KR20110069846A - Additives to reduce metal pick-up in fuels - Google Patents

Abstract

The present invention relates to fuel additives, fuel additive compositions and fuel compositions, as well as methods for refueling internal combustion engines, which reduce metal pickup by fuel, wherein the compositions of the present invention comprise at least two or more carboxyl functional groups in acid form. Hydrocarbons substituted with one or more carboxyl functional groups.

Description

ADDITIVES TO REDUCE METAL PICK-UP IN FUELS

The present invention relates to fuel additives, fuel additive compositions and methods of fueling internal combustion engines as well as reducing oxidative metal pickup of fuel.

In the past, there has been some uncertainty regarding the effect of pick-up or solubilization of certain oxidative metals by fuel on engine performance. This problem was generally evaluated in terms of corrosion control. However, there is increasing evidence that metal pickups, such as zinc pickups, may be a problem that can affect engine performance.

Trace amounts of dissolved or soluble metals such as zinc (Zn) and copper (Cu) in fuels, such as diesel fuels, have been found to increase contamination of fuel injectors. These trace metals can be introduced into the fuel distribution system through contamination by the fuel or through pickup (dissolution) of the metal by the fuel from the metal parts that make up part of the fuel distribution system that the fuel contacts. For example, diesel fuel may pick up zinc from the galvanized steel surface in the fuel tank to raise the zinc level of the fuel and consequently accelerate the contamination of the fuel injector discussed above. Zinc and other metals may also be picked up by fuel in contact with the metal-containing surface of the vehicle fuel injector system.

Accordingly, there is a need for fuel additives and fuel compositions that effectively reduce the amount of metal pickup, more particularly zinc pickup, while minimizing the impact on cost and complexity of the additive and fuel composition.

Fuel additives, fuel additive compositions and fuel compositions have been found that reduce the amount of metal pickup observed in fuel compositions. The present invention provides methods for reducing contaminating metal pickups such as zinc pickup in such compositions as well as fuel compositions.

According to the invention, the addition of an additive containing a hydrocarbon substituted with at least two carboxyl functional groups in acid form or at least one carboxyl functional group in anhydride form results in a reduction in the amount of oxidative metal pickup of the fuel composition. Found.

In some embodiments, the substituted hydrocarbon additive is a hydrocarbon substituted acylating agent having at least two carboxyl functional groups in acid or anhydride form.

In some embodiments, the substituted hydrocarbon additive and / or hydrocarbon substituted acylating agent has a di-acid functional group. In another embodiment, the additive is a succinyl acylating agent. In another embodiment that can be used in conjunction with one or more of the embodiments described herein, the hydrocarbon group of the additive is from polyisobutylene.

Metals intended to reduce pickup include Group IV transition metals. In some embodiments, the metal is V, Cr, Mn, Fe, Co, Ni, Cu, Zn or a combination thereof. In some embodiments, the metal may be selected from the group consisting of copper, zinc, iron or combinations thereof. In some embodiments, the oxidizing metal is zinc. In another embodiment, the oxidizing metal to reduce the tendency for the fuel composition to pick up may be any of the metals or metal groups described above except for iron.

In addition, the present invention provides a substituted hydrocarbon additive (a) hydrocarbon substituted succinic anhydride; (b) hydrolyzed hydrocarbon substituted succinic anhydride; Or (c) a method as described above which may be a combination thereof.

In some embodiments, the fuel treated by this method has the potential to pick up oxidic metals to levels of at least 0.5 ppm when in contact with solid materials containing oxidic metals for extended periods of time.

The method of the present invention may also reduce the deposit of the fuel injector in an engine to which the fuel composition of the method is applied.

In addition, the present invention (a) fuel; (b) an additive containing a substituted hydrocarbon additive described herein; And (c) an optional additional performance additive. In addition, the present invention is (a) an optional solvent; (b) substituted hydrocarbon additives described herein; And (c) a fuel additive composition comprising an optional additional performance additive.

Various preferred features and aspects will be described below as non-limiting examples.

Field of invention

The present invention provides a fuel additive, a fuel additive composition, a fuel composition and a method for refueling an internal combustion engine. The present invention provides a method of reducing a metal pick-up, in some embodiments a zinc pick-up, during operation of an internal combustion engine in a fuel composition.

The composition of the present invention can be used in fuel compositions to reduce the tendency to pick up metal from the surface with which the fuel is in contact. The additive compositions of the present invention may also provide similar and / or improved cleanliness when used in fuel compositions, specifically improved engine sediment control. These features improve engine performance, such as, but not limited to, reducing fuel injector contamination, reducing sediment derived engine power losses, reducing sediment derived fuel economy losses, and reducing sediment derived engine emissions.

Substituted Hydrocarbon Additives

Substituted hydrocarbon additives of the present invention include hydrocarbons substituted with at least two carboxyl functional groups in acid form or at least one carboxyl functional group in anhydride form. In some embodiments, the additive is a hydrocarbon substituted with two or more carboxyl functional groups in acid or anhydride form. In another embodiment, the additive is a hydrocarbon-substituted succinyl acylating agent. In another embodiment, the substituted hydrocarbon additive is a dimer acid compound. In another embodiment, the substituted hydrocarbon additives of the present invention comprise a combination of two or more additives described in this section.

The substituted hydrocarbon additives of the present invention, when used in the compositions and methods described herein, reduce the tendency of the fuel compositions in which these additives are used to pick up metal.

Substituted hydrocarbon additives include dimer acids. Dimer acids are diacid polymer types derived from fatty acids and / or polyolefins containing acid functionality, such as the polyalkenes described herein. In some embodiments, the dimeric acids used in the present invention are derived from C10 to C20 polyolefins, C12 to C18 polyolefins and / or C16 to C18 polyolefins.

Substituted hydrocarbon additives include succinic acid, halides, anhydrides and combinations thereof. In some embodiments, the additive is an acid or anhydride, in other embodiments, the additive is an anhydride, and in another embodiment, the additive is a hydrolyzed anhydride. Primary hydrocarbon groups of hydrocarbon and / or hydrocarbon-substituted succinyl acylating agents of substituted hydrocarbon additives generally average at least about 8, about 30, about 35 to up to about 350, or about 200, or about 100 Contains two carbon atoms. In one embodiment, the hydrocarbon group is derived from a polyalkene.

