SE446012B - FUEL COMPOSITION BASED ON DISTILLATE FUEL OIL AND TREE COMPONENT COMPOSITION FOR USE IN PREPARATION OF THEREOF - Google Patents

Description

7904580-3 polymer, which are wax crystal modifiers and cold flow improvers for intermediate distillate fuels, in particular diesel oil.

U.S. Pat. Nos. 3,444,082 and 3,846,093 disclose various kinds of amides and salts of alkenyl succinic anhydride reacted with amines, in combination with ethylene copolymer pour point depressants, for distillate fuels.

The distillate fuel oil to which flow-improving agents can be added is stored in tanks of various sizes at refineries, at market depots or at final distribution terminals. P.g.a. the large volume of oil in such tanks lowers the bulk oil temperature slowly, although the ambient temperature may be considerably lower than the cloud point (the temperature at which wax begins to crystallize out and becomes visible, i.e. the oil becomes cloudy).

If the winter is particularly cold and prolonged so that the bulk oil is stored for a long period of time in very cold weather, the bulk oil may eventually fall below the cloud point. These conditions can cause crystallized wax to deposit on the bottom of the tank and also form a bottom layer of oil having a higher wax content and a cloud point significantly higher than the cloud point of the fuel originally pumped into the tank while the upper layers of the oil are partially dewaxed and has a relatively low cloud point. The crystalline bottom layer of oil will therefore be more prone to wax agglomeration than the upper layers, and such wax agglomeration in many cases causes clogging of screens and other flow restricting means in the oil distribution systems because the outlets from the tanks are located near their bottom. If oil is drained with an abnormally high amount of wax in the form of relatively large crystallites due to this crystal agglomeration, even if they pass through the filters of the tank, the agglomerates can block protective filters or protective strainers on the tanker or clog small-diameter filters or fuel lines in the customer's storage system.

It has been found according to the invention that these problems can be reduced by using an additive combination with three (or more) components for distillate fuel oils comprising (A) a distillate flow improving composition (B) a lubricating oil pour point depressant and (C) a polar oil-soluble compound other than components (A) and (B) and of the formula RX in which R represents an oil-soluble hydrocarbon group and X is a polar group, this compound acting as an anti-agglomerating agent for the wax particles in the fuel oil. It has been found that this combination is particularly useful in distillate fuel oils having a boiling point in the range of 120 DEG-50 DEG C., in particular 160 DEG-40 DEG C., for controlling the size of wax crystals formed at low temperature.

In general, an additive combination of three components according to the invention has been found to be effective not only for keeping the originally formed wax crystals small but also for inhibiting agglomeration of wax particles formed.

In addition, the additives delay the deposition of the wax crystals under the influence of gravity.

According to a preferred embodiment, the present invention relates to a fuel composition comprising distillate fuel oil and from 0.001 - 0.5% by weight and preferably 0.01 - 0.2% by weight and especially 0.05 - 0.1% by weight of a flow and filterability improving multicomponent. additive composition comprising: (A) a part by weight of a distillate flow enhancing composition (B) 0.1 - 10 and preferably 0.5 - 5 and in particular 1 - 2 parts by weight of a lubricating oil pour point depressant (C) 0.1 - 10 , preferably 0.5 - 5 and in particular 1 - 2 parts by weight of a polar oil-soluble compound of the formula RX according to the preceding definition which acts as an anti-agglomerating agent for the wax particles. For ease of handling, the additives are usually added as a concentrate containing 30 to 80% by weight of a hydrocarbon diluent and 70 to 20% by weight of the additive mixture of (A), (B) and (C) dissolved therein. The invention also relates to such concentrates.

The flow improving agent (A) for the distillate used in the additive combinations of the invention is a wax crystalline growth inhibitor and may also contain a wax crystallizing agent. These agents are preferably ethylene polymers of the type previously known as wax crystal modifiers, for example pour point depressants and cold flow enhancers for distillate fuel oils. These polymers have a polymethylene backbone which is subdivided into segments of hydrocarbon or oxy-hydrocarbon side chains, of alicyclic or heterocyclic structures or of chlorine atoms. They may consist of homopolymers of ethylene which may be produced by free radical polymerization which results in a certain degree of branching. Typically, they comprise copolymers of about 3 to 40; preferably 4 to 20 molar parts of ethylene per molar of a second ethylenically unsaturated monomer which may be a single monomer or a mixture of monomers in arbitrary proportions. The polymers generally have a number molecular weight in the range of about 0500 to 50,000 ooh, preferably about 800 to about 20,000, for example 1,000 to 6,000, measured by Vapor Pressure Osmometry (VPO), for example using a Mechrolab Vapor device. Pressure Osmometer Model 302B ".

The unsaturated monomers which are copolymerizable with ethylene include unsaturated mono- and diesters of the general formula: in which R 1 is hydrogen or methyl, R 2 is a group -OOCR 4 in which R 4 is hydrogen or a C 1 - C 28 -, usually C 1 - C 16 -, and preferably a C 1 - C 8, straight or branched chain alkyl group, or R 2 is a group -COOR 4 in which R 4 has the meaning given above and R is hydrogen or -COOR 4 as defined above. When R 1 and R 2 represent hydrogen and R 2 represents -OOCR 4, monomers include vinyl alcohol esters of C 1 -C 29, usually C 1 -C 17, monocarboxylic acid and preferably C 2 -C 5 monocarboxylic acid. Examples of such esters include vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate and vinyl palmitate, with vinyl acetate being the preferred ester. When R 4 represents -COOR 4 and R 3 represents hydrogen, such esters include methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, C 13 oxo alcohol esters of methacrylic acid, etc. -COOR4, includes mono- and diesters of unsaturated dicarboxylic acids, for example: mono-C13 oxofumarate, di-C13 oxofumarate, diisopropyl maleate, di-lauryl fumarate and ethyl methyl fumarate.

Another class of monomers that can be copolymerized with ethylene includes C3 - C16 alpha monoolefins, which may be either branched or unbranched, for example propylene, isobutylene, n-octene-1, isooctene-1, n-decene-1, dodecene-1, etc.

Still other monomers include vinyl chloride, but substantially the same result can be obtained by chlorinating polyethylene, for example to a chlorine content of about 10 to 35% by weight.

Distillate flow improvers also include hydrogenated polybutadiene flow improvers having substantially 1,4-addition and some 1,2-addition, such as those described in U.S. Pat. No. 3,600,311.

The preferred ethylene copolymers are ethylene vinyl ester, especially vinyl acetate copolymers. These can be prepared by processes operating at high pressure and without solvents or by the preferred process according to the invention in which solvents and 5 to 50% by weight of the total amount of monomer charge other than ethylene are charged in a stainless steel pressure vessel which is equipped with a stirring device and heat exchanger. The temperature in the pressure vessel is then brought to the desired reaction temperature, for example 70 - 200 ° C, by passing water vapor through the heat exchanger and by raising the pressure to the desired pressure with ethylene, for example 49 - 1150 and usually 63 - 490 atm. The initiator, usually a concentrate in a solvent (usually the same solvent used in the reaction) so that the material can be pumped, and an additional amount of the monomer charge in addition to ethylene, for example vinyl ester, can be added to the vessel continuously or at least periodically during the reaction time.

During the reaction time, ethylene is also consumed in the polymerization reaction and an additional amount of ethylene is also added to a pressure regulating regulator to maintain the desired reaction pressure relatively constant at all times, and the reactor temperature is kept substantially constant by means of the heat exchanger. of the reaction, a total reaction time of 1/4 to 10 hours usually being sufficient, the liquid phase is discharged from the reactor and solvent and other volatile constituents in the reaction mixture are evaporated off leaving the copolymer as a residue. To facilitate handling and mixing, the polymer is usually dissolved in a mineral oil, preferably an aromatic solvent, for example heavy aromatic naphtha, to form a concentrate which usually contains 10 to 60% by weight of copolymer.

Usually about 50 - 1,200, preferably 100 - 600 parts by weight of solvent based on 100 parts of copolymer to be prepared are used. A hydrocarbon solvent, for example benzene, hexane, cyclohexane, t-butanol, etc. and about 0.1 to 5 parts by weight of initiator are generally used.

