 50 ppm; FIG. 3 is a chart of the results of wear scar testing of Sample 13 at various doses; and FIG.4 is a chart of the results of wear scar testing of Sample 1 at various doses. Detailed Description of the Invention New compositions have been discovered which are useful as fuel lubricity aids, and which may contain, in some embodiments, higher amounts of saturated monomeric (e.g. stearic acid) and oligomeric fatty acids. Customarily, lubricity aids have been limited to use in diesel fuels used in diesel engines having distributors and rotary type fuel injection pumps which rely totally on the fuel for lubrication. Gasoline engines, having a different design with different requirements have not required lubricity aids, but it has been unexpectedly discovered herein that gasolines and gasoline engines benefit from the lubricity aids of the invention, which would not have been expected due to the different structure and design of a gasoline engine. The invention relates to lubricity additives for distillate fuels, as contrasted with products from resid. In the context of this invention, distillate fuels include, but are not necessarily limited to diesel fuel, kerosene, gasoline and the like. It will be appreciated that distillate fuels include blends of conventional hydrocarbons meant by these terms with oxygenates, e.g. alcohols, such as methanol, and other additives or blending components presently used in these distillate fuels, such as MTBE (methyl- tert-butyl ether) or used in the future. Generally, in one embodiment of the invention the composition for improving the lubricity of distillate fuels is a mixture or blend of at least one monomeric fatty acid component with at least one oligomeric fatty acid component, and in another embodiment is a mixture or blend of at least one saturated, monomeric fatty acid with an amine. The monomeric fatty acid components may be a saturated, monomeric fatty acid having from 12 to 22 carbon atoms, an unsaturated, monomeric fatty acid having from 12 to 22 carbon atoms, or a synthetic monomeric fatty acid having from 12 to 40 carbon atoms. In one general embodiment of the invention, a synthetic monomeric fatty acid is any monomeric fatty acid within the given carbon number range that does not occur in nature. In one non-limiting embodiment of the invention, a synthetic monomeric fatty acid is one that results from the modification of a natural fatty acid by a process including, but not limited to, alkylation, hydrogenation, arylation, isomerization or combinations of these modifications. In another, non-limiting embodiment of the invention, the synthetic monomeric fatty acid is formed by dimerizing any of the an unsaturated, monomeric fatty acids having from 12 to 22 carbon atoms mentioned above, and then hydrogenating them. Specific examples of suitable saturated, monomeric fatty acids include, but are not limited to, lauric acid (dodecanoic acid); myristic acid (tetradecanoic acid); palmitic acid (hexadecanoic acid); stearic acid {octadecanoic acid); and the like. Specific examples of suitable unsaturated, monomeric fatty acids include, but are not limited to, oleic acid (ct ' s-9- octadecenoic acid); tall oil fatty acid (e.g. Westvaco L-5); and the like. Specific examples of suitable synthetic, monomeric fatty acids include, but are not limited to, Union Camp Century 1105 and the like. The oligomeric fatty acid components may be a saturated, oligomeric fatty acid having from 24 to 66 carbon atoms, or an unsaturated, monomeric fatty acid having from 24 to 66 carbon atoms. In one general embodiment of the invention, the oligomeric fatty acids may be made by dimerizing or trimerizing any of the unsaturated monomeric acids suitable for the monomeric fatty acid component described above. Specific examples of suitable saturated, oligomeric fatty acids include, but are not limited to, dimer acid (Unichema Pripol 1009); and the like. Specific examples of suitable unsaturated, oligomeric fatty acids include, but are not limited to, dimer acid {e.g. Westvaco DTC-595); trimer acid (e.g. Westvaco DTC-195); and the like. In one embodiment of the invention it is preferred that the oligomeric fatty acid component be a dimer, although trimers are acceptable. In another embodiment of the invention, it is preferred that the monomeric fatty acid component comprise from about 4 to about 90 weight % of the total composition, preferably from about 4 to about 50 wt.% of the total, most preferably from about 4 to about 15 or 10 wt.% of the total. Of course, in one embodiment of the invention, the monomeric fatty acid component is 100% of the total composition of acids. In another embodiment of the invention, the lower limit of these ranges is 5 wt.%. The stable compositions which have been discovered include, but are not necessarily limited to: 1. Mixtures of at least one pure, saturated, monomeric, fatty acid with at least one pure, saturated, oligomeric fatty acid. One specific, non-limiting example of this embodiment of the invention includes, but is not limited to: In Example 170, a 75% of a blend of 65:10 Unichemica PRIPOL ® 1009 hydrogenated dimer acid /palmitic acid gave a wear scar value of 274 microns. (Percentages herein should be understood to be weight percentages unless otherwise noted. Ratios herein should be understood to be weight ratios unless otherwise noted.) 