The polyalkenes may be characterized as having Mn (number average molecular weight) of at least about 300. In general, polyalkenes are characterized in that Mn is about 500, about 700, about 800, or even about 900 to up to about 5000, or about 2500, or about 2000, or even about 1500. In another embodiment, n varies between about 300, or about 500, or about 700 and up to about 1200 or about 1300.

Polyalkenes include homopolymers and copolymers of polymerizable olefin monomers having 2 to about 16, about 6 or about 4 carbon atoms. The olefins are monoolefins such as ethylene, propylene, 1-butene, isobutene and 1-octene; Or polyolefinic monomers such as diolefin monomers such as 1,3-butadiene and isoprene. In one embodiment, the copolymer is a homopolymer. One example of a polymer is polybutene. In one case, about 50% of the polybutenes are from isobutylene. Polyalkenes are prepared by conventional procedures.

In one embodiment, the hydrocarbon group is derived from a polyalkene where n is at least about 1300, about 1500, or about 1600 to up to about 5000, about 3000, about 2500, about 2000, or about 1800, and Mw / Mn is from about 1.5 to about 1.8, or about 2, or about 2.5 to about 3.6, or about 3.2. In some embodiments, the polyalkene is polyisobutylene having a molecular weight of 800 to 1200. The preparation and use of substituted hydrocarbons and / or substituted succinyl acylating agents from which hydrocarbons and / or substituents are derived from such polyalkenes is described in US Pat. No. 4,234,435, which is incorporated herein by reference.

In another embodiment, the substituted hydrocarbon and / or succinyl acylating agent reacts the aforementioned polyalkene with excess maleic anhydride such that the number of succin groups for each equivalent of substituents is at least 1.3, or up to about 1.5, or up to about 1.7. Or up to about 1.8 substituted succinyl acylating agents. The maximum number generally does not exceed 4.5, or up to about 2.5, or up to about 2.1, or up to about 2.0. Wherein the polyalkene may be any of the polyalkenes described above.

In another embodiment, the hydrocarbon and / or hydrocarbon group contains about 8, about 10 or about 12 to up to about 40, or about 30, or about 24 or about 20 carbon atoms on average. In one embodiment, the hydrocarbon group contains about 16 to about 18 carbon atoms on average. In another embodiment, the hydrocarbon group is a tetrapropenyl group. In one embodiment, the hydrocarbon group is an alkenyl group.

Hydrocarbons and / or hydrocarbon groups may be derived from one or more olefins or oligomers thereof having about 2 to about 40 carbon atoms. Such olefins are preferably alpha-olefins (sometimes also called mono-1-olefins) or isomerized alpha-olefins. Examples of alpha-olefins include ethylene, propylene, butylene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicocene, 1-docosene, 1-tetracosene and the like. Which may be used commercially available alpha-olefin fraction is a C _{15 -18} alpha-olefins, C _{12 -16} alpha-olefins, C _{14 -16} alpha-olefins, C _{14 -18} alpha-olefins, C _{16 -18} alpha-olefins, C _{16 -20} alpha-olefins, C _{22 -28} alpha-olefins, and the like. According to one embodiment, the olefins are C ₁₆ and C _{16 -18} alpha-olefins. It is also possible to use C ₃₀ + alpha-olefin fractions such as those available from the Gulf Oil Company under the trade name Gulftene. In one embodiment, the olefin monomers comprise ethylene, propylene and 1-butene.

Isomerized alpha-olefins are alpha-olefins converted to internal olefins. Isomerized alpha-olefins suitable for use herein are usually in the form of a mixture of some existing alpha-olefins and internal olefins. Procedures for isomerizing alpha-olefins are known in the art. Briefly, this procedure involves contacting an alpha-olefin with a cation exchange resin at a temperature in the range of about 80 to about 130 ° C. until the desired degree of isomerization is achieved. This procedure is described in U.S. Pat. 4,108,889.

Mono-olefins can be derived from the cracking distillation of paraffin wax. Wax decomposition distillation process is 85% to 90% to produce C _{6 -20} liquid olefins of even and odd straight-chain 1-olefin. The remainder of the cracked and distilled wax olefins consists of internal olefins, branched olefins, diolefins, aromatic compounds and impurities. Produce-distillation of the C _{6 -20} liquid olefins obtained from the wax decomposition distillation process useful in preparing the succinic acylating agent oil (for example, olefins, C _{15 -18} alpha).

Other mono-olefins can be derived from ethylene chain growth processes. This process produces an even number of straight chain 1-olefins from the controlled Ziegler polymerization. Other methods of preparing mono-olefins include chlorination-dehydrochlorination of paraffins and catalytic dehydrogenation of paraffins.

Such procedures for preparing mono-olefins are known to those skilled in the art and are cited for reference to related descriptions of methods for making mono-olefins in "Olefins" in the Encyclopedia of Chemical Technology, Second Edition, Kirk and Othmer, Supplement, Pages 632,657, Interscience Publishers, Div. of John Wiley and Son, 1971.

The succinyl acylating agent may be prepared by mixing the aforementioned olefin, isomerized olefin or oligomer thereof with an unsaturated carboxy acylating agent such as itacone, citracon or male acylating agent at about 160 ° C, about 185 ° C up to about 240 ° C, or about 210 ° C. Prepared by reaction at temperature. Male acylating agents are preferred unsaturated acylating agents. Procedures for preparing acylating agents are known to those skilled in the art and are described, for example, in US Pat. Nos. 3,412,111; And in Ben et al., "The Ene Reaction of Maleic Anhydride With Alkenes", J.C.S. Perkin II (1977), pages 535-537. These documents are incorporated by reference for the disclosure of the procedure for preparing the acylating agents. In one embodiment, the alkenyl group is derived from an oligomer of a lower olefin, ie an olefin containing 2 to about 6, or about 4 carbon atoms. Examples of such olefins include ethylene, propylene and butylene.

