Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
• • 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
  • C10L1/188—Carboxylic acids; metal salts thereof
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
  • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid 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
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
• • 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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

• This invention relates to a method of operating diesel engines equipped with an exhaust system particulate trap, to fuel compositions useful in operating diesel engines, and to certain titanium and zirconium complexes which are useful in the method and fuel of the invention.
• the fuels and titanium or zirconium compounds of the invention are useful in operating diesel engines and are effective in lowering the ignition temperature of exhaust particulates collected in the particulate traps of diesel exhaust systems.
• Diesel engines have been employed as engines for over-the-road vehicles because of relatively low fuel costs and improved mileage.
• diesel engines discharge a larger amount of carbon black particles or very fine condensate particles or agglomerates thereof as compared to the gasoline engine.
• These particles or condensates are sometimes referred to as "diesel soot", and the emission of such particles or soot results in pollution and is undesirable.
• diesel soot has been observed to be rich in condensed, polynuclear hydrocarbons, and some of these have been recognized as carcinogenic. Accordingly, particulate traps or filters have been designed for use with diesel engines that are capable of collecting carbon black and condensate particles.
• the particulate traps or filters have been composed of a heat-resistant filter element which is formed of porous ceramic or metal fiber and an electric heater for heating and igniting carbon particulates collected by the filter element.
• the heater is required because the temperatures of the diesel exhaust gas under normal operating conditions are insufficient to burn off the accumulated soot collected in the filter or trap. Generally, temperatures of about 450-600°C are required, and the heater provides the necessary increase of the exhaust temperature in order to ignite the particles collected in the trap and to regenerate the trap. Otherwise, there is an accumulation of carbon black, and the trap is eventually plugged.
• the above-described heated traps do not provide a complete solution to the problem because the temperature of the exhaust gases is lower than the ignition temperature of carbon particulates while the vehicle runs under normal conditions, and the heat generated by the electric heater is withdrawn by the flowing exhaust gases when the volume of flowing exhaust gases is large.
• higher temperatures in the trap can be achieved by periodically enriching the air/fuel mixture burned in the diesel engine thereby producing a higher exhaust gas temperature.
• the particle build-up in the traps can be controlled by lowering the ignition temperature of the particulates so that the particles begin burning at the lowest possible temperatures.
• One method of lowering the ignition temperature involves the addition of a combustion improver to the exhaust particulate, and the most practical way to effect the addition of the combustion improver to the exhaust particulate is by adding the combustion improver to the fuel.
• Manganese or copper compounds have been suggested as combustion improvers for fuels and fuel oils.
• U.S. Patent 4,505,718 describes the treatment of lubricating oils and fuels to improve various properties thereof. When added to fuels, the combustion characteristics of the fuels are improved.
• the organic acids utilized to make the transition metal salts may be sulfonic acids, carboxylic acids, and phosphorus acids.
• the addition of transition metal salts of mixed organic carboxylic and sulfonic acids as anti-knock agents, combustion improvers and smoke suppressants is described in U.S. Patent 4,162,986.
• Manganese soaps and fuels are described in U.S. Patent 3,762,890, and organic magnesium compounds as fuel conditioners are described in U.S. Patent 4,202,671.
• Various titanium containing organic salts have been described as being useful in fuels, lubricants, etc., in, for example, U.S. Patents 4,093,614; 4,077,941; 3,355,270; and 3,493,508.
• a fuel composition comprising a major amount of a normally liquid fuel and a minor, property-improving amount of at least one titanium or zirconium complex effective in lowering the ignition temperature of exhaust particulates collected in the particulate traps of diesel exhaust systems, characterized by the formula: (RO) x M(Ch) y (I) wherein R is hydrogen or a hydrocarbyl group containing from 1 to 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and, Ch is derived from at least one metal chelating agent.
• a titanium or zirconium complex characterized by the formula: (RO) x M(Ch) y (I) wherein R is hydrogen or a hydrocarbyl group containing from 1 to 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from a metal chelating agent selected from the group consisting of:
• a fuel additive concentrate comprising a normally liquid organic diluent and from 10% to 99% by weight of the complex according to the present invention.
• a method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in said trap comprising operating said diesel engine with a fuel according to the present invention.
• a method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in said trap comprising operating said diesel engine with a fuel containing at least one of the titanium or zirconium complexes according to the present invention.
• the invention relates to a method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in the trap.
• the method comprises operating the diesel engine with a fuel containing at least one compound according to the present invention effective to lower the ignition temperature of the exhaust particulates collected in the said trap.
