Improvements in fuels

Abstract

One or more additives are used to reduce the filter clogging tendency of a fuel composition having a filter clogging tendency, wherein the fuel composition comprises a renewable diesel component and a biodiesel component; and wherein the one or more additives are selected from the group consisting of (d) copolymers comprising units of formula (I) and units of formula (II): # imgabs0 # wherein R is an alkyl group and R1 and R2 are each an alkyl or alkenyl group having 6 to 22 carbon atoms; (e) a reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; and (f) a reaction product of a secondary amine and a copolymer of maleic anhydride and an alpha-olefin.

Description

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

[0002] Due to environmental concerns, great efforts have been made to develop hydrocarbon fuels to replace fossil fuels for powering internal combustion engines. The present invention particularly relates to alternatives to mineral diesel fuels.

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

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

[0005] Renewable diesel contains mainly saturated, straight-chain or branched aliphatic hydrocarbons. Biodiesel consists mainly of monoalkyl esters. Mineral diesel usually contains aromatic and sulfated substances as well as aliphatic hydrocarbons.

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

[0007] The present invention seeks to address some of the problems that may arise when using a blend of renewable diesel and biodiesel.Due to the different chemical properties of the renewable component and the biodiesel component of the blended fuel, problems may arise when storing the fuel, particularly when 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 becomes cloudy (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); and the changes caused by additives to these (ΔCP, ΔPP, ΔCFPP).

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

[0010] Diesel vehicle fuel systems are equipped with filters to prevent particulate matter from reaching the final injection system. If these particles are not removed, they may cause failure of the fuel injection system.

[0011] When a filter becomes clogged, problems can occur because 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, during which 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 in the fuel, especially during storage. In recent years, problems with filter clogging have become more prominent. This is because more complex 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 problems with filter clogging. A clogged filter will restrict or prevent fuel from reaching the engine. This can cause problems with engine starting and power loss. In some cases, a clogged filter may cause the engine to shut down completely until the filter is replaced to protect the injection system, which is a great inconvenience for the user.

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

[0013] According to a first aspect of the present invention, there is provided the use of one or more 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; and wherein the one or more additives are selected from:

[0014] (a) A copolymer comprising units of formula (I) and units of formula (II):

[0015]

[0016] Wherein, R is an alkyl group, and R 1 and R 2 Each is an alkyl or alkenyl group having 6 to 22 carbon atoms;

[0017] (b) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; and

[0018] (c) The reaction product of a secondary amine with a copolymer of maleic anhydride and an alpha-olefin.

[0019] 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 the filter, wherein the fuel composition comprises a biodiesel component and a renewable diesel component, the method comprising adding to the fuel one or more additives selected from the group consisting of:

[0020] (a) A copolymer comprising units of formula (I) and units of formula (II):

[0021]

[0022] Wherein, R is an alkyl group, and R 1 and R 2 Each is an alkyl or alkenyl group having 6 to 22 carbon atoms;

[0023] (b) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; and

[0024] (c) The reaction product of a secondary amine with a copolymer of maleic anhydride and an alpha-olefin.

[0025] According to a third aspect of the present invention, there is provided a fuel composition comprising a renewable diesel component, a biodiesel component and one or more additives; wherein the fuel composition has a reduced tendency to plug filters compared to an otherwise identical fuel composition that does not comprise the one or more additives and has a tendency to plug filters; and wherein the one or more additives are selected from:

[0026] (a) A copolymer comprising units of formula (I) and units of formula (II):

[0027]

[0028] Wherein, R is an alkyl group, and R 1 and R 2 Each is an alkyl or alkenyl group having 6 to 22 carbon atoms;

[0029] (b) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; and

[0030] (c) The reaction product of a secondary amine with a copolymer of maleic anhydride and an alpha-olefin.

[0031] Preferred features of the first, second and third aspects of the invention will now be described. Any feature of any aspect may be applicable to any other aspect as appropriate.

[0032] The first, second and third aspects of the present invention relate to one or more additives selected from components (a), (b) and (c). The present invention may relate to the use of one such additive or a mixture of two or more such additives. References herein to the additive or one additive include embodiments in which two or more additives are present.

[0033] The present invention is directed to reducing the filter plugging tendency of a fuel composition comprising a biodiesel component and a renewable diesel component.

[0034] The fuel composition may also optionally comprise a mineral diesel component.

