EP0290534B1 - Metallsalzbrennstoffzusatz, stabilisiert mit einem thiadiazol - Google Patents

Metallsalzbrennstoffzusatz, stabilisiert mit einem thiadiazol Download PDF

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Publication number
EP0290534B1
EP0290534B1 EP87907567A EP87907567A EP0290534B1 EP 0290534 B1 EP0290534 B1 EP 0290534B1 EP 87907567 A EP87907567 A EP 87907567A EP 87907567 A EP87907567 A EP 87907567A EP 0290534 B1 EP0290534 B1 EP 0290534B1
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Prior art keywords
fuel
additive
hydrocarbon
independently
metal salt
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EP0290534A1 (de
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Casper John Dorer
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Lubrizol Corp
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Lubrizol Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2443—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds
    • C10L1/2456—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds sulfur with oxygen and/or nitrogen in the ring, e.g. thiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • 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 the field of fuel additives and fuel compositions and concentrates containing such additives. More specifically, the invention relates to additive compositions comprised of an overbased transition metal salt of an organic acid and a hydrocarbyl substituted dimercaptothiadiazole as well as a means for stabilizing a fuel which includes a combustion promoter by including a thiadiazole additive in the fuel.
  • transition metal-containing compounds both organic and inorganic, are known to be used for treatments for hydrocarbon systems. These compounds may be included within a hydrocarbon system such as a lubricant (e.g. greases, lubricating oils and the like) and hydrocarbon fuels of both the solid and normally liquid type. Such transition metal-containing compounds are effective catalysts for promoting combustion. Further, the components can promote conversion to cohesion films in the case of paints; and with respect to fuels such compounds can improve combustion properties.
  • a lubricant e.g. greases, lubricating oils and the like
  • hydrocarbon fuels of both the solid and normally liquid type.
  • Such transition metal-containing compounds are effective catalysts for promoting combustion. Further, the components can promote conversion to cohesion films in the case of paints; and with respect to fuels such compounds can improve combustion properties.
  • U.S. Patent 4,505,718 to Dorer disclosed that the inclusion of transition metal salts of an organic acid can give property improving results when included within lubricants and fuels. Specifically, the inclusion of such metal salts into fuels can improve fuel efficiency. Specifically, manganese salt compounds are effective in reducing the combustion temperature of soot in diesel soot traps. However, it was also found that the inclusion of such metal salts into systems such as fuels sometimes causes deleterious as well as beneficial effects. Among the deleterious effects are the promotion of sediment and sludge in that a fuel containing a high concentration of a manganese salt is unstable with respect to oxidation. Sediments and sludges were found to form within such fuels.
  • Cost is often a tremendously important factor in that all compounds or compositions included within lubricating oils and fuels must be relatively inexpensive to make it commercially feasible to include the compounds within such hydrocarbon systems.
  • compounds and compositions themselves being inexpensive by combining certain ones in certain proportions it may be possible to eliminate the inclusion of other compounds or compositions which were previously required to obtain acceptable performance. This further reduces costs and increases the desirability of using such a combination.
  • metal salts to improve efficiency was mentioned above with respect to U.S. Patent 4,162,986. More recently such salts were found to be useful in connection with the spontaneous regeneration of a soot trap present in the exhaust system of a diesel engine. Such soot traps may be included in the exhaust system of a diesel engine in order to trap exhaust particles. A build-up of such particulate material could clog the system and prevent the engine from operating.
  • the metal salts By including the metal salts in the fuel, the combination temperature of the soot in the trap is effectively lowered and the trap is spontaneously regenerated and clogging is prevented.
  • concentration of the metal in the fuel is increased, the oxidative stability of the fuel is decreased. This decreased stability results in the formation of sediments and sludge during storage.
  • a fuel additive composition and more specifically an additive comprising:
  • the additive includes: (A) an overbased transition metal salt of a carboxylic acid; (B) a compound represented by the general formula II: wherein R, and R 2 are independently hydrocarbyl; and a third component (C) which is a hydrocarbon-soluble ashless dispersant.
  • a fuel composition comprising a major amount of a liquid hydrocarbon fuel and a minor amount of an additive comprising:
  • a method for stabilizing a liquid hydrocarbon based diesel fuel composition comprised of a major amount of a liquid hydrocarbon diesel fuel and a minor fuel efficiency improving amount of an overbased manganese salt of a carboxylic acid, comprising:
  • the invention also includes a means for stabilizing a fuel against oxidation during storage when the fuel is treated with a high concentration of metal salts (A).
