EP1250402A2 - Liquid compositions containing a stable boric acid suspension - Google Patents

Liquid compositions containing a stable boric acid suspension

Info

Publication number
EP1250402A2
EP1250402A2 EP01906647A EP01906647A EP1250402A2 EP 1250402 A2 EP1250402 A2 EP 1250402A2 EP 01906647 A EP01906647 A EP 01906647A EP 01906647 A EP01906647 A EP 01906647A EP 1250402 A2 EP1250402 A2 EP 1250402A2
Authority
EP
European Patent Office
Prior art keywords
liquid hydrocarbon
hydrocarbon fuel
fuel
accordance
ppm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01906647A
Other languages
German (de)
French (fr)
Inventor
Mohan L. Sanduja
Carl Horowitz
Satyabrata Mukherjee
Paul Thottahil
William Olliges
Charles T. Foscue
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Advanced Lubrication Technology Inc
Original Assignee
Advanced Lubrication Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/488,423 external-priority patent/US6368369B1/en
Application filed by Advanced Lubrication Technology Inc filed Critical Advanced Lubrication Technology Inc
Publication of EP1250402A2 publication Critical patent/EP1250402A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/08Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/12Inorganic compounds
    • C10L1/1291Silicon and boron containing compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/30Organic compounds compounds not mentioned before (complexes)
    • C10L1/301Organic compounds compounds not mentioned before (complexes) derived from metals
    • C10L1/303Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/02Use of additives to fuels or fires for particular purposes for reducing smoke development
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/04Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation

Definitions

  • This invention relates to the chemical arts.
  • liquid compositions including hydrocarbon fuel compositions, such as low-sulfur diesel and low- sulfur gasoline fuel compositions and lubricants, such as engine oils, hydraulic fluids, transmission fluids, cutting oils, synthetic oils, and mixtures thereof.
  • Liquid hydrocarbon fuels typically contain up to as much as 40,000 ppm sulfur.
  • the sulfur imparts several desirable properties to the fuels.
  • sulfur provides high lubricity in rolling, rotating, or sliding engine parts such as piston rings and liners, fuel pumps, and injector systems.
  • sulfur suffers from serious disadvantages. It causes environmental problems in the form of high levels of sulfur dioxide (SO 2 ) and hazardous particulates in engine exhaust gases. Because of high SO 2 paniculate and emissions, diesel- powered engines are not widely used or permitted in many large cities.
  • low-sulfur No.2 diesel fuel currently contains about 500 ppm sulfur and numerous attempts are being made to further reduce the sulfur content to about 300 ppm sulfur or less.
  • removing the sulfur reduces the lubricating capacity of the diesel fuel, accelerating wear in fuel system and combustion chamber components.
  • Boric acid is environmentally safe, inexpensive, and has an unusual capacity to enhance the antifriction and antiwear properties of sliding metal surfaces.
  • the Erdemir patent teaches that boric acid can be dispersed in the greases and o ils simply by using conventional equipment and techniques.
  • This patent also describes solid polymers having boric acid incorporated in the polymeric structure.
  • This patent does not suggest that boric acid can be added to improve the performance of low-sulfur hydrocarbon fuels.
  • the patent suggest a method for preparing stable suspensions of boric acid in liquid hydrocarbon fuels or any other such low-viscosity hydrocarbon media.
  • U. S. Patent No. 3,929,800 to Horowitz, describes a process for simultaneously polymerizing and grafting monomers onto liquid hydrocarbons, to improve various properties including viscosity.
  • liquid hydrocarbons disclosed in the Horowitz patent are post pyrolytic gasoline, catalytic cracking fractions, and lubricating oils.
  • the patent does not suggest adding boric acid to the liquid hydrocarbons or modifying the process to form stable suspensions of paniculate boric acid in such hydrocarbons.
  • liquid hydrocarbon fuel compositions that provide high lubricity and low wear in various engine components, such as fuel pumps and injector systems, a clean environment (resulting from the use of low-sulfur fuels), and low cost.
  • stable liquid suspensions containing paniculate boric acid in hydrocarbon fuels and lubricants The invention meets these needs and provides related advantages as well.
  • liquid compositions containing stable boric acid suspensions including liquid hydrocarbon fuel concentrates containing from about 50,000 ppm to about 250,000 ppm paniculate boric acid, based on the total weight of the concentrate, suspended in a liquid hydrocarbon fuel.
  • the liquid hydrocarbon fuels include gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel.
  • the liquid hydrocarbon fuel contains less than 500 ppm or less than 300 ppm sulfur or even substantially no sulfur.
  • the boric acid has a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns or from about 0.5 to about 1 micron.
  • the concentrate is diluted to form a finished liquid hydrocarbon fuel containing only from about 10 ppm to about 50,000 ppm boric acid, preferably about 30 ppm to about 5,000 ppm, boric acid based on the total weight of the finished fuel, suspended in the fuel composition.
  • liquid hydrocarbon fuel compositions formed of a reaction product of boric acid having a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns, and in some embodiments from about 0.5 to about 1 micron, associated with a liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon.
  • the liquid hydrocarbon fuels include gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel and in some embodiments contains less than 500 ppm, or less than 300 ppm or even substantially no sulfur.
  • the monomer or prepolymer is a silane monomer or prepolymer.
  • the liquid hydrocarbon fuel composition additionally contains from about 200 ppm to about 600 ppm surfactant, based on the weight of the fuel concentrate and from about 2 ppm to about 6 ppm surfactant, based on the weight of the finished fuel.
  • the finished liquid hydrocarbon fuel when combusted in an internal combustion engine provides superior lubricity and reduced engine wear, causes less hazardous particulates and gases to be emitted, prevents conosion, and provides a certain degree of increased fuel economy. Additionally, the boric acid remains suspended in both the concentrate and the finished inventive fuel compositions providing a shelf-life of one to two years.
  • paniculate boric acid reaction products are added to liquid lubricants, such as hydrocarbon-based oils, synthetic oils, mineral oils, silicon oils, transmission fluids, hydraulic fluids, or any other lubricants which do not react with boric acid.
  • the lubricant compositions contain concentrations of paniculate boric acid ranging from about 50,000 ppm to about 250,000 ppm particulate boric acid, based on the total weight of the concentrate, suspended in a lubricant.
  • the boric acid has a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns or from about 0.5 to about 1 micron.
  • the concentrate is diluted to form a lubricant compositions containing only from about 10 ppm to about 50,000 ppm boric acid, preferably about 30 ppm to about 5,000 ppm, boric acid based on the total weight of the finished lubricant composition, suspended in the lubricant composition.