2. Mixtures of at least one pure, saturated, monomeric, fatty acid with at least one pure, unsaturated, oligomeric fatty acid. Specific, non-limiting examples of this embodiment of the invention include, but are not limited to: In Example 171, a75% blend of 65:10 Westvaco DTC-595/ palmitic acid gave a wear scar value of 382 microns. In Example 172, a 75% blend of 65:10 Westvaco DTC-595/ palmitic acid gave a wear scar value of 363 microns. 3. Mixtures of at least one pure, unsaturated, monomeric, fatty acid with at least one pure, saturated, oligomeric fatty acid. One specific, non-limiting example of this embodiment of the invention includes, but is not limited to: In Example 166, a 75% of a blend of 50:50 Unichemica PRIPOL ® 1009 hydrogenated dimer acid/ Westvaco L-5 gave a wear scar value of 428 microns. 4. Mixtures of at least one pure, unsaturated, monomeric, fatty acid with at least one pure, unsaturated, oligomeric fatty acid. One specific, non- limiting example of this embodiment of the invention includes, but is not limited to: In Example 167, a 75% of a blend of 50:50 Westvaco DTC- 595/ Westvaco L-5 gave a wear scar value of 496 microns. 5. Mixtures of at least one pure, saturated, monomeric, fatty acid with an amine and, optionally, at least one pure, saturated or unsaturated, oligomeric fatty a d. Specific, non-limiting examples of this embodiment of the invention include, but is not limited to, the following combinations of monomeric acid component with amine (without including an oligomeric add component, which should be understood as present): In Example 173, a 75% of a blend of 44:31 stearic acid/RohMax Primene 81 R gave a wear scar value of 299 microns. Pure stearic add + tri-n-butylamine (aliphatic tertiary amine). Pure stearic acid + CS1246 ® (heterocyclic amine). Pure stearic acid + alkyl pyridine (heterocyclic amine). Pure stearic acid + N,N-di-n-butylethylenediamine (polyamine). Pure stearic acid + TOMAH E-17-2 ® (oxyalkylated amine). 6. Mixtures of at least one synthetic monomeric acid with at least one pure, saturated or unsaturated, oligomeric fatty acid. Spedfic, non-limiting examples of this embodiment of the invention include, but are not limited to: In Example 168, a 75% of a blend of 50:50 Unichema Pripol 1009/ Union Camp Century gave a wear scar value of 236 microns. In Example 169, a 75% of a blend of 50:50 Westvaco DTC-195 / Union Camp Century gave a wear scar value of 378 microns. A blend of pure isostearic acid with Westvaco 1500, a pure, unsaturated, oligomeric fatty add. In one non-limiting embodiment of the invention, the composition for improving the lubricity of distillate fuels of invention excludes mixtures of a saturated, monomeric fatty acid having from 12 to 22 carbon atoms with an unsaturated, monomeric fatty add having from 12 to 22 carbon atoms. Also excluded would be mixtures of a saturated, oligomeric fatty add having from 24 to 66 carbon atoms with an unsaturated, oligomeric fatty acid having from 24 to 66 carbon atoms, in another non-limiting embodiment of the invention. In a broad embodiment of the invention, the suitable stabilizing amine is any inert amine, i.e. an amine which does not react with the acids present to form an amide. In another embodiment of the invention, the amine is a tertiary amine or an amine where the carbon adjacent the amine nitrogen contains no hydrogen atoms (e.g. t-butyl amine). In another embodiment of the invention, the amine may be an amine having at least one amine functional group selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, cycloaliphatic amines, heterocyclic amines, aromatic amines (e.g. aniline), and oxyalkylated amines. Heterocyclic amines in the context of this invention encompass multiple structures which include, but are not necessarily limited to, structures such as pyridines, pyrimidines, and imidazoles. In one preferred embodiment of the invention, the ratio of amine to acid is near molar equivalent; that is, near stoichiometric. In another embodiment of the invention, the ratio of amine to at least one pure, saturated, monomeric, fatty add ranges from about 1 part amine to 9 parts add to about 9 parts amine to 1 part add, by weight. In another embodiment the molar equivalent ratio proportion of amine to saturated monomeric fatty add in the total composition ranges from about 0.1:1 to about 1:1. Optionally, the amine/monomer mixture may comprise from 100% to 1% of the mixture with the oligomeric fatty acid. The optional amine component in approximate stoichiometric equality with the monomer component permits the composition to be more stable with higher proportions of monomer. In one non-limiting explanation of how the amines impart stability, it is believed that the amines prevent the saturated monomeric fatty adds from reacting. The optional amine component preferably contains from about 4 to about 36 carbon atoms. Typically, a solvent is preferably used in the compositions of the invention, where the solvent may be aromatic solvents and pure paraffinic solvents. Aromatic solvents are particularly preferred. The proportion of solvent in the total fuel lubricity aid composition ranges from about 0 to 50 weight %. The use of a solvent is optional. Spedfic examples of suitable solvents include, but are not limited to, aromatic naphtha; kerosene; diesel; gasoline; xylene; toluene; and the like. The term "pure" is used in the specification herein to means essentially none of another component, as far as such a component is commercially available. With respect to a saturated add, "pure" means essentially no unsaturated material is present, and vice versa. For example, "pure" commercially