• the titanium and zirconium compounds according to the present invention are titanium and zirconium complexes characterized by the formula (RO) x M(Ch) y (I) wherein R is hydrogen or a hydrocarbyl group containing from 1 to about 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from at least one metal chelating agent.
• the metal chelating agents used in the preparation of the complexes (I) generally contain a hydrocarbon linkage and at least two functional groups on different carbon atoms. Generally, the functional groups are in vicinal or beta position to each other on the carbon skeleton of the hydrocarbon linkage.
• the hydrocarbon linkage may be aliphatic, cycloaliphatic or aromatic.
• metal chelating agent is the accepted terminology for a well known class of chemical compounds which have been described in several texts including Chemistry of the Metal Chelate Compounds , by Martell and Calvin, Prentice-Hall, Inc., N.Y. (1952).
• functional groups which may be present in the chelating agent include hydroxy groups, carboxy groups, carbonyl groups, amino groups, or mercapto groups.
• the chelating agent (Ch) may be aliphatic in nature and selected from the group consisting of diols, dithiols, mercapto alcohols, diamines, amino alcohols, aminothiols, ortho-aminophenol, dicarboxylic acids, hydroxy carboxylic acids, mercapto carboxylic acids, amino carboxylic acids, diketones, ketocarboxylic acids or esters, etc.
• aromatic chelating agents examples include dihydroxy benzenes, dimercapto benzenes, mercaptohydroxy benzenes, diamino benzenes, aminohydroxy benzenes, aminomercapto benzenes, hydroxy-carboxy benzenes, aminocarboxy benzenes and mercapto-carboxy benzenes having the two functional groups in vicinal or beta position to one another on the benzene nucleus.
• the titanium and zirconium complexes represented by Formula I generally are prepared by reacting one or more chelating agents with a titanium or zirconium compound represented by the formula M(OR)4 wherein M is titanium or zirconium and each R group is independently hydrogen or a hydrocarbyl group containing from 1 to about 30 carbon atoms. Generally, all of the R groups are hydrocarbyl groups.
• the number of chelate groups (Ch) which enter into the complex is dependent upon the relative amounts of the reactants, and generally, either two or three equivalents of the chelating group are reacted with two or one equivalents (respectively) of the compound of the formula M(OR)4.
• the mixtures generally are heated to accelerate the reaction and to remove the alcohol (ROH) formed in the reaction.
• the preferred complexes represented by Formula I are soluble in fuel, and the chelating agents accordingly are selected to impart fuel-solubility to the complex.
• the chelating agents will contain a carbon skeleton of from 2 to about 18 carbon atoms.
• suitable metal chelating agents within the above-described groups include vicinal- and beta-diols such as ethylene glycol and 2-ethyl-1,3-hexanediol; vicinal- and beta-dithiols such as ethylene mercaptan and 1,3-propanediol; vicinal- and beta-mercapto alcohols such as beta-mercaptoethanol, 3-mercapto-1-propanol; vicinal- and beta-diamines such as ethylene diamine and propylene diamine; vicinal- and beta-amino alcohols such as ethanolamine and 3-amino-1-propanol; vicinal- and beta-aminothiols such as thioethanolamine and 3-amine-1-mercaptopropane; vicinal- and beta-dicarboxylic acids such as oxalic acid and malonic acids vicinal- and beta-hydroxy carboxylic acids such as glycolic acid and beta-hydroxy butyric acid
• the metal chelating agents also may be alicyclic chelating agents or aromatic chelating agents such as represented by the structural formula wherein R1 is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta positions relative to X, and X and Y are each independently functional groups such as OH, NH2, NHR, SH, COOR, or C(O)H wherein R is hydrogen or a hydrocarbyl group, preferably a lower aliphatic group.
• R1 is a hydrocarbyl group containing 1 to about 100 carbon atoms
• n is an integer from 0 to 4
• Y is in the ortho or meta positions relative to X
• X and Y are each independently functional groups such as OH, NH2, NHR, SH, COOR, or C(O)H wherein R is hydrogen or a hydrocarbyl group, preferably a lower aliphatic group.
