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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
• • 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
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • 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
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2691—Compounds of uncertain formula; reaction of organic compounds (hydrocarbons acids, esters) with Px Sy, Px Sy Halz or sulfur and phosphorus containing compounds
• • 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
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • 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
  • C10L1/12—Inorganic compounds
  • C10L1/1283—Inorganic compounds phosphorus, arsenicum, antimonium containing compounds
• • 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
  • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • 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
  • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
• • 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
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
• • 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
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • 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
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
• • 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
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
  • C10L1/2616—Organic compounds containing phosphorus containing a phosphorus-carbon bond sulfur containing
• • 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
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
  • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
• • 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
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
  • C10L1/265—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen and/or sulfur bonds

Definitions

• This invention relates to additives for distillate fuels which reduce deposit formation in fuels that are thermally stressed. More specifically, the invention is directed to a fuel additive that comprises the reaction product of a hydrocarbyl substituted dicarboxylic acid or derivative thereof, a polyhydroxyl compound, and a phosphorus containing compound. This reaction product when added to fuels, such as jet fuels, stabilizes the fuels and reduces or prevents the build up of deposits in the fuel system.
• the invention also relates to the inclusion of an ester, formed by reacting a) a hydrocarbyl substituted dicarboxylic acid or derivative thereof, with b) a polyhydroxyl compound and a phosphorus-containing compound in a distillate fuel to reduce the thermal degradation of the fuel.
• thermal stress When liquid hydrocarbon fuels are subjected to transportation, storage and use, they are exposed to thermal stress. This exposure to elevated temperatures, or thermal stress, causes the fuel to deteriorate. Thermal stress usually results in the formation of sediment, sludge, or gum and can also manifest itself visibly by a color change in the fuel.
• Sediment, sludge or gum formation can cause blocking of the fuel system, or at least reduced performance of the fuel system.
• the fuel system is used to cool various components, such as engine parts, prior to its combustion in the engine (turbine). This thermal exposure has been shown to cause the formation of deposits on heat exchangers, fuel lines and on the injection nozzles of the engine. It is apparent that the reduction or elimination of such deposits would be an advancement in the state of the art. It is particularly desirable to reduce deposit formation without the use of reactive nitrogen-containing components in the fuel which can interfere with other commonly used additives.
• U.S. Patent 4,292,186 to Chibnik et al. discloses a fuel additive that is a metal salt complex containing a 5- or 6- membered ring.
• the metal complex is prepared by forming a non-acidic reaction product of a polyalkenyl succinic acid or anhydride and a polyhydric alcohol or aminoalcohol. This reaction product is then reacted with a metal salt, the metal being selected from Groups IB, IIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table.
• This patent does not suggest nor disclose a fuel additive that is derived from a polyalkenyl succinic acid/alcohol reaction product that is reacted with a phosphorus-containing compound.
• EP288246 to Kendall teaches a composition for stabilizing fuel oil which comprises a phosphite compound and a carboxylic acid having from 2-20 carbon atoms. This reference does not disclose the fuel stabilizing additive of this invention
• U.S. Patent 5,160,507 to Horodysky discloses an ester-type ashless dispersant that contains additional integral sulfur-ester moieties that are effective in providing thermal stability to fuels. This patent teaches that the sulfur-ester moieties are required for imparting thermal and oxidative stability to hydrocarbon fuels.
• U.S. Patent 5,382,266 to Lin et al. relates to an additive that inhibits the degradation of fuel oils.
• the additive is disclosed as a phosphine or phosphite, such as triphenylphosphite and triphenylphosphine.
• This reference does not suggest the reaction product of the present invention as a stabilizer for liquid hydrocarbon fuels.
• U.S. Patent No. 5,596,130 to Wright et al. discloses a jet fuel additive that is a derivative of (thio)phosphonic acid.
• This patent specifically discloses the use of a pentaerythritol ester of polyisobutenylthiophosphonic acid in turbine combustion fuel oils to inhibit the formation and emission of soot and smoke from the engine.