[0035] In some embodiments, the fuel composition used in the present invention can include petroleum-based fuel oil, especially middle distillate fuel oil. The boiling point of such distillate fuel oil is generally 110° C. to 500° C., for example 150° C. to 400° C. Diesel fuel can include a mixture of atmospheric distillate or vacuum distillate, cracked gas oil or any proportion of straight run fraction (stream) and refinery fraction (e.g., thermal and / or catalytic cracking and hydrocracking fraction).

[0036] In a preferred embodiment the fuel composition does not comprise a mineral diesel component.

[0037] In this specification, biodiesel refers to esters of fatty acids. Such fuels are generally referred to as first generation biodiesel. Biodiesel as defined herein contains esters of, for example, vegetable oils, animal fats and waste cooking fats. This form of biodiesel can be obtained by transesterification of oil with an alcohol (usually a monohydric alcohol) usually in the presence of a catalyst. Fatty acids used to produce the fuel can be derived from a variety of natural sources, including, but not limited to, vegetable oils, rapeseed oil, safflower oil, sunflower oil, nasturtium seed oil, canola 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, lupine oil, jatropha oil, coconut oil, linseed oil, evening primrose oil, jojoba oil, camelina oil, tallow, beef tallow, butter, chicken fat, lard, cream, shea butter, waste frying oil, oil blends, waste cooking oil, yellow trap grease, hydrogenated oils, derivatives of oils, fractions of oils, conjugated derivatives of oils, and any mixtures thereof.

[0038] In this specification, renewable diesel refers to diesel fuel obtained by hydrodeoxygenation of fats and oils. Such fuels are often referred to as second-generation biodiesel and are derived from renewable resources such as vegetable oils and animal fats and are often processed in refineries, for example using hydroprocessing such as the H-Bio process developed by Petrobras. Second-generation biodiesel is sold by ConocoPhillips under the name of Renewable Diesel and by Neste under the name of NExBTL. Renewable diesel fuel is sometimes referred to as hydrogenated vegetable oil (or HVO).

[0039] Preferably, the renewable diesel component comprises less than 5 wt% aromatics, preferably less than 1 wt%, suitably less than 0.1 wt%.Most preferably, the renewable diesel used in the present invention is substantially free of aromatics.

[0040] The renewable diesel component may comprise greater than 4 wt%, preferably greater than 5 wt%, C14 to C16 normal alkanes.

[0041] The renewable diesel component may comprise greater than 5 wt%, preferably greater than 7 wt%, more preferably greater than 10 wt% C14 to C18 normal alkanes.

[0042] The renewable diesel component may comprise less than 8 wt%, preferably less than 6 wt%, C14 to C16 normal alkanes.

[0043] The renewable diesel component may comprise less than 20 wt%, preferably less than 18 wt%, more preferably less than 16 wt% C14 to C18 normal alkanes.

[0044] The renewable diesel component may comprise greater than 4 wt%, preferably greater than 5 wt%, C14 to C16 normal alkanes and less than 8 wt%, preferably less than 6 wt%, C14 to C16 normal alkanes.

[0045] The renewable diesel component may comprise greater than 5 wt%, preferably greater than 7 wt%, more preferably greater than 10 wt% C14 to C18 normal alkanes and less than 20 wt%, preferably less than 18 wt%, more preferably less than 16 wt% C14 to C18 normal alkanes.

[0046] The renewable diesel component may comprise 4 to 8 wt%, preferably 5 to 6 wt%, C14 to C16 normal alkanes.

[0047] The renewable diesel component may comprise 5 to 20 wt%, preferably 7 to 18 wt%, more preferably 10 to 16 wt% C14 to C18 normal alkanes.

[0048] The renewable diesel component may comprise 3 to 30 wt % C6 to C24 normal alkanes (ie, normal paraffins).

[0049] 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.

[0050] 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.

[0051] The renewable diesel component may comprise up to 99 vol%, preferably up to 95 vol%, suitably up to 90 vol%, for example up to 85 vol% of all fuel components present in the fuel composition.

[0052] 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 %.

[0053] The biodiesel component can account for 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 account for up to 25 volume % of all fuel components present in the fuel composition.

[0054] 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.

[0055] 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.

[0056] In some particularly preferred embodiments, the fuel composition comprises about 80% by volume of the renewable diesel component and about 20% by volume of the biodiesel component.

[0057] 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.