• aromatic compounds include hydrocarbyl-substituted and unsubstituted vicinal-di-hydroxy aromatic compounds such as pyrocatechol and 4-t-butyl-pyrocatechol; vicinal-dimercapto-aromatic compounds such as thiocatechol; vicinal-mercapto-hydroxyaromatic compounds such as monothio-catechol or a mercaptohydroxy benzene; vicinal-diamino-aromatic compounds such as orthophenylenediamine; vicinal-amino-hydroxyaromatic compounds such as ortho-aminophenol; vicinal-aminomercapto aromatic compounds such as orthoaminothiophenol; vicinal-hydroxycarboxy aromatic compounds such as salicyclic acid; vicinal-aminocarboxy aromatic compounds such as orthoaminobenzoic acid; vicinal-mercaptocarboxy aromatic compounds such as ortho-mercaptobenzoic acid, etc.
• alicyclic compounds include 1,2-dihydroxycyclohexane and, amino, 2-hydroxycyclohexane.
• the above-described alicyclic and aromatic chelating agents may have various other ring substituents including aromatic and substituted aromatic rings; hydroxy, alkoxy, and aryloxy groups, sulfhydryl, alkylthioether, arylthioether, alkylthioester, and arylthioester groups; acyl, aroyl, thioacyl and thioaroyl groups; amino, alkylamino, aryl- amino, acylamido and aroylamido groups; and nitro, halogen and sulfato groups.
• the metal chelating agent (Ch) may be selected from the group consisting of:
• the Mannich reaction between active hydrogen compounds, aldehydes such as formaldehyde and amino compounds is well known.
• the Mannich condensation products utilized in the present invention are those which are derived from hydroxy aromatic compounds, amines or hydroxy amines, and aldehydes or ketones.
• the metal chelating agent (Ch) is an aromatic Mannich base which is the reaction product of (A-1) a hydrocarbon-substituted aromatic phenol or thiol phenol, (A-2) an aldehyde or ketone, and (A-3) an amine which contains at least one primary or secondary amino group.
• the metal chelating agent (Ch) is an aromatic Mannich base which is the reaction product of
• the (A-1) hydrocarbyl-substituted hydroxyl and/or thiol-containing aromatic compound of the present invention generally has the formula (R1) n -Ar-(XH) m wherein Ar is an aromatic group such as phenyl or polyaromatic group such as naphthyl, and the like.
• Ar can be coupled aromatic compounds such as naphthyl, phenyl, etc., wherein the coupling agent is O, S, CH2, a lower alkylene group having from 1 to about 6 carbon atoms, NH, and the like with R1 and XH generally being pendant from each aromatic group.
• specific coupled aromatic compounds include diphenylamine, diphenylmethylene and the like.
• the number of "m” XH groups is usually from 1 to 3, desirably 1 or 2, with 1 being preferred.
• the number of "n" substituted R1 groups is usually from 1 to 4, desirably 1 or 2 with a single substituted group being preferred.
• X is 0 and/or S with 0 being preferred. That is, if m is 2, X can be both 0, both S, or one 0 and one S.
• R1 can be a hydrogen or a hydrocarbyl-based substituent having from 1 to about 100 carbon atoms.
• hydrocarbyl-based substituent or “hydrocarbyl” denotes a substituent having carbon atoms directly attached to the remainder of the molecule and having predominantly hydrocarbyl character within the context of this invention.
• substituents include the following:
• R1 is hydrogen, or a hydrocarbyl group.
• the hydrocarbyl groups may contain from 1 to about 100 carbon atoms such as an alkyl, or alkyl groups may be mixtures of alkyl groups having from 1 up to an average of about 70 carbon atoms, more desirably from about 7 to about 20 carbon atoms, an alkenyl having 2 to about 30 carbon atoms, more desirably from about 8 to about 20 carbon atoms, a cycloalkyl having from 4 to about 10 carbon atoms, an aromatic group having from about 6 to about 30 carbon atoms, an aromatic-substituted alkyl or alkyl-substituted aromatic having a total of from about 7 to about 30 carbon atoms and more desirably from about 7 to about 12 carbon atoms.
• the hydrocarbyl-based substituent preferably is an alkyl having from 7 to about 20 carbon atoms with from about 7 to about 14 carbon atoms being highly preferred.
• suitable hydrocarbyl-substituted hydroxyl-containing aromatics include the various naphthols, and more preferably, the various alkyl-substituted catechols, resorcinols, and hydroquinones, the various xylenols, the varous cresols, aminophenols, and the like.
• suitable (A) compounds include heptylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, tetrapropylphenol, eicosylphenol, and the like.
• Dodecylphenol, tetrapropylphenol and heptylphenol are especially preferred.
• suitable hydrocarbyl-substituted thiol-containing aromatics include heptylthiophenol, octylthiophenol, nonylthiophenol, dodecylthiophenol, tetrapropylthiophenol, and the like.