The olefin, olefin oligomer or polyalkene may react with the carboxy reagent such that at least one mole of carboxy reagent per mole of olefin, olefin oligomer or polyalkene reacted. It is preferred that an excess of carboxy reagent be used. In one embodiment, this excess is between about 5% and about 25%. In another embodiment, the excess is at least 40%, at least 50%, even at least 70%.

Conditions for the preparation of hydrocarbon-substituted succinyl acylating agents, ie temperatures, shaking, solvents and the like are known to those skilled in the art. Examples of patents describing various procedures for preparing useful acylating agents include US Pat. No. 3,172,892 to Le Suer et al .; 3,215,707 (Rense); 3,219,666 to Norman et al .; 3,231,587 (Rense); 3,912,764 to Palmer; 4,110,349 (Cohen); And 4,234,435 to Meinhardt et al .; And United Kingdom 1,440,219. The specification of these patents is incorporated by reference.

In some embodiments, substituted hydrocarbon additives and / or hydrocarbon substituted succinyl acylating agents suitable for use in the present invention contain diacid functional groups. According to another embodiment which may be used alone or in combination with the foregoing embodiments, the hydrocarbon group of a hydrocarbon substituted succinyl acylating agent is derived from polyisobutylene, and the diacid functional group of this acylating agent is a carboxylic acid group, such as a hydrocarbon substituted succinic acid. Derived from.

In some embodiments, the hydrocarbon substituted acylating agent comprises at least one hydrocarbon substituted succinic anhydride group. In some embodiments, the hydrocarbon substituted acylating agent comprises one or more hydrolyzed hydrocarbon substituted succinic anhydride groups.

In some embodiments, hydrocarbon substituents of the aforementioned acylating agents are derived from homopolymers and / or copolymers containing from 2 to 10 carbon atoms. In some embodiments, the hydrocarbon substituents of any of the aforementioned acylating agents are derived from polyisobutylene.

The fuel additive of the present invention may be solid, semisolid or liquid (oil) depending on the particular alcohol (s) and / or amine (s) used to prepare it. For use as an additive in oily compositions, including lubricating compositions and fuel compositions, it is preferred that the fuel additive is soluble and / or stable dispersible in the oily composition. That is, compositions for example for use in fuels are generally dispersible and / or fuel-soluble that are stable to the fuel to be used. The term "fuel-soluble" as used herein and in the subsequent claims does not necessarily mean that all of the compositions in question must be miscible or soluble in all proportions in all fuels. Rather, it is intended that the composition be soluble in fuel (hydrocarbons, non-hydrocarbons, mixtures, etc.), which means that the solution will act to such an extent that it exhibits one or more desired properties. Likewise, such a "solution" need not be a true solution in the strict physical or chemical sense. Instead, it may be a microemulsion or colloidal dispersion which, for the purposes of the present invention, exhibits properties close enough to a true solution to be compatible in the context of the present invention for practical purposes.

As indicated above, the metal anti-pickup additive of the present invention is useful as an additive for fuels, which may also act as a cleaning agent. The fuel additive of the present invention may be present in the fuel composition at 1 to 10,000 ppm (where ppm is calculated by weight: weight). In other embodiments, the fuel additive is present in the fuel composition in the range of the lowest limits 1, 3, 5, 10, 50, 100, 150, and 200 ppm, the highest limits 10,000, 7,500, 5,000, and 2,500, with any highest limit. May be combined with any of the lowest limits to provide a range of fuel additives present in the fuel composition.

It is contemplated that the additives of the present invention may form salts or other complexes and / or derivatives when they interact with other components of the composition in which they are used. Forms of such additives are also part of the present invention and are included in the embodiments described herein. Some succinyl acylating agents of the present invention and methods for their preparation are disclosed in US Pat. Nos. 5,739,356; 5,777,142; 5,786,490; 5,856,524; 6,020,500 and 6,114,547. Other methods of preparing hydrocarbon substituted acylating agents are described in US Pat. Nos. 5,912,213; 5,851,966; And 5,885,944. In some embodiments, the succinyl acylating agents of the present invention are prepared only by a heat treatment process and / or a chlorine free process as described in EP0355895, which is incorporated by reference.

Fuel additive composition

The fuel additive composition of the present invention comprises the fuel additive described above and further comprises a solvent and / or one or more additional performance additives. Such additive compositions, also known as additive concentrates and / or concentrates, can be used to prepare fuel compositions by adding an additive composition to a fuel that has not been added.

Suitable solvents for use in the present invention include hydrocarbon solvents that provide compatibility and / or homogeneity of the additive compositions and facilitate their handling and delivery, and may include fuels as described below. The solvent may be an aliphatic hydrocarbon, an aromatic hydrocarbon, an oxygen-containing composition or a mixture thereof. In some embodiments, the flash point of the solvent is generally at least about 25 ° C. In some embodiments, the hydrocarbon solvent is aromatic naphtha having a flash point of 62 ° C. or higher or aromatic naphtha having a flash point of 40 ° C. or kerosene having a 16% aromatic content having a flash point of 62 ° C. or higher.

Aliphatic hydrocarbons include various naphtha and kerosene boiling fractions, most of which are aliphatic constituents. Aromatic hydrocarbons include benzene, toluene, xylene and various naphtha and kerosene boiling fractions, most of which are aromatic components. Alcohols are usually aliphatic alcohols having about 2 to 10 carbon atoms and include ethanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutyl alcohol, amyl alcohol and 2-methyl-1-butanol.

The oxygen containing composition may comprise alcohols, ketones, esters of carboxylic acids, glycols and / or polyglycols, or mixtures thereof. In one embodiment of the present invention the solvent is substantially or completely free of sulfur, in some cases having a sulfur content of up to 50 ppm, 25 ppm, up to 18 ppm, up to 10 ppm, up to 8 ppm, up to 4 ppm or up to 2 ppm. The solvent may be present in the additive concentration composition at 0-99% by weight, in other cases at 3-80%, or 10-70% by weight. The friction modifiers and additional performance additives of the present invention, each provided or provided together, may be present in the additive concentration composition at 0.01 to 100% by weight, and in other cases 0.01 to 95%, 0.01 to 90%, or 0.1 to 80%. It may be present in weight percent.