available stearic acid is free from oleic acid. When the term "only one" is employed, it is meant that the respective one monomeric fatty acid component be essentially the only monomeric fatty add present, and the one oligomeric fatty acid component is essentially the only oligomeric fatty acid present. In one particularly preferred embodiment of the invention, the composition consists of just a single pure monomeric fatty acid component, and just a single pure oligomeric fatty add component. It has been unexpectedly discovered that the particularly exemplified combinations of a monomeric fatty acid component, and an oligomeric fatty add component give better results than complex mixtures of saturated and unsaturated monomeric fatty acids and oligomers, for example, TOLAD ® 9103 lubricity aid sold by Baker Petrolite Corporation, which is a complex mixtures of saturated and unsaturated monomeric fatty adds and oligomers having about 3.8% of a particular fatty acid (stearic add). As noted, the compositions of this invention can be used in various distillate hydrocarbon fuels in concentrations effective to improve the lubricity thereof including, but not necessarily limited to diesel fuel, kerosene or gasoline. Concentrations of the above compositions in hydrocarbons to improve lubridty thereof range from about 10 to about 400 ppm, preferably from about 10 to about 200 ppm, and most preferably from about 25 to about 100 ppm. The invention will be illustrated further with respect to the following non-limiting Examples which are to further illuminate the invention only EXAMPLE 1 A Mixture of a Single Pure, Saturated, Monomeric, Fatty Acid with an Aliphatic Amine To a 100 cc vessel were charged 28.4 g (0J mole) stearic add and 19.5 g (0.1 mole) PRIMENE 81R and mixed to give Sample 1. In one embodiment of this invention, this mixture was diluted 30% by weight with Solvent 14 (aromatic naphtha solvent) This is an example using 100% pure, saturated, monomeric, fatty acid with an amine. EXAMPLES 2-25 Samples 2 through 8 were prepared according to Example 1, except that proportions of the acids and amines shown Table I were used. Table I presents Wear Scar Diameter (WSD) results conducted according to the procedure used in the BOTD Test (Ball on Three Disc Test) developed by Falex Corporation, for Samples 1-8 as well as some commercial lubricity aids such as TOLAD ® 9103 (T-9103). All runs in Table I were at the indicated doses in Shell P-50 Diesel — except where the hydrocarbon fuel is indicated as Kero (kerosene) or SW-1 (Swedish Class 1 diesel). It can be readily seen that Inventive Sample 1 gives one of the lowest WSD results of all twenty- four examples. In Example 18, Sample 8, the ratio of HOAc to CRO-111 is 7.5 wt.% HOAc to 92.5 wt.% CRO-111 by weight. Both components were weighed into a bottle and shaken. Solubility was complete at ambient temperature. Stability was tested by adding 1 drop deionized water to a 2.0 g sample and heating overnight. Any solids formed was noted. Sample 8 stayed solids free. TABLE I Comparative WSD Results px. Sample # Description Dose, ppm WSD. mm 2 2 Xylylstearic add + AEAE 100 0.3208 3 3 Xylylstearic add + DE A 100 0.2842 4 4 Ricinoleic add + AEAE 100 0.2742 5 5 Dimer add (T-9103) + DEA 100 0.2925 6 6 Ricinoleic acid + DEA 100 0.2975 7 7 Hamposil O + DEA 100 0.2733 8 Witcamide 5138 200 0.2125 9 // 100 0.3242 10 a 25 0.3841 11 25 0.2050 12 CRO-111 25 0.3258 13 CRO-290 25 0.4467 14 CRO-111 (Kero) 25 0.1858 15 CRO-290 (Kero) 25 0.2658 16 Hamposil O 100 0.2658 17 Hamposil C 100 0.3075 18 8 CRO-lll/HOAc 25 0.4792 19 1 Stearic add + Primene 91R 100 0.2650 20 T-9103 100 0.3192 21 « « 0.3417 22 « 0.2433 23 " (SW-1) 50 0.3492 24 " (SW-1) 100 0.2733 25 " (SW-1) 200 0.2692 EXAMPLES 26-37 Samples 1 and 9 through 12 were tested at 100 ppm doses in Class 1 Diesel according to ASTM-6079 High Frequency Reciprocating Rig (HFRR) at 60°C. The results are presented in Table π and charted in FIG. 1. In this testing the Inventive Sample 1 composition gave the best results of any compositions tested. Usually, a level of 450 μm or below is considered a "good" WSD value to have for a fuel, although some areas use a 460 μm level. TABLE π Wear Scar Testing of Various Lubricity Aids at 100 ppm Wear Scar Ex. £amg Average (urn) Description 26 Blank 600 27 Blank 620 28 9 617 Oleic Add /Propane Diamine Diamide 29 9 614 30* 10 611 Oleic Acid /Propane Diamine 31* 10 598 « 32 11 593 Xylylstearic Acid /Propane Diamine Diamide 33 11 599 34 12 485 CRO-11 + Acetic Add (92.5/7.5 Parts) 35 12 488 36 1 451 Stearic Acid/Primene 81R Amine 37 1 447 *Due to the difference in reaction conditions from Examples 28 and 29, tetrahydropyrimidines were formed in these Examples. EXAMPLES 38-47 Samples 1 and 9 through 12 were tested at 50 ppm doses in Class 1 Diesel according to ASTM-6079 (HFRR). The results are presented in Table HI and charted in FIG. 2. In this testing the Inventive Sample 1 composition once again gave the best results of any compositions tested. TABLE in Wear Scar Testing of Various Lubridty Aids at 50 ppm Wear Scar Sample Average (μm) Description 26 Blank 600 27 Blank 620 38 9 595 Oleic Add /Propane Diamine Diamide 39 9 599 40* 10 615 Oleic Acid /Propane Diamine 41* 10 623 II 42 11 616 Xylylstearic Acid /Propane Diamine Diamide 43 11 607 44 12 553 CRO-11 + Acetic Add (92.5/7.5 Parts) 45 12 612 46 1 545 Stearic Acid/Primene 81R Amine 47 1 533 *Due to the difference in reaction conditions from Examples 38 and 39, tetrahydropyrimidines were formed in