  • the boric acid has a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns, and in some embodiments from about 0.5 to about 1 micron, and are associated with a lubricant having a monomer or prepolymer chemically grafted thereon.
  • the monomer or prepolymer is a silane monomer or prepolymer.
  • the finished lubricant compositions provide superior lubricity thereby reducing wear on treated mechanical parts. Additionally, high concentrations of boric acid remains suspended in both the concentrates and the finished lubricant compositions providing a shelf-life of one to two years.
  • Boric acid is advantageously added to any liquid hydrocarbon fuel for use in an internal combustion engine such as gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel and, in particular, it is advantageously added to low-sulfur liquid hydrocarbon fuels.
  • Low sulfur liquid hydrocarbon fuel are fuels containing less than 40,000 ppm sulfur. It is an advantage of the liquid hydrocarbon fuels in accordance with the invention that they can contain less than 500 ppm or less than 300 ppm or even substantially no sulfur.
  • Boric acid useful in accordance with the invention is advantageously produced by the low temperature jet-milling of commercially available boric acid.
  • the conditions of the low temperature jet-milling process can be adjusted to produce boric acid particles having particle size of 65 microns or less, as desired.
  • the boric acid has a particle size in the range of from about 0.1 to about 2.5 microns, preferably in the range of from about 0.5 to about 1 micron. It is most efficient to initially prepare a concentrated suspension of the boric acid in the liquid hydrocarbon fuel.
  • the concentrate preferably contains from about 50,000 ppm and preferably up to about 250,000 ppm paniculate boric acid, based on the weight of the suspension.
  • the concentrate can then be diluted with additional liquid hydrocarbon fuel to obtain the final desired concentration.
  • concentration of boric acid in the finished fuel composition will depend on the particular fuel and the particular engine system. Typically, however, the final boric acid concentration will be in the range of from about 10 ppm to about 50,000 ppm and more preferably in the range of from about 30 ppm to about 5,000 ppm, based on the weight of the liquid hydrocarbon fuel composition.
  • the paniculate boric acid concentration in no.2 diesel fuel is in the range of from about 50 ppm to about 25,000 ppm and more preferably in the range of from about 100 ppm to about 1500 ppm, based on the weight of the finished liquid hydrocarbon fuel composition.
  • the liquid hydrocarbon fuel compositions can contain other conventional fuel additives.
  • Representative additives include antioxidants, metal passivators, rust inhibitors, dispersants, detergents, and the like.
  • the liquid hydrocarbon fuel compositions also can contain additional lubricity-enhancing agents, such as stearic acid.
  • the boric acid is stabilized by forming a reaction product with chemically grafted liquid hydrocarbon fuel.
  • boric acid's hydroxyl groups can become loosely associated with liquid hydrocarbon fuel.
  • suitable monomers or prepolymers are chemically grafted onto the liquid hydrocarbon fuel, the resulting polymer chains effectively stabilize the boric acid-liquid hydrocarbon fuel association and create a stable reaction product, effectively suspending the boric acid particles in the liquid hydrocarbon fuel.
  • Any polymerizable monomer or prepolymer can be chemically grafted onto the liquid hydrocarbon, so long as it does not adversely effect the properties of the fuel.
  • Suitable monomers include methyl methacrylate (also oleyl, alpha-decyl, octadecyl, cyclohexyl, n-butyl, amyl, cetyl acrylates and others), acrylic acid and its derivatives (also butyl, amyl, octyl hexadecyl etc.), methylacrylate vinyl acetate, vinyl chloride, vinylidene chloride, isobutylene, vinyl ethers, acrylonitrile, maleic acid and esters, crotonic acid and esters, itaconic acid and its esters, allylic esters, allyl vinyl esters, vinlypyridine and its derivatives (also 2-methyl-5-vinyl pyridine), bisbetachloro ethylvinyl phosphonate
  • Suitable monomers include mono-, di-, tri-, tetra-, and poly-ethene glycoldimethacrylate, methylvinylpyridine, allylacrylate and methacrylate, allylchloride, allyl alcohol, perfluoro alkyl acrylates and methacrylates, p-amino-styrene, vinyl bromide and vinylidene bromide trimethylvinylbenzylammonium chloride, vinyltrifluoroacetate (followed by hydrolysis to poly-vinyl alcohol), diallyl chloromethyl phosphonate, diallyl benzene phosphonate, diallyl dimethyl ammonium chloride, diallyl diethyl ammonium bromide, glycidyl acrylate and methacrylate, ethylene glycol, diethyleneglycol, an polyethylene glycol acrylates and methacrylates, vinyl perfluoro octaneate, and the like.
  • the monomeric tertiary amines can be quaternized with benzyl chloride, ethyl iodide, methyl or ethylsulfate. Conversely, monomeric chlorides can be quaternized with tertiary amines to give quaternary ammonium compounds.
  • Some suitable tertiary amines are: N-ethyl morpholine, pyridine, cetyldimethyl pryidine, dimethyl aniline, and the like. Also mixtures of two or more monomers can be used.
  • the monomer can be dissolved in a solvent, before adding the monomer to the liquid hydrocarbon.
  • suitable solvents include dimethylformamide, tetrahydrofurane, tetrahydrofurfuryl alcohol, dimethylsulfoxide, water, methyl, ethyl or isopropyl alcohol, acetone, methyl ethyl ketone and acetate or mixtures of two or more of the solvents.
  • the preferred monomers/prepolymers are silane monomers/prepolymers, such as silicones and other related prepolymers, having siloxy functional groups for complexing with the boric acid.
  • Suitable silane monomers/prepolymers include Dow Corning 174 silane monomer and Dow Corning 1248 silicone prepolymer.
  • Chemically grafting silicone polymer chains to the liquid hydrocarbon fuel is particularly effective because the silicone chains double as surfactants. Polar sites on the polymer chains form bridges between the boric acid and the liquid hydrocarbon thus stabilizing the interaction between the two.
  • the boric acid-chemically grafted liquid hydrocarbon reaction product is prepared by first adding one or more surfactants to a liquid monomer or prepolymer.
  • Suitable surfactants include dispersants such as glucose ether, sulphonated castor, and salts of calcium and zinc. Especially useful are Ircosperse 2174 alkyl aminoester, Ircosperse 2176 alkenylsuccinic anhydride, and Ircogel 905 calcium sulfonate, all available from Lubrizol, Inc., Witcliffe, Ohio. Sufficient surfactants are used so that when the particulate boric acid is added to the monomer/prepolymer/surfactant mixture, the macro globule particles of the boric acid are broken up and prevented from reforming.