[0058] 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.

[0059] In a particularly preferred embodiment, the fuel composition comprises no mineral diesel component.

[0060] 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 one or more additives selected from components (a), (b) and (c) as further defined herein.

[0061] The present invention may involve the use of a single additive, or it may involve the use of a mixture of additives.

[0062] The present invention may relate to the use of one or more additives of component (a) and / or one or more additives of component (b) and / or one or more additives of component (c).

[0063] In some embodiments, the one or more additives used in the present invention comprise (a) a copolymer comprising units of formula (I) and units of formula (II):

[0064]

[0065] Where R is an alkyl group, and R 1 and R 2 Each is an alkyl group or alkenyl group having 6 to 22 carbon atoms.

[0066] Additive (a) can be prepared by copolymerizing a vinyl ester monomer and a fumaric acid monomer, and then esterifying the acid residue.

[0067] Preferably, the additive (a) is prepared by copolymerizing a vinyl ester monomer and a dialkyl fumarate monomer.

[0068] Additive (a) is preferably a copolymer prepared by reacting a vinyl ester monomer of formula (III) with a dialkyl fumarate monomer of formula (IV):

[0069]

[0070] The monomers of formula (III) used to prepare the copolymer additive (a) may be the same, or the copolymer may be prepared from a mixture of two or more different monomers of formula (III).

[0071] R is an alkyl group, preferably an unsubstituted alkyl group.

[0072] Preferably, R is an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0073] Preferably, R is an unsubstituted alkyl group having 1 to 4 carbon atoms.

[0074] Most preferably, R is methyl and the monomer of formula (III) is vinyl acetate.

[0075] The monomers of formula (IV) used to prepare the copolymer additive (a) may be the same, or the copolymer may be prepared from a mixture of two or more different monomers of formula (IV).

[0076] Preferably, all monomers of formula (IV) used to prepare additive (a) are identical.

[0077] R 1 and R 2Each may be the same or different. Preferably, R 1 With R 2 same.

[0078] R 1 and R 2 Each is an alkyl or alkenyl group. Preferably, each is an alkyl group, preferably an unsubstituted alkyl group. 1 and R 2 It can be straight chain or branched. Preferably, R 1 and R 2 Each is a straight-chain alkyl group.

[0079] In some embodiments, R 1 and R 2 Each is an alkyl group having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.

[0080] Preferably, R 1 and R 2 Each is an alkyl group having 6 to 14 carbon atoms, preferably 8 to 14 carbon atoms, more preferably 10 to 14 carbon atoms, and most preferably 12 to 14 carbon atoms.

[0081] Additive (a) is a copolymer comprising formula (I) unit and formula (II) unit. In some embodiments, additive (a) may include other additional units that do not belong to formula (I) or formula (II). In such embodiments, copolymer is suitably prepared by vinyl ester monomer, fumaric acid derived monomer (preferably dialkyl fumarate) and one or more other monomeric units. In a preferred embodiment, one or more other monomeric units account for less than 20 mol %, preferably less than 10 mol %, more preferably less than 5 mol %, more preferably less than 1 mol % of all monomeric units used to prepare additive (a).

[0082] In a preferred embodiment, additive (a) consists essentially of units of formula (I) and units of formula (II). This means that units of formula (I) and units of formula (II) together provide at least 80 mol%, preferably at least 90 mol%, more preferably at least 95 mol%, more preferably at least 99 mol%, for example at least 99.5 mol% or at least 99.9 mol% of all monomer-derived units present in the copolymer.

[0083] Suitable additives (a) contain 10 to 90 mol % of units of formula (I) and 90 to 10 mol % of units of formula (II); preferably 25 to 75 mol % of units of formula (I) and 25 to 75 mol % of units of formula (II); more preferably 40 to 60 mol % of units of formula (I) and 60 to 40 mol % of units of formula (II).

[0084] Preferably, additive (a) is a random copolymer.

[0085] Suitably, the copolymer additive (a) has a number average molecular weight of from 1,000 to 100,000, preferably from 2,000 to 50,000, more preferably from 5,000 to 25,000, for example from 6,000 to 20,000.

[0086] In some particularly preferred embodiments, the number average molecular weight of the copolymer additive (a) is from 4000 to 25000, preferably from 5000 to 20000, more preferably from 6000 to 15000. In some embodiments, the number average molecular weight of the copolymer additive (a) is from 8000 to 10000.