As allowed by the above ranges, in one embodiment the additive concentrate may comprise the fuel additive of the present invention and may be substantially free of any additional solvent. In this embodiment, the additive concentrate containing the fuel additive of the present invention is pure in that it does not contain any additional solvent added to improve the material handling of the concentrate, such as viscosity.

In various aspects of the invention, the fuel composition, fuel additive concentrate and / or fuel additive itself are substantially free of or at least one component selected from the group consisting of sulfur, phosphorus, sulfated ash, and combinations thereof, and According to an embodiment, the fuel composition is one or all of the above components of 50 ppm or less, 20 ppm, 15 ppm or less, 10 ppm or less or 1 ppm or less.

In one aspect of the invention, the additive concentrate composition or fuel composition containing the fuel additive of the present invention may be prepared by mixing the components of the composition at room temperature to elevated temperature, usually up to 60 ° C. until the composition is homogeneous.

Additional performance additives that may be included in the additive compositions of the present invention are described below.

fuel

The fuel composition of the present invention comprises the fuel additive and liquid fuel described above and is useful for refueling an internal combustion engine. In addition, the fuel may be a component of the additive composition described above.

It is well known in the art that many types of commercial fuels, in particular commercial diesel fuels and / or biofuels, have the ability to pick up or solubilize some oxidizing metal when in direct contact with sensitive metal surfaces. There is also evidence that most, but not all, fuels, particularly commercial diesel fuels, tend to be slightly metallic pick-up. It is also known that many fuel additives can increase the tendency of the fuel to pick up oxidative metals in the fuel and fuel additive composition in which it is used. The present invention reduces the propensity to pick up oxidizing metals in such fuel and fuel additive compositions.

In some embodiments, fuels suitable for use in the present invention include any commercial fuel, in some embodiments any commercial diesel fuel and / or biofuel. According to another aspect, fuels suitable for use in the present invention include any commercial fuel with room for metal pickup, and in some embodiments, any commercial diesel fuel and / or biofuel with room for metal pickup. Include.

In another embodiment, a fuel suitable for use in the present invention is any fuel that is capable of picking up an oxidizing metal to a level of at least 0.5 ppm when contacted with an oxidizing metal containing solid material for a long time, or any diesel fuel and / or It is a biofuel. In some embodiments, the exposure time involved is at least 72 hours, at least 48 hours, or at least 24 hours.

The present invention includes fuel compositions that may contain fuel and fuel additive concentrate compositions. The fuel used in the composition may or may not be inclined to pick up the oxidizing metal and may actually be any fuel or combination thereof described in this application. The fuel used in the composition need not be a fuel such as a fuel to which the additives of the present invention can be added in the methods described herein. That is, the additive of the present invention may be present in a composition further comprising a fuel. This fuel may or may not exhibit a propensity to pick up oxidizing metals. The additive-containing composition may then be added to the fuel and / or fuel additive composition. The identity of the fuel present in the composition is independent of the identity of the optional fuel component present in the additive containing composition. The oxidative metal pickup propensity of the fuel and / or fuel additive composition may be a result of the nature of the fuel and / or the nature of one or more additives present in the fuel and / or additive composition. The addition of additive-containing compositions, as described in the methods and compositions of the present invention, results in a reduction in the oxidative metal pickup propensity of the fuel and / or fuel additive compositions.

The following description of suitable fuel types for use in the present invention relates to fuels that may be present in the additive containing compositions of the present invention, as well as fuels and / or fuel additive compositions to which the additive containing compositions may be added.

Fuels suitable for use in the present invention are not overly limited. In general, suitable fuels are generally liquid at ambient conditions, such as room temperature (20-30 ° C.). The liquid fuel may be a hydrocarbon fuel, a non-hydrocarbon fuel or a mixture thereof.

The hydrocarbon fuel may be petroleum distillate, including gasoline as defined in ASTM specification D4814 or diesel fuel as defined in ASTM specification D975. In one embodiment, the liquid fuel is gasoline, and in another embodiment, the liquid fuel is unleaded gasoline. In another embodiment, the liquid fuel is diesel fuel. The hydrocarbon fuel may be a hydrocarbon produced by the gas-liquid method, such as a hydrocarbon produced by a method such as the Fischer-Tropsch method. In some embodiments, the fuel used in the present invention is diesel fuel, biodiesel fuel or combinations thereof.

Non-hydrocarbon fuels may be oxygen-containing compositions, also often referred to as oxygenates, examples of which include alcohols, ethers, ketones, esters of carboxylic acids, nitroalkanes or mixtures thereof. Non-hydrocarbon fuels may include, for example, methanol, ethanol, methyl t-butyl ether, methyl ethyl ketone, transesterified oils and / or fats from plant and animal, such as rapeseed methyl ester and soy methyl ester, and nitromethane. Can be.

Mixtures of hydrocarbon fuels and non-hydrocarbon fuels may include, for example, gasoline and methanol and / or ethanol, diesel fuel and ethanol, and diesel fuel and transesterified vegetable oils such as rapeseed methyl ester and other bio-derived fuels. In one embodiment, the liquid fuel is an emulsion in which water is emulsified in hydrocarbon fuels, non-hydrocarbon fuels or mixtures thereof. In some embodiments of the present invention, the liquid fuel may have a sulfur content of 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less or 10 ppm or less.

The liquid fuel of the present invention is generally present in the fuel composition in a major content of at least 95% by weight, in other embodiments at least 97% by weight, at least 99.5% by weight, or at least 99.9% by weight.

Additive performance additives

The additive compositions and fuel compositions of the present invention may further comprise one or more additional performance additives. Additional performance additives may be added to the fuel composition depending on various factors, including the type of internal combustion engine and the type of fuel used in the engine, the quality of the fuel, and the operating conditions under which the engine operates.

In some embodiments, the additional performance additives described herein can increase the tendency of the fuel composition to pick up metal, such as zinc. In such circumstances the use of the present invention can reduce and / or eliminate the aforementioned effects of additive additives.