The initiator is selected from the group of compounds which, at elevated temperature, undergo decomposition to give radicals, for example, peroxide or azo type initiators, including acyl peroxides of branched or unbranched G2 to C18 carbons, as well as other commonly used initiators. Examples of such initiators include dibunsoyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, t-butyl hydroperoxide, α, - α ', azo diisobutyronitrile, dilauroyl peroxide, etc. The choice of peroxide used is determined the polymerization conditions, the desired polymer structure and the activity of the initiator. t-butyl peroctenoate, di-lauroyl peroxide and di-t-butyl peroxy are preferred initiators.

Mixtures of ethylene copolymers can also be used. Thus, U.S. Pat. No. 3,916,916 states that improved results can be obtained using an ethylene-copolymer blend containing components with different solubilities, one of which acts primarily as a nucleator to effect nucleation of wax crystals while the other more soluble the component acts as a wax crystal for growth inhibitors and inhibits the growth of the wax crystals after they are formed. One such combination of nucleator and plant growth inhibitor is the preferred distillate flow enhancer in compositions of the invention.

The lubricating oil pour point depressant is preferably an oil soluble ester and / or higher olefin polymer and generally has a number average molecular weight in the range of about 1,000 to 20,000, for example 1,000 to 100,000, preferably 1,000 to 50,000, measured for example by "Vapor Pressure Osmometry", for example by a device of the type "Mechrolab Vapor Pressure Osmometer" or by gel permeation chromatography (Gel Permeation Chromatography). These other polymers include (a) polymers, both homopolymers and copolymers of unsaturated alkyl esters, including copolymers with other unsaturated monomers, for example olefins such as ethylene, nitrogen-containing monomers, etc. and (b) homopolymers and copolymers of olefins other than ethylene. In the preferred lubricating oil pour point depressant according to the invention, at least 10% by weight, preferably at least 25% by weight and often 50% by weight or more of the polymer consists of straight-chain G6- to C30-, for example C8- to Czu-, e.g. C8 to C16 or an ester, for example the alkyl part of an alcohol as α-alkyl groups, usually of α-olefin was used to esterify a mono- or dicarboxylic acid, or anhydride. By way of example, using a straight chain C16 alkyl acrylate as the source of the aforementioned straight chain alkyl group, one can obtain a homopolymer or a copolymer of this n-hexadecyl acrylate with a short chain monomer, for example, a copolymer of n -hexadecyl acrylate with methyl acrylate. Alternatively, n-hexadecyl acrylate copolymerized with docosanyl acrylate can be used. Alternatively, a terpolymer of methyl acrylate, n-hexadecyl acrylate and branched chain C30 alkyl acrylate may be used, and alternatively the n-hexadecyl acrylate may be copolymerized with an unsaturated ester other than an ester derived from acrylic acid, this ester having its in either the acid or the alcohol moiety.

Among esters which can be used for the preparation of these lubricating oil pour point depressants, including homopolymers and copolymers of two or more monomers, are ethylenically unsaturated mono- and diesters corresponding to the formula: pa-wnvlW Il: d-f fl- O fl- * In which R 1 is hydrogen or C 1 to C 6 hydrocarbyl, preferably alkyl group, for example methyl; H2 is a group -OOCRÄ or -COORÄ in which Ru is hydrogen or a C1- to C50-, for example C1- to Cqq- straight- or branched-chain hydrocarbyl group, for example -alkyl group; and H 3 is hydrogen or -COORH, wherein at least one of and Ru contains a straight chain O 6 to C 3 pre-R 1, H 2, H 3 O, preferably a G 8 to Can, in particular a C 8 to C 16 alkyl group. When B1 and H3 are hydrogen and R2 is -OOCRH, the monomer comprises vinyl alcohol esters of monocarboxylic acids. Examples of such esters include vinyl laurate, vinyl myristate, vinyl palmitate, vinyl behenate, vinyl tricosanoate, etc. Examples of esters in which R 2 is -COORM include lauryl acrylate, C 1-5 oxo alcohol esters of methacrylic acid, behenyl acrylate, behenyl methacrylate monomers, tricosyl acrylate monomers, etc. R 1 is hydrogen and R 2 and R 2 are both groups -COORU include: mono- and diesters of unsaturated dicarboxylic acids, for example mono-C 3 oxofumarate, di-C 13 oxomaleate, dieicosyl fumarate, laurylhexyl fumarate, didocosyl fumarate, dieicosyl maleate, ditraconosyl monodocosyl maleate, dieicosyl citraconate, di (tricosyl) fumarate, dipentaacosyl citraconate. Short chain alkyl esters, for example vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, isobutyl acrylate, mono-isopropyl maleate and isopropyl fumarate can be used in copolymers with longer-chain alkyl esters.

In addition, minor molar amounts, for example 0 to 20 mole percent, for example 0.1 to 10 mole percent, nitrogen-containing monomers may be copolymerized in the polymer together with the monomers given above. These nitrogen-containing monomers include those corresponding to the formula R - CH = C - H 2 R is a 5- or 6-membered heterocyclic nitrogen-containing ring which may contain one or more substituent hydrocarbon groups in addition to the vinyl group. In the above formula, the vinyl group may be attached to the Nitrogen or to a carbon atom of the group R. Examples of such vinyl groups include 2-vinylpyridine, H-vinylpyridine, 2-methyl-2-vinylpyridine, 2-ethyl-5-vinylpyridine, U-methyl-5-vinylpyridine, N-vinylpyrrolidone and H-vinylpyrrolidone. Other monomers which may be included are unsaturated amides, for example those of the formula: in which B1 is hydrogen or methyl, and R2 is hydrogen, alkyl or alkoxy group, generally having up to about 2 to carbon atoms. such amides are obtained by reacting lower molecular weight acrylic acid or acrylic ester with an amine, for example butylamine; hexylamine, tetrapropyleneamine, cetylamine, ethanolamine and tertiary alkyl primary amine.

As an alternative embodiment of the invention, a certain part of the lubricating oil pour point lowering additives may contain polar functions which have an anti-agglomerating effect on the wax and thus constitute component C in the additive combination according to the invention. Preferred examples are compounds containing esters of the type described above in which Ru is an alkoxyamine.

Preferred ester polymers for use in the invention are, in view of their availability and cost, copolymers of vinyl acetate and a dialkyl fumarate in approximately equimolar proportions, as well as polymers or copolymers of acrylic esters or methacrylic esters. The alcohols used to prepare the fumarate and the acrylic and methacrylic esters are usually monohydric, saturated, straight chain primary aliphatic alcohols containing from H to 50 carbon atoms. These esters do not have to be pure but can be prepared from mixtures of technical quality.

Acceptable mixtures of two or more polymers of indicated esters may be used. These may be simple mixtures of such polymer or may be copolymers which may be prepared by polymerizing a mixture of two or more of the monomeric esters. Mixed esters resulting from the reaction of simple or mixed acids with a mixture of alcohols can also be used.

The ester polymers are generally prepared by polymerizing a solution of the ester in a hydrocarbon solvent such as heptane, benzene, cyclohexane or white oil at a temperature of from 60 to 25,000 under a protection of refluxing solvent or an inert gas, for example nitrogen or carbon dioxide to exclude oxygen. The polymerization is preferably facilitated by a peroxide or azo-free radical initiator, with benzoyl peroxide being preferred.

The unsaturated carbonic acid ester can be copolymerized with an olefin. If a dicaronic anhydride is used, for example maleic anhydride, it can be polymerized with the olefin and then esterified with alcohol. By way of example, the ethylenically unsaturated carboxylic acid or its derivative may be reacted with an α-olefin, for example a G8-C32-, preferably a C10-C26- and in particular a C10-C18-olefin, by mixing the olefin and acid, for example maleic anhydride, usually in approximately equimolar amounts, and heating to a temperature of at least SOOC, preferably at least 12,500, in the presence of a free radical polymerization promoter, for example benzoyl peroxide or t-butyl hydroperoxide or di-t-butyl peroxide. Other examples of copolymers are those of maleic anhydride with the styrene, or cleaved wax olefins, which copolymers are then usually completely esterified with alcohol, as are the other examples of olefin ester polymers given above.

Alternatively, the lubricating oil ~ point lowering additive used in the compositions of the invention may be olefin polymers, which may be either homopolymers and copolymers of long chain C 8 to C 32, preferably C 10 to C 26 and especially C 10 -C 18 aliphatic d-mono-olefins. or copolymers of such long chain d-mono-olefins with shorter C3-C7 aliphatic d-olefins, or with styrene or derivatives thereof, for example copolymers comprising 20 to 90% by weight of C8 to C32-α-olefin and 80 to 10% by weight of such G3 to C7 aliphatic mono-olefin or styrene-type olefin.

