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Fuel Additive Patentamt JEuropaischesEuropean Patent Office (jj) Publication number: 0185 083 B1 Office europeen des brevets ® EUROPEAN PATENT SPECIFICATION (45) Date of publication of patent specification: 22.08.90 (jjj) Int. CI.5: C 10 L 1/22 ® Application number: 85903467.0 (§) Date of filing: 06.06.85 (8) International application number: PCT/US85/01064 (fj) International publication number: WO 86/00088 03.01 .86 Gazette 86/01 3) FUEL ADDITIVE. (§) Priority: 15.06.84 US 621073 ® Proprietor: KITCHEN, George Holcum P.O. Box 15212 ~ Rio Rancho, NM 87124 (US) (43) Dateof publication of application: 25.06.86 Bulletin 86/26 ® Inventor: KITCHEN, George Holcum _ P.O. Box 15212 (45) Publication of the grant of the patent: Rio Rancho, NM 87124 (US) 22.08.90 Bulletin 90/34 ® zsj. „ . Representative: Sommerville, John Henry etal (H) Designated Contracting States: SOMMERVILLE & RUSHTON 11 Holywell Hill AT BE CH DE FR GB IT LI LU NL SE St. Albans Hertfordshire, AL1 1 EZ (GB) @ References cited: FR-A-2177 954 FR-A-2411882 GB-A-1 398 067 US-A-1 973 676 m US-A-2 534309 US-A-3 334046 US-A-3493 354 US-A-3 888 773 US-A-3 907 518 US-A-4155 718 US-A-4 173456 US-A-4585462 i\oie. vvunin nine monins Trom tne puDiication or the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall ae filed in written reasoned a. a statement. It shall not be deemed to have been filed until the opposition fee has been said. (Art. 99(1 ) European patent convention). LU Courier Press, Leamington Spa, England. 1 EP 0 185 083 B1 2 Description the best yardstick of an inhibitor's usefulness in prolonging fuel storage life. The first test is a This invention relates to fuel additives and more variation of the color-stability test in Federal particularly to diesel fuel additives which inhibit Specification VV-K-211 Kerosene. In addition to the polymerization of fuel components, the growth 5 observing the color change, the amount of filter- of bacteria in stored fuel, and corrosion inside the able sludge and sediment is also measured. The fuel tank. It also relates to a method of storing fuel. second test is a prolonged version of the Gulf Oil With the increasing prevalence of standby Company's Fuel Corrosion of Steel Test. The Bell power generation equipment for essential ser- Laboratories' version of these tests have been vices, including hospitals, communication equip- io correlated against fuels actually stored in a stand- ment and the like, it has become increasingly by power fuel tank. The first test is run at 99°C important to protect the fuel from degradation (210°F) until an observable amount of sludge has when stored for long periods of time. More formed. This test is essentially an accelerated heat- recently, many of these standby motor generator stability test and is run in the absence of water. The systems have employed diesel engines making 15 second test is run at49°C (120°F) over water in the the stability of stored fuel an even more important presence of 1020 steel strip. This test is concluded consideration. Distillate fuels in general and diesel after 12 weeks or when an observable quantity of fuel in particular are prone with prolonged storage rust and sludge has been deposited. to form polymerizates which agglomerate into The accelerated heat-stability test is compara- what is referred to as sludge which can clog fuel 20 tively quick and useful for screening out the poorer lines and fuel injectors preventing the reliable additives; but because water is absent from this operation of the engine. In addition, water in the test, it is not capable of differentiating between fuel and in the form of condensates in a partially those additives that are either ineffective rust filled storage tank will attack the metal of the tank inhibitors, or incapable of protecting the fuels forming rust which also promotes the polymeriza- 25 when stored in contact with water and steel, and tion of components in the fuel. those that are effective under such storage con- In addition, new regulations promulgated by the ditions. It is precisely these conditions that are of Environmental Protection Agency have importance since stand-by fuels are frequently in recognised the problem of rusting tanks and contact with metal and condensate water, and require measures to prevent contamination of 30 rusting may be often as severe a problem as ground water which can occur from fuel leaking sludge formation. A 12-weekstability-and-rust test underground from rust perforated tanks. was designed to evaluate these effects. Likewise, sludge formation can be accelerated Because of the importance of stabilizing fuelsfor by the growth of bacteria in the fuel. extended periods of up to 10 years with the fuels in Therefore, modern inhibitors should have the 35 contact with metal and water, it is also important following characteristics in use. that the additive exhibit properties which would The material should be a sludge dispersant. It is enable it to be used as a reinhibitor and depoiy- known that the deterioration of fuel oils involves merizer during its repeated use over prolonged polymerization reactions resulting in the agglom- periods of time. eration of macroscopic polymerizates into sludge. 