Additional performance additives include antioxidants such as hindered phenols or derivatives thereof and / or diarylamines or derivatives thereof; Corrosion inhibitors; And / or other detergent / dispersion additives, such as polyetheramines or nitrogen-containing detergents such as PIB amine dispersants, quaternary salt dispersants and succinimide dispersants such as derivatives of succinimide dispersants, such as 4, in addition to the fuel additives of the present invention. Secondary ammonium salts .

In addition, the additive performance additives may include low temperature flow enhancers such as esterified copolymers of maleic anhydride and styrene and / or copolymers of ethylene and vinyl acetate; Foam inhibitors and / or antifoams such as silicone fluids; Anti-emulsifiers such as polyalkoxylated alcohols; Lubricants such as fatty carboxylic acids; Metal deactivators such as, but not limited to, aromatic triazoles or derivatives thereof such as benzotriazoles; And / or valve seat corrosion additives such as alkali metal sulfosuccinate salts.

Suitable antifoaming agents also include organic silicones such as polydimethyl siloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates and polymethacrylates, trimethyl-trifluoro-propylmethyl siloxane and the like.

Additional additives also include biocides; Antistatic agents, anti-ice agents, glidants such as mineral oil and / or poly (alpha-olefins) and / or polyethers, and combustion modifiers such as octane or cetane modifiers.

Fuel additive compositions of the present invention and additional performance additives that may be present in the fuel composition are also optionally in the presence of known esterification catalysts, with amines and / or alcohols and dicarboxylic acids (eg tartaric acid) and / or tricarboxylic acids (eg Diesters, diamides, ester-amides and ester-imide friction reducing agents prepared by reacting citric acid). Such friction reducers, often derived from tartaric acid, citric acid or derivatives thereof, may be derived from amines and / or alcohols branched such that the friction reducer itself is a significant amount of branched hydrocarbon groups present in the structure. Can be. Examples of suitable branched alcohols used to prepare such friction reducing agents include 2-ethylhexanol, isotridecanol, gerbe alcohol or mixtures thereof.

Additional performance additives may include high TBN nitrogen containing dispersants such as poly (alkyleneamine) and succinimide dispersants which are the condensation products of hydrocarbon-substituted succinic anhydrides. Succinimide dispersants are very well known in the lubricant formulation art. Such molecules are generally derived from the reaction of polyamines with alkenyl acylating agents, and various moieties are possible between the two moieties, such as simple imide structures as well as various amide and quaternary ammonium salts. Succinimide dispersants are described in more detail in US Pat. Nos. 4,234,435 and 3,172,892. Such materials may also contain ester linkages or ester functional groups.

Another class of nitrogen-containing dispersants is Mannich bases. It is a substance formed by the condensation of high molecular weight, alkyl substituted phenols, alkylene polyamines and aldehydes such as formaldehyde. Such materials are described in more detail in US Pat. No. 3,634,515.

Other nitrogen-containing dispersants generally include polymeric dispersion additives that are hydrocarbon-based polymers that contain nitrogen-containing polar functional groups that impart dispersing properties to the polymer.

Amines are generally used to prepare high TBN nitrogen-containing dispersants. One or more poly (alkyleneamines) may be used, which may include one or more poly (ethyleneamines) having 3 to 5 ethylene units and 4 to 6 nitrogens. Such materials include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA). Such materials are generally commercially available as mixtures of various isomers containing various numbers of ethylene units and nitrogen atoms, as well as various isomeric structures, such as various cyclic structures. Poly (alkyleneamines) may likewise comprise relatively high molecular weight amines known in the art as ethylene amine still bottoms.

Additional performance additives include (i) (a) a condensation product of a compound having an oxygen or nitrogen atom capable of condensation with the acylating agent and a hydrocarbon-substituted acylating agent and further condensation product having a tertiary amino group; (b) polyalkene-substituted amines having at least one tertiary amino group; And (c) at least one compound having a tertiary amino group and selected from the group consisting of Mannich reaction products prepared from the reaction of hydrocarbon-substituted phenols, aldehydes and amines; And (ii) a quaternizing agent suitable for converting tertiary amino groups of compound (i) to quaternary nitrogen, wherein the quaternizing agent is dialkyl sulfate, benzyl halide, hydrocarbon substituted carbonate; hydrocarbon epoxide in combination with acid or Quaternary salts containing the reaction product of the above).

In one embodiment, the quaternary salt comprises (i) at least one compound selected from the group consisting of polyalkene-substituted amines bearing at least one tertiary amino group and / or Mannich reaction products bearing tertiary amino groups; And (ii) the reaction product of the quaternization agent.

In another embodiment, the quaternary salts are (i) the product of the reaction of succinic anhydride with an amine; And (ii) the reaction product of the quaternization agent. In this embodiment, the succinic anhydride may be derived from polyisobutylene and anhydride, wherein the polyisobutylene has a number average molecular weight of about 800 to about 1600. In some embodiments, the succinic anhydride is chlorine free.

In some embodiments, the hydrocarbon substituted acylating agents of component (i) (a) described above are long-chain hydrocarbons, generally such as (1) monounsaturated C ₄ to C ₁₀ dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid; (2) derivatives of (1), such as anhydrides or C ₁ to C ₅ alcohol derived monoesters or diesters of (1); (3) monounsaturated C ₃ to C ₁₀ monocarboxylic acids such as acrylic acid and methacrylic acid; Or (4) a polyolefin substituted with a monounsaturated carboxylic acid reactant, such as a derivative of (3), such as an ester derived from C ₁ to C ₅ alcohols of (3), with formula (I) (R ¹ ) (R ¹ ) C = Is a reaction product of any compound containing an olefin bond represented by C (R ¹ ) (CH (R ¹ ) (R ¹ )), wherein each R ¹ is independently hydrogen or a hydrocarbon group.

Olefin polymers for reaction with monounsaturated carboxylic acids may include polymers containing a major molar content of C ₂ to C ₂₀ , such as C ₂ to C ₅ monoolefins. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-1 or styrene. Polymers include homopolymers such as polyisobutylene as well as copolymers of two or more of these olefins, such as copolymers of ethylene and propylene; Copolymers of butylene and isobutylene; It may be a copolymer of propylene and isobutylene. Other copolymers include small molar amounts of copolymer monomers, such as copolymers in which 1 to 10 mol% are C ₄ to C ₁₈ diolefins, such as copolymers of isobutylene and butadiene; Or copolymers of ethylene, propylene and 1,4-hexadiene.