these Examples. EXAMPLES 48-61 Sample 13 was tested at various doses in Class 1 Diesel according to ASTM-6079 HFRR. The results are presented in Table IV and charted in FIG. 3. Sample 13 was 92.5% CRO-111 and 7.5% HOAc, % w/ w (the same composition as Ex. 18, Sample 8, and Ex. 44, Sample 12). TABLE IV Wear Scar Testine of Samole 13 at Various Doses Ex. Dose Wear Scar Average (um) 26 0 600 27 0 620 48 50 556 49 50 612 50 100 485 51 100 488 52 120 447 53 120 418 54 140 399 55 140 438 56 160 462 57 160 502 58 180 480 59 180 476 60 200 455 61 200 423 EXAMPLES 62-75 Sample 1 was tested at the same various doses in Class 1 Diesel as was Sample 13 in Examples 48-61; also according to ASTM-6079 HFRR. The results are presented in Table V and charted in FIG.4. Again, a comparison of the results using Sample 1 v. Sample 13 (Tables V v. IV or FIGS. 4 v. 3) demonstrate that Sample 1 of this invention consistently gives better results at every dosage level. TABLE V Wear Scar Testing of Samole 1 at Various Doses Ex. Dose Wear Scar Average ( m) 26 0 600 27 0 620 62 50 545 63 50 533 64 100 451 65 100 447 66 120 431 67 120 432 68 140 433 69 140 404 70 160 414 71 160 414 72 180 410 73 180 435 74 200 419 75 200 415 EXAMPLE 76 Solubility of Witco Stearic Adds in Pure Solvents 25 g Total Sample Wt. 2.5 g Witco HYSTRENE ® 9718 Stearic Add 22.5 g Ethyl Acetate 10% HYSTRENE 9718 by weight The components were placed into an empty prescription bottle. At 75°F (24°C, room temperature), the stearic acid did not go into solution in the ethyl acetate. The stearic acid settled to the bottom of the test jar. Heating the sample to 120°F (49°C) for 15 minutes caused the stearic add to be totally dissolved in the ethyl acetate. The sample was allowed to cool to room temperature. After 30 minutes, solids started to form. Overnight at room temperature, the sample turned cloudy with suspended particles. EXAMPLE 77 Solubility of Stearic Acid in Acetic Acid 25 g Total Sample Wt. 1.25 g Witco HYSTRENE ® 9718 Stearic Add 23.75 g Acetic Add 5% HYSTRENE 9718 by weight The components were placed into an empty prescription bottle. At 75°F (24°C, room temperature), the stearic acid would not dissolve in the acetic add. The sample was placed in an 120°F (49°C) oven for 15 minutes. The sample totally dissolved at 120°F (49°C). The sample was allowed to cool to room temperature, whereupon the stearic add dropped out. EXAMPLE 78 Solubility of Stearic Acid in Valeric Acid (Saturated Monomer in Saturated Dimer) 25 g Total Sample Wt. 1.25 g Witco HYSTRENE ® 9718 Stearic Acid 23.75 g Valeric Acid 5% HYSTRENE 9718 by weight Stearic acid (5 wt.%) went into solution in valeric acid at room temperature. Additional stearic add (1.5 g) was added to the mixture to make a total of 26.50 g containing 10.37 wt.% stearic add. The 10 wt.% proportion would not blend into valeric acid at room temperature. When the sample was placed in 120°F (49°C) oven for 15 minutes, the stearic acid went into solution. The sample was allowed to cool to room temperature (75°F, 24°C). The sample looked clear after cooling to room temperature. However after 2 hours at 5°F (24°C), the sample was frozen solid. More valeric add (8.4 g) was added to the sample. This reduced the stearic add proportion to 7.8 wt.%. The sample was heated to 120°F (49°C); all of the stearic acid was soluble in the valeric add and allowed to cool to room temperature (75°F, 24°C). After 24 hours at room temperature, the sample was dear. EXAMPLE 79 Solubility of Stearic Acid i Unichemica PRIPQ 1009 Dimer Acid 25 g Total Sample Wt. 1.25 g Witco HYSTRENE ® 9718 Stearic Add 23.75 g PRIPOL 1009 Dimer Add (extremely viscous) 5% HYSTRENE 9718 by weight The sample was placed in a 120°F (49°C) oven to heat. The sample was slow to mix; a few particles were in suspension after 65 minutes. After 5 minutes in a 180°F (82°C) oven, all of the stearic acid dissolved into the dimer add. The sample was allowed to cool to room temperature (75°F, 24°C) and 1.5 g (approximately 5%) more stearic acid was added to make the total 10.37 wt.%. The sample was placed in a 180°F (82°C) oven to help solubilize the mixture. Upon cooling for an hour, the sample started clouding. The sample was reheated to 180°F (82°C) and 8.5 more grams of the dimer add was added reducing the stearic add proportion to 7.85 wt.%. EXAMPLE 80 Solubility of Stearic Acid in Soybean Oil 1.25 g Witco HYSTRENE ® 9718 Stearic Add + 23.75 g Soybean oil 25 g Total Sample Wt The sample was hazy at room temperature (75°F, 24°C). The sample was placed in a 120°F (49°C) oven for about 25 minutes, but the stearic acid did not solubilize. Nor did the stearic add solubilize after the sample was placed in a 180°F (82°C) oven. EXAMPLE 81 Solubility of Stearic Acid in Unichemica PRIPQi 1013 Dimer Acid 25 g Total Sample Wt. 1.25 g Witco HYSTRENE ® 9718 Stearic Add 23.75 g PRIPOL 1013 Dimer Acid (extremely viscous) The sample was placed in a 180°F (82°C) oven to help solubilize the stearic add in the viscous dimer acid. EXAMPLE 82 Solubility of Saturated Monomer (Stearic Acid) in Saturated Ester (Exxate 1300 Solvent) 10 wt.% Witco HYSTRENE ® 9718 Stearic Add 90 wt.% Exxate 1300 Solvent The sample at room temperature was cloudy white. The sample was placed in a 120°F (49°C) oven to help solubilize the stearic add in the saturated ester, but solubility did not occur after 30 minutes. The sample was placed in a 180°F (82°C) oven and after 15 minutes all of the stearic add was soluble. The sample was taken out of the oven and allowed to cool to 75°F (24°C). The sample froze at 75°F (24°C) indicating 10% stearic acid was not soluble. Additional solvent (5 g) was added which adjusted the total stearic add proportion to 8.0 wt.