  • An advantage of this invention is that the additive is inexpensive to produce.
  • the essence of the invention is a fuel additive composition which is comprised of (A) an overbased transition metal salt of an organic acid; (B) a compound represented by the general formula 1: wherein R 1 and R 2 are independently hydrocarbyl and x and y are independently an integer in the range from about 1 to about 8. More preferably x and y are each 2 and R 1 and R 2 are independently selected from the group consisting of alkyl, aryl, and aralkyl containing at least 6 carbon atoms. Still more preferably R 1 and R 2 are independently an alkyl moiety containing from about 6 to about 24 carbon atoms.
  • R 1 and R 2 are independently selected from the group consisting of t-octyl, dodecyl, nonyl, decyl and ethylhexyl.
  • a particularly preferred (B) is bis-2,5-tert-octyldithio-1,3,4-thiadiazole and 2-dodecyldithio-5-mercapto-1,3,4-thiadiazole.
  • the additive components (A) and (B) are used in combination with a hydrocarbon-soluble ashless dispersant (C).
  • the component (A) is preferably a carboxylic acid salt of titanium or manganese.
  • transition metals in the organic salts of this invention are chosen from the group consisting of copper, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and mixtures of two or more of these Manganese salts and salts containing manganese in a mixture with other metals are most commonly used. Often salts containing only manganese are used. Lead salts can also be used but are not preferred due to environmental related reasons.
  • the organic acids used to make the transition metal salts used in this invention contain carbon atoms and include carboxylic acids, particularly those containing from 1 to 30 carbon atoms, sulfonic acids, particularly those containing an aromatic ring structure (e.g., benzene ring) substituted with one or more alkyl groups of 4 to about 22 carbon atoms, and phosphorus acids, containing within their structures one or more organic groups of 1 to about 30 or more carbon atoms.
  • carboxylic acids particularly those containing from 1 to 30 carbon atoms
  • sulfonic acids particularly those containing an aromatic ring structure (e.g., benzene ring) substituted with one or more alkyl groups of 4 to about 22 carbon atoms
  • phosphorus acids containing within their structures one or more organic groups of 1 to about 30 or more carbon atoms.
  • carboxylic, sulfonic and phosphorus acids are well known to the art.
  • the carboxylic acids can be mono- or polycarboxylic acids (if the latter, typically they are di- or tricarboxylic acids).
  • Monocarboxylic acids include C 1 - 7 lower acids (acetic, propionic, etc.) and high Cg + acids (e.g., octanoic, decanoic, etc.) as well as the well known fatty acids of from about 12-30 carbon atoms.
  • the fatty acids are often mixtures of straight and branched chain acids containing, for example, from 5 to about 30% straight chain acids and about 70 to about 95% (mole) branched chain acids. Other commercially available fatty acid mixtures containing much higher proportions of straight chain acids are also useful.
  • Mixtures produced from dimerization of unsaturated fatty acid can also be used, as well as naphthenic acids and various cyclic acids.
  • Higher carboxylic acids include the well known dicarboxylic acids made by alkylating maleic anhydride or its derivatives. The products of such reactions are hydrocarbon substituted succinic acids, anhydrides, and the like. Lower molecular weight dicarboxylic acids, such as the polymethylene bridged acids (glutaric, adipic, and the like), can also be used to make the salts of this invention as well as the lower molecular weight substituted succinic acids such as tetrapropenyl succinic acid and its analogs containing up to about C 30 substituted acids.
  • Typical high molecular weight acids are those made by reacting a poly(isobutene) fraction having between 30 and 400 (usually 5-250) carbon atoms with maleic anhydride. Such materials are described in U.S. Patent Nos. 3,172,892, 3,219,666 and 3,272,746 which disclose high molecular weight carboxylic acids.
  • monocarboxylic acids of similar molecular weight can be made by alkylating acrylic acid and its analogs. Mixtures of such acids can also be used.
  • Useful salts can also be made from carbocyclic carboxylic acid and even acidic hydroxy compounds such as alkylated phenols. Such materials are disclosed in U.S. Patent No. 4,100,082, particularly columns 15-17.
