Improvements in fuels

Abstract

Use of at least one wax anti-settling additive, optionally in combination with one or more other additives, to reduce the filter clogging propensity of a fuel composition having a filter clogging propensity, wherein the fuel composition comprises a renewable diesel component and a biodiesel component.

Description

[0001] The present invention relates to improvements in fuel compositions, and in particular to improving the properties of blended fuel compositions comprising renewable diesel and biodiesel.

[0002] Due to environmental concerns, a great deal of effort has been made to develop alternative hydrocarbon fuels to fossil fuels for driving internal combustion engines. The present invention particularly relates to alternatives to mineral diesel fuels.

[0003] One alternative fuel suitable for use in diesel engines is biodiesel. Biodiesel is produced by transesterification of lipids obtained from plants or animals, such as tallow oil, soybean oil or other vegetable oils. Transesterification of triglycerides obtained from these plant or animal sources with alcohols such as methanol, ethanol or propanol produces monoalkyl esters as biodiesel fuel.

[0004] Renewable diesel is produced from biomass sources by biological, thermal and chemical methods. Typically, renewable diesel is obtained by hydrotreating vegetable oils with hydrogen at elevated temperatures and pressures in the presence of a catalyst. Renewable diesel is sometimes referred to as hydrogenated vegetable oils.

[0005] Renewable diesel contains mainly saturated, mostly straight-chain aliphatic hydrocarbons. Biodiesel consists mainly of monoalkyl esters. Mineral diesel usually contains aromatic compounds and sulfates as well as aliphatic hydrocarbons.

[0006] New challenges may arise when replacing part or all of mineral diesel with renewable diesel and / or biodiesel due to the different chemical compositions of the fuels.

[0007] The present invention seeks to address some of the problems that can arise when using renewable diesel and biodiesel blends.Due to the different chemical properties of the renewable and biodiesel components of the blended fuel, problems can arise when storing the fuel, particularly if stored at low temperatures.

[0008] Three measurements are commonly used to evaluate the low temperature performance of diesel fuels. Standardized tests have been designed to measure the temperature at which the fuel fogs (cloud point - CP), the lowest temperature at which the fuel can flow (pour point - PP), and the lowest temperature at which the fuel flows through a filter (cold filter plugging point - CFPP); as well as their changes caused by additives (ΔCP, ΔPP, ΔCFPP).

[0009] The present invention is not about using additives to change the cloud point, pour point or cold filter plugging point of a fuel. Rather, the present invention seeks to address problems that may occur in a fuel when it is above the cloud point.

[0010] Diesel vehicle fuel systems are equipped with filters to prevent particulate matter from entering the final injection system. If such particulate matter is not removed, it may cause fuel injection system failure.

[0011] Problems can arise when filters become clogged, as this affects the rate at which fuel is delivered to the engine. This problem is different from the problems that occur during cold filter clogging, where wax forms at very low temperatures and clogs the filter until the wax re-dissolves. Filter clogging can occur due to the formation of particulate matter within the fuel, especially during storage. In recent years, the problem of filter clogging has become more prominent. This is because more sophisticated injection systems have been developed in order to reduce emissions and improve engine performance. Since these fuel injection systems operate at high temperatures and pressures, they are more susceptible to wear and damage if exposed to particulate matter in the fuel. As a result, the pore size of fuel filters has been reduced, and in some cases the diameter can be as low as 2 to 5 microns. The reduction in filter pore size inevitably leads to an increase in filter clogging problems. A clogged filter will restrict or prevent fuel from entering the engine. This can lead to engine starting problems and loss of power. In some cases, a clogged filter can cause the engine to shut down completely until the filter is replaced to protect the injection system, which causes great inconvenience to the user.

[0012] The present invention seeks to reduce the filter plugging tendency of fuels containing blends of renewable diesel and biodiesel fuels.The properties of these fuels are different from mineral diesel fuels and blends containing mineral diesel.

[0013] According to a first aspect of the present invention, there is provided the use of at least one wax anti-settling additive, optionally in combination with one or more other additives, to reduce the filter plugging tendency of a fuel composition having a tendency to plug filters, wherein the fuel composition comprises a renewable diesel component and a biodiesel component.

[0014] According to a second aspect of the present invention, there is provided a method for reducing the filter clogging tendency of a fuel composition having a tendency to clog filters, the fuel composition comprising a biodiesel component and a renewable diesel component, the method comprising adding to the fuel at least one wax anti-settling additive and optionally one or more other additives.

[0015] According to a third aspect of the present invention, there is provided a fuel composition comprising a renewable diesel component, a biodiesel component, at least one wax anti-settling additive and optionally one or more other additives; wherein the fuel composition has a reduced tendency to filter plugging compared to an otherwise identical fuel composition that does not comprise the wax anti-settling additive and has a tendency to plug the filter.

[0016] Preferred features of the first, second and third aspects of the invention will now be described.

[0017] The first, second and third aspects of the present invention relate to at least one wax anti-settling additive. This may relate to one wax anti-settling additive or a mixture of two or more wax anti-settling additives. The wax anti-settling additives mentioned herein include embodiments in which two or more wax anti-settling additives are present.

[0018] The present invention is directed to reducing the filter plugging tendency of a fuel composition comprising a biodiesel component and a renewable diesel component.

[0019] The fuel composition may optionally further comprise a mineral diesel component. In a preferred embodiment, the fuel composition does not comprise a mineral diesel component.

[0020] In this specification, by biodiesel, we mean esters of fatty acids. This fuel is commonly referred to as first generation biodiesel. Biodiesel as defined herein contains esters of, for example, vegetable oils, animal fats and waste edible fats. This form of biodiesel can be obtained by transesterification of oil with an alcohol, typically a monohydric alcohol, in the presence of a catalyst. The fatty acids used to produce the fuel can be derived from a variety of natural sources, including but not limited to vegetable oils, canola oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, sesame oil, soybean oil, corn oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, rapeseed oil, canola oil, palm kernel oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, camelina oil, tallow, beef tallow, butter, chicken fat, lard, dairy butter fat, shea butter, waste frying oil, oil miscella, waste cooking oil, yellow trap grease), hydrogenated oil, derivatives of said oil, fractions of said oil, conjugated derivatives of said oil, and any mixture thereof.