%, and the sample was placed into a 180°F (82°C) oven. The sample was allowed to cool and the stearic acid dropped out. EXAMPLE 83 Solubility of Saturated Monomer (Stearic Acid) in Aliphatic Primary Amine (Primene 81R) 2 g (10 wt.%) Witco HYSTRENE ® 9718 Stearic Add 18 g Primene 81R At room temperature (75°F, 24°C), the stearic add dissolved. The stearic acid proportion was increased to 20 wt.% in a separate run: 4 g (10 wt.%) Witco HYSTRENE ® 9718 Stearic Add 16 g Primene 81R At room temperature (75°F, 24°C), the stearic add dissolved. This sample was allowed to sit at room temperature to see if settling occurs, and it did not. The 20 wt.% mixture of stearic acid in Primene 81R was tested to see how much (%) will be soluble in Pripol 1009 dimer acid: 10 g Pripol Dimer Acid 10 g 20 wt.% stearic acid in Primene 81R (10 wt.% stearic acid in total solution) The sample was placed in 120°F (49°C) oven, then a 180°F (82°C) oven for 30 minutes. All components blended well. The sample was allowed to cool to room temperature (75°F, 24°C). EXAMPLE 84 Solubility of Saturated Monomer (Stearic Add) in Aliphatic Primary Amine (Primene 81R) and FAS 150 70 wt.% 20 wt.% stearic acid in Primene 81R 30 wt.% FAS 150 The sample was heated to 180°F (82°C) oven to help solubilize it. 5 g 20 wt.% stearic add in 80 wt.% Primene 81R 2 g FAS 150 solvent (70.1% active in FAS 150) The sample was clear yellow and looked good. EXAMPLE 85 Solubility of Saturated Monomer (Stearic Acid) in Aliphatic Primary Amine (Primene SIR), FAS 150 and Fripol 1009 28.0 g FAS 150 added first 38.4 g Primene 81R added second 9.6 g Stearic add added third 24.0 g Pripol 1009 dimer add added fourth 100 g Total sample The sample mixed well at 75°F (24°C). Some heat was released. The sample was only stirred and not heated, and was clear yellow in color. EXAMPLE 86 Solubility of Saturated Monomer (Stearic Acid) in Aliphatic Primary Amine (Primene 81 R) 23.2 g Stearic add (58 wt.%) 16.8 g Primene 81R (42 wt.%) 40.0 g Total sample (100 wt.%) The sample mixed well at 5°F (24°C). There was still a little stearic add undissolved on bottom of bottle. The sample was placed in a 180°F (82°C) oven overnight. All of the stearic add dissolved. The sample was allowed to cool to room temperature (75°F, 24°C) and the solution was still clear. EXAMPLE 87 Solubility of Stearic Acid in Dicyclohexylamine 2 g Stearic add (10 wt.%) 18 g Dicyclohexylamine (90 wt.%) 20 g Total sample (100 wt.%) The sample did not mix well at 75°F (24°C) and was a cloudy white paste. When it was placed in a 180°F (82°C) oven, there was a distinct separation into two phases. When the sample was shaken, it turned cloudy again. After the sample was allowed to cool to 75°F (24°C), the two liquid phases appeared again and eventually the sample turned solid. EXAMPLE 88 Solubility of Qleic Acid in Dimer Acid 10 g Priolene 6933 Oleic add (50 wt.%) Ifi-g Pripol 1009 (50 wt.%) 20 g Total sample (100 wt.%) The sample mixed well at room temperature (75°F, 24°C) and after 24 hours the sample still looked good. EXAMPLE 89 Solubility of Stearic Acid in Tri-N-butylamine 18 g Stearic add (90 wt.%) 2 g Tri-n-butylamine (10 wt.%) 20 g Total sample (100 wt.%) The sample mixed well at room temperature (75°F, 24°C) into a clear, water white solution. After 5 days, however, the sample was cloudy. EXAMPLE 90 Solubility of Stearic Acid in Primene SIR 2 g Stearic add (67 wt.%) Ig Primene 81R (33 wt.% ) 3 g Total sample (100 wt.%) The sample was heated to 180°F (82°C) to help solubilize the sample completely. The sample was allowed to cool to 75°F (24°C). The stearic add dropped out and turned solid. EXAMPLE 91 Solubility of Stearic Acid in Propoxylated Amine 1 g Stearic add (10 wt.%) 9 g Propomeen T/ 12 Propoxylated amine (90 wt.%) 10 g Total sample (100 wt.%) The sample was heated to 180°F (82°C) and allowed to cool to 75°F (24°C). The mixture resulted in a light yellow solid. EXAMPLE 92 Solubility of Stearic Acid in Octylamine 1 g Stearic add (10 wt.%) ±g. Octylamine (90 wt.%) 10 g Total sample (100 wt.%) The sample solubilized easily at 75°F (24°C) and was clear, water white. EXAMPLE 93 Solubility of Stearic Acid in Heterocyclic Amine 1 g Stearic add (10 wt.%) 9 g Amine CS 1246 heterocyclic amine (90 wt.%) 10 g Total sample (100 wt.%) The sample was a little hard to solubilized at 75°F (24°C). The sample was placed in a 180°F (82°C) oven which solubilized the stearic add. After the sample cooled to 75°F (24°C), it had a clear, water white appearance. EXAMPLE 94 Solubility of Stearic Aci in N-N-Diborylethylene Amine 1 g Stearic add (10 wt.%) £g N,N-Diborylethylene amine (98%) (90 wt.%) 10 g Total sample (100 wt.%) The sample dissolved at 75°F (24°C) into a clear white liquid. EXAMPLE 95 Solubility of Stearic Acid in Ethoxylated Alkylamine 1 g Stearic acid saturated monomer (10 wt.%) 9 g E-14-5 ethoxylated alkylamine (90 wt.%) sold by Tomah Chemical Co. 10 g Total sample (100 wt.%) The sample was a sticky, white material at 75°F (24°C). The sample was placed into a 180°F (82°C) oven, and then allowed to cool to 75°F <24°C), when it turned into a light brown solid. EXAMPLE 96 Solubility of Stearic Acid in Ethoxylated Alkylamine 1 g Stearic acid saturated monomer (10 wt.%) 9 g E-17-2 ethoxylated alkylamine (90 wt.%) sold by Tomah Chemical Co. 10 g Total sample (100 wt.