  • The'082 patent just identified also describes a number of sulfonic acids, which are useful in making the salts of this invention, particularly columns 12-14.
  • Transition metal salts made from phosphorus acids are also useful in this invention. Such phosphorus acids have been disclosed in a number of U.S. patents and other literature. Exemplary of the former is U.S. Patent No. 4,191,658 which discloses phosphorus acid salts of the formula wherein M is a transition metal described above; each R 1 and R is hydrocarbon radical; each of X 1 , X 2 , x 3 and X 4 is oxygen or sulfur; and each of a and b is 0 or 1.
  • the organic acids used to make the salts of this invention ae carboxylic acid, sulfonic acid, or mixtures thereof.
  • a particularly useful group of such salts are those described in U.S. Patent No. 4,162,986 to Alkaitis et al, which discloses metallic organic compositions and, particularly, transition metal salts of organic acids which are useful in the composition of the present invention.
  • the present invention has been found to provide particularly advantageous results when the metal salt is an overbased manganese salt used as the only metal salt and present in a relatively high concentration.
  • transition metal salts used in this invention are often overbased; that is, they contain more than sufficient metal to neutralize the acid present. In other words, they contain in excess of one quivalent of metal per equivalent of acid derived moiety.
  • Such salts are known in the art. See, for example, the just cited U.S. Patent No. 4,162,986 as well as the following U.S.
  • the component (B) is represented by the general formula I: wherein R 1 and R 2 are independently hydrogen or a hydrocarbyl and x and y are independently an integer in the range from about 1 to about 8. More preferably x and y are each 2 and R 1 and R 2 are independently selected from the group consisting of alkyl, aryl, and aralkyl containing at least 6 carbon atoms. Still more preferably R 1 and R 2 are independently an alkyl moiety containing from about 6 to about 24 carbon atoms. Some particularly preferred forms of R 1 and R 2 are independently selected from the group consisting of t-octyl, dodecyl, nonyl, decyl and ethylhexyl.
  • a particularly preferred (B) is bis-2,5-tert-octyldithio-1,3,4-thiadiazole and mixtures of such compounds with a similar compound wherein one or both of the (-S, tert- octyl) moieties is replaced with hydrogen and 2-dodecyldithio-5-mercapto-1,3,4-thiadiazole and mixtures of such compounds with a structurally similar compound where one or both of the (-S, dodecyl) moieties is replaced with hydrogen.
  • hydrocarbyl or “hydrocarbon-based” denote a radical having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention.
  • radicals include the following:
  • alkyl-based radical and the like have meaning analogous to the above with respect to alkyl and aryl radicals and the like.
  • radicals are usually hydrocarbon. Some radicals may be described as lower hydrocarbon, the word “lower” denoting radicals containing up to seven carbon atoms. Such radicals are generally lower alkyl or aryl radicals, most often alkyl.
  • the thiadiazole compound (B) is used in combination with the metal salt (A) in order to stabilize the fuel against oxidation during storage without destroying the combustion improving effect of (A).
  • ashless dispersants useful in the present invention are known to the art and are those dispersants commonly used in lubricants based on oils of lubricating viscosity and hydrocarbon fuels such as normally liquid hydrocarbon fuels. Ashless dispersants are those which leave little or no metallic residue or ash on combustion. Generally, this means that they are substantially metal free though they may contain, in addition to carbon, oxygen, hydrogen and often, nitrogen elements such as phosphorus, sulfur, boron etc.
  • the ashless dispersants of the present invention contain only C, H, O and N.
  • ester type dispersants can contain only C, H, and O.
  • More complex ashless dispersants, while still metal free, may also contain other elements, such as sulfur, boron, phosphorus, and the like.
  • the ashless dispersants used in this invention are of the nitrogen-containing or nitrogen-free ester type.
  • hydrocarbon-soluble ashless dispersants are:
  • acylating agents e.g., carboxylic acid or anhydride
  • amino compound such as amine, polyamine, or other compounds containing an -NH-group.
  • Typical acylating agents include the substituted succinic acids described above and in the '082 patent.
  • Other useful acylating agents have been described in detail in any other patents, such as U.S. Pat. No. 4,234,435 which describes in detail both acylating agents and amino-containing and non-amino containing compounds which can be used to prepare ashless dispersants.