[0021] In this specification, by renewable diesel, we intend to refer to diesel fuel obtained by hydrodeoxygenation of fats and oils. This fuel is often referred to as second generation biodiesel and is derived from renewable resources such as vegetable oils and animal fats and is typically processed in refineries using, for example, hydroprocessing such as the H-Bio process developed by Petrobras. Second generation biodiesel is sold by ConocoPhillips as Renewable Diesel and by Neste as NExBTL. Renewable diesel fuel is sometimes referred to as hydrogenated vegetable oil (or HVO).

[0022] The fuel composition comprises a renewable diesel component and a biodiesel component. Preferably, the renewable diesel component accounts for at least 10% by volume of all fuel components present in the composition, preferably at least 30% by volume, more preferably at least 40% by volume, preferably at least 50% by volume.

[0023] Suitably the renewable diesel component comprises at least 60% by volume of all fuel components in the fuel composition, suitably at least 70% by volume, for example at least 75% by volume.

[0024] The renewable diesel component may provide up to 99%, preferably up to 95%, suitably up to 90%, for example up to 85% by volume of all fuel components present in the fuel composition.

[0025] The biodiesel component can account for at least 1 volume % of all fuel components present in the fuel composition, preferably at least 3 volume %, suitably at least 5 volume %, preferably at least 8 volume %, for example at least 10 volume %. The biodiesel component can account for at least 12 volume % of all fuel components present in the fuel composition, for example at least 15 volume %.

[0026] The biodiesel component can provide up to 90 volume % of all fuel components present in the fuel composition, for example up to 70 volume %, suitably up to 50 volume %, for example up to 40 volume % or up to 30 volume %. The biodiesel component can provide up to 25 volume % of all fuel components present in the fuel composition.

[0027] In some preferred embodiments, the fuel composition comprises 1 to 40 volume %, preferably 5 to 35 volume % of the biodiesel component and 60 to 99 volume %, preferably 65 to 95 volume % of the renewable diesel component.

[0028] In some further preferred embodiments, the fuel composition comprises 10 to 30 vol%, preferably 15 to 25 vol% of the biodiesel component and 70 to 90 vol%, preferably 75 to 85 vol% of the renewable diesel component.

[0029] In some particularly preferred embodiments, the fuel composition is a blended fuel comprising about 80% by volume of a renewable diesel component and about 20% by volume of a biodiesel component.

[0030] Preferably, the fuel composition comprises less than 10 vol% mineral diesel, preferably less than 5 vol%, more preferably less than 3 vol%, preferably less than 1 vol%, for example less than 0.5 vol% or less than 0.1 vol% mineral diesel.

[0031] In some embodiments, the fuel composition may contain trace amounts of mineral diesel. Such trace amounts may be present due to contamination of the fuel composition during transportation and / or storage using pipelines and / or tanks that previously contained mineral diesel.

[0032] In a particularly preferred embodiment, the fuel composition comprises no mineral diesel component.

[0033] In the present invention, the filter plugging tendency of a fuel composition comprising a biodiesel component and a renewable diesel component is reduced by adding a wax anti-settling additive and optionally one or more other additives.

[0034] Preferably, the wax anti-settling additive is selected from one or more of the following:

[0035] (a) reaction products of polycarboxylic acids having at least one tertiary amino group and primary or secondary amines;

[0036] (b) reaction products of α,β-dicarboxylic acids or their derivatives with primary amines;

[0037] (c) Reaction products of polyamines and fatty acids

[0038] (d) the reaction product of a secondary amine with a copolymer of maleic anhydride and an α-olefin;

[0039] (e) the reaction product of an anhydride of a polycarboxylic acid with at least two equivalents of a secondary amine;

[0040] (f) spirodilactone derivatives; and

[0041] (g) Mannich modified alkylphenol-formaldehyde resin.

[0042] This type of additive is known in the art as a wax anti-settling additive (WASA).In some embodiments, the wax anti-settling additive includes (a) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine.

[0043] The polycarboxylic acid with at least one tertiary amino group preferably has 2 to 20 carbon atoms, at least one tertiary amino group and 2 to 12 carboxylic acid groups. Each carboxylic acid group in the polycarboxylic acid preferably has 2 to 10 carbon atoms. The polycarboxylic acid groups can be the same or different. Preferably, each carboxylic acid group is an acetic acid group. The polycarboxylic acid preferably has 1 to 3 tertiary amino groups and 2 to 8 carboxylic acid groups. In a preferred embodiment, the polycarboxylic acid has 3 to 5, preferably 3 or 4 carboxylic acid groups and 1 to 3, preferably 1 or 2 tertiary amino groups.

[0044] In some preferred embodiments, the polycarboxylic acid has formula (I) or (II):

[0045]

[0046] wherein A is a linear or branched C2-C6 alkylene or HOOC-BN(CH2CH2)2, and B is a C1 to C 19 Alkylene.

[0047] Preferably, A has 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms.

[0048] Preferably, B has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.

[0049] Preferred carboxylic acids for preparing additive (a) include nitrilotriacetic acid, ethylenediaminetetraacetic acid and 1,2-propylenediaminetetraacetic acid.

[0050] The additive (a) is formed by reacting a polycarboxylic acid with a primary or secondary amine. Most preferably, the polycarboxylic acid is reacted with a secondary amine, preferably a secondary amine of formula HNR2, wherein each R is independently a linear or branched C 10 To C 30 Alkyl or alkenyl, preferably C 14 To C 24 Preferably, each R is an alkyl group. Preferably, each R is the same.

[0051] The secondary amines can react with the polycarboxylic acids to form amides and / or ammonium salts. In a preferred embodiment, all amines react to form amides.