These olefin polymers can be conveniently prepared by polymerizing the monomers under relatively mild temperature and pressure conditions in the presence of a Friedel-Crafts type catalyst, for example AlCl5, which gives an irregular polymer, or an organometallic catalyst by Ziegler. -Night type, ie a mixture of a compound derived from a metal belonging to Group IV, V or VI of the Periodic Table in combination with an organometallic compound of a metal belonging to Group I, II or III of the Periodic Table, wherein the amount of compound derived from a metal belonging to group IV, V or VI can vary from 0.01 to 2.0 moles per mole of organometallic compound.

Examples of Ziegler-Natta type catalysts include the following combinations: aluminum triisobutyl, aluminum chloride, and vanadium trichloride; vanadium tetrachloride and aluminum trihexyl; vanadium trichloride and aluminum trihexyl; vanadium triacetyl acetonate and aluminum diethyl chloride; titanium tetrachloride and aluminum trihexyl; vanadium trichloride and aluminum trihexyl; titanium trichloride and aluminum trihexyl; titanium dichloride and aluminum trihexyl, etc.

The polymerization is usually carried out by mixing the catalyst components in an inert diluent, for example hydrocarbon solvent, for example hexane, benzene, toluene, xylene, heptane, etc. followed by adding the monomers to the catalyst mixture at atmospheric pressure or superatmospheric pressure and temperatures in the range of about 10 and 8200. Atmospheric pressure is usually used in the polymerization of monomers containing more than U carbon atoms in the molecule and elevated pressure is used if more volatile G5 or Cu-α olefins are present. The reaction time depends on and is related to the reaction temperature, the choice of catalyst and the pressure used. In general, however, the reaction is completed within a period of 1/2 to 5 hours.

The polar compound constituting component (C) is separate from the distillate flow improver and the lubricating oil pour point depressant and is usually monomeric and may be ionic or non-ionic. The compound inhibits agglomeration of wax particles in the oil and examples of suitable ionic compounds are those in which the anion is the oil-soluble group R5Y. When Y is the polar end group and R5 is an oil-solubilizing group, which may be one or more substituted or unsubstituted unsaturated or saturated hydrocarbon groups, which may be aliphatic or cycloaliphatic or aromatic, H 5 is preferably alkyl, alkaryl or alkenyl. H5 should preferably contain a total of 8 to 150 carbon atoms. If the compound is nonionic, it is suitable that R 5 contains from 8 to 50 and preferably 12 to 2, and in particular 12 to 18 carbon atoms.

If the compound is ionic, it is preferred that it contains from 8 to 150 carbon atoms, preferably 50 to 120 carbon atoms, in particular 70 to 100 carbon atoms, and in particular consists of compounds derived from alkyl groups containing from 1 to 30 and preferably 12 to 30 carbon atoms. It is convenient that when R 5 is alkyl groups these are straight chain.

Alternatively, R 5 may be an alkoxylated chain.

Examples of suitable polar end groups Y include sulfonate group SOš, _ sulphate group OSOš, phosphate group POE, phenate group PhO_ * and borate group BO '. Preferred anions include R5SOš, R5OSOš; (R5O) 2 P0š; R5PH0- and (R50) 2BO where R5 is the oil-solubilizing hydrocarbon group. 7904580-3 lä If the anion is a sulfonate, it is convenient to use an alkaryl sulfonate which may be any of the well known neutral or basic sulfonates.

If the anion is phenate, it is convenient that it be derived from alkylphenol, or crosslinked phenols, including those of the general formula O (t in which M is a crosslinking group of one or more, e.g. to H carbon atoms or sulfur atoms and R 5 have the meaning given above.In this case, too, the phenate used may be any of the well-known neutral or basic compounds.

If the anion consists of borate, sulphate or phosphate, R5 may alternatively consist of alkoxylated chains. Examples of such compounds in the case of sulphates include (H6 - (OCH2CH2) n O) - group, and in the case of phosphates and borates (R6 - (ocH2cH2) n -o) š group wherein R6 is alkylg alkaryl or alkenyl.

The cation for these salts is preferably a mono-, di-, tri- or tetraalkylammonium or phosphonium ion of the formula + + + + R7zH3, (R7) 2zH2, (R7) 3zH, (R7) hz in which RT is hydrocarbyl, preferably alkyl, and when the cation contains more than one such group, these may be the same or different groups, and Z is nitrogen or phosphorus. H7 preferably contains the amount of carbon indicated for R5 above.

Examples of suitable alkyl groups include methyl, ethyl, propyl, n-octyl, n-dodecyl, n-tridecyl, C13-oxo-, coconut, tallow behenyl, lauryl, dodecyl-octyl, coconut-methyl, tallow-methyl, methyl -n-octyl, methyl-n-dodecyl, methyl-behenyl, tallow- gPUppGP.

Group R? may be substituted by, for example, hydroxy or amino groups (such as in the polyamine). As an alternative embodiment, the hydrocarbyl bucket in the cation may provide the oil solubility, for example in salts of fatty amines, such as tallowamine.

Alkyl-substituted dicarboxylic acids or anhydrides thereof or derivatives thereof can also be used as the polar compound. Examples are succinic acid derivatives of the general formula o Ra and RQ (P o wherein at least one of R8 or R9 is a long chain alkyl group (for example having BO to 150 carbon atoms), preferably polyisobutylene or polypropylene. The other of H8 or R9 may be P groups and O may be the same or different and may consist of carboxylic acid groups, esters or may together form an anhydride ring.

As a less preferred alternative, the cation may be metal ion, and in such a case the metal is preferably an alkali metal, for example sodium or potassium, or an alkaline earth metal such as barium, calcium or magnesium.

The ion-type compounds described above constitute preferred polar oil-soluble compounds according to the invention, but it has been found that polar non-ionic compounds are also effective. As examples, primary amines of the formula B10-NH2, secondary amines R10H2 and primary alcohols B10-OH can be used provided they are oil-soluble, and for this reason R preferably contains at least 8 carbon atoms and preferably has 10 Rio in the case of non-ionic compounds. the number of carbon atoms given above for H5 Nitrogen compounds are particularly effective polar compounds for keeping the wax crystals separate from each other, i.e. by inhibiting agglomeration of the wax crystals, and constitutes component (C) of the additive mixtures preferred according to the invention. Examples of suitable compounds include oil-soluble ammonium salts, amine salts and / or amides, which are generally prepared by reacting an amine with at least one molar moiety of hydrocarbylic acid with 1-10 carboxylic acid groups, or anhydrides thereof.

In the case of polycarboxylic acids or anhydrides thereof, all acid groups may be converted to amine salts or amides, or some of the acid groups may be converted to esters by reaction with hydrocarbyl alcohols, or some of the acid groups may be left unreacted.

The hydrocarbyl groups of the nitrogen compounds described above may be straight or branched chain, saturated or unsaturated, aliphatic, cycloaliphatic aryl or alkaryl compounds and are long chain, for example C12 to Cuo, eg «C14 to Czu. However, a certain amount of short chain substances, for example C1 to C11, can be incorporated provided that the total number of carbon atoms is sufficient for the solubility in the distillate fuel oil.

In general, a total amount of 50 to 300, for example 36 to 160 carbon atoms is sufficient for oil solubility even if the number of carbon atoms required varies with the degree of polarity of the compound. With amides, 36 or more carbon atoms are generally preferred for each amide bond present in the compound, and for more polar amine salts, 72 carbon atoms or more are preferred for each amine salt group present. The compound preferably also contains at least one straight chain alkyl segment extending from the compound containing 8 to NO and preferably 12 to 30 carbon atoms. This straight chain alkyl segment may be present in one or more of the amine or ammonium ion, or in the acid, or in the alcohol (if an ester group is also present). At least one ammonium salt, or amine salt, or amide bond is required in the molecule.

The hydrocarbyl groups may contain other groups, or atoms, for example hydroxy groups, carbonyl groups, ester groups or oxygen, or sulfur, or chlorine atoms.

The amines that can be reacted with hydrocarbyl alcohols include primary, secondary, tertiary and quaternary but preferably secondary. If amides are to be prepared, primary or secondary amine is used.

Examples of primary amines include n-dodecylamine, n-tridecylamine, C13-oxoamine, coconut amine, tallowamine, and behenylamine.

