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(11) | EP 0 290 534 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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METAL SALT FUEL ADDITIVE STABILIZED WITH A THIADIAZOLE METALLSALZBRENNSTOFFZUSATZ, STABILISIERT MIT EINEM THIADIAZOL ADDITIF POUR CARBURANT, CONSTITUE D'UN SEL METALLIQUE ET STABILISE AVEC UN THIADIAZOLE |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
[0001] 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.
[0002] A number of 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.
[0003] 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. Accordingly, the use of such metal salts can cause dewposits which interfere with the storage and transport of oil by promoting corrosion as well as interfering with pumps, meters and associated equipment. Accordingly, it was suggested within U.S. Patent No. 4,505,718 to include an ashless dispersant preferably in the form of an acylated nitrogen-containing dispersant in combination with the transition metal salt in an attempt to eliminate the formation of the sediment and sludge.
[0004] Prior to the disclosure by U.S. Patent No. 4,505,718 it had been known to include various types of transition metal salts into hydrocarbon systems such as fuels as disclosed by U.S. Patent No. 4,162,986 to Alkitis etal. Further the inclusion of acylated nitrogen-containing dispersants into hydrocarbyl systems was previously known as indicated within U.S. Patent No. 4,000,082. However, prior to the disclosure within the '718 patent the improved results obtained by including the dispersant in combination with the transition metal salt within a fuel composition was not known.
[0005] The literature includes literally hundreds of different disclosures of various compounds and compositions which have been found to be useful as used in connection with hydrocarbon systems such as lubricating oils and fuels. (See for example the citation of patents listed in U.S. Patent 4,505,718). One type of compound which is known to be used in connection with certain types of hydrocarbon containing systems is a dimercaptothiadiazole. Such compounds may be included within hydrocarbon systems in order to act as elemental sulfur scavengers as disclosed within U.S. Patent No. 3,840,549.
[0006] Although numerous compounds and compositions are disclosed as being used in connection with hydrocarbon systems such as lubricating oils and fuels, from time to time it is found that particular combinations of these compounds or compositions improves the properties of the resulting products. However, most combinations would tend to result in an undesirable interaction of the components. An example of a desirable combination was discussed above with respect to U.S. Patent No. 4,505,718 wherein the conventional dispersant was used in connection with the transition metal salt in order to prevent the formation of sediments and sludge. The discovery of the usefulness of such combinations of known components can result in an extremely useful and commercially successful product. The reasons for this include (1) the relatively low cost; and (2) prior acceptability of such compounds and compositions within similar systems. 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. In addition to the 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.
[0007] The use of 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. 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. However, as the 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.
[0008] According to one aspect of the present invention there is provided a fuel additive composition and more specifically an additive comprising:
(A) an overbased transition metal salt of an organic acid; and
(B) a compound represented by the general formula 1:
wherein R1 and R2 are independently hydrogen or a hydrocarbyl and x and y are independently an integer
in the range of from about 1 to about 8; and
(C) a hydrocarbon-soluble ashless dispersant. which are generally present in a liquid hydrocarbon based fuel. A preferred form of the fuel composition of the invention is comprised of a major amount of a liquid hydrocarbon diesel fuel and a property improving amount of the additive. A property improving amount of the additive is an amount sufficient to reduce or eliminate the formation of sludge and sediment and/or reduce the rate of formation of sludge and sediment while reducing the ignition temperature of the soot in a soot trap of a diesel engine exhaust system. The reduced ignition temperature is obtained by adding a metal salt (A) and the reduced sludge is obtained by adding a thiadiazole compound (B).
[0009] 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 R2 are independently hydrocarbyl; and a third component (C) which is a hydrocarbon-soluble ashless dispersant.
[0010] According to another aspect of the present invention there is provided a fuel composition comprising a major amount of a liquid hydrocarbon fuel and a minor amount of an additive comprising:
(A) an overbased transition metal salt of an organic acid; and
(B) a mixture of compounds represented by the general formula I:
wherein R1 and R2 are independently hydrogen or a hydrocarbyl and x and y are independently an integer
in the range of from about 1 to about 8 with the proviso that at least some (B) includes
compounds wherein X is 1 and R, is hydrogen; and
(C) a hydrocarbon-soluble ashless dispersant in the form of a derivative of a substituted succinic acid and the substituent groups are derived from a polyalkylene characterized by a Mn value of about 500 to 10,000 and Mw/Mn value of about 1.0 to about 4.0.
[0011] According to a further aspect of the present invention there is provided 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:
adding to the fuel a compound represented by the general structural formula (II):
wherein R1 and R2 are independently selected from alkyl, aryl and aralkyl containing at least 6 carbon
atoms; and
adding a hydrocarbon-soluble ashless dispersant in the form of a derivative of a substituted succinic acid.
[0012] 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).
[0014] We have also found it possible to stabilize a diesel fuel containing a transition metal salt.
[0016] We have further found it possible to increase fuel efficiency while preventing the formation of sludge and sediment in the fuel.