[0052] Preferred amines for reaction with the polycarboxylic acids include dioleylamine, dipamitylamine, dicoconut fatty amine, distearylamine, dibehenylamine, and hydrogenated and / or unhydrogenated ditallow fatty amine. Ditallow fatty amine is particularly preferred. Hydrogenated ditallow fatty amine is preferred.

[0053] Those skilled in the art will appreciate that natural sources of fatty amines often contain mixtures of compounds, such as mixtures of isomers and / or mixtures of homologs.

[0054] Preferably, the amine is reacted with the carboxylic acid in a ratio of 0.5 to 1.5, preferably 0.8 to 1.2 mol of amine per carboxyl group present in the carboxylic acid.

[0055] An especially preferred additive component (a) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow amine.

[0056] In some embodiments, the wax anti-settling additive comprises (b) the reaction product of an α,β-unsaturated dicarboxylic acid or a derivative thereof and a primary amine. Those skilled in the art will appreciate that such a reaction product may include one or two amides, imides, salts, or mixtures thereof.

[0057] Preferred α,β-dicarboxylic acids for preparing additive (b) include succinic acid, maleic acid, fumaric acid, itaconic acid and derivatives thereof. These acids may be substituted. For derivatives of α,β-dicarboxylic acids, we mean to include carbonyl halides, carboxylic acid esters and carboxylic acid anhydrides. In some preferred embodiments, the α,β-dicarboxylic acid derivative is an anhydride. Most preferably, component (b) is the reaction product of maleic anhydride and a primary amine.

[0058] Preferred primary amines for reacting with α,β-unsaturated dicarboxylic acids are alkyl, alkenyl, aryl, alkaryl or aralkyl amines, preferably having 8 to 30 carbon atoms, more preferably 12 to 22 carbon atoms. Preferred amines are alkyl or alkenyl amines. The alkyl or alkenyl chain may be linear or branched, saturated or unsaturated. Mixtures of alkyl or alkenyl amines may be used. It will be appreciated by those skilled in the art that commercial sources of these amines typically contain mixtures of isomers and / or mixtures of homologues. In some preferred embodiments, natural sources of fatty amines are used, such as coconut amine, tallow amine, hydrogenated tallow amine, oleyl amine, arachidyl amine and behenyl amine.

[0059] The additive component (b) preferably comprises the monoamide or bisamide of maleic acid. Component (b) may also comprise a small amount of an ammonium salt.

[0060] In a preferred embodiment, component (b) comprises 1 mol of maleic anhydride and 1 mol of C 13 Reaction products of alkylamines.

[0061] In some embodiments, the wax anti-settling additive may include (c) a reaction product of a polyamine and a fatty acid.

[0062] Preferred polyamines are polyethylene polyamines. Examples of suitable polyamines that can be used to prepare the amines of component (c) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, polyethyleneimine having an average degree of polymerization (number of nitrogen atoms) of 10, 35, 50 or 100, and polyamines obtained by reacting oligoamines with acrylonitrile and subsequently hydrogenating, such as N,N'-bis-(3-aminopropyl)ethylenediamine.

[0063] Suitable fatty acids for reaction with the polyamine include pure fatty acids and commercial sources containing mixtures of fatty acids, including, for example, stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and linolenic acid. Particularly useful for preparing component (c) are mixtures of naturally occurring fatty acids, such as tallow fatty acid, coconut oil fatty acid, fish oil fatty acid, coconut palm kernel oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid and palm oil fatty acid. Compounds including monoesters of long chain alcohols and dicarboxylic acids may also be used as the fatty acid component.

[0064] Preferably, component (c) is prepared from polyethylene polyamines having 2 to 6 nitrogen atoms and fatty acids having 16 to 20 carbon atoms.

[0065] In a preferred embodiment, component (c) comprises the reaction product of 3 moles of oleic acid and 1 mole of diethylenetriamine.

[0066] In some embodiments, the wax anti-settling additive comprises the reaction product of (d) a secondary amine and a copolymer of an α,β-unsaturated dicarboxylic acid anhydride and an α-olefin.

[0067] Preferred compounds of this type are copolymers based on α,β-unsaturated dicarboxylic acid anhydrides, α,β-unsaturated compounds and optionally polyoxyalkylene ethers of lower unsaturated alcohols, comprising:

[0068] a) 20-80 mol % of divalent structural units A1 and / or A2

[0069]

[0070]

[0071] Where R 1 and R 2 are independently hydrogen or methyl,

[0072] X and Y are the same or different groups and are selected from N-HR 3 Group, where R 3 C6-C 40 -alkyl, C5-C 20 -cycloalkyl or C6-C 18 -aryl; N-(R 3 )2 group, wherein each R 3 the same or different and as defined above; and OR 4 Group, where R 4 Hydrogen, formula H2N + (R 3 )2 or H3N + R 3 Cations, C6-C 40 -alkyl, C5-C 20 -cycloalkyl or C6-C 18 - aryl;

[0073] b) 19-80 mol % of divalent structural units D

[0074]

[0075] Where R 5 is hydrogen or C1-C4-alkyl, and R 6 C6-C 60 -alkyl or C6-C 18 - aryl; and

[0076] c) 0-30 mol% of divalent structural units E

[0077]

[0078] Where R 7 is hydrogen or methyl, R 8 is hydrogen or C1-C4-alkyl, Z is C1-C4-alkylene

[0079] m is a number between 1 and 100, R 9 C1-C 24 -alkyl, C5-C 20 -Cycloalkyl, C6-C 18 -Aryl or --C(O)--R 10 , where R 10 C1-C 40 -alkyl, C5-C 10 -cycloalkyl or C6-C 18 -Aryl.

[0080] As will be understood by those skilled in the art, the copolymer may contain a small amount of un-ring-opened anhydride or imide structural units derived from the α,β-unsaturated dicarboxylic acid anhydride structural units A1 and / or A2.

[0081] Preferred copolymers do not contain the structural unit E. In a preferred embodiment, X is of the formula N-(R 3 )2, wherein R 3 C6-C 40 alkyl, and Y is of the formula OR 4 A group in which R 4 Formula H2N + (R 3 )2 cation, where R 3 C6-C 40 alkyl.