• This reference makes no suggestion or disclosure of the use of a succinic anhydride or dicarboxylic acid to form an ester with a polyol that is subsequently reacted with a phosphorus-containing compound.
• WO96/23855 to Dillworth et al. discloses a fuel oil lubricity additive that comprises an ashless dispersant and a carboxylic acid.
• the carboxylic acid may be in the form of an ester with an alcohol of one or more carbon atoms.
• This reference does not suggest a stabilizing additive for jet fuel which comprises the reaction product of 1) a hydrocarbyl substituted dicarboxylic acid, or derivative thereof, 2) a polyhydroxyl compound, and 3) a phosphorus containing compound.
• composition of matter comprises the reaction products of:
• Hydrocarbyl as used herein and in the claims, means alkyl, alkenyl, aryl, aralkyl, and alkaryl and may be cyclic or polycyclic and may contain O, N, S or mixtures thereof.
• R 1 and R 2 are -O-, and thereby the compound (I) is a succinic anhydride of the structural formula
• the mole ratio of a) to b) can range from 1:2 to 5:1, more preferably 1:2 to 3:1 and most preferably from about 1:2 to 2:1.
• the molar ratio of the reaction product of a) and b) (ester) to the phosphorus containing compound can range from 10:1 to 1:10, with 5:1 to 1:5 being more preferred and about 3:1 being most preferred.
• the present invention also relates to the use of the physical admixture of the ester and the phosphorus-containing compound in a distillate fuel.
• the ester can be prepared as described below and then added to a fuel that already contains a phosphorus-containing compound.
• the ester and the phosphorus-containing compound can be combined in the form of a concentrate or additive package that can be added to the distillate fuel.
• a fuel composition which comprises a distillate fuel and an additive, the additive comprising:
• the admixture of the ester and the phosphorus containing compound is useful in a method of reducing deposit formation in engines, wherein said deposit formations are a result of distillate fuel subjected to thermal stress.
• the method comprises fueling said engine with and operating said engine on a fuel composition comprising a distillate fuel and an additive, the additive comprising:
• the two components, i) and ii), or the three-component reaction product can be added to the distillate fuel by any conventional method.
• the two components can be added to the distillate fuel as a single mixture containing both compounds or the individual components can be added separately or in any other desired combination.
• the additives according to the invention may be added either as a concentrate or as a solution using a suitable carrier solvent, which is compatible with the components and the distillate fuel.
• the present invention also relates to an additive fluid concentrate for use in distillate fuels containing at least the three-part reaction product set forth above and/or the two part physical admixture described above.
• the present invention further relates to a jet fuel composition
• a jet fuel composition comprising as a major portion a jet fuel and as a minor portion an additive comprising the three-part reaction product set forth above and/or the two part physical admixture described above.
• the methods and additives of the instant invention effectively stabilize the distillate fuels during storage.
• stabilized means that particulate formation in the distillate fuel and color deterioration of the fuel are inhibited.
• particle formation is meant to include the formation of insoluble solids, sediment and gum.
• An additional aspect of the invention is directed to a process for inhibiting the degradation of distillate fuels and for stabilizing fuels which comprises adding to the distillate fuel an effective inhibiting amount of the three part reaction product described herein or the admixture described herein.
• the invention is also directed to a method of reducing deposit formation in engines, the method comprises fueling the engine with, and operating the engine on, a fuel composition comprising a distillate fuel and an additive that is the three-part reaction product described herein or the admixture described herein.
• the present invention is also directed to a process for inhibiting the thermal degradation of jet fuel which comprises adding to said jet fuel an effective amount of a reaction product derived from reacting a hydrocarbyl substituted dicarboxylic acid, or derivative thereof with a polyhydroxyl compound to create a first reaction product (the ester), and thereafter reacting said first reaction product with a phosphorus containing compound.