[0087] In a particularly preferred embodiment, additive (a) is a copolymer comprising units of formula (I) and units of formula (II):

[0088]

[0089]

[0090] Where R is an alkyl group, and R 1 and R 2 Each is an alkyl group having 10 to 14 carbon atoms, and preferably 12 to 14 carbon atoms, and the number average molecular weight of the copolymer is 4000 to 25000, preferably 5000 to 20000, more preferably 6000 to 15000. Most preferably, the copolymer comprises 40 to 60 mol % of units of formula (I) and 60 to 40 mol % of units of formula (II).

[0091] In some embodiments, the one or more additives used in the present invention comprise (b) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine.

[0092] 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. In the polycarboxylic acid, each carboxylic acid group preferably has 2 to 10 carbon atoms. The polycarboxylic acid groups may be identical 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.

[0093] In some preferred embodiments, the polycarboxylic acid has formula (V) or (VI):

[0094]

[0095] wherein A is a linear or branched C2-C6 alkylene or HOOC-BN(CH2CH2)2, and B is C1 to C19 Alkylene.

[0096] Preferably, A has 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms.

[0097] Preferably, B has 1 to 10, more preferably 1 to 4 carbon atoms.

[0098] Preferred carboxylic acids for preparing additive (b) include nitrilotriacetic acid, ethylenediaminetetraacetic acid, and 1,2-propylenediaminetetraacetic acid.

[0099] To form additive (b), the polycarboxylic acid is reacted 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.

[0100] Secondary amines can react with polycarboxylic acids to form amides and / or ammonium salts. In a preferred embodiment, all amines react to form amides.

[0101] Preferred amines for reaction with the polycarboxylic acid include dioleylamine, dipalmitylamine, dicocoamine, distearylamine, dibehenylamine and hydrogenated and / or unhydrogenated ditallow amine. Ditallow amine is particularly preferred.

[0102] 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 carboxylic acid group present in the carboxylic acid.

[0103] A particularly preferred additive component (b) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated tallow fatty amine.

[0104] Other preferred compounds of this type include the N,N dialkylammonium salts of 2-N-,N' dialkylamide benzoates, such as the reaction product of 1 mole of phthalic anhydride with 2 moles of ditallow amine and the reaction product of 1 mole of alkenyl-spiro-dilactone with 2 moles of a dialkylamine, such as ditallow amine (hydrogenated or unhydrogenated).

[0105] In some embodiments, the one or more additives used in the present invention comprise the reaction product of (c) a secondary amine and a copolymer of an α,β-unsaturated dicarboxylic acid anhydride and an α-olefin.

[0106] Preferred compounds of this type are copolymers based on polyoxyalkylene ethers of α,β-unsaturated dicarboxylic acid anhydrides, α,β-unsaturated compounds and optionally lower unsaturated alcohols, including

[0107] a) 20-80 mol % of divalent structural units (VII) and / or (VIII)

[0108]

[0109]

[0110] Where R 1 and R 2 are independently hydrogen or methyl,

[0111] X and Y are the same or different groups and are selected from: and 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 R 3 each being 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;

[0112] b) 19-80 mol % of divalent structural units (IX)

[0113]

[0114] Where R 5 is hydrogen or C1-C4-alkyl and R 6 C6-C 60- Alkyl or C6-C 18 - aryl; and

[0115] c) 0-30 mol% of divalent structural units (X):

[0116]

[0117] Where R 7 is hydrogen or methyl, R 8is hydrogen or C1-C4-alkyl, Z is C1-C4-alkylene

[0118] m is a number from 1 to 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.

[0119] It will be appreciated by those skilled in the art that the copolymer may contain small amounts of unopened anhydride or imide structural units derived from the α,β-unsaturated dicarboxylic acid anhydride structural units (VII) and / or (VIII).

[0120] Preferred copolymers do not contain the structural unit X. 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.

[0121] Preferred additives (c) are derived from copolymers of maleic anhydride and α-olefins having 6 to 30 carbon atoms reacted with 2 equivalents of aliphatic amine.

[0122] A particularly preferred additive (c) is prepared by reacting a copolymer of maleic anhydride and a C18 alpha olefin with 2 equivalents of ditallow fatty amine.

[0123] In some embodiments, one or more additives used in the present invention comprise component (a).

[0124] In some embodiments, one or more additives used in the present invention comprise component (b).