[0082] Preferred wax anti-settling additives (d) are derived from the reaction of a copolymer of maleic anhydride and an alpha-olefin having 6 to 30 carbon atoms with 2 equivalents of a fatty amine.

[0083] Particularly preferred compounds (d) are derived from copolymers of maleic anhydride and C18 alpha-olefins reacted with 2 equivalents of ditallow amine.

[0084] In some embodiments, the wax anti-settling additive includes (e) the reaction product of an anhydride of a polycarboxylic acid and at least two equivalents of a secondary amine.

[0085] Suitable wax anti-settling additives (e) have a total of 30-300, preferably 50-150 carbon atoms, and are oil-soluble amine salts and amides formed by reacting at least 1 molar part of a hydrocarbyl-substituted amine with 1 molar part of an anhydride (preferably a dicarboxylic anhydride) of an aromatic or alicyclic polycarboxylic acid having, for example, 2 to 4 carboxyl groups.

[0086] The amine may be a primary amine, a secondary amine, a tertiary amine or a quaternary amine, but is preferably a secondary amine. Tertiary amines and quaternary amines can only form amine salts. Examples of amines include tetradecylamine, coconut amine, hydrogenated tallow amine, and the like. Examples of secondary amines include coconut methylamine, dioctadecylamine, methyl-behenylamine, and the like. Amine mixtures are also suitable, and many amines derived from natural materials are mixtures. A preferred amine is of the formula HNR 1 R 2 Hydrogenated tallow secondary amine (secondary hydrogenated tallow amine), wherein R 1 and R 2 It is an alkyl group derived from tallow fat containing approximately 4% C14, 31% C16, 59% C18.

[0087] Examples of suitable carboxylic acids (and their anhydrides) include cyclohexane dicarboxylic acids, cyclohexene dicarboxylic acids, cyclopentane dicarboxylic acids, naphthalene dicarboxylic acids, and the like. Typically, these acids will have about 5 to 14 carbon atoms in the cyclic portion. Preferred acids useful in the present invention are phthalic acids, such as orthophthalic acid, terephthalic acid, and isophthalic acid.

[0088] Preferred compounds of this type have at least one linear alkyl segment extending from a compound containing 8 to 40 carbon atoms, preferably 14 to 24 carbon atoms. Preferably, the compound contains at least three alkyl chains, each containing 8 to 40 carbon atoms, and at least one ammonium salt, amine salt or amide bond.

[0089] A particularly preferred compound is the amidoamine salt formed by reacting 1 molar part of phthalic anhydride with 2 molar parts of hydrogenated ditallowamine.

[0090] Another preferred compound is the reaction product of pyromellitic anhydride and four equivalents of a secondary amine, particularly hydrogenated ditallow amine.

[0091] In some embodiments, the wax anti-settling additive includes (f) a spirodilactone derivative.

[0092] A preferred compound of this type is of the formula NR 1 R 2 R 3 The reaction product of an amine with an alkenyl-spirodilactone of the formula

[0093]

[0094] where R is in each case C8-C 200 -alkenyl, and R 1 , R 2 and R 3 are the same or different, and these groups R 1 , R 2 , R 3 At least one of them is C8-C 36 -alkyl, C8-C 26 -alkenyl or cyclohexyl, and the other groups are hydrogen or of the formula -(AO) x H or -(CH2) n -NYZ, A is C2H4 and / or C3H5, x is a number from 1 to 20, n is 2 or 3, and Y and Z are the same or different and are hydrogen or a group of formula (-AO) x H group.

[0095] Preferred wax anti-settling additives (f) include the reaction product of 1 mole of an alkenyl-spiro-bislactone with 2 moles of a dialkylamine such as ditallowamine (hydrogenated or unhydrogenated).

[0096] In some embodiments, the wax anti-settling additive comprises (g) a Mannich-modified alkylphenol-formaldehyde resin.

[0097] Mannich modified alkylphenol-formaldehyde resins can be obtained by Mannich reaction of alkylphenol-formaldehyde resins with at least one aldehyde and / or one ketone having 1 to 8 carbon atoms, preferably having 1 to 4 carbon atoms; and at least one compound having at least one alkylmonoamine or alkylpolyamine group (i.e. having multiple amine groups) (having 4 to 30 carbon atoms, hereinafter referred to as alkylamine). Alkylphenol-formaldehyde resins themselves can be obtained by condensation of at least one alkylphenol (preferably monoalkylphenol) substituted with at least one linear or branched alkyl group having 1 to 30 carbon atoms,

[0098] The at least one aldehyde and / or the at least one ketone has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

[0099] Alkylphenol-formaldehyde resins are known per se and can be obtained from at least one para-substituted alkylphenol, preferably nonylphenol. The average number of phenolic nuclei per molecule of the preferred nonylphenol-formaldehyde resins is preferably 6 to 25, more preferably 8 to 17 or 9 to 16, and can be determined by NMR or GPC.

[0100] The Mannich-modified alkylphenol-aldehyde resin is obtained from at least one aldehyde and / or one ketone (selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, acetone, preferably formaldehyde); and at least one alkylamine having at least one primary amine group, and advantageously at least one compound, all amine groups are primary amines. According to a preferred embodiment, the Mannich-modified alkylphenol-aldehyde resin can be obtained from at least one alkylamine having an aliphatic chain, the aliphatic chain having 12 to 24 carbon atoms, preferably 12 to 22 carbon atoms. According to a particularly preferred embodiment, the Mannich-modified alkylphenol-aldehyde resin according to the present invention can be obtained from at least one alkylamine having at least one primary amine group and comprising an aliphatic chain having 12 to 24 carbon atoms, preferably 12 to 20 carbon atoms.

[0101] Further preferred features of compounds of this type are described, for example, in US Pat. No. 9,169,452.

[0102] In some embodiments, the wax anti-settling additive comprises component (a).

[0103] In some embodiments, the wax anti-settling additive comprises component (b).

[0104] In some embodiments, the wax anti-settling additive comprises component (c).

