Fuel improvement

Abstract

At least one nitrogen-containing cleaning agent is 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.

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] An 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, 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 by biological, thermal and chemical methods. 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 oils.

[0005] Renewable diesel contains mainly saturated, linear or branched aliphatic hydrocarbons. Biodiesel consists mainly of monoalkyl esters. Mineral diesel usually contains aromatic hydrocarbons 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 may arise when using a blend of renewable diesel and biodiesel.Due to the different chemical properties of the renewable and biodiesel components of the blended fuel, problems may arise when storing the fuel, particularly 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); as well as the changes caused by adding additives to them (ΔCP, ΔPP, ΔCFPP).

[0009] The present invention does not involve the use of nitrogen-containing detergents (as 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, it can cause problems because it affects the rate at which fuel is delivered to the engine. This problem is different from what occurs 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 particulate matter forming in the fuel, especially during storage. In recent years, filter clogging has become a more prominent problem. 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, can be as low as 2 to 5 microns in diameter. The reduction in filter pore size inevitably leads to an increase in filter clogging problems. A clogged filter can restrict or prevent fuel from reaching the engine. This can cause problems with engine starting and loss of power. In some cases, a clogged filter can cause the engine to shut down completely until the filter is replaced, which is a great inconvenience for the user in order to protect the injection system.

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

[0013] According to a first aspect of the present invention, there is provided the use of at least one nitrogen-containing detergent 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 invention there is provided a method of reducing the filter plugging tendency of a fuel composition having a tendency to plug filters and comprising a biodiesel component and a renewable diesel component, the method comprising dosing at least one nitrogen-containing detergent into the fuel.

[0015] According to a third aspect of the present invention, there is provided a fuel composition comprising a renewable diesel component, a biodiesel component and at least one nitrogen-containing detergent; wherein the fuel composition has a reduced tendency to plug filters compared to an otherwise identical fuel composition that does not comprise the nitrogen-containing detergent and has a tendency to plug filters.

[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 nitrogen-containing cleaner. This may relate to one nitrogen-containing cleaner or a mixture of two or more nitrogen-containing cleaners. References to nitrogen-containing cleaners herein include embodiments in which two or more nitrogen-containing cleaners 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 also optionally comprise a mineral diesel component. In a preferred embodiment, the fuel composition does not comprise a mineral diesel component.

[0020] 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 (typically a monohydric alcohol), typically in the presence of a catalyst. The fatty acids used to produce the fuel can be derived from a wide 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, lupin 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.

[0021] 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, such as by hydrotreating 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 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.

[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 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 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 comprises about 80% by volume of the renewable diesel component and about 20% by volume of the 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 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 at least one nitrogen-containing detergent.

[0034] The present invention relates to the use of at least one nitrogen-containing cleaner as an additive. Thus, the present invention may include the use of one nitrogen-containing cleaner as an additive or of a plurality of nitrogen-containing cleaners as a plurality of additives.

[0035] For the avoidance of doubt, each nitrogen-containing detergent used in the present invention (i.e., as an additive) may include a mixture of compounds, and references to nitrogen-containing detergents (or additives) or nitrogen-containing detergents (or additives) include mixtures unless otherwise specified. In particular, mixtures of isomers and mixtures of homologs are within the scope of the present invention. Those skilled in the art will appreciate that commercial sources of some of the nitrogen-containing detergent compounds described herein may include mixtures of isomers and / or mixtures of homologs.

[0036] The present invention relates to the use of at least one nitrogen-containing cleaning agent. Preferably, at least one nitrogen-containing cleaning agent is selected from one or more of the following:

[0037] (a) quaternary ammonium salts;

[0038] (b) the reaction product of a carboxylic acid-derived acylating agent and an amine;

[0039] (c) products of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol;

[0040] (d) the reaction product of a carboxylic acid derived acylating agent and hydrazine;

[0041] (e) a salt formed by reacting a carboxylic acid with di-n-butylamine or tri-n-butylamine; and

[0042] (f) The reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride with an amine compound or salt, said product comprising at least one aminotriazole group.

[0043] The at least one nitrogen-containing cleaning agent is preferably selected from one or more of the following:

[0044] (a) quaternary ammonium salts;

[0045] (b) the reaction product of a carboxylic acid derived acylating agent and an amine; and

[0046] (c) Products of the Mannich reaction between aldehydes, amines and optionally substituted phenols.

