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(12) Patent Application Publication (10) Pub. No.: US 2008/0000148A1 Cunningham Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2008/0000148A1 Cunningham Et Al US 20080000148A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0000148A1 Cunningham et al. (43) Pub. Date: Jan. 3, 2008 (54) FUEL COMPOSITION CONTAINING RON (22) Filed: Jun. 29, 2006 AND MANGANESE TO REDUCE SPARK PLUG FOULING Publication Classification (76) Inventors: Lawrence J. Cunningham, (51) Int. C. Mechanicsville, VA (US); Allen A. CIOL L/18 (2006.01) Aradi, Glen Allen, VA (US) CIOL I/30 (2006.01) (52) U.S. Cl. ............................................ 44/359: 44/361 Correspondence Address: MH2 TECHNOLOGY LAW GROUP (Cust. No. (57) ABSTRACT w/NewMarket) 1951 KIDWELL DRIVE, SUITE 550 There is disclosed a method of reducing the conductivity of TYSONS CORNER, VA 22182 deposits formed from the combustion of a fuel comprising an iron-containing compound, said method comprising add (21) Appl. No.: 11/427,630 ing a manganese-containing compound to the fuel. US 2008/0000148A1 Jan. 3, 2008 FUEL COMPOSITION CONTAINING RON phosphonates, chelates, phenates, crown ethers, naphthen AND MANGANESE TO REDUCE SPARK ates, carboxylic acids, amides, acetyl acetonates, and mix PLUG FOULING tures thereof. 0010 Organometallic iron compounds, such as fer FIELD OF THE DISCLOSURE rocene, are known, for example, for octane enhancement (U.S. Pat. No. 4,139,349, the disclosure of which is hereby 0001. The present disclosure relates to the use of a incorporated by reference in its entirety). Ferrocene manganese-containing compound to improve spark plug Fe(CHs), comprises two cyclopentadienyl rings bound on performance and reduce the conductivity of deposits in the opposite sides of a central iron atom and forming an orga presence of an iron-containing compound in a fuel being nometallic sandwich compound. combusted. 0011. The ferrocene can be present in a fuel composition in any desired or effective amount. In an aspect, the fuel can BACKGROUND OF THE DISCLOSURE be treated with from about 2 mg iron/liter of fuel to about 35 0002 The use of ferrocene compounds in fuels is known. mg iron/liter of fuel, for example from about 5 mg/liter to However, the iron containing deposits formed from fer about 25 mg/liter, and as a further example from about 10 rocene can form a conductive coating on the sparkplug mg/l to about 20 mg/1 Surfaces leading to sparkplug failure. 0012. The fuel composition can comprise an organome tallic compound that is different from ferrocene. In an 0003) What is needed is a fuel composition wherein the aspect, the organometallic compound can be a manganese life of the spark plug is extended, for example, because containing compound. In the case of a manganese-contain deposits formed on the spark plug are reduced and/or the ing compound, there are numerous monoatomic compounds conductivity of the spark plug deposits are reduced thereby that include methylcyclopentadienyl manganese tricarbonyl, resulting in a reduction of spark plug misfires. manganocene, and many other monomanganese organome tallics that exist in the literature. There are also binuclear SUMMARY OF THE DISCLOSURE metallics Such as manganese heptoxide (Mn2O7), manga 0004. In accordance with the disclosure, there is provided nese decacarbonyl (Mn(CO)o), etc. An example of a herein a method of reducing the conductivity of deposits trinuclear manganese cluster is manganese 11 citrate, (Mn formed from the combustion of a fuel comprising an iron (CH4O7)). containing compound, said method comprising adding a 0013 Manganese-containing organometallic compounds manganese-containing compound to the fuel. can include, for example, manganese tricarbonyl com 0005. In addition is provided herein a fuel composition pounds. Such compounds are taught, for example, in U.S. comprising a fuel, ferrocene, in an amount up to about 35 mg Pat. Nos. 4,568,357; 4,674,447; 5,113,803; 5,599,357: iron/liter of fuel, and methylcyclopentadienyl manganese 5,944,858 and European Patent No. 466 512 B1, the disclo tricarbonyl. sures of which are hereby incorporated by reference in their 0006 Additional objects and advantages of the disclosure entirety. will be set forth in part in the description which follows, 0014 Suitable manganese tricarbonyl compounds which and/or can be learned by practice of the disclosure. The can be used include, but are not limited to, cyclopentadienyl objects and advantages of the disclosure will be realized and manganese tricarbonyl, methylcyclopentadienyl manganese attained by means of the elements and combinations par tricarbonyl, dimethylcyclopentadienyl manganese tricarbo ticularly pointed out in the appended claims. nyl, trimethylcyclopentadienyl manganese tricarbonyl, tet 0007. It is to be understood that both the foregoing