[0105] In some embodiments, the wax anti-settling additive comprises component (d).

[0106] In some embodiments, the wax anti-settling additive comprises component (e).

[0107] In some embodiments, the wax anti-settling additive comprises component (f).

[0108] In some embodiments, the wax anti-settling additive comprises component (g).

[0109] In some preferred embodiments, the wax anti-settling additive comprises one or more of component (a), component (b), component (c), and component (d).

[0110] In some preferred embodiments, the wax anti-settling additive comprises two or more of component (a), component (b), component (c), component (d), component (e), component (f), and component (g).

[0111] The wax anti-settling additive is suitably present in the fuel composition in an amount of at least 1 ppm, preferably at least 2 ppm, suitably at least 5 ppm.

[0112] The wax anti-settling additive may be present in the fuel composition in an amount of up to 1000 ppm, suitably up to 750 ppm, for example up to 500 ppm.

[0113] Preferably, the wax anti-settling additive is present in the fuel composition in an amount of from 1 to 1000 ppm, preferably from 2 to 500 ppm, for example from 5 to 250 ppm.

[0114] For the avoidance of doubt, when the fuel composition comprises a mixture of two or more wax anti-settling additives, the above amounts refer to the total amount of all wax anti-settling additives present in the composition. Unless otherwise stated, all ppm referred to in this specification are parts per million by weight.

[0115] According to the present invention, one or more other additives may be used with the wax anti-settling additive to provide a reduced tendency for filter plugging.

[0116] In some preferred embodiments, the one or more other additives include a copolymer obtained by reacting the following monomers:

[0117] (x) α-olefins;

[0118] (y) an ester of an unsaturated alcohol; and optionally

[0119] (z) a third monomer containing an alkene functional group different from (x) and (y).

[0120] Each of monomers (x), (y) and (z) may comprise a mixture of compounds, for example a mixture of isomers and / or a mixture of homologs.

[0121] Monomer component (x) is an alpha-olefin. Suitable alpha-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and higher monounsaturated homologues with up to 40 carbon atoms. Preferably, alpha-olefin component (x) is selected from ethylene, propylene and 1-butene, more preferably selected from ethylene and propylene. Most preferably, component (x) comprises ethylene.

[0122] Monomer (y) is an ester of an unsaturated alcohol. The term unsaturated alcohol is intended to refer to an alcohol containing a double bond. Preferably, the alcohol contains one double bond. Preferably, the double bond is adjacent to the hydroxyl functional group. In a preferred embodiment, the ester of the unsaturated alcohol is a vinyl ester.

[0123] Preferred esters are C1 to C 20 Esters of carboxylic acids, in particular vinyl esters of acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, neopentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, neononanoic acid, neodecanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid. Propylene esters of these acids may also be used.

[0124] In a particularly preferred embodiment, monomer (y) is vinyl ester of acetic acid, also known as vinyl acetate.

[0125] In some embodiments, the copolymer is prepared from monomers (x) and (y) only, and the copolymer is an ethylene vinyl acetate (or EVA) copolymer. Compounds of this type are well known to those skilled in the art. For example, suitable EVA copolymers for use herein are described in US3048479, GB1263152 and US3961916.

[0126] In some embodiments, the copolymer is a terpolymer obtained by reacting monomers of (x), (y), and (z).

[0127] Monomer (z) is different from (x) and (y) and comprises an olefin functionality. For this we mean that monomer (z) comprises a double bond. Preferably, monomer (z) comprises a single double bond.

[0128] In some embodiments, monomer (z) comprises an ester containing a double bond. The double bond may be present in the alcohol-derived portion of the ester or in the acid-derived portion of the ester.

[0129] In some embodiments, (z) may comprise an olefin. In some embodiments, (z) may comprise an ester of an unsaturated alcohol different from monomer (x).

[0130] Preferably, monomer (z) is selected from:

[0131] - olefins, especially α-olefins;

[0132] -α,β-unsaturated carboxylic acid or its ester; and

[0133] - Esters of unsaturated alcohols.

[0134] In some embodiments, the polymer may be prepared from a mixture of monomers (z).

[0135] In some embodiments, monomer (z) comprises an olefin, especially an α-olefin different from component (x). Suitable α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and higher monounsaturated homologues having up to 40 carbon atoms.

[0136] In a preferred embodiment wherein component (x) comprises ethylene, component (z) comprises propylene.

[0137] In some embodiments, component (z) comprises an α,β-unsaturated carboxylic acid or an ester thereof. Preferred monomers are esters of α,β-unsaturated carboxylic acids. Suitable α,β-unsaturated acids that can be used to prepare monomer (z) include acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid. Preferred monomers are these acids with C1 to C 20 Esters of alcohols.

[0138] In some preferred embodiments, monomer (z) is selected from methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, neopentyl acrylate, heptyl acrylate, octyl acrylate, neooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, neononyl acrylate, decyl acrylate, neodecyl acrylate, lauryl acrylate, palmityl acrylate and stearyl acrylate.

[0139] Preferred monomers (z) include methyl acrylate and 2-ethylhexyl acrylate.

[0140] In a preferred embodiment, component (z) comprises 2-ethylhexyl acrylate.

[0141] In some embodiments, component (z) comprises an ester of an unsaturated alcohol different from monomer (y).

[0142] In such an embodiment, component (z) is preferably a vinyl ester of a fatty acid having a linear or branched alkyl group having 1 to 30 carbon atoms, especially 1 to 18 carbon atoms. Examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl heptanoate, vinyl octanoate, vinyl laurate and vinyl stearate, and esters of vinyl alcohol based on branched fatty acids, such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl isononanoate, vinyl neononanoate, vinyl neodecanoate and vinyl neoundecanoate.

[0143] In a preferred embodiment, component (z) comprises the vinyl ester of neononanoic acid.