  • acylated ashless dispersants useful in the present invention can be either the high or low molecular weight type. In addition to portions from amino compounds, they may also incorporate portions from mono and poly-alcohols, including amino hydroxy compound groups such as the well known amino alcohols.
  • Typical ashless dispersants include those made from alkylene polyamines having 2 to 7 amino groups and 1 to 6 alkylene groups, each containing 2 to 4 carbon atoms. The commercially available ethylene polyamines are useful reagents in this regard.
  • Lower molecular weight acylated nitrogen-containing compounds are also useful as dispersants in the compositions of this invention.
  • Such compounds are made from the aforedescribed amino compounds and mono and dicarboxylic acid acylating agents containing about 12 to about 20 carbon atoms.
  • Such dispersants often contain imidazoline groups and are known to the art; see, for example, U.S. Pat. Nos. 3,405,064 and 3,240,575.
  • esters are made by reacting the aforedescribed acylating agents (e.g., poly(isobutene) succinic anhydride with polyols and monoalcohols and are well known; see for example, U.S. Pat. No. 3,522,179.
  • acylating agents e.g., poly(isobutene) succinic anhydride with polyols and monoalcohols and are well known; see for example, U.S. Pat. No. 3,522,179.
  • Hydrocarbyl substituted amines useful as ashless dispersants are known in the art; see for example, U.S. Pat. Nos. 3,275,554,3,438,757,3,454,555, and 3,565,804. A discussion of such materials also appears in the aforementioned '082 patent.
  • Condensates made from reacting a penol, aldehyde (such as formaldehyde) and amino compounds (such as those described above) are useful as ashless dispersants in the compositions of this invention.
  • These materials are often generically known as Mannich condensates. Generally, they are made from reacting a hydrocarbon substituted phenol (e.g., an alkylated phenol having an alkyl group of about 34-400 carbon atoms), formaldehyde and an amino or polyamino compound having at least one -NH-group.
  • a hydrocarbon substituted phenol e.g., an alkylated phenol having an alkyl group of about 34-400 carbon atoms
  • formaldehyde and an amino or polyamino compound having at least one -NH-group e.g., an alkylated phenol having an alkyl group of about 34-400 carbon atoms
  • hydrocarbon-soluble compositions of this invention are made by combining (A) one or more of the aforedescribed transition metal salts of organic acids with (B) at least one of the aforedescribed hydrocarbon-soluble ashless dispersants.
  • hydrocarbon soluble in describing this invention means that the material in question has a solubility at 25°C. of at least 0.0001 parts by weight in the hydrocarbon system in which it is to function.
  • the combination of the materials (A) and (B) can be effected in any convenient manner. Usually, it is advantageous to avoid combining the salt and the dispersant directly since precipitation problems can thus be avoided.
  • the dispersant or the salt with an inert, solvent diluent and then combine this material with the other and/or auxiliary agents.
  • the solvent/diluents used in the composition of this invention are usually hydrocarbyl in nature although they may contain small amounts of other hereto elements and are often highly aromatic to promote solubility.
  • Auxiliary agents used in the compositions of this invention include dyes, anti-oxidants, metal deactivators, and, particularly, demulsifying agents which inhibit the tendency of the dispersant and/or the salt to promote emulsion formations in the vehicles it is used to treat, such as fuel, oils, lubricants and the like.
  • demulsifying agents are known; see, for example, Encyclopedia of Chemical Technology-Kirk-Othmer, Volume 8, pages 151 et seq. and Volume 19, pages 507 et seq. (1965).
  • Typical demulsifying agents are surface active agents containing hydrophilic and lipophilic portions in the molecule. Such agents are often made by reacting a hydroxy compound, such as a phenol or alcohol, with materials such as ethylene oxide and propylene oxide and their mixtures in various proportions.
  • compositions of this invention are used to treat lubricants based on lubricating oils of lubricating viscosity and hydrocarbon fuels.
  • lubricating oils are typically hydrocarbon in nature although they may contain non-hydrocarbyl portions, such as a synthetic ester, ether, and similar oils.
  • the fuels treated with the compositions of this invention include both solid and normally liquid fuels.
  • the solid fuels are coal, shale, peat, wood, organic refuse, charcoal and the like.