  • ppm to about 6 ppm surfactant preferably from about 2.5 ppm to about 4.5 ppm surfactant, are added, based on the weight of the reaction product, when the concentrations of the ingredients are chosen, so that the concentrated boric acid suspension is produced.
  • liquid hydrocarbon is added and the resulting mixture stirred vigorously until it is homogeneous.
  • sufficient liquid hydrocarbon fuel is added so that the concentration of boric acid after reaction is from about 50,000 ppm to about
  • liquid hydrocarbon fuel 250,000 ppm, although greater or lesser amounts of liquid hydrocarbon fuel can be added if desired.
  • additional surfactant such as Ircogel 905, Ircosperse 2174, and or Dow Corning 57 silicone glycol surfactant are included along with the liquid hydrocarbon.
  • the additional surfactant facilitates the contact between the different monomers/prepolymers.
  • the additional surfactant also helps to adjust the rheology of the composition, enhancing the association between the boric acid and the chemically grafted liquid hydrocarbon, thereby adding to the stability of the suspension.
  • Catalyst, additional monomer, and the other additional ingredients are added either before, during, or after the addition of the liquid hydrocarbon.
  • the catalysts that can be used are ammonium persulfate, hydrogen peroxide, tert-butylhydroperoxide, ditert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, methylethlylketone peroxide, and peracetic acid.
  • the concentration of the monomer in the reaction solution can vary within practically any limits, for example, from between about 1,000 ppm to 500,000 ppm. However, the preferred concentration for facility of use is between about 10,000 ppm and about 200,000 ppm, based on the weight of the solution.
  • a graft initiator such as ferrous sulphate or a silver salt, is added. Suitable silver salts include silver nitrate, silver acetate, silver sulfate, silver carbonate, and silver perchlorate. Silver perchlorate is a preferred graft initiator, since it is soluble in liquid hydrocarbon fuel, such as diesel fuel.
  • the concentration of the graft initiator can vary within a wide range, though it is preferably between about 0.0001 to about 0.01 percent. An amount of about 0.001 percent or lower is preferable for reasons of economy.
  • the mixture is then allowed to react while stined at ambient temperature and pressure until a concentrated suspension containing the boric acid-chemically grafted liquid hydrocarbon is formed.
  • a concentrated boric acid suspension in liquid hydrocarbon fuels having a sulfur content of less than 40,000 ppm, such as liquid hydrocarbon fuels having a sulfur content of less than 500 ppm, or less than 300 ppm sulfur or even no sulfur at all.
  • dilute the concentrate to form a finished liquid hydrocarbon fuel containing from about 10 ppm to about 50,000 ppm and more preferably in the range of from about 30 ppm to about 5,000 ppm paniculate boric acid, based on the weight of the finished liquid hydrocarbon fuel.
  • the concentration of surfactant in the finished hydrocarbon fuel is preferably from about 2 ppm to about 6 ppm. Both the concentrate and the finished fuel remain stable, even when subjected to a variety of potentially destabilizing conditions. For example, the boric acid remains suspended at temperatures ranging from about to about -30° F. to 150° F. and is shelf stable for one to two years.
  • the finished liquid hydrocarbon fuel compositions when combusted in an internal combustion engine provides superior lubricity and reduced wear on the components of the internal combustion engine, while preventing conosion, and providing a certain degree of increased fuel economy. In addition, the finished compositions when combusted in an internal combustion engine reduce hazardous paniculate and gaseous (i.e. , sulfur dioxide, carbon dioxide) emissions as compared to traditional liquid hydrocarbon fuels.
  • EXAMPLE 1 This example illustrates the preparation of a suspension of 17 wt.% boric acid in a low sulfur diesel fuel.
  • EXAMPLE 2 This example illustrates the preparation of a liquid hydrocarbon fuel containing 10 ppm particulate boric acid from a concentrate.
  • Five parts Dow Coming 1248 silicone prepolymer (based on 1,000,000 parts) are added to a five gallon reaction vessel, followed by the addition of 0.3325 parts Dow Coming 57 silicone glycol surfactant, Ircosperse 2176 alkenylsuccinic anhydride, 0.3325 parts , and 2.4475 parts diesel fuel.
  • 10 parts boric acid are slowly added to the other ingredients in the reaction vessel and a homogeneous slurry formed.
  • a mixture is made by dissolving 0.5 parts stearic acid in 5 parts diesel fuel heated to
  • a second mixture is made by dissolving 2 parts stearic acid in 10 parts heated diesel fuel and then adding 2 parts Ircogel 905 calcium sulfonate, 2 parts Ircosperse 2174 alkyl amino ester, and 2 parts Ircosperse 2176 alkenylsuccinic anhydride. This mixture is then added to the other ingredients after the reaction product is cooled to ambient temperature and allowed to sit for twenty-four hours.
  • Useful boric acid reaction products also can be formed with chemically-grafted lubricants.
  • Such reaction products are advantageously added to lubricants such as petroleum- based oils, cutting oils, synthetic oils and blends therewith, mineral oils, silicon oils, engine oils, hydraulic fluids, mineral oils, vegetable oils, oils for automatic transmissions, dry film lubricants, grease for bearings and jet turbines, and to other lubricants non-reactive to boric acid.
  • the concentrate preferably contains from about 50,000 ppm and preferably up to about 250,000 ppm particulate boric acid, based on the weight of the suspension.
  • the concentrate can then be diluted with additional lubricant to obtain the final desired concentration.
  • the concentration of boric acid in the finished lubricant composition will depend on the desired use. Typically, however, the final boric acid concentration will be in the range of from about 10 ppm to about 50,000 ppm and more preferably in the range of from about 30 ppm to about 5,000 ppm, based on the weight of the lubricant composition.
  • the less viscous the lubricant the greater the amount of surfactant that is required.
  • the less viscous the lubricant the greater the amount of monomer and hence, the greater the extent of chemical-grafting, that is required.
  • EXAMPLE 3 This example illustrates the preparation of a hydrocarbon oil lubricant containing 10 ppm particulate boric acid from a concentrate.
  • a second mixture is made by dissolving 2 parts stearic acid in 10 parts heated solvent
  • both the concentrate and the finished lubricant composition remain stable, even when subjected to a variety of potentially destabilizing conditions.
  • the boric acid remains suspended at temperatures ranging from about to about -30° F. to 150° F. and is shelf stable for one to two years.
  • the finished lubricant compositions provide superior lubricity and reduced wear on mechanical components of the internal combustion engine, while preventing corrosion.