[0144] Some preferred terpolymers are formed from ethylene, vinyl acetate and vinyl neononanoate; or from ethylene, vinyl acetate and vinyl neodecanoate; or from ethylene, vinyl acetate and vinyl neoundecanoate; or from ethylene, vinyl acetate and vinyl 2-ethylhexanoate. Particularly preferred terpolymers of vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate and vinyl 2-ethylhexanoate contain, in addition to ethylene, 7.7 to 15.9 mol %, in particular 9.5 to 15.4 mol % and especially 10.0 to 15.0 mol %, for example 10.5 to 15.0 mol % of vinyl acetate, and 0.1 to 6 mol %, in particular 0.2 to 5 mol %, and especially 0.3 to 5 mol % of corresponding long-chain vinyl esters, with a total comonomer content of 8.0 to 16.0 mol %, in particular 10.0 to 15.5 mol %, and especially 10.5 to 15.0 mol %, for example 10.5 to 14.5 mol %.

[0145] (Meth) acrylic acid esters suitable as comonomers are esters of acrylic acid and methacrylic acid, and preferably those having 1 to 20 carbon atoms in the alkyl group, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate. Also suitable are mixtures of two, three, four or more of these comonomers. In a preferred embodiment, terpolymers of ethylene, vinyl esters and (meth) acrylic acid esters can be used, for example terpolymers of ethylene, vinyl acetate and methyl acrylate, terpolymers of ethylene, vinyl acetate and isobutyl acrylate, or terpolymers of ethylene, vinyl acetate and 2-ethylhexyl acrylate. Particularly preferred terpolymers contain, in addition to ethylene, 1 to 20 mol %, in particular 2 to 18 mol % and especially 5 to 15 mol %, for example 8 to 12 mol % of vinyl acetate and 0.1 to 10 mol %, in particular 2 to 8 mol % and especially 4 to 6 mol % of a specific (meth)acrylic acid ester, with a total comonomer content of 5 to 30 mol %, in particular 10 to 20 mol % and especially 12 to 18 mol %, for example 13 to 17 mol %.

[0146] Further preferred terpolymers contain, in addition to ethylene and 8.0 to 17 mol %, more preferably 10 to 16.0 mol %, and in particular 10.5 to 15.5 mol %, for example 10.5 to 15.0 mol %, of one or more vinyl esters, 0.1 to 5 mol %, preferably 0.2 to 4 mol %, of one or more olefins having 3 to 8 carbon atoms, for example propene, butene, isobutene, hexene, 4-methylpentene, octene, diisobutene and / or norbornene, in which case their molar content is deducted from the molar content of ethylene. The preferred olefin is propene. Particularly preferred terpolymers of ethylene, one or more vinyl esters and propene have 0.5 to 4.0 methyl groups derived from propene per 100 aliphatic carbon atoms. By 13 C NMR spectroscopy determines the number of methyl groups derived from propylene (propylene CH3) per 100 aliphatic carbon atoms.

[0147] The number average molecular weight Mn of the terpolymer is preferably from 1000 to 7000 g / mol and in particular from 1200 to 5000 g / mol. The weight average molecular weight is preferably from 2000 to 20000 g / mol, more preferably from 3000 to 15000 g / mol and in particular from 3500 to 12000 g / mol, in each case determined by gel permeation chromatography (GPC) in THF relative to poly(styrene) standards. The molecular weight of the copolymers can also be characterized by their melt viscosity; preferred copolymers preferably have a melt viscosity of 20 to 5000 mPas, in particular from 30 to 2000 mPas and in particular from 50 to 1500 mPas, measured at 140° C. (solvent-free).

[0148] Some preferred copolymers for use herein include terpolymers of ethylene, vinyl acetate and propylene; terpolymers of ethylene, vinyl neononanoate and propylene; terpolymers of ethylene, vinyl neodecanoate and propylene; terpolymers of ethylene, vinyl 2-ethylhexanoate and propylene; and terpolymers of ethylene, vinyl acetate and 2-ethylhexyl acrylate.

[0149] Preferred copolymers include polymers described in US7713316, US66306186, US8642521, US78115697 and US2017 / 0233670.

[0150] When the copolymer is present it is suitably included in the fuel composition in an amount of at least 1 ppm, preferably at least 5 ppm, suitably at least 10 ppm.

[0151] When the copolymer is present it is suitably included in the fuel composition in an amount of up to 1000 ppm, suitably up to 750 ppm, for example up to 500 ppm.

[0152] Preferably, when the copolymer is present it is suitably included in the fuel composition in an amount of from 1 to 1000 ppm, preferably from 5 to 500 ppm, for example from 10 to 250 ppm.

[0153] Other additives that may be used in combination with the wax anti-settling additive to reduce the filter plugging tendency of the fuel composition include alkyl phenolic resins.

[0154] Suitable alkylphenol-formaldehyde resins are known to the person skilled in the art. They are described, for example, in Rompp Chemie Lexikon (Rompps Chemistry Lexicon), 9th edition, Thieme Verlag 1988-92, volume 4, pp. 3351ff.

[0155] The alkyl groups of the ortho- or para-alkylphenols have 1 to 20, preferably 4 to 16, and in particular 6 to 12 carbon atoms; they are preferably n-, tert- and isobutyl, n- and isopentyl, n- and isohexyl, n- and isooctyl, n- and isononyl, and n- and isodecyl, n- and isododecyl. The alkylphenol-formaldehyde resin may also contain up to 50 mol % of phenol units. For the alkylphenol-formaldehyde resin, the same or different alkylphenols may be used. The aliphatic aldehyde in the alkylphenol-formaldehyde resin B has 1 to 4 carbon atoms and is preferably formaldehyde. The molecular weight of the alkylphenol-formaldehyde resin is suitably 400-10,000, preferably 400-5000 g / mol. Preferably the resin is oil-soluble.

[0156] Alkylphenol-formaldehyde resins can be prepared in a known manner by base catalysis to form condensation products of the resol type, or by acid catalysis to form condensation products of the novolak type. Alkylphenol-formaldehyde resins prepared in both ways are suitable for use herein. Preferred are those alkylphenol-formaldehyde resins prepared by condensation in the presence of an acid catalyst.

