Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1915—Esters ester radical containing compounds; ester ethers; carbonic acid esters complex esters (at least 3 ester bonds)

Definitions

• This invention relates to alkanol fuel compositions, more particularly to the use therein of selected additives to reduce or inhibit wear.
• alkanol fuels containing a selected additive which is an ester of a carboxylic acid and a polyhydric alcohol and have at least two free hydroxyl groups have improved wear and lubricity characteristics.
• this invention is directed to a fuel composition
• a fuel composition comprising a major amount of a monohydroxy alkanol having from 1 to 5 carbon atoms and an effective wear reducing amount of an additive which is an ester of a monocarboxylic or polycarboxylic acid and a polyhydric alcohol, said acid having up to about 4 carboxylic acid groups and about 12 to 90 carbon atoms, said alcohol having about 2 to 10 hydroxyl groups and about 2 to 30 carbon atoms and said ester having at least two free hydroxyl groups.
• the composition has improved lubricity properties and provides improved wear reduction.
• This invention is directed to alkanol fuel compositions containing a selected additive which is an ester of a carboxylic acid and a polyhydric alcohol and having at least two free hydroxyl groups, said com­position having improved wear and lubricity characteristics.
• the selected ester additive used in this invention is generally derived from the esterification of a monocarboxylic or polycarboxylic acid and a poly­hydric alcohol with said ester having at least two free hydroxyl groups. More particularly, the ester additive used in this invention is a hydroxy-containing ester of a monocarboxylic or polycarboxylic acid and a poly­hydric alcohol, said acid having up to about 4 car­boxylic acid groups and about 8 to about 90 carbon atoms, said alcohol having about 2 to 10 hydroxyl groups and about 2 to 90, preferably 2 to 30, carbon atoms.
• the preferred carboxylic acid used is an aliphatic, saturated or unsaturated, straight chained or branched mono- or polycarboxylic acid having up to about 4 carboxylic acid groups and about 8 to about 90 carbon atoms.
• a monocarboxylic acid it generally will contain about 8 to about 30, pref­erably about 10 to about 28 and more preferably about 12 to about 22 carbon atoms.
• the acid used in preparing the ester additive of this invention is a polycarboxylic acid
• it generally will be an aliphatic saturated or un­saturated, preferably saturated polycarboxylic acid having about 2 to about 4, preferably about 2 to about 3 and more preferably about 2 carboxylic acid groups.
• the acid will normally contain 12 to 90, preferably about 24 to about 90 and more preferably about 24 to about 65 carbon atoms. Acids having about 9 up to about 42, preferably about 12 to about 42 and more preferably about 16 to about 22 carbon atoms between the car­boxylic acid groups, will normally be employed.
• the alcohol used in preparing the ester addi­tive of this invention is generally an aliphatic, saturated or unsaturated, straight chained or branched polyhydric alcohol having about 2 to about 10, pref­erably about 2 to about 6 and more preferably about 2 to about 4 hydroxyl groups, and about 2 to about 90, preferably about 2 to 30, more preferably about 2 to about 12, and most preferably about 2 to about 5 carbon atoms in the molecule.
• the alcohol selected is pref­erably saturated.
• the final compound must have at least two free hydroxyl groups and preferably is hydroxyl terminated.
• the proportions of alcohol and acid can be varied but are selected so as to minimize the amount of free acid remaining in the final product. In many cases a molar excess of alcohol to acid will be used. The amounts, however, are dependent on the particular acid and alcohol used in preparing the ester additive.
• the preferred ester additive used in this invention is one derived from the esterification of a polycarboxylic acid with a glycol or glycerol, pref­erably a glycol.
• Such an ester may typically be a di- or polyester having the following general formulas when using a glycol: (1) HO-R-OOC-R ⁇ -COOR ⁇ -OH (2) HO-R-OOC-R ⁇ -COOR-OOC-R ⁇ -COOR ⁇ -OH wherein R ⁇ is the hydrocarbon radical of said acid and each R and R ⁇ may be the same or different hydrocarbon radicals associated with glycol or diol as defined herein.
• esters of the type illustrated by the foregoing formulas can be obtained by esterifying a polycarboxylic acid, or a mixture of such acids, with a diol or mixture of such diols.
• the oil insoluble glycol which is reacted with the polycarboxylic acid may be an alkane diol, i.e., alkylene glycol or an oxa-alkane diol, i.e., polyalkylene glycol, straight chain or branched.
• the alkane diol may have from about 2 to about 12 carbon atoms and preferably about 2 to about 5 carbon atoms in the molecule and the oxa-alkane diol will, generally, have from about 4 to about 200, preferably about 4 to about 100 carbon atoms.
• the oxa-alkane diol (poly­alkylene glycol) will, of course, contain periodically repeating groups of the formula: wherein R may be H, CH3, C2H5 or C3H7, and x is 2 to 100, preferably 2 to 25.
• the preferred alkane diol or alkylene glycol is ethylene glycol and the preferred oxa-alkane diol or polyalkylene glycol is diethylene glycol.
• glycerol may also be used in preparing the ester of polycarboxylic acid and it is contemplated that such component will also in­clude its higher molecular weight analogues.