Examples of secondary amines include methyl-laurylamine, dodecyl-octylamine, coconut-methylamine, tallow-methylamine, methyl-n-octylamine, methyl-n-dodecylamine, methyl-behenylamine and ditalgamine. Examples of tertiary amines include coconut-diethylamine, cyclohexyl-diethylamine, coconut-dimethylamine and methyl-cetyl-stearyl-amine, methyl-ethyl-coconut-amine, methyl-cetyl-stearyl-amine, etc.

Examples of quaternary amine bases or salts include dimethyl dicetylamino and dimethyl distearyl amino chloride.

Amine mixtures can also be used and many amines derived from natural materials are mixtures. Thus, coconut amines derived from coconut oil are a mixture of primary amines having straight chain alkyl groups ranging from G8 to C18. Another example is tallow amine derived from hydrogenated tallow acids, and this amine is a mixture of Clu to C18 straight chain alkyl groups. Talgamine is especially preferred. Examples of carboxylic acids or anhydrides include formic acid, acetic acid, hexanoic acid, lauric acid, myristic acid, palmitic acid, hydroxystearic acid, behenic acid, naphthenic acid, salicylic acid, acrylic acid, linoleic acid, dilinolic acid, trilicaric acid, maleic acid, maleic acid, maleic acid , succinic anhydride, alkenyl succinic anhydrides described above, adipic acid, glutaric acid, sebacic acid, lactic acid, malic acid, malonic acid, citraconic acid, phthalic acids (ortho, meta or para), for example terephthalic acid, phthalic anhydride, citric acid, citric acid and citric acid di-hydroxystearic acid.

Examples of alcohols which can also be reacted with the acids include 1-tetradecanol, 1-hexadecanol, 1-octadecanol, C12 to C18 oxo alcohols prepared from a mixture of decomposed wax olefins, 1-hexadecanol, 1-octadecanol, behenyl alcohol , 1,2-dihydroxyoctadecane and 1,10-dihydroxydecane. The amides can be prepared in a conventional manner by heating a primary or secondary amine with acid or acid anhydride. Similarly, the ester can be prepared in a conventional manner by heating the alcohol and polycarboxylic acid to partially esterify the acid or anhydride (so that one or more carboxyl groups remain to react with the amine to form amide or amine salt). The ammonium salts are also conventionally prepared by simply mixing the amine (or ammonium hydroxide) with the acid or acid anhydride, or the partial ester of a polycarboxylic acid, or the partial amide of a polycarboxylic acid, with stirring, generally with gentle heating (e.g. 70 - SOOC). Particularly preferred are nitrogen compounds of the above type made from dicarboxylic acids. Mixed amine salts / amides are particularly preferred and these can be prepared by heating maleic anhydride, alkenyl succinic anhydride or phthalic acid or anhydride with a secondary amine, preferably tallow amine at mild temperatures, for example 8000, without removing the water. 7904580-3 19 It has been found that although these polar compounds have little effect on wax formation or crystal size when they are the only additives in a fuel, they can substantially reduce the degree to which already formed wax crystals agglomerate. A less important effect of these compounds is that many of them reduce the rate at which wax is deposited from fuels containing nucleation and / or growth inhibitory additives. It has been found according to the invention that the presence of these polar compounds is effective under normal fuel storage conditions even when the fuel is stored for a long time at low temperature and when its temperature is lowered very slowly (i.e. 0.5 ° C / hour).

The distillate fuel oils in which the additive combinations of the invention are particularly useful generally boil in the range of 120 to 50,000, for example 150 to 100 ° C. The fuel oil may contain atmospheric distillate or vacuum distillate or cracked gas oil or a mixture in arbitrary proportions of fractional distilled (straight run) and thermally and / or catalytically distilled distillates. The most common petroleum distillate fuels consist of kerosene, reactive fuels, diesel fuels and fuel oils. The fuel oil can be either a fractionally distilled distillate or a decomposed gas oil or a combination thereof. The low temperature flow problems avoided by using the additive combinations of the invention usually arise with diesel fuels and with heating oils.

There has recently been a tendency to increase the final boiling point (FBP) of the distillates so that the yield of the fuels is maximized. However, these fuels have more long-chain paraffins in the fuel and therefore generally have a higher cloud point. This in turn complicates the difficulties that arise in the handling of these fuels in cold weather and increases the need to include buoyancy-enhancing additives.

When measuring the boiling properties of these fuels with a high final boiling point, ASTM-1160 distillation (distillation under vacuum) can be used and the obtained boiling points are then corrected to boiling points at atmospheric pressure. Alternatively, you can use ASTM Method D-86, which is atmospheric distillation, but usually a certain thermal decomposition occurs so that the results of D-86 distillation are less accurate.

By the term oil soluble is meant that the additive is soluble in the fuel at ambient temperature, for example at least to a degree of 0.1% by weight addition in the fuel oil at 2590, even if at least a certain amount of additive passes out of solution near the cloud point of cloud wax formation.

The invention is further illustrated in the following by examples which do not limit the scope of the invention.

In these examples, the distillate flow enhancer A used was a concentrate in an aromatic diluent of about 50% by weight of a mixture of two ethylene-vinyl acetate copolymers having different degrees of oil solubility, so that one acts primarily as a plant growth inhibitor and the others as nucleating agents, in accordance with the disclosure of U.S. Pat. No. 3,916,916. In particular, the polymer consists of an inclination of about 75% by weight of growth growth inhibitor and about 25% by weight of nucleating agent. The growth inhibitor consists of ethylene and about 58% by weight of vinyl acetate and has a molecular weight of about 1,800 (VPO). This material is identified in the aforementioned U.S. Patent No. 5,916,916 as Copolymer B of Example 1 (ßpal fi 8, Pad 25-35). The nucleation meol consists of ethylene and about 16% by weight of vinyl acetate and has a molecular weight of about 3000 (VPO). This substance is identified in U.S. Pat. No. 3,916,916 as copolymer H (see Table 1, columns 7-8).

The lubricating oil pour point depressant B consisted of an oil concentrate of about 50 weight percent mineral lubricating oil and about 50 weight percent of a copolymer of dialkyl fumarate and vinyl acetate in about equimolar proportions having a number average molecular weight (VPO) prepared by about 15,000 by conventional means. use of a peroxide initiator and a solvent. The fumarate was prepared by esterifying fumaric acid with a mixture of straight chain alcohols having an average of about C12. A typical analysis of alcohol mixture is as follows: 0.7 weight percent C69 10 weight percent C8, 7 weight percent C10, Ä? weight percent C 17 weight percent Clu, 8 weight percent C16, 12 ”10 weight percent C18.

The fuels in which the additives were tested are described in the following table: Fuel l 2 3 H Grumiingspunxc, ° c + 2, o + 3, o +2,0 0,0 (measured according to Asmm D-3117) Wax milling point, C -2,5 -4, H -2,0 -3,5 (see ASTM D-3117) Distillation, OC (ASTM D ~ ll60) Initial boiling point ° c 18A 185 162 179 20% "" 2H9 230 203 22M 90% 351 BU5 537 330 slub boiling point 383 376 340 377 The following polar compounds (C) were used according to the examples. 1. cgu fi ugpn sou 'fi nu 2. "ÉHZ (c12H25) 2 3. 09Hl9 Pno" "u. Cl7H55 C02 7904580-3 22 5. CH3 (CH2) l5_l7 NH2 5. (CH5 (CH2) l5_l7) 2 NH 7. Cl8H37 OH 8 ClÄH29 OH In all cases the hydrocarbyl groups were straight chain.

The polymer additives A and B were added in the form of the aforementioned oil concentrates while the polar compound was added to the oil directly.

The initial response of the oil to the additives was measured by the cold filter insert point test (CFPPT) which is carried out using the method described in detail in "Journal of the Institute of Petroleum", Volume 52, Number 510, June 1966, p. l75 - l85. Briefly, a sample with the volume ÄO ml of the oil to be tested in a bath is cooled to about -BNOC.

Periodically (at each degree of temperature drop starting from at least 200 above the cloud point) the cooled oil is tested for the ability to flow through a fine mesh for a predetermined period of time using a test device consisting of a pipette at the lower end of which an inverted funnel is attached arranged below the surface of the oil to be tested. Extending across the mouth of the funnel is a mesh with a mesh size of 350 mesh with an aria of about 12 mm in diameter. The periodic tests are initiated by applying a vacuum to the upper end of the pipette, drawing oil through the mesh into the pipette to a mark indicating 20 ml of oil. The test is repeated at each temperature drop until the oil cannot fill the pipette within 60 seconds. The results of the test are given as the temperature (clogging point) in OC at which the oils do not fill the pipette within 1 minute.