[0157] To prepare the alkylphenol-formaldehyde resins, difunctional o- or p-alkylphenols or mixtures thereof having 1 to 20 carbon atoms, preferably 4 to 16 and in particular 6 to 12 carbon atoms per alkyl group are reacted with aliphatic aldehydes having 1 to 4 carbon atoms, using about 0.5 to 2 mol, preferably 0.7 to 1.3 mol and in particular an equimolar amount of aldehyde per mole of alkylphenol compound.

[0158] Suitable alkylphenols are in particular C4-C12-alkylphenols, such as o- or p-cresol, n-, sec- and tert-butylphenol, n- and isoamylphenol, n- and isohexylphenol, n- and isooctylphenol, n- and isononylphenol, n- and isodecylphenol, n- and isododecylphenol.

[0159] The alkylphenols used may comprise small amounts, preferably up to about 10 mol %, particularly up to 7 mol %, and especially up to 3 mol %, of dialkylphenols.

[0160] Particularly suitable aldehydes are formaldehyde, acetaldehyde and butyraldehyde; preference is given to formaldehyde or a reactive equivalent thereof.

[0161] Formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% strength by weight aqueous formalin solution. Corresponding amounts of trioxane can also be used.

[0162] Further preferred features of alkylphenol-formaldehyde resins suitable for use herein and methods of preparing such compounds are described in US5998530.

[0163] When present, the alkylphenol resin is suitably included in the fuel composition in an amount of at least 0.1 ppm, preferably at least 0.5 ppm, suitably at least 1 ppm.

[0164] When an alkylphenol resin is present it is suitably included in the fuel composition in an amount of up to 500 ppm, suitably up to 250 ppm, for example up to 100 ppm.

[0165] Preferably, when an alkylphenol resin is present, it is suitably included in the fuel composition in an amount of from 0.1 to 500 ppm, preferably from 0.5 to 250 ppm, for example from 1 to 100 ppm.

[0166] The diesel fuel composition of the present invention may include one or more other additives such as those common in diesel fuels. These include, for example, antioxidants, dispersants, detergents, metal deactivating compounds, wax anti-settling agents, low temperature flow improvers, cetane improvers, demisters, stabilizers, demulsifiers, defoamers, corrosion inhibitors, lubricity improvers, dyes, markers, combustion improvers, metal deactivators, odor masking agents, drag reducers, and conductivity improvers. Examples of suitable amounts of each of these types of additives will be known to those skilled in the art.

[0167] The present invention relates to reducing the filter plugging tendency of a fuel composition having a tendency to plug filters.

[0168] The fuel composition with the tendency of blocking filter that we are talking about refers to the fuel composition that will cause filter blocking if do not use additive as described herein to handle.The tendency of fuel composition blocking filter can be measured by many standard industrial tests.The fuel composition that is suitable for handling according to the present invention is the fuel composition that does not meet the requirements of this type of standard test when not adding the claimed additive.The reduction of the filter blocking tendency of fuel composition can be proved by the performance that realizes improvement in one of these tests.

[0169] A standard test method for determining filter plugging tendency (FBT) is described in ASTM D2068 / IP387. This general procedure is commonly used for middle distillate fuels containing biodiesel and biodiesel blends. Another test suitable for measuring filter plugging tendency is listed in IP618. One of these tests can be used to evaluate the present invention.

[0170] A preferred method for determining the clogging tendency of the filters of the present invention is the Canadian Cold Soak Filter Clogging Tendency Test (CSFBT). In this test, the fuel is stored at 1°C for 16 hours before evaluating filterability. The procedure for this test is listed in CAN / CGSB 3.0 No. 142.0-2019, and a modified version in which a renewable fuel is used instead of the specified isoparaffin solvent is described in Example 2. A similar test is the European Cold Soak Test CS IP387, in which the fuel is stored at 5°C for 16 hours.

[0171] In a preferred embodiment, the present invention reduces the filter plugging tendency of the fuel composition, as measured by the CSFBT test method. According to this method, the CSFBT test fuel composition is cooled to 1°C for 16 hours and then tested by filtration to provide a unitless value. This value is an indicator of how likely the fuel is to plug a filter, and values ​​less than 2 are generally considered acceptable.

[0172] Preferably, the present invention reduces the filter plugging tendency of a fuel composition which prior to treatment with the additive according to the present invention achieves a CSFBT test result of greater than 2. Suitably, the fuel composition provided by the present invention achieves a CSFBT test result of less than 2.

[0173] Preferably, the invention reduces the score of a fuel composition in a CSFBT test by at least 10%, suitably at least 20%, more preferably at least 30%, for example at least 40% or at least 50%.

[0174] The invention will now be further described by way of the further following non-limiting examples.

[0175] Example 1

[0176] A commercially derived fuel composition comprising a blend of 80 volume % renewable diesel and 20 volume % biodiesel was treated with 250 ppm of an additive comprising an aromatic solvent and approximately 50% of an active ingredient comprising a wax anti-settling additive.

[0177] Untreated blended fuel has the following properties:

[0178]

[0179] Example 2

[0180] The unadditised and additised fuel compositions described in Example 1 were tested according to a modification of the procedure of the standard CSFBT test method set forth in CAN / CGSB 3.0, No. 142-2019.

[0181] A summary of the modified test methods is as follows:

[0182] 1. The fuel composition sample is first conditioned to eliminate its thermal history.

[0183] 2. The fuel composition was then maintained at 1°C for 16 hours.

[0184] 3. The fuel composition was then heated to 25°C for 2-4 hours.

[0185] 4. After heating, the fuel composition was then passed through a glass fiber filter medium (pore size 1.6 μm) at a constant flow rate (20 mL / min).

[0186] 4.1. Monitor the pressure drop across the filter until 300 mL of the fuel composition has passed through the filter and use the maximum pressure drop to calculate the CSFBT result, or

[0187] 4.2. If the pressure drop reaches 105 kPa before filtering 300 mL of the fuel composition, use the volume filtered when 105 kPa is reached to calculate the CSFBT result.