In one embodiment, at least one R of formula (I) is derived from a polymer of polybutene, ie C ₄ olefins such as 1-butene, 2-butene and isobutylene. In another embodiment, at least one R of formula (I) is derived from an ethylene-alpha olefin polymer such as ethylene-propylene-diene polymer. Ethylene-alpha olefin copolymers and ethylene-lower olefin-diene terpolymers are described in a number of patent documents, such as European Patent Publication EP 0279863 and in US Pat. No. 3,598,738; 4,026,809; 4,032,700; 4,137,185; 4,156,061; 4,320,019; 4,357,250; 4,658,078; 4,668,834; 4,937,299; 5,324,800, each of which is incorporated by reference for the relevant disclosure of said ethylene-based polymers.

In another embodiment, the olefin linkages of formula (I) are primarily vinylidene groups represented by the following formulas (II) and (III):

Formula (II)

-(H) C = C (R ² ) (R ² )

(Wherein R ² is a hydrocarbon group and in some embodiments both R ² groups are methyl groups)

Formula (III)

-(H) (R ³ ) C (C (CH ₃ ) = CH ₂ )

(Wherein R ³ is a hydrocarbon group)

In one embodiment, the vinylidene content of formula (I) may comprise at least about 30 mol% vinylidene groups, at least about 50 mol% vinylidene groups or at least about 70 mol% vinylidene groups. Such materials and methods of making them are described in US Pat. No. 5,071,919, which is expressly incorporated herein by reference; 5,137,978; 5,137,980; 5,286,823, 5,408,018, 6,562,913, 6,683,138, 7,037,999 and US Publication Nos. 20040176552A1, 20050137363 and 20060079652A1, which are commercially available from BASF under the trade name GLISSOPAL®, and Texas Petrochemicals under the tradename TPC 1105 ™ and TPC 595 ™. There is a commercial item sold by SLP.

Methods of preparing hydrocarbon substituted acylating agents from the reaction of compounds of formula (I) with monounsaturated carboxylic acid reactants are known in the art and are disclosed in the following patents: US Pat. Nos. 3,361,673 and 3,401,118 (heat " ene) "reaction); U.S. Patent 3,087,436; 3,172,892; 3,272,746, 3,215,707; 3,231,587; 3,912,764; 4,110,349; 4,234,435; 6,077,909; 6,165,235 (reference cited).

In another embodiment, a hydrocarbon substituted acylating agent can be prepared from the reaction of any compound containing an olefin bond represented by formula (I) with at least one carboxy reactant represented by the following formula:

Formula (IV)

(R ⁴ C (O) (R ⁵ ) _n C (O)) R ⁴

Formula (V)

(Wherein each R ⁴ is independently H or a hydrocarbon group, each R ⁵ is a divalent hydrocarbylene group, n is 0 or 1). Compounds and methods of preparing these compounds are described in US Pat. No. 5,739,356; 5,777,142; 5,786,490; 5,856,524; 6,020,500; And 6,114,547.

Other methods of preparing hydrocarbon substituted acylating agents are described in the following references, US Pat. No. 5,912,213; 5,851,966; And 5,885,944.

Compounds having an oxygen or nitrogen atom that can be condensed with an acylating agent and additionally possess a tertiary amino group can be represented by the following formula (VI) or (VII):

Formula (VI)

(Wherein X is an alkylene group containing about 1 to about 4 carbon atoms; each R ⁶ is independently a hydrocarbon group, and R ^{6 ′} is a hydrogen or hydrocarbon group),

Formula (VII)

(Wherein X is an alkylene group containing about 1 to 4 carbon atoms; each R ⁷ is independently a hydrocarbon group).

Examples of nitrogen or oxygen containing compounds that can be condensed with acylating agents and additionally possess tertiary amino groups include ethylenediamine, 1,2-propylenediamine, 1,3-propylene diamine, isomer butylenediamine, pentanediamine, hexanediamine , Heptanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, and bis (hexamethylene) triamine; Diaminobenzenes, diaminopyridine or mixtures thereof, but is not limited thereto. In addition, nitrogen or oxygen containing compounds which can be alkylated to contain tertiary amino groups can also be used. Examples of nitrogen or oxygen-containing compounds that can be alkylated to bear tertiary amino groups and then condensed with acylating agents include dimethylaminopropylamine, N, N-dimethyl-aminopropylamine, N, N-diethylaminopropylamine, N , N-dimethyl-aminoethylamine or mixtures thereof, but is not limited thereto. Nitrogen or oxygen containing compounds capable of condensing with acylating agents and additionally carrying tertiary amino groups are also aminoalkyl substituted heterocyclic compounds such as 1- (3-aminopropyl) imidazole and 4- (3-aminopropyl ) Morpholine, 1- (2-aminoethyl) piperidine, 3,3-diamino-N-methyldipropylamine, 3,3-aminobis (N, N-dimethylpropylamine) . Other types of nitrogen or oxygen containing compounds that may be condensed with acylating agents and possess tertiary amino groups include alkanolamines such as triethanolamine, N, N-dimethylaminopropanol, N, N-diethylaminopropanol, N, N -Diethylaminobutanol, N, N, N-tris (hydroxyethyl) amine, or mixtures thereof, but is not limited thereto.

Examples of quaternary ammonium salts and methods of making them are described in the patents cited herein, US 4,253,980, US 3,778,371, US 4,171,959, US 4,326,973, US 4,338,206 and US 5,254,138.

Each of the additional performance additives may be added directly to the additive compositions and / or fuel compositions of the present invention, but generally may be mixed with fuel additives to form an additive composition or concentrate, and then mixed with fuel to produce a fuel composition. . Additive concentrate compositions are described in more detail above.