[0017] Various aims, advantages, preferred features and embodiments of the invention will now be described by way of non-limiting example.
[0018] 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 R1 and R2 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 R1 and R2 are independently selected from the group consisting of alkyl, aryl, and aralkyl containing at least 6 carbon atoms. Still more preferably R1 and R2 are independently an alkyl moiety containing from about 6 to about 24 carbon atoms. Some particularly preferred forms of R1 and R2 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).
(A) The transition metal salts
[0021] The 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.
[0022] 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.
[0023] Such 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 C1-7 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.
[0024] 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 C30 substituted acids. Higher molecular weight substituted succinic anhydrides, acids, and analogs useful in making the salts of this invention have been described in a number of patents, particularly those dealing with acylated compounds useful as dispersants. 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.
[0025] Other monocarboxylic acids of similar molecular weight can be made by alkylating acrylic acid and its analogs. Mixtures of such acids can also be used.
[0026] 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.
[0027] 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.
[0028] 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 R1 and R is hydrocarbon radical; each of X1, X2, x3 and X4 is oxygen or sulfur; and each of a and b is 0 or 1.
[0029] Typically, 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.
[0030] It should be noted that the 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. Patent Nos.: 3,827,979 to Piotrowski et al., 3,312,618 to LeSuer et al., 3,616,904 and 3,616,905 to Asseff et al., 2,595,790 to Norman et a/., and 3,725,441 to Murphy et al, which disclose overbased salts of organic acids.
[0031] The component (B) is represented by the general formula I:
wherein R1 and R2 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 R1 and R2 are independently selected from the group consisting of alkyl, aryl, and aralkyl containing at least 6 carbon atoms. Still more preferably R1 and R2 are independently an alkyl moiety containing from about 6 to about 24 carbon atoms. Some particularly preferred forms of R1 and R2 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.
[0032] Also, as used herein, the terms "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. Such radicals include the following:
(1) Hydrocarbon radicals; that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic radicals, and the like, as well as cyclic radicals wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic radical). Such radicals are known to those skilled in the art; examples are
(2) Substituted hydrocarbon radicals; that is, radicals containing non-hydrocarbon substituents, in the context of this invention, do not alter the predominantly hydrocarbon character of the radical. Those skilled in the art will be aware of suitable substituents; examples are
(3) Hetero radicals; that is, radicals which, while predominently hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.
[0033] Terms such as "alkyl-based radical," and the like have meaning analogous to the above with respect to alkyl and aryl radicals and the like.
[0034] The 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.
[0035] 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).
(C) The ashless dispersants
[0036] The 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.
[0037] Generally, the ashless dispersants of the present invention contain only C, H, O and N. Occasionally, ester type dispersants (see below) 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. Typically, however, the ashless dispersants used in this invention are of the nitrogen-containing or nitrogen-free ester type.
[0038] Many types of ashless dispersants are known; see, for example, the descriptions in "Lubricant Additive Recent Developments" and the earlier "Lubricant Additives", both by M. W. Ranney, published by Noyes Data Corporation, Park Ridge, N.J., 1978 and 1973, respectively.
[0039] Among the more commonly available and, therefore, useful hydrocarbon-soluble ashless dispersants are:
[0040] (1) Acylated nitrogen-containing dispersants such as those described in U.S. Pat. No. 4,100,082 particularly at columns 18-20.
[0041] These dispersants are made by reaction of an acylating agent (e.g., carboxylic acid or anhydride) with an 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.
[0042] The 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.
[0043] 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.
[0044] High molecular weight acylated nitrogen-containing ashless dispersants wherein an amino acid and alcohol compound (or amino-alcohol) both are acylated are also known and useful in the compositions of this invention; these are described in U.S. Pat. No. 4,136,043.
[0046] These esters, as indicated above, 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.
[0047] (3) 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.
[0049] 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 number of such materials are known to the art; see for example, the aforementioned '082 patent, particularly columns 21-22, which discloses Mannich condensates and methods for making them.
[0050] The 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. It should be noted that "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. Therefore, it is common to combine either 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. Many such 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.
[0051] As indicated above, the compositions of this invention are used to treat lubricants based on lubricating oils of lubricating viscosity and hydrocarbon fuels. The lubricating oils are typically hydrocarbon in nature although they may contain non-hydrocarbyl portions, such as a synthetic ester, ether, and similar oils.
[0052] The fuels treated with the compositions of this invention include both solid and normally liquid fuels. Among 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. Typically 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.
[0053] 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. In fuel oils, particularly, 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).
[0054] * The concentration of salt is expressed in terms of metal alone, but can be described in terms of grams of metal/gal of fuel. A liquid fuel composition will generally contain about 0.05 to about 7.5 grams metal/gal (13.21-1981.50 g/m3) of fuel, more preferably 0.15 to about 1.5 grams metal/gal (39.63-396.30 g/m3) and most preferably about 0.75 grams metal/gal (198.15 g/m3).