• suitable thiol and hydroxyl-containing aromatics include dodecylmonothioresorcinol.
• the aldehyde or ketone (A-2) used in the present invention has the formula or a precursor thereof, wherein R2 and R3 independently can be hydrogen, a hydrocarbon such as an alkyl having from 1 to about 18 carbon atoms and more preferably 1 or 2 carbon atoms.
• the hydrocarbon can also be a phenyl or an alkyl-substituted phenyl having from 1 to about 18 carbon atoms and more preferably from 1 to about 12 carbon atoms.
• suitable (A-2) compounds include the various aldehydes and ketones such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde, and the like, as well as acetone, methyl ethyl ketone, ethyl propyl ketone, butyl methyl ketone, glyoxal, glyoxylic acid, and the like.
• Precursors of such compounds which react as aldehydes under reaction conditions of the present invention can also be utilized and include paraformaldehyde, formalin, trioxane and the like. Formaldehyde and its polymers, for example, paraformaldehyde are preferred.
• Mixtures of the various (A-2) reactants also can be utilized.
• the third reactant used in preparing the Mannich base is (A-3) an amine which contains at least one primary or secondary group.
• the amine is characterized by the presence of at least one -N-H group.
• the remaining valences of the above nitrogen atom preferably are satisfied by hydrogen, amino, or organic groups bonded to said nitrogen atom through direct carbon-to-nitrogen linkages.
• the compound may be a hydrocarbyl amine containing from zero to 10 hydroxyl and thiol groups and from 1 to 10 amine groups.
• the amine (A-3) may be represented by the formula wherein R1 is a hydrocarbyl group, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy-substituted hydrocarbyl group, and R2 is hydrogen or R1.
• R1 is a hydrocarbyl group, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy-substituted hydrocarbyl group
• R2 is hydrogen or R1.
• the compounds from which the nitrogen-containing group may be derived include principally ammonia, aliphatic amines, aliphatic hydroxy or thioamines, aromatic amines, heterocyclic amines, or carboxylic amines.
• the amines may be primary or secondary amines and may also be polyamines such as alkylene amines, arylene amines, cyclic polyamines, and the hydroxy-substituted
• amines of these types are methylamine, N-methyl-ethylamine, N-methyl-octylamine, N-cyclohexylaniline, dibutylamine, cyclohexylamine, aniline, di(p-methyl)amine, dodecylamine, octadecylamine, o-phenylenediamine, N,N'-di-n-butyl-p-phenylenediamine, morpholine, piperazine, tetrahydropyrazine, indole, hexahydro-1,3,5-triazine, 1-H-1,2,4-triazole, melamine, bis-(p-aminophenyl)methane, phenyl-methylenimine, menthanediamine, cyclohexamine, pyrrolidine, 3-amino-5,6-diphenyl-1,2,4-triazine, ethanolamine, diethanolamine, quinoned
• the hydroxyl-containing amines can be characterized by the formula wherein each of the R1 groups is independently a hydrogen atom or a hydrocarbyl, hydroxyhydrocarbyl, aminohydrocarbyl, or hydroxyaminohydrocarbyl group provided that at least one of R1 is a hydroxyhydrocarbyl or a hydroxyaminohydrocarbyl group, R2 is an alkylene group, and x is an integer from 0 to about 5.
• Examples of specific hydroxyl-containing amines include ethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, di-(3-hydroxypropyl)-amine, 3-hydroxybutyl-amine, 4-hydroxybutyl-amine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-1-propanol, 3-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, diethanolamine, di-(2-hydroxypropyl)-amine, N-(hydroxypropyl)-propylamine, N-(2-hydroxyethyl)-cyclohexylamine, 3-hydroxycyclopentylamine, N-hydroxyethyl piperazine, and the like.
• the amine (A-3) also may be a polyamine conforming for the most part to the formula wherein n is an integer preferably less than about 10, A is a substantially hydrocarbon or hydrogen group, and the alkylene group is preferably a lower alkylene group having less than about 8 carbon atoms.
• the alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, and also the cyclic and the higher homologues of such amines such as piperazines and amino-alkyl-substituted piperazines.
• ethylene diamine triethylene tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene)-triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 4-methyl-imidazoline, 1,3-bis(2-aminoethyl)imidazoline, pyrimidine, 1-(2-aminopropyl)piperazine.
• Hydroxyalkyl-substituted alkylene amines i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are contemplated for use herein.