[0047] The at least one nitrogen-containing cleaning agent may include (a) a quaternary ammonium salt.

[0048] Component (a) may include any suitable quaternary ammonium salt.

[0049] Preferably, the quaternary ammonium salt is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent.

[0050] Any suitable quaternizing agent may be used. The quaternizing agent may suitably be selected from esters and non-esters.

[0051] Suitable quaternizing agents include esters of carboxylic acids, dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides (optionally in combination with an acid), alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.

[0052] In some preferred embodiments, the quaternizing agents used to form the quaternary ammonium salts used in the present invention are esters.

[0053] Preferred ester quaternizing agents are compounds of formula (I):

[0054]

[0055] wherein R is an optionally substituted alkyl, alkenyl, aryl or alkaryl group, and R 1 is a C1 to C22 alkyl, aryl or alkaryl group. The compound of formula (I) is suitably an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt.

[0056] Suitable quaternizing agents include esters of carboxylic acids having a pKa of 3.5 or less.

[0057] The compound of formula (I) is preferably an ester of a carboxylic acid selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids and polycarboxylic acids.

[0058] In some preferred embodiments, the compound of formula (I) is an ester of a substituted aromatic carboxylic acid, and thus R is a substituted aryl group.

[0059] Preferably, R is a substituted aryl group having 6 to 10 carbon atoms, preferably phenyl or naphthyl, most preferably phenyl. R is suitably substituted with one or more selected from alkoxycarbonyl, nitro, cyano, hydroxyl, SR 5 or NR 5 R 6 The group substituted. 5 and R 6 Each may be hydrogen or an optionally substituted alkyl, alkenyl, aryl or alkoxycarbonyl group. 5 and R 6 Each is hydrogen or an optionally substituted C1 to C22 alkyl group, preferably hydrogen or a C1 to C16 alkyl group, preferably hydrogen or a C1 to C10 alkyl group, more preferably hydrogen or a C1 to C4 alkyl group. Preferably, R 5 is hydrogen and R 6 is hydrogen or C1 to C4 alkyl. Most preferably, R 5 and R 6All are hydrogen. Preferably, R is an aryl substituted by one or more groups selected from hydroxyl, alkoxycarbonyl, nitro, cyano and NH2. R can be a polysubstituted aryl, such as trihydroxyphenyl. In some embodiments, R can be an aryl substituted by a hydrocarbyl, such as an aryl substituted by an alkyl. In some embodiments, R can be an aryl substituted by a hydroxyl and a hydrocarbyl (such as an alkyl), such as described in EP2631283.

[0060] Preferably, R is a monosubstituted aryl. Preferably, R is an ortho-substituted aryl. Suitably, R is substituted by a group selected from OH, NH2, NO2 or COOMe. Preferably, R is substituted by an OH or NH2 group. Suitably, R is a hydroxy-substituted aryl. Most preferably, R is 2-hydroxyphenyl.

[0061] Preferably, R 1 is an alkyl group, an aralkyl group or an alkaryl group. 1 It may be a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group, and suitably a C1 to C8 alkyl group. 1 It may be a C7 to C16 aralkyl group or an alkaryl group, and preferably a C7 to C10 aralkyl group or an alkaryl group. 1 It can be methyl, ethyl, propyl, butyl, pentyl, benzyl or isomers thereof. 1 is benzyl or methyl. Most preferably, R 1 It is methyl.

[0062] Particularly preferred compounds of formula (I) are lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n-propyl salicylate and isopropyl salicylate, and butyl salicylate, preferably methyl salicylate.

[0063] In some embodiments, the compound of formula (I) is an ester of an alpha-hydroxycarboxylic acid. In such embodiments, the compound has the following structure:

[0064]

[0065] Where R 7 and R 8 are the same or different and are each selected from hydrogen, alkyl, alkenyl, aralkyl or aryl. Compounds of this type suitable for use herein are described in EP 1254889.

[0066] Examples of compounds of formula (I) in which RCOO is an α-hydroxycarboxylic acid residue include methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxyisobutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-methylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-ethylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of lactic acid; and methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl and phenyl esters of glycolic acid. Among them, the preferred compound is methyl 2-hydroxyisobutyrate.