  • Liquid fuels encompass the lighter petroleum fractions such as gasoline, kerosene, and the like, as well as other fractions such as middle distillate fuel oils.
  • middle distillate fuel oils which can be treated with the compositions in this invention include No. 1, 2, and 4 fuel oils as defined by NASI/ASTM Standard D-396-79 and other such materials. Combinations of such fuel oils with straight run, vacuum run, and other specially treated residual oils can also be advantageously treated with the combinations of the present invention.
  • the concentration of the compositions of this invention in the treated lubricant or oil compositions is such that the treated lubricant or oil compositions contain about 1-500, preferably 5-350 ppm (by weight) transition metal * from component (A).
  • the thiadiazole component (B) of the invention is generally added in an amount proportional to the amount of component (A) such that the weight ratio of (A):(B) is in the range of about (1-20):(1-20).
  • the dispersant (C) is generally added in an amount so as to provide a weight ratio of (A):(B):(C) of about (1-20):(1-20):(2--40) and more preferably about (1):(1):(2).
  • the component (C) is generally added so as to provide a composition which includes about 5-1000, preferably 10-800 ppm (by weight) ashless dispersant.
  • the composition is used to produce a transition metal concentration at about 10-400 ppm (by weight) and ashless dispersant concentration of about 15--450 ppm (by weight).
  • a liquid fuel composition will generally contain about 0.05 to about 7.5 grams metal/gal (13.21-1981.50 g/m 3 ) of fuel, more preferably 0.15 to about 1.5 grams metal/gal (39.63-396.30 g/m 3 ) and most preferably about 0.75 grams metal/gal (198.15 g/m 3 ).
  • the most preferred metal salt (A) used is an overbased manganese salt which is most preferably present with both (B) and (C).
  • the concentration of the Mn is generally described in terms of Mn/gal (Mn/ m 3 ) of fuel. It is difficult to describe the preferred ranges for the amount of manganese in that the results desired vary. For example, to increase the amount of soot burnt out of a soot trap the amount of manganese might be raised beyond the ranges indicated above.
  • Such high concentrations of manganese e.g. 5-20 grams/gal (1321.00-5248.01 g/m 3 )
  • a known ashless acylated nitrogen-containing dispersant may be prepared by reacting a mixture of poly(isobutene) substituted succinic anhydride acylating agent (having a substituent with a number average molecular weight equal to about 1,000) with a commercial mixture of ethylene polyamines averaging in composition triethylamine tetra-amine. Carry out the reaction in aromatic solvent/diluent with the proportion of acid to polyamine, by weight, of approximately 100 to 9; remove water and other low boiling products and impurities by heating to give the desired ashless dispersant having a nitrogen content of about 2% (by weight).
  • a hydrocarbon-soluble composition may be prepared by combining by weight, the following: (1) an overbased manganese carboxylate (containing 40% by weight Mn) -10.82 parts, (2) the ashless dispersant (of Example 1) 14.43 parts, (3) a first demulsifier -0.18 parts, (4) a second demulsifier -0.14 parts, (5) an aromatic solvent -74.43 parts, and (6) a thiadiazole compound 10 parts.
  • the above combination may be made by using the aromatic solvent in such a way as to avoid direct combination of the concentrated carboxylate and ashless dispersant.
  • the combination has a specific gravity at 15.6° of 0.94, a pour point of -57°C, and a manganese content of 3.8 ⁇ 4.6 percent by weight.
  • An additive composition of the present invention may be formed by adding 10 parts by weight of an over based manganese carboxylate (A); 10 parts by weight of a thiadiazole and 20 parts by weight of a dispersant (C) of Example 1.
  • A over based manganese carboxylate
  • C dispersant
  • a suitable (A) is sold by Mooney Chemical Company as Mooney 910
  • suitable (B) compounds include bis 2,5-tert-octyldithio-1,3,4,-thiadiazole and/or 2-dodecyldithio-5-mercapto-1,3,4-thiadiazole.
  • the composition of Example 2 may be used to treat a typical commercially available No. 2 middle distillate fuel oil.
  • the treatment level is 1 part composition to 4600 parts by weight of fuel oil. This treatment level is equivalent to 10.7 parts per million manganese in the fuel.
  • the treated fuel may be used to operate a commercial boiler and compared with use of untreated fuel in the same boiler under comparable conditions.