• the hydroxyalkyl-substituted alkylene amines are preferably those in which the alkyl group is a lower alkyl group, i.e., having less than about 6 carbon atoms.
• amines examples include N-(2-hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl) ethylene diamine, 1-(2-hydroxyethyl)piperazine, monohydroxypropyl-substituted diethylene triamine, 1,4-bis(2-hydroxypropyl)piperazine, di-hydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxypropyl)tetramethylene diamine, and 2-heptadecyl-1(2-hydroxyethyl)imidazoline.
• the preparation of the Mannich compounds can be carried out by a variety of methods known in the art.
• One method involves adding the (A-1) hydroxyl containing aromatic compound, the (A-2) saturated aldehyde or ketone, and the (A-3) amine compound to a suitable vessel and heating to carry out the reaction.
• Reaction temperatures from about ambient to about the decomposition temperature of any component or the Mannich product can be utilized.
• water is drawn off as by sparging.
• the reaction is carried out in solvent such as an aromatic type oil.
• the amount of the various reactants utilized is desirably on a mole to mole basis of (A-1) and (A-2) for each (A-3) secondary amino group or on a two-mole basis of (A-1) and (A-2) for each (A-3) primary amino group, although larger or smaller amounts can also be utilized.
• the hydroxyl containing aromatic compound (A-1) and the amine compound (A-3) are added to a reaction vessel.
• the aldehyde or ketone (A-2) is generally rapidly added and the exothermic reaction generated is supplemented by mild heat such that the reaction temperature is from about 60°C to about 90°C. Desirably the addition temperature is less than the boiling point of water, otherwise, the water will bubble off and cause processing problems.
• the water by-product is removed in any conventional manner as by evaporation thereof which can be achieved by applying a vacuum, applying a sparge, heating or the like.
• a nitrogen sparge is often utilized at a temperature of from about 100°C to about 130°C. Naturally, higher or lower temperatures can be utilized.
• the reaction is generally carried out in a solvent.
• Any conventional solvent can be utilized such as toluene, xylene or propanol.
• various oils are utilized such as an aromatic type oil, 100 neutral oil, etc.
• amounts of the various (A-1), (A-2) and (A-3) components are set forth above. However, other amounts and ratios can be utilized. For example, for each primary amino group of (A-3) from about 0.5 to about 6 moles of (A-1) and (A-2) can be utilized and more desirably from about 1.8 to about 2.2 moles of (A-1) and (A-2). For each secondary amino group of (A-3), from about 0.2 to about 2 moles of (A-1) and (A-2) can be utilized and more desirably from about 0.9 to about 1.1 moles of (A-1) and (A-2).
• the metal chelating agent (Ch) also may be at least one amino acid compound of the formula wherein R1 is hydrogen or a hydrocarbyl group; R2 is R1 or an acyl group; R3 and R4 are each independently hydrogen or lower alkyl groups; and z is 0 or 1.
• the hydrocarbyl groups R1 and R2 may be any one of the hydrocarbyl groups as broadly defined above. In particular, R1 and R2 are alkyl, cycloalkyl, phenyl, alkyl-substituted phenyl, benzyl or alkyl-substituted benzyl groups.
• R1 and R2 of Formula VI are each independently alkyl groups containing from 1 to about 18 carbon atoms, cyclohexyl, phenyl, phenyl groups containing alkyl substituents containing from 1 to about 12 carbon atoms at the 4-position of the phenyl ring, benzyl or benzyl having an alkyl group of from 1 to about 12 carbon atoms at the 4-position of the phenyl ring.
• R1 in Formula VI is a lower alkyl such as a methyl group
• R2 is an alkyl group having from about 4 to about 18 carbon atoms.
• R1 is as defined above and R2 is an acyl group.
• R2 is an acyl group.
• the acyl group generally can be represented by the formula R2'C(O)- wherein R2' is an aliphatic group containing up to about 30 carbon atoms. More generally, R2' contains from about 12 to about 24 carbon atoms.
• Such acyl-substituted amino carboxylic acids are obtained by reaction of an amino carboxylic acid with a carboxylic acid or carboxylic halide.
• a fatty acid can be reacted with an amino carboxylic acid to form the desired acyl-substituted amino carboxylic acid.
• Acids such as dodecanoic acid, oleic acid, stearic acid, linoleic acid, etc., may be reacted with amino carboxylic acids such as represented by Formula VI wherein R2 is hydrogen.