The behavior of the oils while maintaining the low temperature was determined by subjecting the oils to cold storage testing whereby separate samples with the volume of 500 ml of each sample mixture in an additional giastr-to first cooled. Inea 1 ° c and 0.300 per hour from room temperature, about 2000, to -8OC. The sample mixture was then kept at -800 for the specified time.

A 50 ml volume of this cold-tested fuel mixture was withdrawn from the bottom of the funnel and transferred to another container and subjected to modified cold filter clogging point test (CFPPT). In this test, a sample at the cold storage temperature is sucked with a vacuum of 200 mm water column through a filter gauge, and the minimum mesh value through which the oil passes is measured. The quantity of oil was then allowed to return to room temperature (about 2000) after which it was subjected to cloud point determination according to ASTM.

Example 1 Visible wax deposition in fuel 1 treated with ethylene backbone copolymer, lubricating oil pour point depressant additive and some of the polar compounds (C) were observed and the following Table 1 shows the advantages of the three component mixtures for inhibiting wax deposition. 7904580 ~ 3 2H TABLE 1 Additive concentration (ppm) Wax layer (volume%) AB c ma) æhpg Swgæ- menu rang r rlng vad -8 ° c at -s ° c 'at -s ° c 100 - - 15 15 19 500 - - 15 15 13 500 - - 15 15 12 100 100 50 (1) 88 86 77 100 100 50 (2) 87 86 79 100 100 50 (3) - 89 _ - 86 79 100 100 50 (u) 89 _ ss 85 100 100 50 (5) 89 87 85 100 100 50 (6) 911 '89 87 100 100 50 _ (7) 88 U 0 89 86 Example 2 Wax deposition was determined quantitatively_by the wax enrichment of the bottom layer in cold-stored fuels. The greater the correlation of the wax development points (WAP) for the top and bottom (top and bottom) 10% layers in relation to the WAP for the original fuel, the less wax deposition has occurred. Table 2 shows that reduced wax deposition is obtained when the three component mixture is used in fuel 2. TABLE 2 Additive conc. (ppm) Wax developing point OC AB c No. (5) Top 10% Bottom 10% - - - - U, H -M, h 30o} - - -11.0 +5.5 'noo - - -11.5 +5 , - 600 - _ -12,0-, + H, 0 noo 200 1.00 - I:, 5 _ 41,11 In this test the fuel is cooled by 0,300 / h down to -800 and kept at this temperature for 70 hours.

Example 5 The polar compounds (C) were tested only in fuel 3 using standard CFPP test. The results in Table 5 show that these compounds do not in themselves have any significant wax crystal modifying properties. The results of the tests using conventional flow-enhancing additive (A) are added for comparison. TABLE 5 Additive I Concentration (ppm) CFPP (OC) None - -2 01. _ 100 '_ -3 Cl 300 -5 C2 100' -U 02 300 det -3 CB 100 -3 Cš 300 -S 100 -ll A 300 -15 7904580 ~ 3 26 Examples Eat Samples of fuel Ä treated with certain amounts of distillate flow enhancing additive (A), lubricating oil pour point depressant additive (B) and polar compound (C) were cooled to 5 ° below wax production points at 0.5 ° c / h and kept at this temperature for 35 hours. Table M shows the advantage of the three-component mixture over the conventional infant enhancement kit (A) for preventing wax deposition and obtaining improved filterability as shown by the modified CFPP test.

TABLE H Additive Conc. (ppm) Wax layer WAP for Minimum passed (v01. t) mesh mesh strength, A B 0 (No.) 10% (° 0) mesh _ _ _. _ _. .ögo 100- - - 10 -10,0 100 200 - - 10 100 H00 - - 10 - 150 100 200 100 (3) 1001 -u, 0 250 100 200 100 (8) 1001 -u, 0 Q 150 100 200 100 (5) 1001 -u, 5 250 100 200 100 (6) 1001 -H, o 250 l The three-component mixtures produced a completely cloudy sample with a slightly denser wax layer at the bottom while the fuel treated with A above had a clear supernatant. standing liquid above the deposited wax, which shows a smaller degree of wax deposition using the three-component mixture. Example 5 Fuel 2 was treated with A only and with the mixture of A, B and C. Table 5 shows the advantage of the three-component mixture compared to the conventional flow-enhancing additive (A) to reduce wax deposition and improve filterability. . The fuel is cooled to -800 (HOC below the normal wax development point -NCC) and kept at this temperature for 20 hours. The filterability was tested with the modified CFPP test at -800.

TABLE 5 Wax layer Wax induction - Minimum Additive Conc. (ppm) (vol.%) níngpunkt tpasserade _. gets 10% bottom mesh A _ B 0 (No.) (01 - - -. -u, 0 400 - - 9 5,5 60 600 - - 10 7,5 60 200 200 100 (1) 1001 - 150 200 200 100 (3) 1001 - 120 200 200 100 (M) 1001 -u, 0 150 200 200 100 (7) 1001 - 120 200 200 100 <5) 1001 3.0 250 200 200 100 (6) 1001 3.0 " 150.1 As Table Ä 7904580 ~ 3 as Example 6 Comparative tests were performed with fuel 1 using the polar compound C6 to show the advantages of using the three-component mixture instead of the combination of two of the components.

The fuel samples were cooled at 0.5 ° C / h down to e8 ° C and kept at this temperature for 72 hours and the results are shown in Table 6.

TABLE 6 Wax layer Passed Additive conc. (ppm) vol.% minimum mesh size, A _ ¿B C6 mesh 100 10 100 Gel is formed 100 Gel is formed 100 100 10 20 i 100 100 Gel is formed 100 lOO ll 20 1 W 100 200 100 100 ho l. As table H 7904580- Example 29 In the experiments according to this example, the flow-improving additive A1 consisted of the flow-improving additive A according to the previous example, and the lubricating oil pour point lowering additive B1 consisted of the additive B according to the previous example.

The lubricating oil pour point lowering additive B2 was Acryloid 157 which is a lubricating oil pour point lowering additive for high paraffinic oils sold by Rohm and Haas Co.

Dialysis showed that Aoryloid 157 consists of about 57% by weight of light hydrocarbon oil and about 53% by weight of active ingredient. The active ingredient has a specific viscosity of about 0.1U at 2% concentration in xylene at 10,000 and is a polymer comprising mainly alkyl methacrylate syrup. The polar compound C9 was prepared according to U.S. Patent No. 5,982,908 and consists of an amine salt of mono- amide of maleic anhydride. The compound was prepared by reacting maleic anhydride with secondary hydrogenated tallowamine (molecular weight about 505). The structure and composition of its main component are: CH = CH 0 = Å C = 0 R I RI 11> N O_H ° Reach 1.

E12 RI? The secondary hydrogenated tallow amine consists of a commercially available product sold by Armak Co., Chemicals Division, Chicago, Illinois and designated Armeen ZHT. For this reason, the R - and R12-n-alkyl groups in II are mixed because they are derived from tallow fat which consists of about 3% clnazg, 3h% cl6H33 and 65% cl8H57.

Laboratory preparation of C9 is carried out as follows: 10 g (0.01 mol) of maleic anhydride, 100 g (0.8 mol) of second hydrogenated tallow amine having a molecular weight of about 505, and 200 ml of benzene as solvent are heated under reflux for 3 hours to 85 ° C in an H-necked flask equipped with stirrer, thermometer, condenser and water trap. No water was formed under these conditions. The reaction mixture was removed and the solvent was distilled off to give 109.3 g of a maleic acid amine salt having a melting point of eu ° e.

C10 was a diamide prepared by reacting 2 moles of the aforementioned hydrogenated tallow amine with 1 mole of maleic anhydride and dehydrating the reaction product by heating to about 15,000.

The oil consisted of a distillate fuel oil with a WAP value (wax development point according to ASTM D-3117) of -1,500 and a distillation range as follows: I.B.P. (initial boiling point) 162 ° C, 20% distillation point 203 ° C, 90% distillation point 357 ° C and FBP (final boiling point) 375 ° C.