Abstract

Disclosed are liquid hydrocarbon fuel concentrates, including low sulfur liquid hydrocarbon fuel concentrates containing at least 50,000 ppm boric acid suspended in the liquid hydrocarbon fuel. The liquid hydrocarbon fuels include gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel. Also disclosed are low sulfur liquid hydrocarbon fuel compositions formed by diluting the concentrate to form low sulfur fuel compositions containing only from about 10 ppm to about 50,000 ppm boric acid. Also disclosed are liquid hydrocarbon fuel compositions formed of a reaction product of boric acid having a particle size of about 65 microns or less, associated with a liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon.

Description

LIQUID COMPOSITIONS CONTAINING A STABLE BORIC ACID SUSPENSION
BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to the chemical arts. In particular, it relates to liquid compositions, including hydrocarbon fuel compositions, such as low-sulfur diesel and low- sulfur gasoline fuel compositions and lubricants, such as engine oils, hydraulic fluids, transmission fluids, cutting oils, synthetic oils, and mixtures thereof.
2. Discussion of the Related Art
Liquid hydrocarbon fuels typically contain up to as much as 40,000 ppm sulfur. The sulfur imparts several desirable properties to the fuels. For example, sulfur provides high lubricity in rolling, rotating, or sliding engine parts such as piston rings and liners, fuel pumps, and injector systems. However, sulfur suffers from serious disadvantages. It causes environmental problems in the form of high levels of sulfur dioxide (SO2) and hazardous particulates in engine exhaust gases. Because of high SO2 paniculate and emissions, diesel- powered engines are not widely used or permitted in many large cities.
Consequently, there has been a longstanding need to develop low-sulfur hydrocarbon fuel compositions. For example, low-sulfur No.2 diesel fuel currently contains about 500 ppm sulfur and numerous attempts are being made to further reduce the sulfur content to about 300 ppm sulfur or less. Unfortunately, removing the sulfur reduces the lubricating capacity of the diesel fuel, accelerating wear in fuel system and combustion chamber components. When sulfur is eliminated from fuels, high friction and wear occur on sliding surfaces of fuel-delivery systems and cause catastrophic failure. Boric acid is environmentally safe, inexpensive, and has an unusual capacity to enhance the antifriction and antiwear properties of sliding metal surfaces. U. S. Patent No. 5,431,830, to Erdemir, describes adding boric acid to greases, oils, and the like to improve lubricity. Lubricity is an essential element for lengthening the usefulness of various motor and mechanical components which rely on lubricants such as petroleum-based greases and oils, synthetic oils, mineral oils, silicon oils, cutting oils, transmission fluids, hydraulic fluids, and the like. The patent suggests that the particles of boric acid, under high pressure and frictional traction, interact with the load-bearing surfaces to provide excellent resilience and load carrying capacity. The layer structure of crystalline boric acid particles can slide over each other with relative ease and can reduce friction and wear. Boric acid is a crystalline compound, insoluble in hydrocarbons such as greases and oils.
Because of the viscous nature of greases and oils, the Erdemir patent teaches that boric acid can be dispersed in the greases and o ils simply by using conventional equipment and techniques. This patent also describes solid polymers having boric acid incorporated in the polymeric structure. This patent does not suggest that boric acid can be added to improve the performance of low-sulfur hydrocarbon fuels. Nor does the patent suggest a method for preparing stable suspensions of boric acid in liquid hydrocarbon fuels or any other such low-viscosity hydrocarbon media.
U. S. Patent No. 3,929,800, to Horowitz, describes a process for simultaneously polymerizing and grafting monomers onto liquid hydrocarbons, to improve various properties including viscosity. Among the liquid hydrocarbons disclosed in the Horowitz patent are post pyrolytic gasoline, catalytic cracking fractions, and lubricating oils. The patent does not suggest adding boric acid to the liquid hydrocarbons or modifying the process to form stable suspensions of paniculate boric acid in such hydrocarbons.
Accordingly, there remains a great need for liquid hydrocarbon fuel compositions that provide high lubricity and low wear in various engine components, such as fuel pumps and injector systems, a clean environment (resulting from the use of low-sulfur fuels), and low cost. There is a further need for stable liquid suspensions containing paniculate boric acid in hydrocarbon fuels and lubricants. The invention meets these needs and provides related advantages as well.
SUMMARY OF THE INVENTION
Now in accordance with the invention there have been found liquid compositions containing stable boric acid suspensions, including liquid hydrocarbon fuel concentrates containing from about 50,000 ppm to about 250,000 ppm paniculate boric acid, based on the total weight of the concentrate, suspended in a liquid hydrocarbon fuel. The liquid hydrocarbon fuels include gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel. In some embodiments the liquid hydrocarbon fuel contains less than 500 ppm or less than 300 ppm sulfur or even substantially no sulfur. In some embodiments, the boric acid has a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns or from about 0.5 to about 1 micron. In some embodiments, the concentrate is diluted to form a finished liquid hydrocarbon fuel containing only from about 10 ppm to about 50,000 ppm boric acid, preferably about 30 ppm to about 5,000 ppm, boric acid based on the total weight of the finished fuel, suspended in the fuel composition.
Also in accordance with the invention, there have been found liquid hydrocarbon fuel compositions formed of a reaction product of boric acid having a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns, and in some embodiments from about 0.5 to about 1 micron, associated with a liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon. The liquid hydrocarbon fuels include gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel and in some embodiments contains less than 500 ppm, or less than 300 ppm or even substantially no sulfur. In some embodiments, the monomer or prepolymer is a silane monomer or prepolymer.
And in some embodiments, the liquid hydrocarbon fuel composition additionally contains from about 200 ppm to about 600 ppm surfactant, based on the weight of the fuel concentrate and from about 2 ppm to about 6 ppm surfactant, based on the weight of the finished fuel.
The finished liquid hydrocarbon fuel when combusted in an internal combustion engine provides superior lubricity and reduced engine wear, causes less hazardous particulates and gases to be emitted, prevents conosion, and provides a certain degree of increased fuel economy. Additionally, the boric acid remains suspended in both the concentrate and the finished inventive fuel compositions providing a shelf-life of one to two years.
Also in accordance with the invention, paniculate boric acid reaction products are added to liquid lubricants, such as hydrocarbon-based oils, synthetic oils, mineral oils, silicon oils, transmission fluids, hydraulic fluids, or any other lubricants which do not react with boric acid. In some embodiments, the lubricant compositions contain concentrations of paniculate boric acid ranging from about 50,000 ppm to about 250,000 ppm particulate boric acid, based on the total weight of the concentrate, suspended in a lubricant. In some embodiments, the boric acid has a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns or from about 0.5 to about 1 micron. In some embodiments, the concentrate is diluted to form a lubricant compositions containing only from about 10 ppm to about 50,000 ppm boric acid, preferably about 30 ppm to about 5,000 ppm, boric acid based on the total weight of the finished lubricant composition, suspended in the lubricant composition.