• a reaction product derived from reacting a hydrocarbyl substituted dicarboxylic acid, or derivative thereof with a polyhydroxyl compound to create a first reaction product (the ester), and thereafter reacting said first reaction product with a phosphorus containing compound.
• This invention also discloses a stabilized distillate fuel composition
• a stabilized distillate fuel composition comprising a distillate fuel and an effective stabilizing amount of the novel composition of matter described herein.
• a composition comprising a major amount of a liquid hydrocarbon fuel and 0.0005 to 2% by weight of the product obtained by reacting a hydrocarbyl substituted dicarboxylic acid, or derivative thereof with a polyhydroxyl compound and a phosphorus containing compound.
• distillate fuels to thermal stress tends to result in significant deposit formation.
• the function of the present invention is to reduce deposit formation anywhere in the fuel and exhaust systems. In jet fuel compositions, for instance, this includes reducing deposit formation in the fuel nozzles and spray rings, and on surfaces such as heat exchangers, manifolds, actuators and turbine vanes and blades. In other distillate fuel compositions, such as diesel fuel, the addition of the additives of the present invention serves to prevent injector deposits and to increase fuel stability.
• Suitable phosphorus compounds for forming the additives of the present invention include phosphorus compounds or mixtures of phosphorus compounds capable of introducing a phosphorus atom into the reaction product of the polyhydroxyl compound and the hydrocarbyl substituted dicarboxylic acid, or derivative thereof. Any phosphorus compound, organic or inorganic, capable of undergoing such a reaction can be used. Accordingly, use can be made of inorganic phosphorus compounds such as the inorganic phosphorus acids and the inorganic phosphorus oxides, including their hydrates.
• Typical organic phosphorus compounds include full and partial esters of phosphorus acids, such as the mono-, di- and triesters of phosphorus acid, thiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid and the tetrathiophosphoric acid; the mono-, di- and triesters of phosphorus acid, thiophosphorus acid, dithiophosphorus acid and trithiophosphorus acid; the trihydrocarbyl phosphine oxides; the trihydrocarbyl phosphine sulfides; the mono- and dihydrocarbyl phosphonates and their mono-, di- and trithio analogs; the mono- and dihydrocarbyl phosphonites, and their mono- and dithio analogs; and the like.
• phosphorus acids such as the mono-, di- and triesters of phosphorus acid, thiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid and the tetrathiophosphoric acid; the
• phosphorous acid H 3 PO 3 , sometimes depicted as H 2 (HPO 3 ), and sometimes called ortho-phosphorus acid or phosphonic acid
• phosphoric acid H 3 PO 4 , sometimes called orthophosphoric acid
• hypophosphoric acid H 4 P 2 O 6
• metaphosphoric acid HPO 3
• pyrophosphoric acid H 4 P 2 O 7
• hypophosphorus acid H 3 PO 2 , sometimes called phosphinic acid
• pyrophosphorus acid H 4 P 2 O 5 , sometimes called pyrophosphonic acid
• phosphinous acid H 3 PO
• tripolyphosphoric acid H 5 P 3 O 10
• tetrapolyphosphoric acid H 6 P 4 O 13
• trimetaphosphoric acid H 3 P 3 O 9
• phosphorus trioxide phosphorus tetroxide
• Partial or total sulfur analogs such as phosphorotetrathioic acid (H 3 PS 4 ), phosphoromonothioic acid (H 3 PO 3 S) and phosphorodithioic acid (H 3 PO 2 S 2 ) can also be used in forming the additives according to this invention.