[0125] In some embodiments, one or more additives used in the present invention comprise component (c).

[0126] In some embodiments, the one or more additives used in the present invention comprise component (a) and component (b).

[0127] In some embodiments, the one or more additives used in the present invention comprise component (a) and component (c).

[0128] In some embodiments, the one or more additives used in the present invention comprise component (b) and component (c).

[0129] In some embodiments, the one or more additives used in the present invention comprise component (a), component (b), and component (c).

[0130] In some embodiments, the one or more additives used in the present invention comprise component (a), but do not comprise component (b) or component (c).

[0131] For the avoidance of doubt, each additive used in the present invention may include a mixture of compounds, and reference to an additive (or to the additive) includes mixtures unless otherwise stated. In particular, mixtures of isomers and mixtures of homologues are within the scope of the present invention. Those skilled in the art will appreciate that commercial sources of some of the additives described herein may include mixtures of isomers and / or mixtures of homologues.

[0132] The present invention relates to the use of one or more additives selected from the group consisting of:

[0133] (a) A copolymer comprising units of formula (I) and units of formula (II):

[0134]

[0135] Wherein, R is an alkyl group, and R 1 and R 2 Each is an alkyl group or alkenyl group having 6 to 22 carbon atoms.

[0136] (b) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; and

[0137] (c) The reaction product of a secondary amine with a copolymer of maleic anhydride and an alpha-olefin.

[0138] The appropriate treat rate of the additive or additives used in the present invention may depend on the type of fuel used, and different levels of additives may be required to achieve different performance levels.

[0139] One or more additives may be added to the fuel at any convenient location in the supply chain. For example, one or more additives may be added to the fuel at a refinery, a distribution terminal, or after the fuel leaves the distribution terminal. One or more additives may be added to the components before the renewable diesel component and / or the biodiesel component are mixed; and / or one or more additives may be added to the mixed fuel after the components are mixed. If one or more additives are added to the fuel after the fuel leaves the distribution terminal, this is referred to as an aftermarket application. Aftermarket applications include situations where one or more additives are added to the fuel in a transport tanker, directly to a customer's bulk storage tank, or directly to an end-user's vehicle tank. Aftermarket applications may include providing one or more additives in vials suitable for direct addition to a fuel storage tank or a vehicle tank.

[0140] The one or more additives are present in the fuel composition in an amount totaling at least 1 ppm, preferably at least 2 ppm, suitably at least 5 ppm.

[0141] The one or more additives may be present in the fuel composition in an amount totaling up to 1000 ppm, suitably up to 750 ppm, for example up to 600 ppm.

[0142] The one or more additives are preferably present in the fuel composition in an amount in total of 1 to 1000 ppm, preferably 2 to 500 ppm, for example 5 to 350 ppm.

[0143] For the avoidance of doubt, when the fuel composition comprises a mixture of two or more additives, the above amounts refer to the total amount of all additives (a), (b) and (c) present in the composition. Unless otherwise stated, all references to ppm in this specification are parts per million by weight.

[0144] In some embodiments, the fuel composition comprises 0.1 to 10000 ppm, preferably 1 to 1000 ppm, preferably 5 to 500 ppm, for example 10 to 250 ppm of (a) a copolymer comprising units of formula (I) and units of formula (II):

[0145]

[0146] Where R is an alkyl group, and R 1 and R 2 Each is an alkyl group or alkenyl group having 6 to 22 carbon atoms.

[0147] In some embodiments, the fuel composition comprises 0.1 to 10000 ppm, preferably 1 to 1000 ppm, preferably 5 to 500 ppm, for example 10 to 250 ppm of (b) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine.

[0148] In some embodiments, the fuel composition comprises 0.1 to 10000 ppm, preferably 1 to 1000 ppm, preferably 5 to 500 ppm, for example 10 to 250 ppm of (c) the reaction product of a copolymer of a secondary amine and maleic anhydride and an alpha-olefin.

[0149] Each of additives (a), (b) and (c) may be provided as a mixture of compounds. Each of additives (a), (b) and (c) may be provided in the form of a crude reaction product, i.e., without purification after preparation. The above amounts refer to the total amount of all such compounds present in the composition.

[0150] For the avoidance of doubt, the above amounts refer to the amount of the additive compound present in the composition and disregard any impurities, solvents or diluents that may be present.