The boric acid has a particle size of about 65 microns or less, preferably, in the range of from about 0.1 to about 2.5 microns, and in some embodiments from about 0.5 to about 1 micron, and are associated with a lubricant having a monomer or prepolymer chemically grafted thereon. In some embodiments, the monomer or prepolymer is a silane monomer or prepolymer.
The finished lubricant compositions provide superior lubricity thereby reducing wear on treated mechanical parts. Additionally, high concentrations of boric acid remains suspended in both the concentrates and the finished lubricant compositions providing a shelf-life of one to two years.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Boric acid is advantageously added to any liquid hydrocarbon fuel for use in an internal combustion engine such as gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel and, in particular, it is advantageously added to low-sulfur liquid hydrocarbon fuels. Low sulfur liquid hydrocarbon fuel are fuels containing less than 40,000 ppm sulfur. It is an advantage of the liquid hydrocarbon fuels in accordance with the invention that they can contain less than 500 ppm or less than 300 ppm or even substantially no sulfur.
Boric acid useful in accordance with the invention is advantageously produced by the low temperature jet-milling of commercially available boric acid. The conditions of the low temperature jet-milling process can be adjusted to produce boric acid particles having particle size of 65 microns or less, as desired. In preferced embodiments, the boric acid has a particle size in the range of from about 0.1 to about 2.5 microns, preferably in the range of from about 0.5 to about 1 micron. It is most efficient to initially prepare a concentrated suspension of the boric acid in the liquid hydrocarbon fuel. The concentrate preferably contains from about 50,000 ppm and preferably up to about 250,000 ppm paniculate boric acid, based on the weight of the suspension.
The concentrate can then be diluted with additional liquid hydrocarbon fuel to obtain the final desired concentration. The concentration of boric acid in the finished fuel composition will depend on the particular fuel and the particular engine system. Typically, however, the final boric acid concentration will be in the range of from about 10 ppm to about 50,000 ppm and more preferably in the range of from about 30 ppm to about 5,000 ppm, based on the weight of the liquid hydrocarbon fuel composition. For example, the paniculate boric acid concentration in no.2 diesel fuel is in the range of from about 50 ppm to about 25,000 ppm and more preferably in the range of from about 100 ppm to about 1500 ppm, based on the weight of the finished liquid hydrocarbon fuel composition.
The liquid hydrocarbon fuel compositions can contain other conventional fuel additives. Representative additives include antioxidants, metal passivators, rust inhibitors, dispersants, detergents, and the like. The liquid hydrocarbon fuel compositions also can contain additional lubricity-enhancing agents, such as stearic acid.
The boric acid is stabilized by forming a reaction product with chemically grafted liquid hydrocarbon fuel. Without wishing to be bound by a theory of the invention, it is believed that boric acid's hydroxyl groups can become loosely associated with liquid hydrocarbon fuel. However, when suitable monomers or prepolymers are chemically grafted onto the liquid hydrocarbon fuel, the resulting polymer chains effectively stabilize the boric acid-liquid hydrocarbon fuel association and create a stable reaction product, effectively suspending the boric acid particles in the liquid hydrocarbon fuel.
Any polymerizable monomer or prepolymer can be chemically grafted onto the liquid hydrocarbon, so long as it does not adversely effect the properties of the fuel. Suitable monomers include methyl methacrylate (also oleyl, alpha-decyl, octadecyl, cyclohexyl, n-butyl, amyl, cetyl acrylates and others), acrylic acid and its derivatives (also butyl, amyl, octyl hexadecyl etc.), methylacrylate vinyl acetate, vinyl chloride, vinylidene chloride, isobutylene, vinyl ethers, acrylonitrile, maleic acid and esters, crotonic acid and esters, itaconic acid and its esters, allylic esters, allyl vinyl esters, vinlypyridine and its derivatives (also 2-methyl-5-vinyl pyridine), bisbetachloro ethylvinyl phosphonate, chloroprene, isoprene, dimethylaminethyl, methacrylate, styrene, 1,3-butylene dimethacrylate, isooctyl vinyl ether, acrylamide, glycidyl methacrylate, N-vinyl caprolactam, N-vinyl pyrrolidone, N-vinyl carbazole, sodium styrene sulfonate, sodium vinyl sulfonate, bis(betachloroethyl) vinyl phosphonate, cetyl vinyl ether, divinylether of ethylene glycol, divinyl ether of butanediol, vinyl toluene, vinyl acetate, octadecyl vinylether.
Other suitable monomers include mono-, di-, tri-, tetra-, and poly-ethene glycoldimethacrylate, methylvinylpyridine, allylacrylate and methacrylate, allylchloride, allyl alcohol, perfluoro alkyl acrylates and methacrylates, p-amino-styrene, vinyl bromide and vinylidene bromide trimethylvinylbenzylammonium chloride, vinyltrifluoroacetate (followed by hydrolysis to poly-vinyl alcohol), diallyl chloromethyl phosphonate, diallyl benzene phosphonate, diallyl dimethyl ammonium chloride, diallyl diethyl ammonium bromide, glycidyl acrylate and methacrylate, ethylene glycol, diethyleneglycol, an polyethylene glycol acrylates and methacrylates, vinyl perfluoro octaneate, and the like.
The monomeric tertiary amines can be quaternized with benzyl chloride, ethyl iodide, methyl or ethylsulfate. Conversely, monomeric chlorides can be quaternized with tertiary amines to give quaternary ammonium compounds. Some suitable tertiary amines are: N-ethyl morpholine, pyridine, cetyldimethyl pryidine, dimethyl aniline, and the like. Also mixtures of two or more monomers can be used.
If the monomer is not soluble in the liquid hydrocarbon, the monomer can be dissolved in a solvent, before adding the monomer to the liquid hydrocarbon. Suitable solvents include dimethylformamide, tetrahydrofurane, tetrahydrofurfuryl alcohol, dimethylsulfoxide, water, methyl, ethyl or isopropyl alcohol, acetone, methyl ethyl ketone and acetate or mixtures of two or more of the solvents.