[0067] In some embodiments, the compound of formula (I) is an ester of a polycarboxylic acid. This limitation refers to carboxylic acids including dicarboxylic acids and having more than two acidic moieties. In this embodiment, RCOO preferably exists in the form of an ester, that is, one or more additional acid groups present in the group R are in esterified form. However, embodiments in which not all acid groups are esterified also belong to the scope of the present invention. Mixed esters of polycarboxylic acids may also be used. Preferred esters are C1 to C4 alkyl esters.

[0068] The ester quaternizing agent may be selected from diesters of oxalic acid, diesters of phthalic acid, diesters of maleic acid, diesters of malonic acid or diesters of citric acid.An especially preferred compound of formula (I) is dimethyl oxalate.

[0069] In a preferred embodiment, the compound of formula (I) is an ester of a carboxylic acid having a pKa of less than 3.5. In embodiments where the compound comprises more than one acid group, the first dissociation constant is referred to.

[0070] The ester quaternizing agent may be selected from esters of carboxylic acids, wherein the carboxylic acids are selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2,4,6-trihydroxybenzoic acid.

[0071] Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.

[0072] In some preferred embodiments, the quaternizing agent used to form the quaternary ammonium salt used in the present invention is an ester selected from dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate, preferably dimethyl oxalate and methyl salicylate.

[0073] Suitable non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides (optionally in combination with an acid), alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.

[0074] In some embodiments, quaternary ammonium salts can be prepared from, for example, alkyl or benzyl halides (especially chlorides), followed by ion exchange reactions to provide different anions as part of the quaternary ammonium salt. This method can be suitable for preparing hydroxides, alkoxides, nitrites or nitrates of quaternary ammonium.

[0075] Preferred non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides in combination with acids, alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, N-oxides, chloroacetic acid or its salts, or mixtures thereof.

[0076] Suitable dialkyl sulfates for use herein as quaternizing agents include those which include an alkyl group having from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl chain. A preferred compound is dimethyl sulfate.

[0077] Suitable benzyl halides include chlorides, bromides and iodides. The phenyl group may be optionally substituted, for example by one or more alkyl or alkenyl groups, particularly when a chloride is used. A preferred compound is benzyl bromide.

[0078] The carbonate ester that suitable alkyl replaces can comprise two alkyls, and they can be identical or different.Each alkyl can contain 1 to 50 carbon atom, preferably 1 to 20 carbon atom, more preferably 1 to 10 carbon atom, suitably 1 to 5 carbon atom.Preferably, described alkyl or each alkyl is alkyl.Preferred compounds of this type comprise diethyl carbonate and dimethyl carbonate.

[0079] Suitable hydrocarbyl substituted epoxides have the formula:

[0080]

[0081] Where R 11 , R 12 , R 13 and R 14 Each is independently hydrogen or a hydrocarbyl group having 1 to 50 carbon atoms. Examples of suitable epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and stilbene oxide. Hydrocarbyl epoxides are used in combination with acids as quaternizing agents.

[0082] In some embodiments, the compound comprising a tertiary amine group also includes an acid functional group. In these embodiments, if an epoxide is used as a quaternizing agent, there is no need to add a separate acid. However, in other embodiments, an acid such as acetic acid may be used.

[0083] Particularly preferred epoxide quaternizing agents are propylene oxide and styrene oxide, optionally in combination with an additional acid.

[0084] Suitable alkyl halides for use herein include chlorides, bromides and iodides.

[0085] Suitable alkyl sulfonates include those having 1 to 20, preferably 1 to 10, more preferably 1 to 4 carbon atoms.

[0086] Suitable sultones include propane sultone and butane sultone.

[0087] Suitable hydrocarbyl-substituted phosphates include monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates and O,O-dialkyl dithiophosphates.Preferred alkyl groups have from 1 to 12 carbon atoms.

[0088] Suitable hydrocarbyl-substituted borate groups include alkyl borates having from 1 to 12 carbon atoms.

[0089] Preferred alkyl nitrites and alkyl nitrates have 1 to 12 carbon atoms.

[0090] Preferably, the non-ester quaternizing agent is selected from dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides (optionally in combination with an additional acid), chloroacetic acid or its salts, and mixtures thereof.