The oil mixtures 1 to H were prepared by dissolving the additives in the fuel oil by stirring, generally while heating the oil on a hot plate to about 90 ° C. The polymer additives were added in the form of the aforementioned oil concentrates while the amine salt was added to the oil directly. The mixtures were placed in a conventional graduated laboratory flask with a volume of 1,000 ml of cold storage by rapid cooling from room temperature to about 2000 to -6,500 in a freezer and then kept at -6,500 for 2U hours and H8 hours. The cold oil mixtures were then inspected visually. Then a bottom layer of 10% of the cold oil mixture was peeled off and subjected to a sight test which involved the use of a test device comprising a 20 ml volume pipette to which a vacuum was connected at the upper end while the lower end was terminated in a reverse funnel across over which was stretched a fine-mesh net with a diameter of about lä mm.

The test device is immersed in a sample with a volume of 50 ml of the cold oil in a CFPP test tube and a vacuum of about 20 cm of water column is applied. Acceptable results were obtained if the cloudy oil filled the pipette to the 20 ml mark without clogging the net. Pipettes with mesh with different mesh sizes were used. The smaller the size of the wax crystals formed, the finer the mesh width is passed by the waxy turbid oil.

The mixtures produced and their properties are summarized in Table 7. 7904580-3 32 I »omm o. @ + 1 1 omw o fi w + - I omm mm 4 om fl oo fl m_o fl + mm man pmm nwwmma nmmmmm oo.mæw nmwa .ø @ fl> xm @: px fi xmcwppøp mod mom & oo fi & om mm fi ^ u fifl mzmH> vm | Ho> Px fl ßmxxæ> 0om. @ | @ fi> wn fl nmm fl r MM S æz hwwmm .Uom.H | Nm saß om fi o fl o aan oo fi | - omm m.m + mom Hq Egg m> H 1 Nm aan mm fl 1 mo amg mp | 1 omm o + Roo fl flfi sam amd M Hm amg ømw mv aan om fi 1 | ømw oH + & ooH H <sam om fl N omm om fi m.o fl + & mH H <saa oom A ww han sms Hwmmma | mwmm @ oo.m <3 ^ u fi Hmsm fi> v Emm ..ocoz * ws fl c QmwE .Oö fl kwxmdwg .wlmfl flm m. px fl xmswppoß & oH »x fi zwxw> nm> cwn fl owmn mmm ^ m <3v: wpxQsQmw: HsHHmxEmnmxm> um Uom. @ | @ fl> ws flfi ww fifl mx Q zw fi mpwm N Qàmmdß 7904530-s kr! kr! Table 7 shows that the three-component additive systems of mixtures 2, 5 and U all gave a higher degree of wax dispersion, and for the bottom fraction lower developing points (WAP), as well as smaller wax crystals, as indicated by the cold oil passing through a mesh of 250 mesh, compared with the mixture l containing only the flowability improving additive. The mixture Ä gave good results in the filterability test as well as the mixtures 2 and 3, despite the fact that, unlike the latter mixtures, it showed considerable wax deposition. This shows that it is not the wax deposit itself but the agglomeration of the wax crystals in the presence of less effective flow-enhancing additives that is detrimental to the properties of an oil.

Example 8 In a number of the mixtures distillate flow-enhancing additive A2 was used which consisted of a concentrate of H5% by weight of the growth-promoting agent A1 (ie ethylene-vinyl acetate copolymer with 38% by weight of vinyl acetate having a molecular weight of 1,800, as previously described). ) in 55% by weight of light hydrocarbon oil. Lubricating oil pour point depressant additive B3 was a concentrate of about U5 weight percent copolymer of about equimolar proportions of vinyl acetate and alkyl fumarate having a specific viscosity of about 0.61 at 2 weight percent concentration in xylene at BBOC and a number average molecular weight of about in about 55% by weight of light hydrocarbon oil. The alkyl groups in the fumarate were derived from a mixture of C8 to C18 linear primary alcohols, and this mixture had an average molecular weight of about 188.

The intermediate distillate fuel oil used had a cloud point of -6 ° c and a WAP value of ~ 6 ° c, a: BP (initial boiling point) of 16000, 20% distillation point 217 ° c, 90% aesthetic boiling point 32700 and final boiling point 361 ° C. I _, ...__ _. ...-..._...._....-, _, _ i ... ..._.....-..-..... ~ ._... ..._. . . , _. 7904580-3 BU Elandníngarna 5 to 10 were prepared in the oil and cooled to -15 ° C in a freezer in a 500 ml graduated measuring tube with 1 ° C / h and was then maintained at -15 ° C for H8 hours. The behavior of the oil was observed and the bottom layer with a volume of 10% of the oil was removed and examined for WAP and for the filterability determined with nets of different mesh sizes using the aforementioned pipette apparatus.

The mixtures and results are given in Table 8 7904580-5 35 oomn mm cmw fl owmn mmm CwvxG3mmwG fi cHHwMEmmmxm> 1- ømm ml m .oø fl - | omw 1- som - | omw w- oo fl I- omm m N- _ oo fl mw om m + mo = Qom mm ~ + mo = llmmnm Illmmm || l1 | l 7: Guam lmmwmm oo.m <3 ^ pH fl m: m «> v QmmE .ps fl m & x fi o > mo fi zmpuom ux fi xmxw> oom fl | U fi> Q wa w flfi hwm fifl mx Awuum w Q fl mm fl ß Nm mo 2 mm mo H4 am mo m <Hm mo H4 N <H4 Emm nmumm fififl ß Emm Emm Emm Emm Emm Emm Emm Emm Emm Emm Emm Emm Emm Emm Emm Om fi ONH OO: Om OON 002 Orm OON 00 : OON OON OO: Qom Ooæ m »O fl m. Mm ¥ mC fl CøQm fi m 7904580-5 56 Table 8 shows that the three-component systems in mixtures 7 to 10 were superior in terms of the ability to keep the wax dispersed, maintain low WAP at the bottom of the oil and keep the wax crystals are small as evidenced by their ability to pass through a 250 mesh screen. This is in contrast to mixtures 5 and 6 which contained 800 ppm of the oil concentrates of the ethylene copolymers. Example 9 The intermediate distillate fuel oil used in this example had a WAP value of + 1 ° C, a cloud point of + 2 ° C, an intrinsic coke point of 177 ° C, a 20% distillation point of 222 ° C, a 90% distillation point of 33900 and a final boiling point of 36T °. C. 7904580-3 oo fi + hm> cm flfi ommn nam so @ x: 3mww: «: H fi mxEmnmxm> | | omm M + oo fl om fl om fi m fi m + om W. _ om: om fi N + oæ mm om fifl + om ow O: mH + ow om: Om fl m + om kan aomsæpw nwmmæm ooammš ^ o fifl m: w fl> v mwwë .px fi m w | Ho > mo fl: wvvom px fi xwxm> oom.o | s «> wsHsww :: ss Q w: swpsm m QQmm k Nm som oo: oo som oow w <som oo: o: Hm som oo: mo som oow N: som om: md mo som omw ~ <som oom: H Hm soo oo: oo sos oom: <som oo: M: oo som omm: <soo oom NH: <sas ooo.HH: Emm .munm flfifl ß «mQ fi Q © Sm fi m 7904580-3 38 Comparison of mixtures 12 and ll shows that the compound C9 in mixture 12 improved the visually determined dispersion of the wax in the oil. The mixture 13 improved the WAP value and the filterability measured by passing the sieve with the indicated 7 mesh size, compared to the mixture 12. The mixture 13 is not directly comparable with the mixture II in this respect due to the significantly lower content of Al, namely H00 millionths in mixture 13 against 1.100 ml of the mixture in mixture 11. however, when comparing the three-component systems in mixtures 15 and 16 and the two-component systems in mixture 1e, it appears that if comparisons are made on the basis of the same content of ethylene-copolymer concentrate (A2), mixtures 15 and 16 superior mixture lä.

EXAMPLE 10 The oil according to this example consisted of intermediate distillate fuel oil with a WAP value of -3.5 ° C and a starting boiling point of 17000, 20% distillation point 22500, 90% distillation point EUOOC 0nh_s1uuk boiling point 377 ° C.

The oil was tested in the same manner as in Example 9 using the aforementioned additives. The results are given in Table 10. 79Û4580 ~ 3 39 oomßml mm> smw fl owmn pmm: wuxc: @wmG fi: H fi mxEd fi Mxm> «| - omw N | §Oo fl || . omm m fi n I xoo fi 1- omw n | wood »I _ omm m“ m f fi oo fi omw on fl o + wow .Hßh nmccmuw uwwmmm oo ~ m <3 ^ uHHw: w fi> v nwmë Aux fi m & | Ho> oo fi swppom px fl xwxm> oom.o | @ fl> wo fi nwm fifi mx Q w: fi wwwm o fi qqmmqa Nm som ow fi o fi o som oo H <son o = ~ fi m Nm emo om fi mo emo om H <.som o fl m om mm Eon omw mo som oo fl H <som oß fl m fi Hm emo omw mo som oo fi H <som o> H. w fi o H4 soo oow »H Emm .mumw flfiflfi * ws fi cv fl m fl m ----> - vu -... w-n ...>. Table 10 shows that the three-component systems of mixtures 18, 19, 20 and 21 were much more effective than the one-component system of mixture 17 in preventing wax deposition.