• R3 and R4 in Formula VI are each independently hydrogen or lower alkyl groups. Generally, R3 and R4 will be independently hydrogen or methyl groups, and most often, R3 and R4 are hydrogen.
• z may be 0 or 1.
• the amino acid compound is glycine, alpha-alanine and derivatives of glycine and alpha-alanine.
• the amino carboxylic acid (VI) is beta-alanine or derivatives of beta-alanine.
• amino acid compounds of Formula VI which are useful as metal chelating agents in the present invention can be prepared by methods described in the prior art, and some of these amino acids are available commercially. For example, glycine, alpha-alanine, beta-alanine, valine, arginine, and 2-methyl-alanine.
• the preparation of amino acid compounds represented by Formula VI where z is 1 is described in, for example, U.S. Patent 4,077,941.
• amines which can be reacted with the unsaturated ester are the following: dicyclohexylamine, benzylmethylamine, aniline, diphenylamine, methylethylamine, cyclohexylamine, n-pentylamine, diisobutylamine, diisopropylamine, dimethylamine, dodecylamine, octadecylamine, N-n-octylamine, aminopentane, sec-butylamine, propylamine, etc.
• the metal chelating agent (Ch) also may be at least one beta-diketone.
• the beta-diketone is characterized by the formula R-C(O)-CH2-C(O)-R1 (VII) wherein R and R1 are each independently hydrocarbyl groups.
• the hydrocarbyl groups may be aliphatic or aromatic hydrocarbyl groups as defined above. Among the aliphatic hydrocarbyl groups, the lower hydrocarbyl groups containing up to about 7 carbon atoms are preferred.
• R1 and R2 groups include methyl, ethyl, phenyl, benzyl, etc.
• specific examples of beta-diketones include acetyl acetone and benzoyl acetone.
• the metal chelating agent (Ch) also may be at least one phenolic compound of the formula wherein each R is a hydrocarbyl group; and X is CH2, S, or CH2OCH2.
• each R is independently an aliphatic group which generally contains from about 4 to about 20 carbon atoms.
• R groups examples include butyl, hexyl heptyl, 2-ethyl-hexyl, octyl, nonyl decyl, dodecyl, etc.
• the phenolic compounds represented by Formula VIII can be prepared by reacting the appropriate substituted phenol with formaldehyde or a sulfur compound such as sulfur dichloride.
• formaldehyde or a sulfur compound such as sulfur dichloride.
• the bridging group X is CH2.
• bis-phenolic compounds bridged by the group CH2OCH2 can be formed as a result of the reaction.
• a bis-phenolic compound is formed which is bridged by a sulfur atom.
• the metal chelating agent (Ch) may be an aromatic difunctional compound of the formula wherein R1 is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta position relative to X, and X and Y are each independently OH, NH2, NR2, COOR, SH, or C(O)H wherein R is hydrogen or a hydrocarbyl group.
• R1 is a hydrocarbyl group containing 1 to about 100 carbon atoms
• n is an integer from 0 to 4
• Y is in the ortho or meta position relative to X
• X and Y are each independently OH, NH2, NR2, COOR, SH, or C(O)H wherein R is hydrogen or a hydrocarbyl group.
• Specific examples of useful aromatic difunctional compounds represented by Formula IX have been given above.
• the metal chelating agent (Ch) is an amino phenol.
• the amino phenol is an ortho-amino phenol which may contain other substituent groups such as hydrocarbyl groups.
• a mixture of 157 parts of dodecylphenol and 296 parts of mineral oil is prepared, and to this mixture there is added with stirring, 20.6 parts of a commercial polyamine mixture by responding to diethylenetriamine over a period of 30 minutes.
• 20.6 parts of formalin solution (37% paraformaldehyde) dropwise over a period of one hour while maintaining the reaction temperature below about 96°C.
• the mole ratio of phenol to formaldehyde to amine is 3:3:1.
• the reaction mixture is maintained at a temperature of about 96-99°C for 3.5 hours.
• the water formed in the reaction is removed by distillation under vacuum and thereafter cooled to room temperature.
• the product that is obtained is a red oil.
• Dodecylphenol 1000 parts is charged to a reaction vessel and the temperature is adjusted to 38-55°C whereupon 290 parts of sulfur dichloride is added at a rate to maintain the temperature of the reaction mixture below about 66°C.
• the mixture is blown with nitrogen while heating to 143-149°C, and the mixture is maintained at this temperature until the direct acid number is less than 1.5 acid.
• the mixture is cooled to about 95-100°C while adding about 788 parts of diluent oil.