[0091] Particularly preferred non-ester quaternizing agents for use herein are hydrocarbyl-substituted epoxides in combination with acids. These may include embodiments in which a separate acid is provided or embodiments in which the tertiary amine compound being quaternized additionally includes an acid group. Preferably, the tertiary amine compound being quaternized additionally includes an acid group.

[0092] Preferred quaternizing agents for use herein include dimethyl oxalate, methyl 2-nitrobenzoate, methyl salicylate, chloroacetic acid or its salts, and styrene oxide or propylene oxide (optionally in combination with an additional acid).

[0093] In some embodiments, mixtures of two or more quaternizing agents may be used.

[0094] To form the quaternary ammonium salt, the quaternizing agent is reacted with the compound containing a tertiary amine group.

[0095] Any suitable compound containing a tertiary amine group may be used.

[0096] The compound comprising a tertiary amine group may be selected from:

[0097] (i) the reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group;

[0098] (ii) a Mannich reaction product comprising a tertiary amine group;

[0099] (iii) a polyalkylene-substituted amine having at least one tertiary amine group; and

[0100] (iv) Alkylamines (eg tertiary alkylamines), alkylalkanolamines (eg dimethylethanolamine) and alkanolamines.

[0101] Examples of quaternary ammonium salts and methods for their preparation are described in the following patents: US2008 / 0307698, US2008 / 0052985, US2008 / 0113890, and US2013 / 031827.

[0102] The preparation of some suitable quaternary ammonium salts is described in WO2006 / 135881, US2020 / 0024536 and WO2011 / 095819, wherein the compound comprising a tertiary amine group comprises component (i).

[0103] Component (ii) is a Mannich reaction product with a tertiary amine. The preparation of compounds containing at least one tertiary amine group including quaternary ammonium salts of component (ii) is described in US 2008 / 0052985.

[0104] The preparation of compounds comprising at least one tertiary amine group, including quaternary ammonium salts of component (iii), is described, for example, in US 2008 / 0113890.

[0105] The preparation of some suitable quaternary ammonium salts of compounds comprising at least one tertiary amine group, including component (i), is described, for example, in WO 2016 / 016641.

[0106] Other suitable quaternary ammonium salts include quaternized terpolymers such as those described in US2011 / 0258917; quaternized copolymers such as those described in US2011 / 0315107; and acid-free quaternized nitrogen compounds disclosed in US2012 / 0010112.

[0107] In some embodiments, the present invention does not encompass acid-free quaternized nitrogen compounds.In preferred embodiments, the quaternary ammonium salts used in the present invention include a single anion and a single cation.

[0108] In some embodiments, the quaternary ammonium compound used in the present invention is the quaternization reaction product of a fatty acid (eg, oleic acid) and dimethylaminopropylamine.

[0109] Further suitable quaternary ammonium compounds for use in the present invention include the quaternary ammonium compounds described in the applicant's co-pending applications WO2011 / 095819, WO2013 / 017889, WO2015 / 011506, WO2015 / 011507, WO2016 / 016641 and WO2017 / 017454.

[0110] Preferably, the nitrogen-containing detergent (a) comprises a quaternary ammonium salt which is the quaternized reaction product of a hydrocarbyl-substituted succinic acid derived acylating agent and a compound capable of reacting with said acylating agent and comprising a tertiary amine group.

[0111] Preferably, the hydrocarbyl-substituted acylating agent is a hydrocarbyl-substituted succinic acid derived acylating agent.

[0112] For the avoidance of doubt, reference to a quaternized reaction product is to a reaction product comprising a tertiary amine which has then been quaternized to form a quaternary ammonium group. The quaternary ammonium salt is formed by the reaction of a quaternizing agent with a hydrocarbyl-substituted succinic acid derived acylating agent and a compound capable of reacting with said acylating agent and comprising a tertiary amine group.

[0113] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

[0114] (i) hydrocarbon groups, i.e., aliphatic (which may be saturated or unsaturated, straight chain or branched, e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic (including aliphatic and alicyclic substituted aromatic) substituents, as well as cyclic substituents wherein the ring is completed by another part of the molecule (e.g., two substituents together form one ring);

[0115] (ii) substituted hydrocarbon groups, i.e. substituents containing non-hydrocarbon groups which, in the context of the present invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g. halogen (e.g. chlorine, fluorine or bromine), hydroxy, alkoxy (e.g. C1 to C4 alkoxy), keto, acyl, cyano, mercapto, amino, amide, nitro, nitroso, sulfoxide, nitryl and carboxyl);

[0116] (iii) heterosubstituents, i.e., in the context of the present invention, substituents which, although predominantly hydrocarbon in nature, contain elements other than carbon in a ring or chain which otherwise consists of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl and imidazolyl. Generally, no more than two non-hydrocarbon substituents, and preferably no more than one non-hydrocarbon substituent, will be present for every ten carbon atoms in the hydrocarbyl group; usually, no non-hydrocarbon substituents will be present in the hydrocarbyl group.