%) The sample did not mix well at 75°F (24°C). The sample was placed into a 180°F (82°C) oven, and then allowed to cool to 75°F (24°C). The sample then had a clear, yellow appearance. EXAMPLE 97 Solubility of Stearic Add in Alkyl Pyridine 1 g Stearic acid saturated monomer (10 wt.%) 9 g Alkyl pyridine (90 wt.%) sold by Reilly Chemical Co. 10 g Total sample (100 wt.%) The sample mixed well at 75°F (24°C) and appeared solubilized. EXAMPLE 98 Solubility of Stearic Acid in Westvaco 15QQ 1 g Stearic add saturated monomer (10 wt.%) 9 g Westvaco 1500 unsaturated oligomeric fatty acid (90 wt.%) 10 g Total sample (100 wt.%) The sample was placed in a 180°F (82°C) oven, where it mixed well. It was allowed to cool to 75°F (24°C), whereupon it turned into a dark brown solid. EXAMPLE 99 Solubility of PRIOLENE 6933 Okie Acid in Westvaco 1500 10 g PRIOLENE 6933 oleic acid (50 wt.%) 10 g Westvaco 1500 unsaturated oligomeric fatty acid (50 wt.%) 20 g Total sample (100 wt.%) The sample mixed well at 75°F (24°C). EXAMPLE 100 Solubility of PRIOLENE 6933 Oleic Acid in PRIPOL 1009 Dimer Add 10 g PRIOLENE 6933 oleic add (50 wt.%) 10 g PRIPOL 1009 Dimer Add (.50 wt.%) 20 g Total sample (100 wt.%) The sample mixed well at 75°F (24 °C). It was a little viscous, but stayed mixed EXAMPLE 101 Solubility of Stearic Acid in Cyclohexylamine 1 g Stearic add (10 wt.%) 9 g Cyclohexylamine (90 wt.%) 10 g Total sample (100 wt.%) The sample was a cloudy paste at 75°F (24°C). It was placed in an oven at 180°F (82°C), whereupon the sample mixed well. It was then allowed to cool to 75°F (24°C), and it turned a solid light brown. EXAMPLE 102 Solubility of Stearic Acid in N.N- imethylaniline 1 g Stearic add (10 wt.%) i-g N,N-Dimethylaniline (99%) (90 wt.%) 10 g Total sample (100 wt.%) The sample did not mix well at 75°F (24°C). It was placed in an oven at 180°F (82°C), and when cooled, the product separated and formed light yellow crystals. EXAMPLES 103-120 Solubility of Mixtures of a Synthetic Monomeric Acid with An Oligomeric Fatty Acid Using MX-Dimer available from Sylva Chemical Co., various samples were prepared which contained 30 wt.% Solvent 14, 38.5 wt.% dimer acid, and the remaining 31.5 wt.% containing as much stearic acid as possible, cut with isostearic or xylylstearic add, synthetic monomer add components. The dimer acid is 1.28 times as much as the Solvent 14 amount; the dimer acid is 1.22 times as much as the other acid. Example 103 Dimer add 20.07 g This mixture was heated until liquid. Solvent 14 15.67 g It was allowed to cool, and it solidified. Stearic add 16.51 g Example 104 Dimer add 23.32 g Solvent 14 18.21 g Stearic add 9.58 g Isostearic add 9.62 g This mixture was heated until liquid. It was allowed to cool, and it solidified. Example 105 Dimer acid 12.49 g Solvent 14 9.79 g Stearic add 514 g Xylylstearic add 512 g This mixture was heated until liquid. It was allowed to cool, and it solidified. Example 106 Dimer add 16.55 g Solvent 14 12.92 g Stearic add 3.39 g Isostearic add 10.17 g This mixture was heated until liquid. It was allowed to cool overnight, Some predpitate was observed. Example 107 Dimer add 14.83 g 38.4 wt.% Solvent 14 11.69 g 30.1 wt.% Stearic add 3.06 g 7.9 wt.% Xylylstearic add 9.19 g 23.6 wt.% Overnight the mixture stayed clear. Some precipitate formed the next day. TABLE VI Solubility of Mixtures of a Synthetic Monomeric Acid with An Oligomeric Fatty Acid 50 wt.% of 50 wt.% of Es-. material from material from Observations * 108 Ex. 105 Ex. 107 Rapid precipitate upon cooling — solid 109 Ex. 104 Ex. 106 Predpitate upon cooling — solid 110 Ex. 104 Ex. 107 Rapid predpitate upon cooling — fluid 111 Ex. 105 Ex. 106 Rapid predpitate upon cooling — fluid 112 Ex. 104 Ex. 105 Rapid predpitate upon cooling — solid 113 Ex. 106 Ex. 107 No predpitate, but one had formed two days later. * When the word "solid" was used, the entire mixture acted as a solid and was unpourable. When the word "liquid" was used, although a precipitate had formed, the mixture was a pourable fluid mixture. Composition of Example 113; Dimer add 38.5 wt.% Solvent 14 30.0 wt.% Stearic add 7.9 wt.% Isostearic add 11.8 wt.% Xylylstearic add 11.8 wt.% EY706 one drop TABLE VII Solubility of Mixtures of a Synthetic Monomeric Acid with An Oligomeric Fatty Acid Additive E 2 gof Quantity Additive Observations 114 Ex.103 1 drop EY706 Solid with white chunks 115 Ex.104 1 scoop* T-3792 Uniform solid 116 Ex.107 1 drop EY706 117 Ex.107 1 scoop T-3792 Cloudy 118 Ex.106 1 drop EY706 119 Ex.106 1 scoop T-3792 Cloudy ' A scoop is defined as a small amount of solid additive on the end of a small spatula. Composition of Example 120 Dimer add 38.5 wt.% Solvent 14 30.0 wt.% Oleic acid (Pamolyn 100 supplied by Arizona Chemical) 31.5 wt.% This composition of Example 122 was liquid and remained liquid. Composition of Example 121; Solvent 14 30.0 wt.% Xylylstearic add 70.0 wt.% This composition of Example 121 was liquid and remained liquid. Composition of Example 122; Dimer acid 38.5 wt.% Solvent 14 30.0 wt.% Xylylstearic add 31.5 wt.