In some embodiments, the above-described additive performance additives may be a cause and / or contributing factor to the propensity of the fuel to pick up the oxidizing metal in the fuel composition in which they are used. In other embodiments, the aforementioned additives may have no effect on the metal pickup properties of the fuel composition in which they are used. In any case, the additive compositions and methods of the present invention can offset the potential effects of these additives and reduce the tendency of the fuel composition to pick up the metal, which tends to be caused by, or expanded by, the additive performance additives described above. It doesn't matter if it causes little change.

Industrial availability

In one aspect, the invention is useful for the operation of internal combustion engines, including liquid fuels and / or compression ignition engines or spark ignition engines. Internal combustion engines include gasoline, diesel, natural gas, mixed gasoline / alcohol or two- or four-stroke engines lubricated with any of the fuels described in the sections above. Compression ignition engines include light and heavy diesel engines. Spark ignition engines include ports and direct injection gasoline engines.

In another aspect, the present invention is useful for additive compositions in that the fuel additives and methods described above reduce metal pickup of the fuel composition to prevent elevated levels of metals such as zinc in the fuel.

In another aspect, the additive compositions of the present invention can be used in lubricating compositions such that the additives are present in the lubrication system of the engine. The additive also contains a small amount of additive due to a phenomenon called "blow by" where the lubricating composition, in this case the additive composition, passes around the piston head in the cylinder and moves from the engine's lubrication system to the combustion chamber. By transferring the lubricating composition to the fuel chamber, it can be introduced into the combustion chamber of the engine during operation of the engine.

In some embodiments, the methods and / or compositions of the present invention provide a reduction in metal pickup of at least 5%, at least 20%, even at least 50%. The reduction in some of these embodiments relates to the results on day 7 and / or day 14 of the test procedure used in the examples below. In another embodiment, the methods and / or compositions of the present invention do not allow metal levels of the fuel composition to rise above the metal content of 10 ppm, 5 ppm, 1 ppm, 0.5 ppm, 0.3 ppm or even 0.1 ppm. In some of these aspects, the reduction relates to results on day 7 and / or day 14 of the inspection procedure used in the examples below. In some embodiments, the methods and / or compositions of the present invention provide a reduction in metal level of at least 30% or at least 80% and / or 1 ppm metal level, as assessed on day 7 by the tests described in the Examples below. Do not rise anymore. In some embodiments, the methods and / or compositions of the present invention provide a reduction in metal level of at least 40% or at least 80% and / or 8 ppm metal level, as assessed on day 14 by the tests described in the Examples below. , Or even no more than 1 ppm.

The present invention includes the use of the substituted hydrocarbons and / or hydrocarbon substituted acylating agents described herein as additives in fuel compositions, as well as the additives themselves and fuel compositions and fuel additive compositions containing such additives. The additives of the present invention may be delivered to the fuel composition and / or fuel additive composition by any method known in the art, and the addition time of the additive is not limited. In other words, the additives of the present invention may be added to the fuel composition before, during or after the production and / or blending of the fuel and / or additive composition. In addition, the additives of the present invention may be added to the fuel and / or additive composition before, during or after addition of other performance additives that may be used in the composition. The additives of the present invention may be added to the fuel and / or additive composition as a top treat, or incorporated into the production and / or distribution of the fuel and / or additive composition in which the additive is used.

As used herein, the terms "hydrocarbon substituent" or "hydrocarbon group" are used in their ordinary meanings known to those skilled in the art. Specifically, it refers to a group having carbon atoms attached directly to the rest of the molecule and exhibiting primarily hydrocarbon properties. Examples of hydrocarbon groups include hydrocarbon substituents, ie aliphatic (eg, alkyl or alkenyl), cycloaliphatic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic- and cycloaliphatic-substituted aromatic substituents, as well as Cyclic substituents on which the ring is completed through another part of the molecule (eg, two substituents together form a ring); Substituted hydrocarbon substituents, ie substituents containing non-hydrocarbon groups which do not primarily alter the hydrocarbon properties of the substituents in the context of the invention (eg halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto , Nitro, nitroso and sulfoxy); Hetero substituents, that is, substituents containing atoms other than carbon in a ring or chain composed of carbon atoms, having mainly hydrocarbon properties in the context of the present invention. Heteroatoms include sulfur, oxygen, nitrogen, and also encompass substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, up to 2, preferably up to 1 non-hydrocarbon substituents will be present for every 10 carbon atoms in the hydrocarbon group; In general, non-hydrocarbon substituents may not be present in hydrocarbon groups.

It is known that some of the materials described above may interact in the final formulation so that the components of the final formulation may differ from those initially added. For example, metal ions (eg, of detergent) may migrate to other acidic or anionic sites of other molecules. In addition, the acylating agents and / or substituted hydrocarbon additives of the present invention may form salts or other complexes and / or derivatives when they interact with other components of the composition in which they are used. The products thus formed, such as those formed when using the compositions of the present invention for their intended use, may be difficult to describe easily. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; The present invention encompasses a composition prepared by mixing the aforementioned components.

Example

The invention will be illustrated in detail by the following examples which describe particularly advantageous embodiments. These examples are intended to illustrate the invention, not to limit it.

Example 1 Fuel Treated with Succinimide Dispersant . EU certified diesel fuel known as RF-06 was treated with 200 ppm of a commercially available succinimide dispersant. Seven 500 mL graduated cylinders to be inspected were prepared, each with a 4 cm section of Goodfellow Zn rod ZN007902, 200 mm long and 2.0 mm in diameter. The weight of each rod section was recorded and an amount of fuel was added to each cylinder so that 1% by weight of zinc was added to the mixture of fuel composition and zinc rod. The amount of fuel was injected slightly differently to ensure that each sample had the same zinc content in each cylinder. One of the seven samples (1-1) was kept at the reference value. The other six samples (1-2 to 1-7) were each independently treated with 200 ppm of the additive additives shown in the table below.