The preferred monomers/prepolymers are silane monomers/prepolymers, such as silicones and other related prepolymers, having siloxy functional groups for complexing with the boric acid. Suitable silane monomers/prepolymers include Dow Corning 174 silane monomer and Dow Corning 1248 silicone prepolymer. Chemically grafting silicone polymer chains to the liquid hydrocarbon fuel is particularly effective because the silicone chains double as surfactants. Polar sites on the polymer chains form bridges between the boric acid and the liquid hydrocarbon thus stabilizing the interaction between the two. The boric acid-chemically grafted liquid hydrocarbon reaction product is prepared by first adding one or more surfactants to a liquid monomer or prepolymer. Suitable surfactants include dispersants such as glucose ether, sulphonated castor, and salts of calcium and zinc. Especially useful are Ircosperse 2174 alkyl aminoester, Ircosperse 2176 alkenylsuccinic anhydride, and Ircogel 905 calcium sulfonate, all available from Lubrizol, Inc., Witcliffe, Ohio. Sufficient surfactants are used so that when the particulate boric acid is added to the monomer/prepolymer/surfactant mixture, the macro globule particles of the boric acid are broken up and prevented from reforming. Typically, from about 2 ppm to about 6 ppm surfactant, preferably from about 2.5 ppm to about 4.5 ppm surfactant, are added, based on the weight of the reaction product, when the concentrations of the ingredients are chosen, so that the concentrated boric acid suspension is produced.
After adding the boric acid, liquid hydrocarbon is added and the resulting mixture stirred vigorously until it is homogeneous. Typically, sufficient liquid hydrocarbon fuel is added so that the concentration of boric acid after reaction is from about 50,000 ppm to about
250,000 ppm, although greater or lesser amounts of liquid hydrocarbon fuel can be added if desired.
In those embodiments where a combination of monomers and/or prepolymers are used, additional surfactant, such as Ircogel 905, Ircosperse 2174, and or Dow Corning 57 silicone glycol surfactant are included along with the liquid hydrocarbon. The additional surfactant facilitates the contact between the different monomers/prepolymers. The additional surfactant also helps to adjust the rheology of the composition, enhancing the association between the boric acid and the chemically grafted liquid hydrocarbon, thereby adding to the stability of the suspension.
Catalyst, additional monomer, and the other additional ingredients are added either before, during, or after the addition of the liquid hydrocarbon. Among the catalysts that can be used are ammonium persulfate, hydrogen peroxide, tert-butylhydroperoxide, ditert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, methylethlylketone peroxide, and peracetic acid.
The concentration of the monomer in the reaction solution can vary within practically any limits, for example, from between about 1,000 ppm to 500,000 ppm. However, the preferred concentration for facility of use is between about 10,000 ppm and about 200,000 ppm, based on the weight of the solution. Finally, a graft initiator, such as ferrous sulphate or a silver salt, is added. Suitable silver salts include silver nitrate, silver acetate, silver sulfate, silver carbonate, and silver perchlorate. Silver perchlorate is a preferred graft initiator, since it is soluble in liquid hydrocarbon fuel, such as diesel fuel.
The concentration of the graft initiator can vary within a wide range, though it is preferably between about 0.0001 to about 0.01 percent. An amount of about 0.001 percent or lower is preferable for reasons of economy.
The mixture is then allowed to react while stined at ambient temperature and pressure until a concentrated suspension containing the boric acid-chemically grafted liquid hydrocarbon is formed. Using this method it is possible to prepare a concentrated boric acid suspension in liquid hydrocarbon fuels having a sulfur content of less than 40,000 ppm, such as liquid hydrocarbon fuels having a sulfur content of less than 500 ppm, or less than 300 ppm sulfur or even no sulfur at all. Further it is possible to dilute the concentrate to form a finished liquid hydrocarbon fuel containing from about 10 ppm to about 50,000 ppm and more preferably in the range of from about 30 ppm to about 5,000 ppm paniculate boric acid, based on the weight of the finished liquid hydrocarbon fuel. The concentration of surfactant in the finished hydrocarbon fuel is preferably from about 2 ppm to about 6 ppm. Both the concentrate and the finished fuel remain stable, even when subjected to a variety of potentially destabilizing conditions. For example, the boric acid remains suspended at temperatures ranging from about to about -30° F. to 150° F. and is shelf stable for one to two years. Moreover, the finished liquid hydrocarbon fuel compositions when combusted in an internal combustion engine provides superior lubricity and reduced wear on the components of the internal combustion engine, while preventing conosion, and providing a certain degree of increased fuel economy. In addition, the finished compositions when combusted in an internal combustion engine reduce hazardous paniculate and gaseous (i.e. , sulfur dioxide, carbon dioxide) emissions as compared to traditional liquid hydrocarbon fuels.
The foregoing examples are intended to further illustrate the invention and are not limitations thereon. All percentages are amounts are based on weight, unless otherwise clearly indicated.
EXAMPLE 1 This example illustrates the preparation of a suspension of 17 wt.% boric acid in a low sulfur diesel fuel.
Eight and one-half parts Dow Corning 1248 silicone prepolymer is added to a reaction vessel, followed by the addition of 1.75 parts Ircosperse 2176 alkenylsuccinic anhydride, 2.30 parts Ircogel 905 calcium sulfonate, 1.77 parts Ircosperse 2174 alkyl aminoester, and 1.91 parts stearic acid, while stirring. Next is added 17.00 parts boric acid having an average particle size of one to two microns. The mixture is vigorously stined for thirty minutes at 2000 RPM using a high speed stirrer. The following ingredients are then added in the amount and in the order indicated:
Ingredient Parts by Weight Lubersol DDM-9
1% methylethylketone peroxide in plasticizer 0.01
Silane A- 174 0.40
Dow Co ing 57 silicone glycol surfactant 0.10
Diesel Fuel (300 ppm Sulfur) 66.25
0.1% Silver perchlorate in diesel fuel 0.01
After addition of the silver perchlorate solution the mixture is stirred for thirty minutes.
There results a stable suspension containing 17 wt.% boric acid in the low-sulfur diesel fuel.
EXAMPLE 2 This example illustrates the preparation of a liquid hydrocarbon fuel containing 10 ppm particulate boric acid from a concentrate. Five parts Dow Coming 1248 silicone prepolymer (based on 1,000,000 parts) are added to a five gallon reaction vessel, followed by the addition of 0.3325 parts Dow Coming 57 silicone glycol surfactant, Ircosperse 2176 alkenylsuccinic anhydride, 0.3325 parts , and 2.4475 parts diesel fuel. Then 10 parts boric acid are slowly added to the other ingredients in the reaction vessel and a homogeneous slurry formed. A mixture is made by dissolving 0.5 parts stearic acid in 5 parts diesel fuel heated to
80° C and then adding 0.665 parts Dow Coming 57 silicone glycol surfactant, and 0.665 parts Ircosperse 2174 alkyl amino ester. This mixture is added to the slurry, after the slurry is stirred for ten minutes with a high speed stirrer. 0.0025 Lubersol DDM-9 1% methylethylketone peroxide in plasticizer, 0.05 parts Silane A-174, and 0.0025 0.1% Silver perchlorate in diesel fuel are then added to the slurry and a reaction product formed.