• the ester also may be prepared by the reac­tion of an alcohol, preferably a polyhydric alcohol, with an ester and/or polyester which also may have some free acid present.
• a preferred ester for reaction is lanolin and a preferred alcohol is sorbitol.
• the alcohol reacts with acid present in the ester and/or via transesterification to form the desired ester com­pound having free hydroxyl groups.
• esters as set forth above can be effectively used, best results are, however, obtained with such compounds wherein the carboxyl groups of the polycarboxylic acid are separated from each other by from about 16 to about 22 carbon atoms and wherein the hydroxyl groups are separated from the closest carboxyl group by from about 2 to about 12 carbon atoms.
• Particularly desirable results have been obtained with additives prepared by esterifying a dimer of a fatty acid particularly those containing con­jugated unsaturation with a polyhydroxy compound.
• dimer acids are produced from linoleic acid, oleic acid and mixtures of these acids.
• the commercial preparation of these fatty acid dimers will, generally, lead to trimer formation and in some cases the product thus obtained will contain minor amounts of unreacted monomer or monomers.
• commercially available dimer acids may contain as much as 25% trimer and the use of such mixtures is within the scope of the present invention.
• the particularly preferred hydroxy-substi­tuted ester additives useful in the present invention will be the reaction product of a dimerized fatty acid, such as those illustrated, a glycol, and preferably an oil insoluble glycol, which may be produced by various techniques.
• Preferred acid dimers are the dimers of linoleic acid, oleic acid or the mixed dimer of linoleic and oleic acids, which may also contain some monomer as well as trimer.
• Other specifically satis­factory glycols in addition to ethylene glycol and polyethylene glycol are, for example, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol and the like.
• the ester additive of this invention when obtained from a mono­carboxylic acid, the polyhydric alcohol will contain at least three hydroxyl groups in order to provide the necessary hydroxyl functionality on the final product.
• a preferred alcohol is glycerol.
• the resulting ester preferably is ethoxylated.
• a preferred fatty acid is coconut acid.
• the fuel composition of this invention pri­marily comprise alkanols, i.e., the alkanols comprise at least 50% by weight, preferably a major part, and more preferably at least 80% by weight of the composi­tion.
• the useful alkanols are monohydroxy alcohols containing from 1 to 5 carbon atoms with saturated aliphatic monohydric alcohols being preferred.
• Illus­trative alcohols of this type are methanol, ethanol, propanol, n-butanol, isobutanol, amyl alcohol and isoamyl alcohol, with methanol being preferred.
• the hydroxyl containing ester additive of this invention will generally be used at an effective wear reducing amount and more particularly at a concen­tration of from about 0.0003 to about 2.0 percent by weight, preferably from about 0.001 to about 1.0 and more preferably from about 0.002 to about 0.5 percent by weight, based on the total weight of the fuel composition.
• additives which are known in the art and which do not adversely affect the selected addi­tives of this invention, may be used in the fuel com­position.
• Such additives may include demulsifying agents, dyes, antioxidants, corrosion inhibitors, igni­tion accelerators, etc.
• this fuel composition was tested to determine the effect on wear using a slant 6 Dodge engine operating under conditions in which wear is accelerated.
• the engine was operated for 10 minutes at 700 rpm, no load, followed by 20 minutes at 2000 rpm and a load of 105 lb. ft. This cycle was repeated for 72 hours with the oil sump temperature maintained at 50°C. Used oil samples were removed at 24 hour inter­vals and analyzed for wear metals by plasma emissions spectroscopy.
• the amount of wear metal in the used oil after 72 hours was 72.7 ppm Fe and 13.8 ppm Cu. This compared with 103.3 ppm Fe and 26.8 ppm Cu (average of 2 runs) when the same methanol fuel without the ester additive was used.
• a fuel composition was prepared comprising methanol and 38 ppm of polyoxyethylene sorbitol lano­lin. This composition was tested as in Example 1 and showed metal wear of 39.6 ppm Fe and 20.9 ppm Cu.
• Oil A A specially formulated oil, designated as Oil A, was used in several of these tests.
• Oil B A conventional, commercial lubricant containing an ester formed by esterification of a dimer acid of linoleic acid and diethylene glycol designated as Oil B, was used in other tests.
• Oil C A third oil, designated as Oil C, similar to Oil B, but without the ester additive, also was tested. The results are presented in Table I below. As before, the Fe concen­tration in the used oil is a measure of engine wear.
• Table II below presents a comparison of the wear in a slant 6 Dodge engine in 72 hours using the specially formulated oil (Oil A) and methanol with an ester additive with the wear resulting from use of a premium unleaded gasoline and previously described commercial lubricant (Oil B).
• the test conditions were similar to those set forth in Example 1.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)

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Cited By (2)

Citations (8)

• 1986
  • 1986-08-21 EP EP86306478A patent/EP0257149A1/fr not_active Withdrawn

Patent Citations (8)

Non-Patent Citations (1)

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