• organic phosphorus compounds such as mono-, di- and triesters of phosphoric acid (e.g., trihydrocarbyl phosphates, dihydrocarbyl monoacid phosphates, monohydrocarbyl diacid phosphates and mixtures thereof), mono-, di- and triesters of phosphorus acid (e.g., trihydrocarbyl phosphites, dihydrocarbyl hydrogen phosphites, hydrocarbyl diacid phosphites and mixtures thereof), esters of phosphonic acids (both "primary” and “secondary"), esters of phosphinic acids, phosphonyl halides, halophosphites, halophosphates, tertiary pyrophosphate esters and the partial sulfur analogs of any of the foregoing organic phosphorus compounds and the like, wherein each hydrocarbyl group contains up to about 100 carbon atoms, preferably up to about 50 carbon atoms
• hydrocarbyl substituted dicarboxylic acids, and derivatives thereof suitable for use in the present invention may be compounds of the structural formula wherein R is hydrocarbyl, preferably an alkyl or alkenyl group having 1 to 300 carbon atoms, preferably 6 to 150 carbon atoms, more preferably 10 to 100 carbon atoms; R 1 and R 2 are each independently selected from -OH, -Cl, -O-lower alkyl, and when taken together, R 1 and R 2 are -O-.
• hydrocarbyl substituted dicarboxylic acids include hydrocarbyl substituted succinic anhydrides.
• the hydrocarbyl substituent is usually a polyolefin, and preferably a polyisobutylene group, having a number average molecular weight of from about 500 to 5000, more preferably 600 to 3000 and most preferably from about 950 to about 2000.
• Suitable polyhydroxyl alcohols for use in the present invention include any compound that contains 2 or more hydroxyl groups (-OH) and which will react with the selected hydrocarbyl substituted dicarboxylic acid will be useful in preparing the fuel additives according to the invention.
• Preferred polyhydroxyl alcohol are selected from compounds of the structural formulae: R 3 - (OH) x wherein x is an integer of 2 or more, and R 3 is a hydrocarbyl group of 1 to 20 carbon atoms; HO - ((CH 2 ) y -O) z -H wherein y is an integer of 1 to 10 and z is an integer of 1 to 100; wherein each R 4 can be independently H or -CH 3 ; and x, y and n can each independently range from 1 to 20; and mixtures thereof.
• Representative compounds of the above formulae, suitable for use in the present invention include alkyl diols, alkyl triols, glycols, glycerol, pentaerythritol, tripentaerythritol, trimethylolethane, triethylolpropane, 1,2,6-hexanetriol, sorbitol, inositol and polyvinyl alcohol.
• Pentaerythritol propoxylates and pentaerythritol ethoxylates are also useful polyols in preparing the additives according to the invention.
• the preferred polyol for use in the present invention is pentaerythritol.
• any temperature at which the desired reaction occurs at a satisfactory reaction rate can be used.
• the reaction is conducted in a solvent, such as mixed xylenes and thus an appropriate reaction temperature is the reflux temperature of the mixture.
• the phosphorylation reaction (whether conducted concurrently or separately) is conducted at temperatures in the range of 80 to 200°C, more preferably 100 to 180°C. However, departures from those ranges can be made whenever deemed necessary or desirable.
• These reactions may be conducted in the presence or absence of an ancillary diluent or liquid reaction medium.
• catalysts may be used to prepare the compounds of the invention, for example, any material that supplies a free proton may be used.
• catalysts includes sulfuric acid, acidic ion exchange resin and hydrocarbon soluble sulfonic acids.
• Base catalysts are also useful and include the hydrocarbon soluble tertiary amines.
• the additives of the present invention are used in a fuel in any amount sufficient to reduce the formation of deposits in the fuel and exhaust systems of an engine, such as an internal combustion engine or a jet engine.
• the additive is used in an amount of from about 1 to about 1000 mg per liter of fuel, more preferably in the range of from about 5 to about 200, and most preferably from about 10 to about 100 mg per liter of fuel on an active ingredient basis, i.e., excluding diluent or solvent.
• the preferred distillate fuels for use in the present invention are diesel fuels and jet fuels, more preferably, JP-8, Jet-A fuels and Jet-A1 fuels.
• inventive additives are typically added to the fuel at ambient temperatures and pressures.