Example 11 The oil according to this example consisted of an atmospheric intermediate distillate fuel oil with the cloud point OOC, the initial boiling point 173 ° C, 20% the boiling point 225 ° C, 90% the boiling point BHBOC and the final boiling point 371 ° C.

A majority of the above-mentioned additives were used for the preparation of fuel oil mixtures. In addition, two additional lubricating oil pour point depressants sold by Rohm and Haas Company, Afs., Under the designation Acryloid 153 and Acryloid 156, were tested. Acryloid 15 H consisted of a mineral oil concentrate containing about 65% by weight of active ingredient determined by dialysis. The specific viscosity of this active ingredient was about 0.21 determined at 2% by weight content of xylene at 38 ° C. The active ingredient mainly comprises a methacrylate polymer. Acryloid 156 was also a mineral oil concentrate containing about 64% by weight of active ingredient determined by dialysis. The active ingredient had a specific viscosity of about 0.1 H 3 at the concentration of 2% in xylene at 38 ° C and mainly comprises a methacrylate polymer. Acryloid 155 is hereinafter referred to as BH and Acryloid 156 is designated B5.

B6 was another lubricating oil pour point depressant additive that was tested. This material consisted of about 50% by weight of light mineral lubricating oil containing about 50% by weight of a copolymer of octadecene-1 and maleic anhydride in approximately equimolar amounts, prepared by free radical polymerization. The copolymer was esterified with about 1.6 mole parts of a mixture of G8-C16 linear primary alcohols having an average molecular weight of about 192, per mole of maleic anhydride in the copolymer. The number average molecular weight of the partially esterified copolymer was of the order of about 6,000.

The oil mixtures in containers with a volume of 500 ml were cooled in the freezer from room temperature down to -YOC at a rate of about 100 / h and cold-stored at -700 for 2 hours with the exception of mixture 23 which was cold-stored for 6 hours. Then the lower 10% bottom portion was peeled off and after warming to room temperature so that the wax redissolved in the oil, the bottom portion was tested for the ASTM cloud point and by CTPP test.

The mixtures prepared and the test results are summarized in Table II below. 7904580-3 H2 m | w ^ @ + v wf m + N: N + a + m + w + fi H +: + m + w: m + mn m + «* m + H fl + oo _ _ @> mmmu u> .. @. fl s:» w zaw < u> | <ø fi> ws fl amm fi f fifl mx Q wm fi wßww qßppop äo fi .U N- @ fi> ws fl pwm fi Q @ fi wpmm * .ooo sm Qm fifi ommm som uxQ: mwm: fi Hs: Lw | 2Bw <wm §N. | H <wmnono Hm mm @ m ~ o “o mu & fi o.o w I H <Rmo.o om Nm & mNo.o av §Ho.o> | H <& mo.o mm mm §m ~ o.o ¶ mo w fi o.o m 1 ~ <mno.o ww rm & m ~ o.o mo & Ho.o \ HH; H <§mo.o NN Hm @ m ~ o.o mo & Ho.o Q | H <wmo.ø mm Hm & ~ o.o. oH | mo & ~ o.o mw Nm & m ~ o.o. m | _ fi <§mo.o: N HH- H <& mo.o mm H 1 wpmm fififi p c @ wzH Nm w flfi hwm fl & IPSH> nnu fi mw flfifi ß, .f wß flfl ö fl d fi m. -fifi mx màßw ¶ oo qmmmo HH> q @ wm f um 79Û458Û ~ 3 113 As shown in Table ll, mixture 22 without any additive met the CFPP test at -l ° C and OOC before resp. after storage. The filterability properties of mixture 23, which contained Al, deteriorated sharply during the cold storage for only 6 hours. If mixture had been cold stored for ZH hours like the other samples, the CFPP value would also have been significantly higher. The three component systems in mixtures 26 to 31 showed CFPP values ranging from no difference between before and after cold storage for mixture 29 to a difference of 1700 for mixture 27. Low CFPP results both before and after storage are of course most desirable. Mixture 2H was a two component system from which the polar compound was omitted and gave a desirable low difference in CFPP before and after storage. However, this mixture contained a significantly larger amount of Al than the other comparative mixtures and also showed the smallest CFPP reduction for storage. The cloud point + 9 ° C for mixture B1 may be due to an anomaly or an error as this value appears high when compared to the low CFPP value after cold storage.

Example 12 The distillate flow enhancing additive A5 consisted of a concentrate of about 60 weight percent copolymer of about 50 weight percent ethylene and about 50 weight percent 2-ethylhexyl acrylate having a number average molecular weight of about 2,000 as measured by vapor phase monometry (VPO) light in about HO weight percent - oil.

The oil according to this example consisted of a distillate fuel oil with the cloud point OOC according to ASTM and the distillation range (ASTM-D-1160) as follows: initial boiling point 17000, 5% distillation point 188 ° C, 20% distillation point 22500, 90% distillation point BHBOC and the final distillation point 57100. 7904580-5 now Oil mixtures were prepared as described above and 500 ml of each mixture in a laboratory addition glass funnel was subjected to gentle cooling at a rate of 1 ° C per hour from room temperature about 2000 until sample the fuel mixture reached a temperature of -7 ° C. The sample mixture was then kept at -700 for a period of EH hours.

Then, a 50 ml volume of this cooled sample fuel mixture was withdrawn from the bottom of the funnel and transferred to another container. This bottom fraction was heated, for example, allowed to return to room temperature (about 2000) so that the wax redissolved in the oil, after which it was subjected to ASTM cloud point measurement and cold filter replacement point test (CFPP).

The results are summarized in the following table 12. 7904580-3 nä n ßo wm fl o Q o N fl- oø fi NH »m <æ fi ono wm \ Hm m ~ o.o fi H + o fl | \ N oH | m <mmo “o mm av @m« @@> m + N + wm fi H | m <fwWo.m am N fl + B + mm m fl »mq m@o.o wm O m x mm m 1 _ cwws fi mm 1: Q Apwcsß Q ^;« ML w fifi nwm WMI: \ | ¶. r fl L_1m4 eñ .. rmw flfifi ëwhwlaßmq. o, .I ufnwo »pm fl w fifi mh fifi .. v ÛÛÛ sk, LÄR .mmhu @z fl Äm« @> @@@ Du fl mmmu mwppon mo fi wow! w fl> wz fi ëwm fifi mx S fi w pmphm N H A fl mm fl m. 7994580-5 us As shown in Table 12, mixture 36 containing the three-component system was superior to the flow-enhancing additive A3 alone (mixture 33) or superior to the two-component system of mixtures BU and 35. Mixture 36 was thus retained completely waxed and pre-dispersed in the oil. deposition of the wax crystals, which is evident from the fact that the wax layer had a volume of 100Z, ie the wax was completely dispersed in the oil.

CFPP testing of the bottom layer 10% gave the value ~ 12 ° C as well as the CFPP value for the whole fuel, i.e. CFPP was very low in both cases. The cloud point for mixture 36 was also the same as for fuel oil without any additive (mixture 32).

Example 13 The following polar compounds were used in this example.

Polar compound C11 consisted of an amide-amine salt prepared by reacting one mold part of phthalic anhydride and two mold parts of the secondary hydrogenated tallow amine (Armeen EHT) used according to Example 7.

The polar compound C12 was a diamide of phthalic anhydride and the same secondary newly hydrogenated amine prepared by reacting one mole of phthalic anhydride with two moles of the amine heated in solvent to dehydrate and form the diamide.

Two intermediate distillate fuels were used with the following properties.

Fuel A was an intermediate distillate fuel oil with WAP -600, ASTM cloud point -306, initial boiling point 180OC, 10% distillation point 21100, 50% distillation point 26800, 90% distillation point BESOC and final boiling point 365OC. The filling point for cold filtration of the fuel only (CFPP test) was -700. . . _- _-..__. ._ ..__..____...., ..V ._.._....._.___.-...__..._ .. 7904580-3 47 Fuel B was an intermediate distillate fuel oil with WAP -2,500, initial boiling point 18400, 20% distillation point 2M9 ° C, o 90% distillation point 35100 and final boiling point 383 C.