[0117] Suitable hydrocarbyl-substituted succinic acid derived acylating agents and methods for their preparation are well known in the art. For example, a common method for preparing hydrocarbyl-substituted succinic acid acylating agents is by reacting maleic anhydride with an olefin using either a chlorination route or a thermal route (the so-called "ene" reaction).

[0118] The example of alkyl substituent group comprises n-octyl, n-decyl, n-dodecyl, tetrapropylene, n-octadecyl, oleyl, chlorooctadecyl, triacontanyl etc.The alkyl substituent group can be made by homopolymer or interpolymer (for example copolymer, terpolymer) of monoolefin and diolefin with 2 to 10 carbon atoms, for example ethylene, propylene, butane-1, isobutylene, butadiene, isoprene, 1-hexene, 1-octene etc.Preferably, these olefins are 1-monoolefins.Or, substituent group can be made by other sources, for example monomer high molecular weight olefin (for example 1-tetradecene), aliphatic petroleum fraction, for example paraffin wax and its cracking analog, white oil, synthetic olefin (for example produced by Ziegler-Natta process) (for example poly (ethylene) grease) and other sources well known to persons skilled in the art.If necessary, any unsaturation in the substituent group can be reduced or eliminated by hydrogenation according to procedures known in the art.

[0119] Preferably, the hydrocarbyl substituents are predominantly saturated, that is, they contain no more than one carbon-carbon unsaturated bond for every ten carbon-carbon single bonds present. Most preferably, they contain no more than one carbon-carbon non-aromatic unsaturated bond for every fifty carbon-carbon bonds present.

[0120] The hydrocarbyl substituent of the succinic acid derived acylating agent preferably comprises at least 10 carbon atoms, more preferably at least 12 carbon atoms, for example at least 30 or at least 40 carbon atoms. It may comprise up to about 200 carbon atoms. Preferably, the hydrocarbyl substituent of the acylating agent has a number average molecular weight (Mn) of from 170 to 2800, for example from 250 to 1500, preferably from 500 to 1500, and more preferably from 500 to 1100. Mn of from 700 to 1300 is particularly preferred.

[0121] The hydrocarbyl-substituted succinic acid derived acylating agent may comprise a mixture of compounds. For example, a mixture of compounds having different hydrocarbyl substituents may be used.

[0122] The preferred hydrocarbyl substituent is polyisobutylene. Such compounds are known to those skilled in the art.

[0123] The preferred hydrocarbyl-substituted succinic acid derived acylating agent is polyisobutenyl succinic anhydride. These compounds are commonly referred to as "PIBSA" and are well known to those skilled in the art.

[0124] Conventional polyisobutylenes and so-called "highly reactive" polyisobutylenes are suitable for use in the present invention. Highly reactive polyisobutylenes in this context are defined as polyisobutylenes in which at least 50%, preferably 70% or more, of the terminal olefinic double bonds are of the vinylidene type, as described in EP 0565285. Particularly preferred polyisobutylenes are those having greater than 80 mol % and up to 100 mol % of terminal vinylidene groups, such as those described in US Pat. No. 7291758. Preferred polyisobutylenes have the preferred molecular weight ranges as generally described above for the hydrocarbyl substituents.

[0125] Other preferred hydrocarbyl groups include those having an internal olefin, such as described in applicant's published application WO2007 / 015080.

[0126] As used herein, internal olefins refer to any olefin containing primarily non-alpha double bonds, i.e., beta or higher olefins. Preferably, such materials are substantially entirely beta olefins or higher olefins, e.g., containing less than 10% by weight of alpha olefins, more preferably less than 5% by weight or less than 2% by weight. Typical internal olefins include Neodene 1518IO available from Shell.