% This composition of Example 122 was liquid and remained liquid. EXAMPLES 123-173 Various other blends and mixtures within the scope of this invention were used in Examples 166-173 as contrasted with comparative Examples 123-165 using various components singly, or various commerdal lubricity additives, with the results reported in Table VIII. The lubricity additives were tested in NARL Blend #1 Fuel (Eastern Canadian Blend). Wear Scar data was obtained using ASTM-6079 HFRR. As can be seen in Table VIII, the wear scar data obtained using the inventive compositions of Examples 166-173 was better than that obtained using conventional lubridty additives, or the fatty add components singly. Table Vffl Lubridty Additives in NARL Blend #1 Fuel (Eastern Canadian Blend) Av. Fricti £ Additive Chemical Name ppm Wear Scar, μm A v. Film (% ) Coefficien 123 Blank 602 21 0.393 124 Akzo Neo-Fat 94-06 Oleic add 1000 233 89 0106 125 Akzo Neo-Fat 94-06 Oleic add 100 399 59 0178 126 Westvaco DTC-595 Dimer acid 100 344 73 0.185 127 Westvaco M28 Mixed dimer /Rosin adds 100 359 70 0.176 128 M-1849 Tetrapropenyl sucdnic acid 100 568 9 0.298 129 Westvaco 1500 Dimer add 100 358 79 0.173 130 Arizona FA-2 Tall oil fatty add 100 346 69 0157 131 Westvaco Rosin R Rosin acid 100 236 87 0.169 132 Aldrich Stearic Acid Stearic add 100 437 65 0.159 133 Union Camp Unitol PDT Mixed monomer /dimer adds 100 449 76 0.170 134 Union Camp Century MO-5 Mixed monomer acids 100 367 71 0162 135 Unichema Pripol 1013 Distilled dimer acid 100 324 84 0.170 136 Xylylstearic Add Xylylstearic add 100 300 84 0.171 137 Unichema Pripol 1040 Trimer add 100 396 80 0196 138 Westvaco OCD-128 Mixed monomer acids 100 294 84 0.161 139 Unichema Palmitic Acid Palmitic acid 100 338 73 0.157 140 Westvaco 1550 Dimer acid 100 441 72 0.179 141 Union Camp Century D-75 Mixed monomer /dimer acids 100 362 78 0.179 142 Union Camp Century 1164 Mixed monomer adds 100 421 67 0170 143 Unichema Laurie Acid Laurie add 100 397 70 0161 144 Unichema Behenic Acid Behenic acid 100 390 74 0.157 145 Westvaco DTC-155 Mixed monomer /dimer acids 100 377 66 0176 146 Westvaco M-15 Mixed dimer /Rosin adds 100 339 79 0162 147 50% Rosin R Rosin acid in solvent 200 354 71 0.184 148 Unichema Pripol 1009 Distilled dimer add 100 366 70 0.185 149 Unichema Pripol 1040 Trimer add 100 537 19 0.286 150 Westvaco OCD-128 Mixed monomer acids 100 341 71 0.167 151 Unichema Pripol 1013 Distilled dimer add 100 341 73 0.180 152 Xylylstearic add Xylylstearic add 100 349 60 0.184 t r-0o 153 Aldrich Stearic Acid Stearic add 100 385 62 0.156 154 CRO-290 Imidazoline salt 100 451 46 0.214 155 25% Westvaco Rosin R Rosin acid 400 373 68 0.189 156 Unichema Priolene 6900 Oleic add 100 363 69 0169 157 Westvaco L-5 Tall oil fatty acid 100 312 80 0155 158 Westvaco L-l Tall oil fatty acid 100 304 79 0.155 159 Westvaco DTC-195 Trimer add 100 315 79 0.185 160 CRO-4080 Tall oil fatty acid anhydride ester 333 376 71 0.199 161 Tolad 9103 Mixed monomer /dimer acids 100 361 67 0178 162 Tolad 9103 Mixed monomer /dimer acids 50 566 13 0.284 163 Tolad 9103 Mixed monomer /dimer adds 75 320 81 0.179 164 Tolad 9103 Mixed monomer /dimer acids 60 512 32 0.244 165 75% 50:50 Pripol 1009/ L-5 Blend 60 428 58 0.205 166 75% 50:50 DTC-195/ L-5 Blend 6 600 4 49966 3 344 0 0..223311 167 75% 50:50 Pripol 1009/ Century 1105 Blend 6 600 2 23366 8 888 0 0..116622 168 75% 50:50 DTC-195/ Century 1105 Blend 60 378 72 0192 169 75% 65:10 Pripol 1009/Palmitic add Blend 60 274 85 0.163 170 75% 65:10 DTC- 195 /Palmitic add Blend 60 382 66 0.197 171 75% 65:10 DTC-595/ Palmitic add Blend 60 363 75 0.186 172 75% 44:31 Stearic acid/ Primene 81R Blend 60 299 85 0.163 O In the foregoing specification, the invention has been described with reference to specific embodiments thereof, and has been demonstrated as effective for improving the lubridty of fuels. However, it will be evident that various modifications and changes can be made thereto without departing from the broader spirit or scope of the invention as set forth in the appended claims. Accordingly, the spedfication is to be regarded in an illustrative rather than a restrictive sense. For example, specific combinations of monomeric fatty acids and oligomeric fatty acids and optional amines falling within the claimed parameters, but not specifically identified or tried in a particular composition to improve the lubricity of fuels herein, are antidpated to be within the scope of this invention. It is anticipated that the compositions of this invention will also impart to the engines in which they are used as fuel lubricity aids, greater horsepower, lower emissions and better fuel economy as a result of less friction, whether they are used in diesel or gasoline engines. GLOSSARY 1500 Dimer acid available from Westvaco. AEAE Aminoethylaminoethanol or 2-(2-aminoethyl- amino)-ethanol. Amine CS 1246 A heterocyclic amine sold by Angus Chemical Co. Century 1105 Synthetic, saturated monomer acid available from Union Camp. Century 1164 Mixed monomer acids available from Union Camp. Century D-75 Mixed monomer /dimer acids available from Union Camp. Century MO-5 Mixed monomer acids available from Union Camp. CRO-111 Fatty add imidazoline sold by Baker Petrolite. CRO-290 Isostearic acid imidazoline sold by Baker Petrolite. CRO-4080 Tall oil fatty acid anhydride ester sold by Baker Petrolite. CS1246 A heterocydic amine sold by Angus Chemical Company. DEA Diethanolamine. DTC-155 Mixed monomer/ dimer acids available from Westvaco. DTC-195 Trimer acids available from Westvaco. DTC-595 Dimer acid available from Westvaco. EXXATE ® 1300 Solvent A saturated ester sold by Exxon Chemical. EY702 An ethylene/ vinyl acetate copolymer sold by Quantum Chemical Co. FA-2 Tall oil fatty add available from Arizona Chemical. FAS ® 150 A heavy aromatic naphtha supplied by Fina. Hamposil C A cocoamine derivative of sarcosine (forming an aminoacid) sold by Hampshire Chemical Co. Hamposil O An oleylamine derivative of sarcosine (forming an aminoacid) sold by Hampshire