A second mixture is made by dissolving 2 parts stearic acid in 10 parts heated diesel fuel and then adding 2 parts Ircogel 905 calcium sulfonate, 2 parts Ircosperse 2174 alkyl amino ester, and 2 parts Ircosperse 2176 alkenylsuccinic anhydride. This mixture is then added to the other ingredients after the reaction product is cooled to ambient temperature and allowed to sit for twenty-four hours.
Next, an additional 30 ppm is heated to 80 °C and added, while stirring to form a concentrated suspension containing 17,000 ppm boric acid. A stable finished diesel fuel containing 10 ppm boric acid is then prepared by adding an additional 999927.0025 parts diesel fuel.
Useful boric acid reaction products also can be formed with chemically-grafted lubricants. Such reaction products are advantageously added to lubricants such as petroleum- based oils, cutting oils, synthetic oils and blends therewith, mineral oils, silicon oils, engine oils, hydraulic fluids, mineral oils, vegetable oils, oils for automatic transmissions, dry film lubricants, grease for bearings and jet turbines, and to other lubricants non-reactive to boric acid.
It is most efficient to initially prepare a concentrated suspension of boric acid in the lubricant composition. The concentrate preferably contains from about 50,000 ppm and preferably up to about 250,000 ppm particulate boric acid, based on the weight of the suspension. The concentrate can then be diluted with additional lubricant to obtain the final desired concentration. The concentration of boric acid in the finished lubricant composition will depend on the desired use. Typically, however, the final boric acid concentration will be in the range of from about 10 ppm to about 50,000 ppm and more preferably in the range of from about 30 ppm to about 5,000 ppm, based on the weight of the lubricant composition.
As a general rule, the less viscous the lubricant, the greater the amount of surfactant that is required. And as a general rule, the less viscous the lubricant, the greater the amount of monomer and hence, the greater the extent of chemical-grafting, that is required.
EXAMPLE 3 This example illustrates the preparation of a hydrocarbon oil lubricant containing 10 ppm particulate boric acid from a concentrate.
Five parts Dow Co ing 1248 silicone prepolymer (based on 1,000,000 parts) are added to a five gallon reaction vessel, followed by the addition of 0.3325 parts Dow Coming 57 silicone glycol surfactant, Ircosperse 2176 alkenylsuccinic anhydride, 0.3325 parts , and 2.4475 parts solvent 320 neutral oil. Then 10 parts boric acid are slowly added to the other ingredients in the reaction vessel and a homogeneous slurry formed. A mixture is made by dissolving 0.5 parts stearic acid in 5 parts solvent 320 neutral oil heated to 80°C and then adding 0.665 parts Dow Coming 57 silicone glycol surfactant, and
0.665 parts Ircosperse 2174 alkyl amino ester. This mixture is added to the slurry, after the slurry is stirred for ten minutes with a high speed stirrer. 0.0025 Lubersol DDM-9 1% methylethylketone peroxide in plasticizer, 0.05 parts Silane A-174, and 0.0025 0.1% Silver perchlorate in solvent 320 neutral oil are then added to the slurry and a reaction product formed.
A second mixture is made by dissolving 2 parts stearic acid in 10 parts heated solvent
320 neutral oil and then adding 2 parts ircogel 905 calcium sulfonate, 2 parts, Ircosperse 2174 alkyl amino ester, and 2 parts Ircosperse 2176 alkenylsuccinic anhydride. This mixture is then added to the other ingredients after the reaction product is cooled to ambient temperature and allowed to sit for twenty-four hours.
Next, an additional 30 ppm is heated to80°C and added, while stirring to form a concentrated suspension containing 17,000 ppm boric acid. A stable finished lubricant containing 10 ppm boric acid is then prepared by adding an additional 999927.0025 parts solvent 320 neutral oil.
Both the concentrate and the finished lubricant composition remain stable, even when subjected to a variety of potentially destabilizing conditions. For example, the boric acid remains suspended at temperatures ranging from about to about -30° F. to 150° F. and is shelf stable for one to two years. Moreover, the finished lubricant compositions provide superior lubricity and reduced wear on mechanical components of the internal combustion engine, while preventing corrosion.

Claims

1. A liquid hydrocarbon fuel concentrate comprising a liquid hydrocarbon fuel; and at least 50,000 ppm particulate boric acid, based on the total weight of the liquid hydrocarbon fuel concentrate, suspended in the liquid hydrocarbon fuel.
2. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein from about 50,000 to about 250,000 ppm boric acid, based on the total weight of the liquid hydrocarbon fuel concentrate, is suspended in the liquid hydrocarbon fuel.
3. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the liquid hydrocarbon fuel contains less than 500 ppm sulfur.
4. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the liquid hydrocarbon fuel contains less than 300 ppm sulfur.
5. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the liquid hydrocarbon fuel contains substantially no sulfur.
6. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the liquid hydrocarbon fuel is gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel.
7. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the liquid hydrocarbon fuel is gasoline or diesel fuel.
8. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the liquid hydrocarbon fuel is diesel fuel.
9. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the boric acid has a particle size of about 65 microns or less.
10. The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the boric acid has a particle size in the range of from about 0.1 to about 2.5 microns.
11 . The liquid hydrocarbon fuel concentrate in accordance with claim 1 wherein the boric acid has a particle size in the range of from about 0.5 to about 1 micron.
12. A low-sulfur liquid hydrocarbon fuel concentrate comprising a gasoline or diesel fuel having a sulfur content of less than 500 ppm, based on the weight of the fuel concentrate; and from about 5,000 ppm to about 25,000 ppm particulate boric acid, based on the total weight of the fuel concentrate, and having a particle size of about 65 microns or less, suspended in the gasoline or diesel fuel.
13. The liquid hydrocarbon fuel concentrate in accordance with claim 12 wherein the liquid hydrocarbon fuel contains less than 300 ppm sulfur.
14 The liquid hydrocarbon fuel concentrate in accordance with claim 12 wherein the liquid hydrocarbon fuel contains substantially no sulfur.