[0188] 5. CSFBT test results can range from 1.0 (a fuel composition with very good filterability, essentially no separated material under the test conditions) to greater than 10 (a fuel composition with poor filterability, relatively high levels of separated material under the test conditions)

[0189] The results are shown in Table 1.

[0190] Table 1

[0191] fuel FBT Base fuel 3.88 Fuel with added additives 1.18

[0192] Example 3

[0193] Additive composition A was prepared, comprising the components listed in Table 2:

[0194] Table 2

[0195]

[0196] Additive composition A was added to a blended fuel containing 80% by volume renewable diesel and 20% by volume biodiesel. The biodiesel fuel component had the following fatty acid methyl ester distribution:

[0197] Components Standardized total amount (weight %) C16:0 9.35 C16:1 0 C18:0 3.88 C18:1 36.62 C18:2 / 3 49.08 C20:0 0.38 C20:1 0.37 C22:0 0.32 total 100

[0198] The renewable diesel component of the blended fuel had a cloud point of -11.5°C and a pour point of -12°C.

[0199] The resulting fuel compositions were tested according to the method described in Example 2.

[0200] The results are shown in Table 3.

[0201] Table 3

[0202] fuel Additive composition A (ppm) FBT Base fuel 0 3.88 Fuel with added additives 1000 1.87

[0203] Example 4

[0204] Additive Composition B was prepared, comprising the components listed in Table 4:

[0205] Table 4

[0206]

[0207] Additive Composition C was prepared, comprising the components listed in Table 5:

[0208] Table 5

[0209]

[0210]

[0211] Additive compositions A, B and C were added to a blended fuel containing 80% by volume renewable diesel and 20% by volume biodiesel. The biodiesel fuel component had the following fatty acid methyl ester distribution:

[0212] Components Standardized total amount (weight %) C14:0 2.56 C16:0 24.65 C16:1 2.45 C17:0 1.21 C17:1 1.14 C18:0 18.85 C18:1 44.02 C18:2 5.11 total 100

[0213] The renewable diesel component of the blended fuel had a cloud point of -11.5°C and a pour point of -12°C.

[0214] The resulting fuel compositions were tested according to the method described in Example 2.

[0215] The results are shown in Table 5.

[0216] Table 5

[0217] fuel Additive Composition Treatment Rate (ppm) FBT Base fuel 0 2.90 Base material + additive B 1000 1.94 Base material + additive C 1000 1.94

Claims

1. Use of at least one wax anti-settling additive, optionally in combination with one or more other additives, to reduce the filter plugging tendency of a fuel composition having a tendency to plug filters, wherein the fuel composition comprises a renewable diesel component and a biodiesel component.

2. A method for reducing the filter plugging tendency of a fuel composition having a tendency to plug filters, and the fuel composition comprises a biodiesel component and a renewable diesel component, the method comprising adding to the fuel at least one wax anti-settling additive and optionally one or more other additives.

3. A fuel composition comprising a renewable diesel component, a biodiesel component, at least one wax anti-settling additive, and optionally one or more other additives; wherein the fuel composition has a reduced tendency to plug filters compared to an otherwise identical fuel composition that does not comprise the wax anti-settling additive and has a tendency to plug filters.

4. The use, method or composition of any preceding claim, wherein the fuel composition comprises 5 to 35 volume % of a biodiesel component and 65 to 95 volume % of a renewable diesel component.

5. The use, method or composition according to any one of the preceding claims, wherein the wax anti-settling additive is selected from one or more of the following: (a) reaction products of polycarboxylic acids having at least one tertiary amino group and primary or secondary amines; (b) reaction products of α,β-dicarboxylic acids or their derivatives with primary amines; (c) reaction products of polyamines and fatty acids; (d) the reaction product of a secondary amine with a copolymer of maleic anhydride and an α-olefin; (e) the reaction product of an anhydride of a polycarboxylic acid with at least two equivalents of a secondary amine; (f) spirodilactone derivatives; and (g) Mannich modified alkylphenol-formaldehyde resin.

6. The use, method or composition according to any one of the preceding claims, wherein the fuel composition comprises a mineral diesel component.

7. The use, method or composition of any one of claims 1 to 5, wherein the fuel composition does not comprise a mineral diesel component.

8. The use, method or composition of any preceding claim, wherein the wax anti-settling additive comprises (a) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine.

9. The use, method or composition of any preceding claim, wherein the wax anti-settling additive comprises (b) the reaction product of an α,β-dicarboxylic acid or a derivative thereof and a primary amine.

10. The use, method or composition of any preceding claim, wherein the wax anti-settling additive comprises (c) the reaction product of a polyamine and a fatty acid.

11. The use, method or composition of any preceding claim wherein the wax anti-settling additive comprises (d) the reaction product of a secondary amine and a copolymer of maleic anhydride and an alpha-olefin.

12. The use, method or composition of any preceding claim, wherein the wax anti-settling additive comprises (e) the reaction product of an anhydride of a polycarboxylic acid and at least two equivalents of a secondary amine.

13. The use, method or composition of any preceding claim, wherein the wax anti-settling additive comprises (f) a spirodilactone derivative.

14. The use, method or composition of any preceding claim, wherein the wax anti-settling additive comprises (g) a Mannich-modified alkylphenol-formaldehyde resin.

15. The use, method or composition of any one of the preceding claims, wherein the wax anti-settling additive comprises two or more of component (a), component (b), component (c), component (d), component (e), component (f) and component (g).

16. The use, method or composition according to any one of the preceding claims, wherein the one or more other additives comprise a copolymer obtained by reacting the following monomers: (x) α-olefins; (y) an ester of an unsaturated alcohol; and optionally (z) a third monomer comprising an olefin functional group different from (x) and (y).

17. The use, method or composition of any preceding claim, wherein the one or more other additives comprises an alkylphenol resin.

18. The use, method or composition of any preceding claim, which provides improved filter plugging tendency as measured by the Canadian Cold Soak Filter Blocking Propensity Test CAN / CGSB-3.0 No. 142.0-2019.

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