  • the use of the compositions of this invention in the fuel, as described above, are believed to produce an efficiency improvement as reflected by reduced fuel consumption.
  • a diesel fuel oil composition can be prepared by adding component (A) to the fuel in the form of Mooney 910 as present in LZ 8220 (a product of the Lubrizol Corporation) so as to provide g/gal (g/m 3 ) as shown in table 1) in the fuel and then adding the thiadiazole in the form of Amoco 140 so as to provide component (B) in the fuel in an amount as shown in table I.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Claims (11)

1. Treibstoffzusatz, umfassend:
(A) ein überbasisches Übergangsmetallsalz einer organischen Säure; und
(B) eine Verbindung der allgemeinen Formel I:
Figure imgb0013
in der R1 und R2 unabhängig voneinander Wasserstoffatome oder Kohlenwasserstoffreste bedeuten und x und y unabhängig voneinander ganze Zahlen im Wert von 1 bis 8 darstellen; und
(C) ein kohlenwasserstofflösliches aschefreies Dispersant.
2. Zusatz nach Anspruch 1, wobei x und y jeweils 2 sind und R1 und R2 unabhängig voneinander einen Alkylrest mit etwa 6 bis etwa 24 Kohlenstoffatomen bedeuten.
3. Zusatz nach Anspruch 1 oder 2, wobei R1 und R2 unabhängig voneinander t.-Octyl-, Dodecyl-, Nonyl-, Decyl- oder Ethylhexylgruppen bedeuten.
4. Zusatz nach einem der vorangehenden Ansprüche, wobei (B) Bis-2,5-tert.-octyldithio-1,3,4-thiadiazol ist.
5. Zusatz nach einem der Ansprüche 1 bis 3, wobei (B) 2-dodecyldithio-5-mercapto-1,3,4-thiadiazol ist.
6. Zusatz nach einem der Ansprüche 1, 2, 3, 4 oder 5, wobei die organische Säure eine Carbonsäure und das Metall Titan oder Mangan ist.
7. Treibstoffzusammensetzung, umfassend eine größere Menge eines flüssigen Kohlenwasserstoff-Treibstoffs und eine geringere Menge eines Zusatzes, der umfaßt:
(A) ein überbasisches Übergangsmetallsalz einer organischen Säure; und
(B) ein Gemisch von Verbindungen der allgemeinen Formel I:
Figure imgb0014
in der R1 und R2 unabhängig voneinander Wasserstoffatome oder Kohlenwasserstoffreste bedeuten und x und y unabhängig voneinander ganze Zahlen im Bereich von 1 bis 8 darstellen, mit der Maßgabe, daß mindestens ein Teil von (B) Verbindungen einschließt, in denen x 1 ist und R ein Wasserstoffatom bedeutet; und
(C) ein kohlenwasserstofflösliches aschefreies Dispersant in Form eines Derivats einer substituierten Bernsteinsäure, wobei die Substituentengruppen von einem Polyalkylen abgeleitet sind, gekennzeichnet durch einen Mn-Wert von 500 bis 10 000 und einem Mw/Mn-Wert von 1,0 bis 4,0.
8. Treibstoffzusammensetzung nach Anspruch 7, in der der flüssige Kohlenwasserstoff-Treibstoff ein Dieseltreibstoff ist, (A) ein überbasisches Mangan-Metallsalz einer Carbonsäure ist, das Gemisch von (B) mindestens einen Teil von (B) einschließt, der eine dialkylsubstituiertes Thiadiazol ist, wobei die Alkylreste 6 bis 24 Kohlenstoffatome enthalten, und wobei (A) in einer Menge von 10 bis 8000 ppm vorhanden ist und (B) in einer Menge von 10 bis 200 ppm vorhanden ist.
9. Verfahren zur Stabilisierung einer Dieseitreibstoff-Zusammensetzung auf der Basis eines flüssigen Kohlenwasserstoffs, die von einer größeren Menge eines flüssigen Kohlenwasserstoff-Dieseltreibstoffs und einer kleineren, den Treibstoff wirksam verbessernden Menge eines überbasischen Mangansalzes einer Carbonsäure umfaßt wird, umfassend:
Zugabe zu dem Treibstoff von einer Verbindung der allgemeinen Formel (II):
Figure imgb0015
in der R1 und R2 unabhängig voneinander Alkyl-, Aryl- oder Aralkylreste mit mindestens 6 Kohlenstoffatomen bedeuten; und
Zugabe eines kohlenwasserstofflöslichen aschefreien Dispersants in Form eines Derivats einer substituierten Bernsteinsäure.