Additives added to the test sample Sample Additional additives (20 ppm in fuel) 1-1 None-threshold 1-2 Hydrolyzed polyisobutylene succinic anhydride with a number average molecular weight of about 1000 MW hydrolyzed PIBSA-polyisobutylene 1-3 550 MW PIBSA-polyisobutylene succinic anhydride with a number average molecular weight of about 550 1-4 Pentasize 68F = commercial succinic anhydride derived from C16-C18 polyolefin 1-5 Dimer Acids (Hydrated)-Commercial acid products containing two carboxyl groups sold by Aldrich as catalog ID 432369-1L. 1-6 Unhydrolyzed polyisobutylene succinic anhydride with a number average molecular weight of about 1000 MW PIBSA-polyisobutylene 1-7 1000 MW mono esterified PIBSA—esterified polyisobutylene succinic anhydride having a number average molecular weight of about 1000 of polyisobutylene, which is not hydrolyzed and esterified with 1 equivalent of n-butanol

The containers were stored at ambient conditions for 14 days in a dark laboratory. Each sample was examined on day 7 and day 14 by inductively coupled plasma (ICP) analysis to determine zinc content. The result of Example set 1 was put together in the following table.

Results of Example Set 1 Sample Additional additives (200 ppm in fuel) Zinc level at 7 days (ppm) Zinc level at 14 days (ppm) 1-1 None-threshold 0.6 1.3 1-2 ~ 1000 MW hydrolyzed PIBSA 0.1 0.1 1-3 ~ 550 MW PIBSA 0.1 0.1 1-4 Pentasize 68F 0.0 0.1 1-5 Dimer Acids (Hydrated) 1-6 ~ 1000 MW PIBSA 0.1 0.1 1-7 ~ 1000 MW monoesterified PIBSA 0.4 0.8

Example Set 2-Biodiesel . Example set 1 was repeated except that the diesel fuel treated with succinimide dispersant was replaced with B100, a commercial biodiesel fuel. In addition, the additive additives of Samples 2-2 to 2-7 are each present at 500 ppm in the fuel composition. Samples 2-1 to 2-7 were examined in the same manner as described above and the results are summarized in the table below.

Results of Example Set 2 Sample Additional additives (200 ppm in fuel) Zinc level at 7 days (ppm) Zinc level at 14 days (ppm) 2-1 None-threshold 1.5 1.7 2-2 ~ 1000 MW hydrolyzed PIBSA 0.2 0.3 2-3 ~ 550 MW PIBSA 0.3 0.3 2-4 Pentasize 68F 0.2 0.2 2-5 Dimer Acids (Hydrated) 0.5 0.8 2-6 ~ 1000 MW PIBSA 2-7 ~ 1000 MW monoesterified PIBSA 3.0 3.8

Each of the documents cited above is hereby incorporated by reference. Except where specifically indicated in the Examples or otherwise, all numerical quantities that specify the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc., are to be understood as having the modifier “about”. All% values and ppm values herein are calculated on a weight percent value and / or weight basis unless otherwise indicated. Each chemical or composition referred to herein is to be interpreted as being a commercial grade material which may contain isomers, by-products, derivatives and such other materials which are commonly understood to be present in the commercial grade unless otherwise indicated. However, the amount of each chemical component is a value excluding any solvent or diluent that may conventionally be present in the commercial material unless otherwise indicated. It is to be understood that the upper, lower, and limit amounts, ranges, and ratio limits set forth herein may be combined independently. Likewise, the range and amount of each element of the present invention may be used with the range or amount of any other element. As used herein, the phrase “consisting essentially of” allows the incorporation of materials that do not significantly affect the basic and novel properties of the composition under consideration.

In addition, all of the above-described aspects have been considered for their use alone and in combination with all the other aspects described above, and such combinations should be considered part of the present invention. Specific embodiments of the foregoing amines and alcohols have been considered in conjunction with certain embodiments of the carboxylic acids useful in the present invention.

Claims (14)

A method for reducing the amount of oxidative metal pickup of a fuel composition, comprising adding an additive containing a hydrocarbon substituted with at least two carboxyl functional groups in acid form or at least one carboxyl functional group in anhydride form. The method of claim 1 wherein the substituted hydrocarbon is a hydrocarbon substituted acylating agent having a diacid functionality. The method of claim 1 wherein the substituted hydrocarbon is a succinyl acylating agent. The method of claim 1, wherein the oxidative metal to which pickup is reduced is selected from the group consisting of copper, zinc, iron or combinations thereof. The process of claim 1, wherein the hydrocarbyl group of the substituted hydrocarbon comprises polyisobutylene. 6. The substituted hydrocarbon agent of claim 1, wherein the substituted hydrocarbon agent is
(a) hydrocarbon substituted succinic anhydrides;
(b) hydrolyzed hydrocarbon substituted succinic anhydride;
(c) selected from the group consisting of combinations thereof. The fuel composition of claim 1, wherein the fuel composition further comprises an anti-emulsifier, antifoaming agent, cold flow agent, dispersant / cleaner additive, or combinations thereof, wherein the fuel is at least 0.5 ppm when in contact with a solid material containing an oxidizing metal for a long time. Where there is room to pick up the oxidizing metal at the level. 8. The method of claim 7, wherein the dispersant / cleaner additive comprises a succinimide dispersant, a quaternary ammonium salt or a combination thereof. The method of claim 1, wherein the fuel composition comprises diesel fuel, biodiesel, or combinations thereof. 10. The method of any one of the preceding claims, wherein the fuel composition is a fuel additive composition. The method of claim 1, wherein the deposit of the fuel injector is reduced in an engine to which the fuel composition is applied. (a) fuel;
(b) an additive containing a hydrocarbon substituted with at least two carboxyl functional groups in acid form or at least one carboxyl functional group in anhydride form; And
(c) a fuel composition containing optional additional performance additives. (a) an optional solvent;
(b) an additive containing a hydrocarbon substituted with at least two carboxyl functional groups in acid form or at least one carboxyl functional group in anhydride form; And
(c) a fuel additive composition containing an optional additional performance additive. Use of a fuel additive containing a hydrocarbon substituted with at least two carboxyl functional groups in the acid form or at least one carboxyl functional group in the anhydride form, which is used in the fuel composition to reduce the amount of oxidative metal pickup in the fuel composition. In some cases, fuel injection system deposit formation is reduced in engines in which additive-containing fuel compositions are used.