• the reaction mixture is filtered, and the filtrate is the desired sulfur-coupled phenol.
• a mixture of 526 parts (2.01 mole) of dodecylphenol, 44.1 parts (1.34 moles) of paraformaldehyde flakes, 60 parts of toluene, 90 parts of isopropyl alcohol and 3 parts of caustic soda and 12 parts of water is prepared with stirring.
• the mixture is heated to a temperature of about 115°C over a period of about 20 minutes to remove solvent.
• the mixture then is maintained at 145°C while sparging with nitrogen until no additional solvent can be removed from the mixture.
• the residue is the desired methylene-coupled phenolic product.
• a reaction flask is charged with 3240 parts of dodecyl phenol, 2772 parts of hydro-refined naphthenyl oil and 380 parts of ethanolamine. The mixture is stirred and heated to 72°C, and 372 parts paraformaldehyde are rapidly charged thereto. The reaction temperature is increased to a maximum of 147°C over a 3-hour period while water is removed by sparging with nitrogen. A total of 218 parts of water is collected versus a theoretical amount of 230 parts. The mixture is cooled and the product is removed.
• the complexes of the present invention may be prepared by the reaction of one or more titanium or zirconium compounds represented by the formula M(OR) 4 wherein M and R are as described above, with one or more of the metal chelating agents (Ch) described above.
• the metal chelating compound (Ch) displaces one or more of the R groups depending upon the number of equivalents of metal chelating agent utilized per equivalent of titanium or zirconium compound. For example, if one equivalent of the metal compound M(OR)4 is reacted with two equivalents of the metal chelating agent, then x and y in Formula I are each 2. Similarly, if one equivalent of the metal compound M(OR)4 is reacted with three equivalents of the metal chelating agent, then x is 1 and y is 3 in Formula I.
• the reaction between the metal compound M(OR)4 and the metal chelating agent is affected by mixing the reactants. In many instances, the reaction is exothermic and external heating of the mixture is unnecessary.
• the alcohol (ROH) formed in the reaction may be left in the reaction product or removed by distillation.
• the reaction mixture can be heated to an elevated temperature to increase the rate of reaction and/or to remove the alcohol found.
• the reaction mixture is heated at an elevated temperature (optionally under reduced pressure) until substantially no additional alcohol can be recovered by distillation.
• the reaction mixture may be purged with nitrogen or other inert gas in order to facilitate the removal of the alcohol.
• Example A To the reaction product obtained in Example A, there is added 56 parts of tetra-n-butyl titanate. This mixture is heated to 110°C at 25-30 mm. Hg. and thereafter at 150°C at 16 mm. Hg. while removing n-butanol. The residue is cooled to 60° and filtered through a filter aid. The filtrate is the desired product.
• a mixture is prepared containing 107 parts of tetra-i-propyl titanate and 520.2 parts of a 50% xylene solution of the Mannich base prepared as in Example A except that the dodecylphenol is replaced by an equivalent amount of heptylphenol and the reaction is conducted in xylene.
• the mixture Upon addition of the titanium compound, the mixture turns red, and an exotherm to about 42°C in five minutes is observed.
• the mixture is stirred for 1.3 hours at a temperature of 35-40°C.
• a mixture of 100 parts of isopropyl alcohol, 47.4 parts of a commercial alcohol mixture containing an average of about 9 to about 11 carbon atoms (Neodol 91, Shell Chemical), and 85.2 parts of tetraisopropyl titanate is prepared, and 30 parts of 2,4-pentanedione is added with stirring. An exothermic reaction occurs, and after a period of about several minutes, the solvent is removed by stripping. The residue, a yellow oil, is the desired titanium complex.
• a mixture of 163 parts of tetraisopropyl titanate and 406 parts of Sarkosyl O (N-oleoyl sarkosine available from Ciba Geigy) is prepared, purged with nitrogen, and heated with stirring under vacuum to a temperature of about 55°C (about 80 mm. Hg.). The mixture then is heated to about 100°C at 70-90 mm. Hg. over a period of about 1.6 hours until no further distillate is obtained. The mixture is vacuum stripped at 100°C at about 10-20 mm. Hg. The residue is filtered at about 100°C through a filter aid. The filtrate is the desired titanium complex.
• Sarkosyl O N-oleoyl sarkosine available from Ciba Geigy
• Example B Into a reaction vessel there is added 604 parts of the product of Example B, and the product is stirred and heated to about 160°C in a nitrogen atmosphere. After cooling to about 60°C, 101 parts of tetraisopropyl titanate is added over a period of 5 minutes. The mixture is heated to 145°C for one hour, and 80 parts of a colorless liquid is removed by distillation. A residue is the desired titanium complex.