• inventive additives are preferably added to the distillate fuel prior to any appreciable deterioration of the fuel. However, the additives are also effective even after some deterioration has occurred.
• distillate fuel compositions of this invention include ashless dispersants, antioxidants, metal deactivators, corrosion inhibitors, conductivity improves (e.g., static dissipators), fuel system icing inhibitors, distillate fuel stabilizers, cetane improvers and demulsifiers.
• ashless dispersants antioxidants, metal deactivators, corrosion inhibitors, conductivity improves (e.g., static dissipators), fuel system icing inhibitors, distillate fuel stabilizers, cetane improvers and demulsifiers.
• the mixture was heated to reflux (about 175°C) and stirred for four (4) hours.
• the mixture was filtered to remove the catalyst and the filtrate was returned to the reaction vessel.
• Diethyl phosphite (4.75 gms) (0.034 moles) was then added to the mixture.
• the molar ratio of PBSA to pentaerythritol to phosphite was thus 1.0:0.78:0.26.
• the mixture was heated at reflux for about one (1) hour with stirring. About 2.0 ml of water was removed by azeotropic distillation. The xylenes were then removed by vacuum distillation.
• the final product contained 0.656% by weight phosphorus.
• the resulting product was tested in the Hot Liquid Process Simulator (HLPS) described below.
• HLPS Hot Liquid Process Simulator
• Example II The procedure described in Example I was used, except that there was no addition of diethyl phosphite. Therefore, this Example is a control and was only the ester between the succinic anhydride and the pentaerythritol. Phosphorus content was zero (0). The molar ratio of PBSA to the pentaerythritol was 1.00:0.78.
• the molar ratio of the PBSA to the pentaerythritol was 1:0.77. This mixture was heated to reflux and stirred for four (4) hours. About 3.0 ml of water was azeotropically removed. The product was then filtered and solvents were removed by vacuum distillation. This sample also served as a control.
• the molar ratio of the PBSA to pentaerythritol to phosphite was 1:1.16:0.44.
• the mixture was heated to reflux (about 173°C) and stirred for four (4) hours.
• About 10.5 ml of water was azeotropically removed from the reaction product which was then filtered.
• the phosphorus content of the final reaction product (without solvent) was 0.663% by weight.
• Table III sets forth various additives that were added to fuels and tested using the HLPS test and/or the PTS Test.
• the ester products without reacted phosphorus such as, the reaction product of Example II, were combined with free (unreacted) sources of phosphorus, for example, Sample Nos. 8 and 9. Sample No.
• reaction products according to the invention are effective fuel stabilizers.
• base catalyzed products (Example V).
• the lower molecular weight PBSAs for example 1050 molecular weight (Example V) are also preferred in the preparation of the fuel stabilizers according to the invention.
• the HLPS results demonstrate that the additives of the present invention provide fuel compositions which exhibit significantly reduced deposit formation upon being subjected to thermal stress as compared to untreated fuel compositions.
• the phosphorus containing reaction product is more effective than the physical mixture of the ester and phosphorus compound. Compare Sample No. 13 with Sample No. 14.
• the lower alkyl moieties present in the -O-lower alkyl groups given as possibilities for R 1 and R 2 in the formula (I) can be any groups which permit the compound of formula (I) to react with the polyhydroxyl alcohol (b) in an esterification reaction. Typically, they are C 1 -C 3 alkyl moieties, preferably methyl or ethyl.
• the parameter x in the compound R 3 -(OH) x is typically from 2 to 10, preferably from 2 to 8.

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• Liquid Carbonaceous Fuels (AREA)
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• 2000
  • 2000-05-16 CA CA002308554A patent/CA2308554A1/en not_active Abandoned
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  • 2000-06-01 AU AU37846/00A patent/AU3784600A/en not_active Abandoned
  • 2000-06-12 JP JP2000175093A patent/JP2001019982A/ja active Pending
  • 2000-06-21 EP EP00305240A patent/EP1063276A1/de not_active Withdrawn
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