[0151] Fuel composition of the present invention can comprise one or more other additives, for example those additives common in the diesel oil.These comprise for example antioxidant, dispersant, washing agent, metal deactivation compound, wax anti-settling agent, cold flow improver, cetane number improver, demister, stabilizing agent, demulsifier, defoamer, corrosion inhibitor, lubricity improver, dyestuff, marking agent, combustion improver, metal deactivator, odor masking agent, drag reducer and conductivity improver.The example of the suitable amount separately of these types of additives will be known to those skilled in the art.

[0152] In some preferred embodiments, the diesel fuel composition of the present invention comprises one or more detergents. Preferred are nitrogen-containing detergents. Suitable detergents will be known to those skilled in the art.

[0153] In some embodiments, the composition may include one or more low temperature enhancement additives. Such compounds are generally referred to as cold flow improvers by those skilled in the art. Additional cold flow improver additives suitable for use herein include ethylene vinyl acetate copolymers; terpolymers of ethylene, vinyl acetate, and a third monomer; polyalkyl methacrylates; alpha olefin maleic anhydride copolymers; ester or imide derivatives of alpha olefin maleic anhydride copolymers; and combinations thereof.

[0154] The present invention relates to reducing the filter plugging tendency of a fuel composition having a tendency to plug filters.

[0155] The fuel composition with the blocking filter trend refers to the fuel composition that will cause the filter to block if not handled with one or more additives as herein described.The trend of the fuel composition blocking filter can be measured by a series of standard industrial tests.The fuel composition that is suitable for processing according to the present invention is the fuel composition that does not meet the requirements of this type of standard test when not adding one or more additives claimed.The reduction of the filter blocking trend of the fuel composition can be demonstrated by realizing improved performance in one of these tests.

[0156] Standard test methods for determining filter plugging tendency (FBT) are described in ASTM D2068 and IP387. This general procedure is typically used for middle distillate fuels containing biodiesel and biodiesel blends. Another test suitable for measuring filter plugging tendency is specified in IP618. One of these tests can be used to evaluate the present invention.

[0157] The preferred method for determining the clogging tendency of the filter of the present invention is the Canadian Cold Soak Filter Blocking Tendency Test (CSFBT). In this test, the fuel is stored at 1 ° C for 16 hours and then the filterability is evaluated. The procedure for this test is specified in CAN / CGSB 3.0 No. 142.0-2019, and a revised version using renewable fuel 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.

[0158] References herein to results achieved or measured by the CSFBT test refer to the method described in Example 2.

[0159] 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 and held for 16 hours, and then tested by filtration to provide a unitless value. This value represents the likelihood of the fuel plugging the filter, and values ​​less than 2 are generally considered acceptable.

[0160] Preferably, the present invention reduces the filter plugging tendency of a fuel composition which, prior to treatment with one or more additives according to the present invention, achieves a CSFBT test result of greater than 2. Suitably, the present invention provides a fuel composition which achieves a CSFBT test result of less than 2.

[0161] Thus, the use of the first aspect and the method of the second aspect of the invention preferably provide a fuel composition having a filter plugging tendency of less than 2 as measured by the CSFBT test method.

[0162] Suitably, the fuel composition of the third aspect has a Filter Plug Propensity of less than 2 as measured by the CSFBT test method.

[0163] 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%.

[0164] The present invention will now be further described by way of the following non-limiting examples.

[0165] Example 1

[0166] The blended fuel composition is prepared by blending the renewable diesel fuel component R1 with the biodiesel fuel component B1 or B2, and has the following characteristics:

[0167]

[0168] Additive A (a copolymer of vinyl acetate and dialkyl fumarate, wherein the alkyl group has 14 carbon atoms, wherein the number average molecular weight of the copolymer is about 9000) is added to the blended fuel to provide the following composition:

[0169]

[0170] Example 2

[0171] Fuel compositions 1 to 6 were tested according to a modified version of the procedures of the standard CSFBT test method specified in CAN / CGSB 3.0, No. 142-2019.

[0172] The revised test method is outlined below:

[0173] 1. The fuel composition sample is first conditioned to eliminate its thermal history.

[0174] 2. The fuel composition was then maintained at 1°C for 16 hours.

[0175] 3. The fuel composition was then warmed to 25°C for 2-4 hours.

[0176] 4. After warming, the fuel composition was then passed through a glass fiber filter medium (1.6 μm pore size) at a constant flow rate (20 mL / min).