[0055] 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/ m3) 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/m3)) are particularly unstable and require the addition of similarly higher amounts of (B) and (C).
Example 1
[0056] 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).
Example 2
[0057] 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.
[0058] 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.
[0059] (1) Sold by the Mooney Chemical Company as Mooney 910. (3) An Ethoxylated/Propylated Hydroxy Compound available as TOLAD 285 from The Tretolite Division of Petrolite Corporation, St. Louis, Missouri. (4) An Ethoxylated Propoxylated Pentaerythritol available as NALCO 5RD-648 from the Nalco Chemical Company of Houston, Texas. (5) HISOL Aromatic Solvent having a Kauri Gum-Butanol Value of 95. (6) Sold by Amoco as AMOCO 150 (other Amoco products which might be useful include AMOCO 158 and AMOCO 153).
Example 3
[0060] 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 suitable (A) is sold by Mooney Chemical Company as Mooney 910 and suitable (B) compounds include bis 2,5-tert-octyldithio-1,3,4,-thiadiazole and/or 2-dodecyldithio-5-mercapto-1,3,4-thiadiazole.
Example 4
[0061] 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.
Examples 5-10
[0062] 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/m3) 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.
(A) an overbased transition metal salt of an organic acid; and
(B) a compound represented by the general formula I:
wherein R1 and R2 are independently hydrogen or a hydro-carbyl and x and y are independently an integer
in the range of from 1 to 8; and
(C) a hydrocarbon-soluble ashless dispersant.
(A) an overbased transition metal salt of an organic acid; and
(B) a mixture of compounds represented by the general formula I:
wherein R1 and R2 are independently hydrogen or a hydro-carbyl and x and y are independently an integer
in the range of from 1 to 8 with the proviso that at least some (B) includes compounds
wherein X is 1 and R, is hydrogen; and
(C) a hydrocabon-soluble ashless dispersant in the form of a derivative of a substituted succinic acid and the substituent groups are derived from a polyalkylene characterized by a Mn value of 500 to 10,000 and a Mw/Mn value of 1.0 to 4.0.
adding to the fuel a compound represented by the general structural formula (II):
wherein R1 and R2 are independently selected from alkyl, aryl and aralkyl containing at least 6 carbon
atoms; and
adding a hydrocarbon-soluble ashless dispersant in the form of a derivative of a substituted succinic acid
(A) an overbased transition metal salt of an organic acid; and
(B) a compound represented by the general formula I:
wherein R1 and R2 are independently hydrogen or a hydrocarbyl and x and y are independently an integer
in the range of from 1 to 8; and
(C) a hydrocarbon-soluble ashless dispersant.
(A) ein überbasisches Übergangsmetallsalz einer organischen Säure; und
(B) eine Verbindung der allgemeinen Formel I:
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.
(A) ein überbasisches Übergangsmetallsalz einer organischen Säure; und
(B) ein Gemisch von Verbindungen der allgemeinen Formel I:
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.
Zugabe zu dem Treibstoff von einer Verbindung der allgemeinen Formel (II):
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.
(A) einem überbasischen Übergangsmetallsalz einer organischen Säure; und
(B) einer Verbindung der allgemeinen Formel I:
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.
(A) un sel sur-basifié de métal de transition d'un acide organique; et
(B) un composé représenté par la formule générale I:
dans laquelle R1 et R2 sont indépendamment un hydrogène ou un groupe hydrocarboné et x et y sont indépendamment
un nombre entier dans l'intervalle de 1 à 8; et
(C) un dispersant sans cendre soluble dans les hydrocarbures.
(A) un sel sur-basifié de métal de transition d'un acide organique; et
(B) un mélange de composés représentés par la formule générale I:
dans laquelle R1 et R2 sont indépendamment un hydrogène ou un groupe hydrocarboné et x et y sont indépendamment
un nombre entier dans l'intervalle de 1 à 8, à condition qu'une partie de (B) au moins
renferme des composés dans lesquels x est égal à 1 et R est un hydrogène; et
(C) un dispersant sans cendre soluble dans les hydrocarbures, sous forme d'un dérivé d'un acide succinique substitué et les groupes substituants sont dérivés d'un polyalkylène, caractérisé par une valeur de Mn de 500 a 10 000 et une valeur de Mw/Mn de 1,0 à 4,0.
ajouter au carburant un composé représenté par la formule générale développée (II):
dans laquelle R1 et R2 sont choisis indépendamment parmi les groupes alkyle, aryle et arylalkyle contenant
au moins 6 atomes de carbone; et
ajouter un dispersant sans cendre soluble dans les hydrocarbures sous forme d'un dérivé d'un acide succinique substitué.
(A) d'un sel de métal de transition sur-basifié d'un acide organique; et
(B) d'un composé représenté par la formule générale I:
dans laquelle R1 et R2 sont indépendamment un hydrogène ou un groupe hydrocarboné et x et y sont indépendamment
un nombre entier dans l'intervalle de 1 à 8; et
(C) d'un dispersant sans cendre soluble dans les hydrocarbures.