Fuel and related compositions – Liquid fuels – Containing organic -s
Reexamination Certificate
1998-07-08
2003-11-25
Medley, Margaret (Department: 1714)
Fuel and related compositions
Liquid fuels
Containing organic -s
C044S385000, C044S403000, C044S435000, C044S450000, C044S457000
Reexamination Certificate
active
06652609
ABSTRACT:
This invention relates to fuel oil, especially middle distillate fuel oil, compositions of improved combustion performance, particularly demonstrating reduced particulate matter emission and/or smoke. This invention is especially directed to hydrocarbon middle distillate fuel oil compositions.
Certain organometallic compounds are known to be effective combustion improvers for distillate fuels such as home heating oils. For example, U.S. Pat. No. 3,112,789 describes the use of cyclopentadienyl manganese tricarbonyls for this purpose.
EP-B-0 476 196 describes an additive composition for hydrocarbonaceous fuel comprising
(a) one or more fuel-soluble manganese carbonyl compounds;
(b) one or more fuel-soluble alkali or alkaline earth metal containing detergents; and
(c) one or more fuel-soluble ashless dispersants;
and its use for reducing the soot, smoke and/or carbonaceous products produced on combustion of the fuel and for reducing the acidity of the carbonaceous products.
U.S. Pat. No. 3,883,320 discloses jet engine fuels comprising an oil-soluble transition metal compound, an oil-soluble compound of a secondary metal selected from the alkaline earths and an oil-soluble ammonium salt for inhibiting the formation of visible smoke and minimising the deposition of ash on jet engine parts.
Canadian Patent No. 1,188,891 describes an additive comprising at least one oil-soluble and/or dispersible compound of a transition metal and/or alkaline earth metal as well as one of several inhibitors against polymerisation and oxidation of hydrocarbons which inhibits the formation of soot. Examples 1 and 2 disclose compositions containing overbased (carbonated) barium sulphonate.
EP-B-0 022 110 describes an emulsifier containing a mixture of a non-ionic surface active ethylene oxide adduct and calcium dodecylbenzene sulphonate and its use for the manufacture of an emulsion of water in mineral oil.
GB-A-2 091 291 discloses an additive for a diesel fuel oil, which comprises on oil soluble or dispersible calcium compound and an oil soluble or dispersible iron compound, for smoke suppression.
U.S. Pat. No. 3,539,312 discloses a hydrocarbon light distillate fuel oil composition containing minor amounts of calcium sulfonate and an overbasing component represented by the formula:
Ca[O(R
1
O)yR]z
in which R represents nil, hydrogen, or an alkyl radical having from 1 to 10 carbons atoms, R
1
is an alkylene radical having from 2 to 4 carbon atoms, y has a value from 0 to 4, z has a value of 1 when R is nil, and z has a value of 2 when R is H or alkyl. Such fuel compositions are discussed in relation to reduction in smoke emissions.
There is, however, a continuing need for fuel oils which on combustion produce lower levels of particulate matter; this is especially important for the middle-distillate fuels, such as diesel fuels and heating oils.
Further, there is an on-going demand to minimise the cost of additives used, and reduce the amount and range of metals used in fuel oils, for example, in order to reduce the formation of ash deposits upon combustion, or in order to preserve metals for other uses.
The present invention meets this need by providing a hydrocarbon middle distillate fuel composition comprising middle distillate fuel oil and at least one fuel-soluble neutral calcium and/or magnesium salt. It has been surprisingly found that such fuel compositions produce a lower amount of particulate matter on combustion.
Accordingly, a first aspect of the present invention is a hydrocarbon middle distillate fuel composition free of transition metal compounds comprising middle distillate fuel oil and at least one fuel-soluble or fuel-dispersible neutral calcium and/or magnesium salt of sulphonic acid, phenol, sulphurised phenol, salicylic acid or carboxylic acid wherein the sulphonic acid contains at least 22 carbon atoms.
A second aspect of the present invention is the use of at least one fuel-soluble or fuel-dispersible neutral calcium and/or magnesium salt of sulphonic acid, phenol, sulphurised phenol, salicylic acid or carboxylic acid, in fuel oil, which is preferably free of transition metal compounds, to reduce particulate emissions during combustion of the fuel oil.
A third aspect of the present invention is a method for reducing particulate emissions during operation of a fuel oil combustion device comprising addition to the fuel oil, which is preferably free of transition metal compounds, used therein of at least one fuel-soluble or fuel-dispersible neutral calcium and/or magnesium salt of sulphonic acid, phenol, sulphurised phenol, salicylic acid or carboxylic acid.
Hydrocarbon Middle Distillate Fuel Oil
The term ‘hydrocarbon middle distillate fuel composition’ as used herein refers to middle distillate fuel oils which are substantially free, and preferably free, of ethers and/or alcohols. As used herein the term ‘substantially free’ with reference to ethers and/or alcohols in fuel oil refers to an amount of up to 20 mass % based on the mass of the middle distillate fuel oil, preferably up to 10 mass %, more preferably up to 5 mass %.
The use of transition metal compounds can be avoided in the present invention and such metals may be preserved for other uses if desired. Examples of transition metal compounds are compounds of the metals manganese, iron, cobalt, nickel, copper, zinc and molybdenum. In particular, use of manganese and iron compounds may be avoided, especially manganese carbonyl compounds, ferrocene or iron naphthenate.
Middle distillate fuel oils generally boil within the range of about 100° C. to about 500° C., e.g. 150° to about 400° C., for example, those having a relatively high Final Boiling Point of above 360° C. (ASTM D-86). Middle distillates contain a spread of hydrocarbons boiling over a temperature range, including n-alkanes which precipitate as wax as the fuel cools. They may be characterised by the temperatures at which various %'s of fuel have vaporised, e.g. 10% to 90%, being the interim temperatures at which a certain volume % of initial fuel has distilled. The difference between say 90% and 20% distillation temperature may be significant. They are also characterised by pour, cloud and CFPP points, as well as their initial boiling point (IBP) and final boiling point (FBP). The petroleum fuel oil can comprise atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates. The most common middle distillate fuels are jet fuels, diesel fuels and heating oils. The heating oil may be a straight atmospheric distillate, or it may contain minor amounts, e.g. up to 35 mass %, of vacuum gas oil or cracked gas oils or of both.
Heating oils may be made of a blend of virgin distillate, e.g. gas oil, naphtha, etc. and cracked distillates, e.g. catalytic cycle shock. A representative specification for a diesel fuel includes a minimum flash point of 38° C. and a 90% distillation point between 282 and 380° C. (see ASTM Designations D-396 and D-975).
The fuel oil may also be an animal or vegetable oil, or a mineral oil as described above in combination with an animal or vegetable oil. Fuels from animal or vegetable sources are known as biofuels and are believed to be less damaging to the environment on combustion, and are obtained from a renewable source. It has been reported that on combustion less carbon dioxide is formed than is formed by the equivalent quantity of petroleum distillate fuel, e.g. diesel fuel, and very little sulphur dioxide is formed. Certain derivatives of vegetable oil, for example rapeseed oil, e.g. those obtained by saponification and re-esterification with a monohydric alcohol, may be used as a substitute for diesel fuel. It has recently been reported that mixtures of a rapeseed ester, for example, rapeseed methyl ester (RME), with petroleum distillate fuels in ratios of, for example, 10:90 by volume are likely to be commercially available in the near future.
Thus, a biofuel is a vegetable or animal oil or both or a derivative thereof, partic
Exxon Chemical Patents Inc
Medley Margaret
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