[0177] 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

[0178] 4.2. If the pressure drop reaches 105 kPa before filtering 300 mL of the fuel composition, the volume filtered when 105 kPa is reached is used to calculate the CSFBT result.

[0179] 5. The results of the CSFBT test range from 1.0 (indicating a very filterable fuel composition) (essentially no separated material under the test conditions) to greater than 10 (indicating a poorly filterable fuel composition) (relatively high levels of separated material under the test conditions).

[0180] The results are shown in Table 1:

[0181] Table 1

[0182]

[0183]

Claims

1. Use of one or more additives for reducing 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; and wherein the one or more additives are selected from (a) A copolymer comprising units of formula (I) and units of formula (II): in, R is an alkyl group, and R 1 and R 2 Each is an alkyl or alkenyl group having 6 to 22 carbon atoms; (b) reaction products of polycarboxylic acids having at least one tertiary amino group with primary or secondary amines; and (c) The reaction product of a secondary amine with a copolymer of maleic anhydride and an alpha-olefin.

2. A method of reducing the filter plugging tendency of a fuel composition, the fuel composition having a tendency to plug a filter and comprising a biodiesel component and a renewable diesel component, the method comprising adding to the fuel one or more additives selected from the group consisting of (a) A copolymer comprising units of formula (I) and units of formula (II): in, R is an alkyl group, and R 1 and R 2 Each is an alkyl or alkenyl group having 6 to 22 carbon atoms; (b) reaction products of polycarboxylic acids having at least one tertiary amino group with primary or secondary amines; and (c) The reaction product of a secondary amine with a copolymer of maleic anhydride and an alpha-olefin.

3. A fuel composition comprising a renewable diesel component, a biodiesel component and one or more additives; wherein: The fuel composition has a reduced tendency to plug filters compared to an otherwise identical fuel composition that does not contain the one or more additives and has a tendency to plug filters; and wherein the one or more additives are selected from (a) A copolymer comprising units of formula (I) and units of formula (II): Wherein, R is an alkyl group, and R 1 and R 2 Each is an alkyl or alkenyl group having 6 to 22 carbon atoms; (b) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; and (c) The reaction product of a secondary amine with a copolymer of maleic anhydride and an alpha-olefin.

4. A composition, method or use according to any one of the preceding claims, wherein R 1 and R 2 Each is an alkyl or alkenyl group having 8 to 14 carbon atoms.

5. A composition, method or use according to any preceding claim, wherein the one or more additives comprises component (a).

6. A composition, method or use according to any preceding claim, wherein the one or more additives comprises component (b).

7. A composition, method or use according to any preceding claim, wherein the one or more additives comprises component (c).

8. The composition, method or use according to any one of the preceding claims, wherein the one or more additives comprise a copolymer comprising units of formula (I) and units of formula (II): Where R is an alkyl group, R 1 and R 2 Each is an alkyl group having 10 to 14 carbon atoms, preferably 12 to 14 carbon atoms, and the number average molecular weight of the copolymer is 4,000 to 25,000, preferably 5,000 to 20,000, more preferably 6,000 to 15,000.

9. The composition, method or use according to claim 8, wherein the copolymer comprises 40 to 60 mol% of units of formula (I) and 60 to 40 mol% of units of formula (II).

10. The composition, method or use of any preceding claim wherein the one or more additives comprises the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated tallow fatty amine.

11. The composition, method or use of any preceding claim wherein the one or more additives comprises the reaction product of a copolymer of maleic anhydride and a C18 alpha-olefin and 2 equivalents of ditallow fatty amine.

12. The use, method or composition of any preceding claim, wherein the fuel composition comprises 1 to 40 vol% (preferably 5 to 35 vol%) of a biodiesel component and 60 to 99 vol% (preferably 65 to 95 vol%) of a renewable diesel component.

13. The use or method of any one of claims 1, 2 or 4 to 12, providing a reduced filter blocking tendency as measured by the modified Canadian Cold Soak Filter Blocking Tendency test CAN / CGSB-3.0 No. 142.0-2019 as described in Example 2.

14. The composition of any one of claims 3 to 12, having a filter blocking tendency of less than 2 as measured by the modified Canadian Cold Soak Filter Blocking Tendency test CAN / CGSB-3.0 No. 142.0-2019 described in Example 2.

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