10. Verfahren nach Anspruch 9, wobei das Gewichtsverhältnis von (Mangansalz):(Verbindung der Formel (11)):(Dispersant) im Bereich von (1-20):(1-20):(2-40) liegt.
11. Verfahren zur Herstellung eines Treibstoffzusatzes nach einem der Ansprüche 1 bis 6, umfassend das Vermischen von
(A) einem überbasischen Übergangsmetallsalz einer organischen Säure; und
(B) einer Verbindung der allgemeinen Formel I:
Figure imgb0016
in der R1 und R2 unabhängig voneinander Wasserstoffatome oder Kohlenwasserstoffreste bedeuten und x und y unabhängig voneinander ganze Zahlen im Bereich von 1 bis 8 sind; und
(C) eine kohlenwasserstofflöslichen aschefreien Dispersant.
EP87907567A 1986-11-06 1987-10-29 Metallsalzbrennstoffzusatz, stabilisiert mit einem thiadiazol Expired - Lifetime EP0290534B1 (de)

Priority Applications (1)

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AT87907567T ATE59201T1 (de) 1986-11-06 1987-10-29 Metallsalzbrennstoffzusatz, stabilisiert mit einem thiadiazol.

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US92806286A 1986-11-06 1986-11-06
US928062 1986-11-06

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EP0290534B1 true EP0290534B1 (de) 1990-12-19

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US4964880A (en) * 1989-06-09 1990-10-23 Exxon Research & Engineering Company Distillate fuels containing mono alkyl substituted derivatives of thiadiazoles
CA2118618C (en) * 1993-03-30 2000-08-15 Marc-Andre Poirier Distillate fuel composition containing combination of copper corrosion inhibitors
CN1122702C (zh) 1998-12-29 2003-10-01 中国石油化工集团公司 一种烃类催化裂化硫转移助剂及其使用方法
US6403725B1 (en) 1999-08-20 2002-06-11 The Lubrizol Corporation Metal containing dispersant polymers from condensation of polymers containing acidic group with overbased compositions containing reactive nucleophilic group
US6617287B2 (en) 2001-10-22 2003-09-09 The Lubrizol Corporation Manual transmission lubricants with improved synchromesh performance
US6573223B1 (en) 2002-03-04 2003-06-03 The Lubrizol Corporation Lubricating compositions with good thermal stability and demulsibility properties
EP1344812A1 (de) * 2002-03-13 2003-09-17 Infineum International Limited Überbasisches Metallsalz enthaltende Dieselkraftstoffzusatzzusammensetzungen zur Partikelfalleverbesserung
JP2004035882A (ja) * 2002-07-03 2004-02-05 Infineum Internatl Ltd 粒状物トラップ改良のための過塩基化金属塩ディーゼル燃料添加剤組成物
US9481841B2 (en) 2004-12-09 2016-11-01 The Lubrizol Corporation Process of preparation of an additive and its use
WO2019036285A1 (en) 2017-08-16 2019-02-21 The Lubrizol Corporation LUBRICATING COMPOSITION FOR HYBRID ELECTRIC VEHICLE TRANSMISSION
WO2019136052A1 (en) 2018-01-04 2019-07-11 The Lubrizol Corporation Boron containing automotive gear oil
US10808198B2 (en) 2019-01-16 2020-10-20 Afton Chemical Corporation Lubricant containing thiadiazole derivatives

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US3663561A (en) * 1969-12-29 1972-05-16 Standard Oil Co 2-hydrocarbyldithio - 5 - mercapto-1,3,4-thiadiazoles and their preparation
US4505718A (en) * 1981-01-22 1985-03-19 The Lubrizol Corporation Organo transition metal salt/ashless detergent-dispersant combinations

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JPH01501232A (ja) 1989-04-27
EP0290534A1 (de) 1988-11-17
AU8273787A (en) 1988-06-01
WO1988003551A1 (en) 1988-05-19
JP2512512B2 (ja) 1996-07-03
AU598329B2 (en) 1990-06-21
ZA878274B (en) 1988-05-03

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