Mixtures 57 to H2 were prepared and about 500 ml of each mixture in a glass addition funnel was subjected to temperature cycling testing. In this case, the oil was cooled at 100 / h for 10 hours to the test temperature starting from the temperature 1000 above the test temperature. As an example, the cooling was started at 100 / h at -100 for a test temperature of -1100, at + 2 ° C for a test temperature of -800 and at 0 ° C for a test temperature of -1000. The mixtures were stored for 30 hours at the test temperature and then heated for a period of 2 hours to the starting temperature, 1000 above the test temperature, and then kept at the starting temperature for 5 hours, then cooled again under 10 hours to the test temperature at the rate of about 100 / h, and then cooled at the test temperature for about 10 hours. A bottom layer with a volume of 10% of the oil mixture was then removed and subjected to modified CFPP testing. In this modified test, the bottom sample with a volume of 50 ml at the test temperature with a vacuum of 200 mm water column is drawn through a filter net into a 20 ml volume pipette according to the CFPP test device, and the mesh size of the smallest net through which the oil mixture passes before clogging of the network was determined. The composition of the tested mixtures and the results are summarized in the following Table 13. 7904580-5 about fi ow fl omm M about fl | , | om fi om fl omm om | oem om om ¶ oow om om »pmw: @wH omñ Q OH: U 1: 111 |: | 1m1mH | ps »wcdcwonm m: fi c> wmm wæaWmEwwmmcHs> onm m w fl wcwnm <m fl wcmmm smmë .øw fi> xmmE @ mQ vmnwmmma mpwøwâ ma AAmm NHQ amg oo fl mm aan oem H <sam Qom Oow H: sam Qom Oow N: fifi o fifi ø saa oo fi mm amg com H <amg oem 0: fi <sam cow mm H <agg com wm H <Emm oem Nm Emm wumw flflfi s ws fi zøsa fl m ___, _, _- .. .__ f- _ .. V .... ._._...-. .__-....._-......__..-._.._._- ..._..__._.___._. As shown in Table 1, the mixtures HO to H2 containing the three components were significantly more effective in keeping the wax crystals small, as evidenced by the ability of these mixtures to pass through nets of finer mesh size than the comparative mixtures 37 to 7904580-3. 59 which contained only the flow-enhancing additive A1. gšgmpel lä The fuel used according to this example had the cloud point -BOC, the WAP value -600, the initial boiling point 18000 and the final boiling point 365 ° C and the CFPP value -YOC. The distillate flow enhancing additive used was Al according to Example 7 and lubricating oil pour point depressant Additive B according to Example 1 while the polar compound C13 was polyisobutyl succinic anhydride, the pol * isobutylene chain having a molecular weight of about 1,000.

The treated fuel was cooled at 1 ° C / h to -1 ° C, it was kept at -1 ° C for 55 hours and then heated to 0 ° C and kept at 0 ° C for 8 hours and cooled again at 1 ° C / h to - 11 ° C and kept at -11 ° C for an additional 9 hours. A sample of the cold-stored fuel was then sucked through a filter under a pressure of 200 ml of water column and the minimum mesh size in mesh through which the material could pass was determined and the results are given in Table lü. . , .- ..,. , ..- .., _.,. -. ......-............ i-, _.__-....._...__ .., ._. 7904580-3 50 TABLE lä Mixture l first passed mesh width, mesh ÄB 150 ppm Al 85 150 ppm B 100 ppm C13 äü 150 ppm Al 100 150 ppm B 150 ppm C15 Example 15 According to this example, a fuel oil with a cloud point + 20C was used. the wax developing point ~ ü0C, the initial boiling point 18500 and the final boiling point 37600. The CFPP temperature of the crude fuel was -500. The polar compound C1a consisted of the diamide of the polyisobutyl succinic anhydride C13 according to Examples 1c and dinormalbutylamine.

The treated fuel was cooled at 100 / h to -800 and kept at -8 ° C for 30 hours, heated to + 2 ° C for 2 hours and held at + 2 ° C for 5 hours and refrigerated again. to -8 ° C but l ° clh and kept again at -8 ° C for a further 10 hours. 20 ml of a bottom layer of 10% by volume of the sample was sucked through a filter under a pressure of 200 mm water column, the minimum mesh size in mesh being passed being given in the following Table 15. '' '7904580-5 51 TABLE iâ Additive Minimum passed Mixture concentration ppm mesh size, mesh H5 150 ppm Al 60 150 ppm B 75 PPM C13 H6 150 ppm Al 250 150 ppm E 75 ppm Cl fl According to the previous example, the polymers were used in the form of concentrates and for this reason the tables indicate the amount of polymer concentrate used . The actual amount of polymer per se, i.e. the active ingredient is smaller. Thus, in a mixture of 500 million parts by weight and based on the weight of the oil, of the flow-improving additive A1 which consisted of a concentrate with H5% of the polymer in question was used.

Thus, 225 ppm of the polymer in question was used in Mixture 1.

The weight percent ranges and the relative amounts of the three additive components of the invention, as set forth in the specification and claims, are based on active ingredients, i.e. polymers per se and nitrogen compound per se.

Claims (5)

7904580-5 52 PATENT CLAIMS 1. A fuel composition characterized in that it comprises distillate fuel oil and from 0.001 to 0.5% by weight of a flowability and filterability enhancing multicomponent additive composition comprising: (A) a part by weight of a distillate flow enhancing composition constituted of a ethylene backbone polymer having a molecular weight of 500 to 500,000 and is selected from the group consisting of branched polyethylene, hydrogenated polybutadiene, chlorinated polyethylene having 10 to 35% by weight chlorine and copolymers comprising substantially 3 to 40 parts by weight of ethylene with one part by weight of monomer selected from the group consisting of: C3 to C16-dimonoolefin, vinyl chloride and ethylenically unsaturated alkyl ester of the formula: ii in which R1 is hydrogen or methyl; R 2 is a group -OOCR 4 or -COOR 4; R 4 is hydrogen or a C 1 to C 28 alkyl group; and R 3 is hydrogen or -COOR 4, and mixtures of these comonomers; (B) 0.1 to 10 parts by weight of a lubricating oil pour-point lowering additive, which is an oil-soluble polymer having a molecular weight of 1,000 to 200,000, wherein at least 10% by weight of the polymer is in the form of straight chain alkyl groups having 6 to 30 carbon atoms and the polymer comprises unsaturated ester and / or olefin groups which constitute a predominant weight fraction of the polymer; (C) 0.1 to 10 parts by weight of a polar oil-soluble compound other than (A) and (B) and of the formula RX in which R is an oil-soluble hydrocarbon group and X is a polar group, the compound having the foregoing defined action and acts as anti-aggregation agents for wax particles in the oil. 2. A fuel composition according to claim 1, characterized in that the polar compound consists of an oil-soluble nitrogen compound containing a total of 30 to 300 carbon atoms and having at least one straight-chain alkyl segment having 8 to 40 carbon atoms selected from the class consisting of amine salts and / or amides of hydrocarbyl carboxylic acids or anhydrides having 1 to 4 carbon atoms. Fuel composition according to claim 2, characterized in that the nitrogen compound consists of an aliphatic C4 dicarboxylic acid or anhydride in which one of the carboxyl groups is reacted with either C12 to C30 straight chain alcohol or a secondary alkyl monoamine having straight chain C12 to C30 alkyl groups, to form a monoester or a monoamide, and the other of the carboxyl groups is reacted to form an amide or amine salt with a secondary alkyl monoamine having straight chain C12 to C30 alkyl groups. 4. A fuel composition according to claim 2, characterized in that the nitrogen compound consists of an aromatic dicarboxylic acid or anhydride which is reacted with a secondary alkyl monoamine having straight chain C12 to C30 alkyl groups. ' Use as an additive for distillate fuels of a three-component combination comprising (A) a distillate flow-improving composition, (B) a lubricating oil-pour-point lowering additive and (C) a polar oil-soluble compound other than (A) and ( B) of the formula RX, in which R represents an oil-solubilizing hydrocarbon group and X is a polar group, which compound acts as an agglomerating agent for wax particles in the fuel oil, characterized in that the combination contains 1 part by weight of the distillate flow-enhancing composition and 0.1 to 10 parts by weight of the polar oil-soluble compound of formula RX.