15. The liquid hydrocarbon fuel concentrate in accordance with claim 12 wherein the liquid hydrocarbon fuel is diesel fuel.
16. The liquid hydrocarbon fuel concentrate in accordance with claim 12 wherein the boric acid has a particle size of from about 0.5 to about 1 micron.
17. A liquid hydrocarbon fuel composition comprising a liquid hydrocarbon fuel; and from about 50 ppm to about 50,000 ppm particulate boric acid, based on the total weight of the fuel liquid hydrocarbon fuel, suspended in the fuel composition.
18. The liquid hydrocarbon fuel composition in accordance with claim 12 wherein from about 30 ppm to about 5000 ppm particulate boric acid based on the total weight of the fuel composition, is suspended in the fuel composition.
19. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the liquid hydrocarbon fuel contains less than 500 ppm sulfur.
20. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the liquid hydrocarbon fuel contains less than 300 ppm sulfur.
21. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the liquid hydrocarbon fuel contains substantially no sulfur.
22. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the liquid hydrocarbon fuel is gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel.
23. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the liquid hydrocarbon fuel is gasoline, or diesel fuel.
24. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the liquid hydrocarbon fuel is diesel fuel.
25. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the boric acid has a particle size of about 65 microns or less.
26. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the boric acid has an average particle size of from about to about micron 0.1 to about 2.5 microns.
27. The liquid hydrocarbon fuel composition in accordance with claim 17 wherein the boric acid has an average particle size of from about 0.5 to about 1 micron.
28. A liquid hydrocarbon fuel composition comprising a suspension of (a) a reaction product of (1) boric acid having a particle size of about 65 microns or less associated with (2) liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon in (b) liquid hydrocarbon fuel.
29. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the boric acid has an average particle size of from about 0.5 to about 1 micron.
30. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the liquid hydrocarbon fuel and the liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon contain substantially no sulfur.
31. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the liquid hydrocarbon fuel and the liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon contain less than 500 ppm sulfur.
32. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the liquid hydrocarbon fuel and the liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon contain less than 300 ppm sulfur.
33. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the liquid hydrocarbon fuel and the liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon are gasoline, diesel fuel, aviation fuel, jet fuel, boat or motorcycle fuel.
34. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the liquid hydrocarbon fuel and the liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon are gasoline, or diesel fuel.
35. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the liquid hydrocarbon fuel and the liquid hydrocarbon fuel having a monomer or prepolymer chemically grafted thereon are diesel fuel.
36. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein monomer or prepolymer is a silane monomer or prepolymer.
37. The liquid hydrocarbon fuel composition in accordance with claim 28 further comprising (c) from about 2 ppm to about 6 ppm of a surfactant, based on the weight of the fuel composition.
38. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the suspension contains at least 50,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
39. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the suspension contains from about 50,000 to about 250,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
40. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the suspension contains from about 5,000 to about 25,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
41. The liquid hydrocarbon fuel composition in accordance with claim 28 wherein the suspension contains from about 50 to about 50,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
42. A low sulfur liquid hydrocarbon fuel composition comprising: a suspension of
(a) a reaction product of
(1) boric acid having a particle size of 65 microns or less associated with
(2) gasoline or diesel fuel having a sulfur content less than about 500 ppm and having a silane monomer or prepolymer chemically grafted thereon;
(b); gasoline or diesel fuel having a sulfur content less than about 500 ppm; and (c) from about 2 ppm to about 6 ppm of a surfactant, based on the weight of the fuel composition.
43. The low sulfur liquid hydrocarbon fuel composition in accordance with claim 42 wherein the boric acid has an average particle size of from about 0.5 to about 1 micron.
44. The low sulfur liquid hydrocarbon fuel composition in accordance with claim 42 wherein the fuel and the fuel having a monomer or prepolymer chemically grafted thereon are diesel fuel.
45. The low sulfur liquid hydrocarbon fuel composition in accordance with claim 42 wherein the fuel and the fuel having a monomer or prepolymer chemically grafted thereon contain substantially no sulfur.
46. The low sulfur liquid hydrocarbon fuel composition in accordance with claim 42 wherein the fuel and the fuel having a monomer or prepolymer chemically grafted thereon contain less than 300 ppm sulfur.
47. The liquid hydrocarbon fuel composition in accordance with claim 42 wherein the suspension contains at least 50,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
48. The liquid hydrocarbon fuel composition in accordance with claim 42 wherein the suspension contains from about 50,000 to about 250,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
49. The liquid hydrocarbon fuel composition in accordance with claim 42 wherein the suspension contains from about 5,000 to about 25,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
50. The liquid hydrocarbon fuel composition in accordance with claim 42 wherein the suspension contains from about 50 to about 50,000 ppm of the associated boric acid, based on the total weight of the liquid hydrocarbon fuel composition.
51. A method of reducing hazardous particulate and gaseous emissions resulting from the combustion of a liquid hydrocarbon fuel within an internal combustion engine comprising the step of combusting within the internal combustion engine a suspension of particulate boric acid suspended in a low-sulfur hydrocarbon fuel.
52. A method of reducing wear on the components of an internal combustion engine comprising the step of combusting within the internal combustion engine liquid hydrocarbon fuel containing a sufficient amount of boric acid to reduce the wear on the components.
EP01906647A 2000-01-20 2001-01-22 Liquid compositions containing a stable boric acid suspension Withdrawn EP1250402A2 (en)

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US09/488,423 US6368369B1 (en) 2000-01-20 2000-01-20 Liquid hydrocarbon fuel compositions containing a stable boric acid suspension
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US7972393B2 (en) 2005-08-10 2011-07-05 Advanced Lubrication Technology, Inc. Compositions comprising boric acid
US9222045B2 (en) 2009-05-08 2015-12-29 Triboron International Ab Method for producing a stable boric solution
US9447340B2 (en) 2012-03-15 2016-09-20 William E. Olliges Hexylene glycol fuel additive containing boric acid for inhibiting phase separation and corrosion in Ethanol Blended Fuels
US9447348B2 (en) 2012-03-15 2016-09-20 William E. Olliges Use of hexylene glycol additive containing boric acid for reducing friction and corrosion in internal combustion engine crankcases
US9212329B2 (en) 2012-03-15 2015-12-15 William E. Olliges Use of hexylene glycol fuel additive containing boric oxide
US10016318B2 (en) 2012-06-13 2018-07-10 Jane Speak Absorbent article with a bacterial isolation pad and hygienic gripping tabs
CN110616092A (en) * 2019-08-28 2019-12-27 刘明波 High-cleanness gasoline fuel

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