• Example C To the methylene-coupled phenolic product prepared in Example C, there is added 138 parts of a diluent oil followed by the addition of 152 parts of tetraisopropyl titanate dropwise over a period of about 6 minutes. The temperature of the reaction mixture is maintained at about 150°C for about one hour while removing about 128 parts of isopropanol. The residue is the desired titanium complex containing 20% diluent oil.
• a mixture of 363 parts of butyl diethanolamine and 388 parts of a diluent oil is prepared and heated to about 100°C at 120 mm. Hg. whereupon 100 parts of tetraisopropyl titanate and 225 parts of tetra-n-butyl titanate are added in three portions with stirring. After reducing the pressure to 20-25 mm. Hg. at 65°C, the mixture is stirred for 1.2 hours as butyl and isopropyl alcohols are removed by distillation. The residue is filtered, and the light red-orange filtrate is the desired titanium complex containing 10.6% titanium (theory, 10.2).
• titanium and zirconium compounds and in particular, the titanium and zirconium complexes described above are particularly useful in fuel compositions which comprise a major proportion of a normally liquid fuel, usually a hydrocarbonaceous petroleum distillate fuel such as diesel fuels, distillate fuels, heating oils, residual fuels, transfer fuels, and motor gasoline as defined by ASTM Specification D-439.
• Diesel fuels may be defined broadly as fuels having a suitable boiling range and viscosity for use as a fuel in a diesel-type engine. Fuels containing alcohols and esters also are included within the definition of a diesel fuel.
• the boiling range of a diesel fuel can vary from about an ASTM boiling range of about 120°C to about 425°C, more desirably from about 140°C to about 400°C, and most often between about 200°C to about 370°C.
• diesel fuels are within grades 1D, 2D and 4D, and usually, the diesel fuels have viscosities of from about 1.3 to about 24.0 centistokes at 40°C.
• the diesel fuel compositions which are treated in accordance with the present invention will contain an amount of the titanium and zirconium compounds described above which is effective in lowering the ignition temperature of exhaust particulates formed on burning of the diesel fuel.
• the fuel compositions generally will contain from 1 to about 5000 parts of titanium or zirconium per million parts of fuel, and most often, the diesel fuels will contain from about 1 to about 500 parts of titanium or zirconium per million parts of fuel.
• the titanium and zirconium compounds be complexes that are hydrolytically stable. Any of the metal chelating agents described above can be included in the complexes of the present invention provided that the complex is hydrolytically stable.
• the Ch group is one or more of the chelate groups identified as A, B, C, D or E above.
• the fuel compositions can contain, in addition to the compositions of this invention, other additives which are well known to those of skill in the art.
• antiknock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes (e.g., ethylene dichloride and ethylene dibromide), deposit preventers or modifiers such as triaryl phosphates, dyes, cetane improvers, antioxidants such as 2,6-ditertiary-butyl-4-methyl-phenol, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants and anti-icing agents.
• antiknock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes (e.g., ethylene dichloride and ethylene dibromide)
• deposit preventers or modifiers such as triaryl
• compositions of this invention are combined with an ashless dispersant in gasoline.
• Suitable ashless dispersants include esters of mono- or polyols and high molecular weight mono- or polycarboxylic acid acylating agents containing at least 30 carbon atoms in the acyl moiety.
• esters are well known to those skilled in the art. See, for example, French Patent 1,396,645; British Patents 981,850; 1,055,337 and 1,306,529; and U.S.
• the weight ratio of the composition of this invention to the aforesaid ashless dispersant is between about 0.1:1 and about 10:1, preferably between about 1:1 and about 10:1.
• the titanium and zirconium compositions of this invention can be added directly to the fuel, or they can be diluted with a substantially inert, normally liquid organic diluent such as naphtha, benzene, toluene, xylene or a normally liquid fuel as described above, to form an additive concentrate.
• a substantially inert, normally liquid organic diluent such as naphtha, benzene, toluene, xylene or a normally liquid fuel as described above, to form an additive concentrate.
• These concentrates generally contain from about 20% to about 90% by weight of the composition of this invention and may contain, in addition one or more other conventional additives known in the art or described hereinabove.

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• 1987
  • 1987-09-25 DE DE8787906884T patent/DE3781557T2/de not_active Expired - Fee Related
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