Chemical Co. HOAc Acetic add (glacial). L-5 Tall oil fatty add sold by Westvaco. M-15 Mixed dimer acid /rosin acids available from Westvaco. M-28 Mixed dimer acid /rosin acids available from Westvaco. M-1849 Tetrapropenyl succinic acid available from Baker Petrolite. Neo-Fat 94-06 Oleic acid available from Akzo. OCD-128 Mixed monomer acids available from Westvaco. PRIMENE 81R ® An aUphatic 2 - 14 primary amine sold by Rohm & Haas. PRIOLENE ® 6900 Oleic acid sold by Unichemica PRIOLENE ® 6933 Oleic acid sold by Unichemica PRIPOL ^ 1009 A hydrogenated dimer acid sold by Unichemica. PRIPOL ® 1013 Distilled dimer acid sold by Unichemica. PRIPOL ® 1040 Trimer acid sold by Unichemica. PROPOMEEN ® T/ 12 A propoxylated amine sold by Akzo Chemical Rosin R Rosin add available from Westvaco. SW-1 Swedish Class 1 diesel fuel — a test fuel. T-3972 TOLAD ® 3792; an ester of an olefin/maleic anhydride copolymer sold by Baker Petrolite Corporation. TOLAD ® 9103 A commerdal lubricity aid sold by Baker Petrolite Corporation, which is a complex mixtures of saturated and unsaturated monomeric fatty adds and oligomers having about 3.8% of stearic add. TOMAH E-17-2 ® A oxyalkylated amine sold by Tomah Chemical Company. Unitol PDT Mixed monomer/ dimer acids available from Union Camp. Westvaco 1500 An unsaturated oligomeric fatty acid sold by Westvaco. WITCAMIDE ® 5138 Alkanolamide from oleic add and monoethanolamine.

Claims: Claims. We Claim: 1. A composition for improving the lubricity of distillate fuels comprising: (a) at least one monomeric fatty acid component selected from the group consisting of a saturated, monomeric fatty acid having from 12 to 22 carbon atoms; an unsaturated, monomeric fatty acid having from 12 to 22 carbon atoms; and a synthetic monomeric acid having from 12 to 40 carbon atoms; and (b) at least one oligomeric fatty acid component selected from the group consisting of a saturated, oligomeric fatty add having from 24 to 66 carbon atoms; and an unsaturated, oligomeric fatty add having from 24 to 66 carbon atoms, excluding a mixture of a saturated, monomeric fatty acid having from 12 to 22 carbon atoms with an unsaturated, monomeric fatty add having from 12 to 22 carbon atoms; a mixture of a saturated, oligomeric fatty add having from 24 to 66 carbon atoms with an unsaturated, oligomeric fatty acid having from 24 to 66 carbon atoms. 2. The composition for improving the lubricity of distillate fuels of claim 1 where the monomeric fatty acid component (a) comprises from about 4 to 90 wt.% of the total composition. 3. The composition for improving the lubricity of distillate fuels of claim 1 where there is only one component (a) and only one component (b) and components (a) and (b) are pure. 4. The composition for improving the lubricity of distillate fuels of any of the preceding claims where the monomeric fatty acid component (a) comprises a saturated, monomeric fatty add and the composition additionally comprises an amine. 5. The composition of claim 4 where the amine is selected from the group consisting of tertiary amines and amines where the carbon adjacent the amine nitrogen contains no hydrogen atoms. 6. The composition of claim 4 where the amine is selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, cycloaliphatic amines, heterocyclic amines, aromatic amines and oxyalkylated amines. 7. The composition of either claims 4, 5 or 6 where the molar equivalent proportion of amine to saturated, monomeric fatty acid (a) in the total composition ranges from about 0.1:1 to about 1:1. 8. The composition for improving the lubridty of distillate fuels of any of the preceding claims further comprising an aromatic solvent. 9. The composition for improving the lubricity of distillate fuels of any of the preceding claims where the proportion of aromatic solvent in the total composition ranges up to 50 wt.%. 10. A distillate fuel having improved lubridty comprising: (A) a hydrocarbon selected from the group consisting of diesel fuel, kerosene, and gasoline; and (B) a composition as described in any of the preceding claims. 11. The distillate fuel of claim 10 where the proportion of the composition for improving the lubricity of the fuel (B) in the total hydrocarbon fuel ranges from 10 to 400 ppm. 12. Use of a composition of any of claims 1 through 9 to improve the lubricity of a distillate fuel, where the distillate fuel comprises a hydrocarbon selected from the group consisting of diesel fuel, kerosene, and gasoline. 13. A composition for improving the lubricity of distillate fuels comprising: (a) at least one monomeric fatty acid component selected from the group consisting of a saturated, monomeric fatty acid having from 12 to 22 carbon atoms; an unsaturated, monomeric fatty acid having from 12 to 22 carbon atoms; and a synthetic monomeric acid having from 12 to 40 carbon atoms; and (b) an amine is selected from the group consisting of a tertiary amine and an amine where the carbon adjacent the amine nitrogen contains no hydrogen atoms. 14. The composition for improving the lubricity of fuels of claim 13 where the molar equivalent proportion of amine (b) to monomeric fatty add component (a) in the total composition ranges from about 0.1:1 to about 1:1.

Inventors: CAPPEL WELDON J JR, GENTRY DAVID R, MCCALLUM ANDREW J, WEERS JERRY J, CAPPEL, WELDON, J., JR., GENTRY, DAVID, R., MCCALLUM, ANDREW, J., WEERS, JERRY, J.
Applicants: BAKER HUGHES INC, BAKER HUGHES INCORPORATED
Application year: 1999
Main classification: C10L1
IPC codes: C10L1, C10L10