40 The major oil companies and chemical manufac- Although this reaction may be initiated by oxygen, turers have provided a wide variety of inhibitors. additives containing antioxidantsrsuch as hin- Exemplary of the types of materials available are dered phenols or diamines of the types used in the following: gasolines as gum inhibitors, are not totally effec- (1 ) nitrogen-containing, surface-active polymers tive for the purpose of preventing the polymeriza- 45 such as duPont FOA-11 and duPont FOA-208. tion mechanisms. The additive materials should (2) organic-soluble, surface-active, oxygenated also have rust-preventive properties. The additive amine such as Enjay Paradyne H04. This product materials should also be effective when the fuels may also contain a minor amount of a polymeric are stored in the presence of metals and water and dispersant. rust. The additive materials should also inhibit the so (3) anionic fuel additives such as Apollo SDI-2R, propagation of bacteria. a proprietary sludge inhibitor and dispersant as The kinds of bacteria that grow in stored fuels well as rust preventive, manufactured by Apollo thrive on nitrogen, sulfur, and phosphorus, as well Chemical Corporation. as iron, generally in theform of its oxides. Bacterial (4) chelating-type metal deactivator such as an growth can be reduced, if not eliminated, by 55 80% solution of N, N' disalicylidene-1-2 propane- employing the following preventive measures. A diamine in aromatic solvents. biocide should be employed. Of course, the elimi- (5) a film-forming metal deactivator such as nation of materials in the fuel tank that contain Vanlube 601, R.T. Vanderbilt Company. nitrogen, sulfur or phosphorus would be helpful. (6) an antioxidant such as 2,6 ditertiarybutyl-4- Since the latter measure is practically impossible, 60 methylphenol provided in Enjay Parabar 441, and these materials must be considered in theformula- also, duPont A029. tion of any additive. In addition, it is important to To varying degrees, these materials alone or in keep the fuel tanks clean and dry, in order to various combinations have in the past provided reduce or eliminate rust formation in the tanks. some measure of protection for stored fuel with Two standard test methods have been used as 65 respect to some of the major properties required. 2 3 EP 0185 083 B1 4 For very long term storage however, it is essen- frequency such as to (a) solubilize or subdivide tial that the inhibitor employed be capable of any macroscopic sludge present, (b) disperse any being employed during routine maintenance to submacroscopic sludge agglomerates present, depolymerize and disperse the sludge that is whereby to retard or prevent any subsequent inevitably formed. 5 agglomeration, and (c) minimise the effect of The document GB-A-1398067 is concerned with bacteria, oxygen and rust formation on polymeri- detergent additives for inhibiting deposits in fuels zation in the fuel. and comprising a high molecular weight hydro- As previously described, a wide variety of carbyl amine, either or both of which may be a chemical compositions have been provided as polymerised ethylene diamine. A poly a-olefin 10 fuel additives. Unfortunately, many of these com- synthetic lubricant may also be present. positions when used as recommended by their The document US-A-3334046 is concerned with manufacturers do not provide all of the properties the use of substituted 1,3,5-triazines as stabilizers which overall are required in an effective of organic material normally subject to deterior- inhibitor, or reinhibitor and depolymerizer for the ation, though no mention is made of these com- 15 long term storage of kerosene and diesel fuel. pounds being suitable for such other uses as, for The composition of the present invention example, biocidal inhibitors. utilizes a major proportion of a proprietary com- It is also important that attempts to eliminate position presently sold by the Ethyl Corporation the problem of injector clogging at low tempera- under the trademark EDA-3. ture by the build-up of hydrocabon waxes in the 20 This clear amber liquid composition contains a fuel does not compound injector scoring high molecular weight amine, is basic and is problems by reducing or eliminating the lubricity believed to be a polymerization product of an a of the fuel.
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