ramethylcyclopentadienyl manganese tricarbonyl, pentam general description and the following detailed description ethylcyclopentadienyl manganese tricarbonyl, are exemplary and explanatory only and are not restrictive of ethylcyclopentadienyl manganese tricarbonyl, diethylcyclo the disclosure, as claimed. pentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manga nese tricarbonyl, tert-butylcyclopentadienyl manganese tri DESCRIPTION OF THE EMBODIMENTS carbonyl, octylcyclopentadienyl manganese tricarbonyl, 0008. The present disclosure is directed to extending the dodecylcyclopentadienyl manganese tricarbonyl, ethylm life of a spark plug and reducing conductivity of combustion ethylcyclopentadienyl manganese tricarbonyl, indenyl man generated deposits by the use of combinations of organo ganese tricarbonyl, and the like, including mixtures of two metallic compounds in fuels. In particular, the fuel can or more such compounds. One example is the cyclopenta comprise at least two organometallic compounds, wherein dienyl manganese tricarbonyls which are liquid at room each of the at least two organometallic compounds is dif temperature such as methylcyclopentadienyl manganese tri ferent. In an aspect, the fuel can comprise an iron-containing carbonyl, ethylcyclopentadienyl manganese tricarbonyl, liq compound Such as but not limited to ferrocene, wherein a uid mixtures of cyclopentadienyl manganese tricarbonyl and manganese-containing compound can be provided to the methylcyclopentadienyl manganese tricarbonyl, mixtures of fuel. In a further aspect, the manganese-containing com methylcyclopentadienyl manganese tricarbonyl, and ethyl pound is or comprises methylcyclopentadienyl manganese cyclopentadienyl manganese tricarbonyl, etc. tricarbonyl (MMTR). 00.15 Preparation of such compounds is described in the 0009 Non-limiting examples of organometallic com literature, for example, U.S. Pat. No. 2,818,417, the disclo pounds include those having an organo group and at least sure of which is incorporated herein in its entirety. one metallic ion or atom. In an aspect, organo groups in the 0016. Additional non-limiting examples of manganese organometallic compounds include, but are not limited to, containing compounds include non-volatile, manganese alcohols, aldehydes, ketones, esters, anhydrides, Sulfonates, containing compounds such as bis-cyclopentadienyl man US 2008/0000148A1 Jan. 3, 2008 ganese, bis-methyl cyclopentadienyl manganese, DIG engines, homogeneous combustion DIG engines, manganese naphthenate, manganese II citrate, etc., that are homogeneous/stratified DIG engines, DIG engines outfitted either water or organic soluble. Further examples include with piezo-injectors with capability of multiple fuel pulses non-volatile, manganese-containing compounds embedded per injection, DIG engines with EGR, DIG engines with a in polymeric and/or oligomeric organic matrices, such as lean-NOx trap, DIG engines with a lean-NOx catalyst, DIG those found in the heavy residue from the column distillation engines with SN-CR NOx control, DIG engines with of crude MMTR). exhaust diesel fuel after-injection (post combustion) for 0017. When formulating additives to be used in one NOx control, DIG engines outfitted for flex fuel operation embodiment of the methods, compositions and systems of (i.e. gasoline, ethanol, methanol, biofuels, synthetic fuels, the present disclosure, the manganese-containing com natural gas, liquefied petroleum gas (LPG), and mixtures pounds are employed in any desired or effective amount thereof), conventional and advanced port-fueled gasoline sufficient to lower the conductivity of combustion-derived engines, with and without advanced exhaust after-treatment products such as spark plug deposits compared to deposits systems capability, with and without turbochargers, with and formed from combustion of fuel treated with ferrocene alone without Superchargers, with combined Supercharger?turbo and otherwise generally extend the life of a spark plug An charger, with and without on-board capability to deliver exemplary treatment rate of the manganese-containing com additive for combustion and emissions improvements, with pound can be less than or equal to 36 mg of manganese/liter and without variable valve timing, gasoline fueled homoge of fuel, for example less than 25 mg of manganese/liter of neous charge compression ignition (HCCI) engines, Diesel fuel, and as a further example about 1 to about 20 mg of HCCI engines, gasoline HCCI-electric hybrid engines, die manganese/liter of fuel. sel HCCI-electric hybrid engines, diesel-electric hybrid 0018 Reference is also made throughout of the term vehicle, gasoline-electric hybrid vehicle, a two-stroke “reduced in the context of operation of an engine and/or engine, diesel fuel engines, automotive diesel engines,
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