[0127] Internal olefins are sometimes referred to as isomerized olefins and may be prepared from alpha olefins by isomerization processes known in the art, or may be obtained from other sources. The fact that they are also referred to as internal olefins reflects that they do not necessarily have to be prepared by isomerization.

[0128] The preferred hydrocarbyl-substituted succinic acid derived acylating agent for preparing the quaternary ammonium salt (a) used in the present invention is polyisobutylene-substituted succinic anhydride or PIBSA. Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

[0129] Hydrocarbyl-substituted succinic acid derived acylating agents are suitably prepared by reacting maleic anhydride with an olefin (e.g. polyisobutylene). The product obtained (e.g. PIBSA) still contains double bonds. Maleic anhydride is present in the resulting molecule as a succinic acid moiety. The initial product is a monomaleated PIBSA.

[0130] The monomaleated PIBSA may have structure (A) or (B):

[0131]

[0132] The double bond in the monomaleated product can react with another molecule of maleic anhydride to form a bismaleated PIBSA having structure (C) or (D):

[0133]

[0134] Thus, a hydrocarbyl group substituted with more than one succinic acid moiety may be provided.

[0135] Those skilled in the art will appreciate that the hydrocarbyl-substituted succinic acid derived acylating agents used in the present invention typically comprise mixtures of compounds, such as mixtures of monomaleated and bismaleated PIBSA.PIBSA can be defined according to its bismaleation level.

[0136] One way this level can be determined is by calculating the average number of succinic acid moieties per molecule of acylating agent.

[0137] Monomaleated PIBSA has one succinic acid moiety per module.

[0138] Bismaleated PIBSA has two succinic acid moieties per molecule.

[0139] A mixture comprising monomaleated PIBSA and bismaleated PIBSA in a 1:1 molar ratio contained an average of 1.5 succinic acid moieties per PIBSA molecule.

[0140] The average number of succinic acid moieties per molecule of acylating agent is sometimes referred to in the art as the "P value."

[0141] Suitably, the quaternary ammonium salt is prepared from a hydrocarbyl-substituted succinic acid derived acylating agent containing an average of 1 to 2 succinic acid moieties per molecule.

[0142] In some preferred embodiments, the present invention may involve the use of quaternary ammonium salts derived from hydrocarbyl-substituted acylating agents containing an average of at least 1.2 succinic acid moieties per molecule.

[0143] Those skilled in the art will appreciate that a single molecule cannot have 1.2 succinic acid moieties. At least 1.2 succinic acid moieties refers to the average number of succinic acid moieties per molecule of acylating agent, which is equal to the sum of all succinic acid moieties present in the sample divided by the total number of acylating agent molecules having one or more succinic acid moieties present in the sample.

[0144] Preferably, the hydrocarbyl-substituted succinic acid derived acylating agent comprises an average of at least 1.21 succinic acid moieties per molecule, more preferably an average of at least 1.22 succinic acid moieties per molecule.

[0145] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may comprise at least 1.23 or at least 1.24 succinic acid moieties per molecule.

[0146] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may comprise at least 1.25, at least 1.26, or at least 1.27 succinic acid moieties per molecule.

[0147] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may comprise at least 1.28, at least 1.29, or at least 1.30 succinic acid moieties per molecule.

[0148] The succinic acid moiety is meant to include the succinic acid residue in either the diacid or anhydride form.

[0149] The hydrocarbyl-substituted succinic acid derived acylating agent is reacted with a compound capable of reacting with the acylating agent and comprising a tertiary amine group. The tertiary amine group is quaternized to give a quaternary ammonium salt.

[0150] Examples of suitable compounds capable of reacting with a hydrocarbyl-substituted succinic acid-derived acylating agent and containing a tertiary amine group may include, but are not limited to: N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylaminoethylamine. Nitrogen-containing compounds or oxygen-containing compounds capable of condensing with an acylating agent and further having a tertiary amino group may also include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3'3-aminobis(N,N-dimethylpropylamine). Other types of nitrogen-containing compounds or oxygen-containing compounds having a tertiary amino group that can be condensed with an acylating agent include alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N-diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine, N,N,N-tris(aminoethyl)amine, N,N-dibutylamine, Aminopropylamine and N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl 1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol, N,N,N'-trimethylaminoethylethanolamine and 3-(2-(dimethylamino)ethoxy)propylamine.

[0151] Preferably, the compound capable of reacting with the hydrocarbyl-substituted succinic acid derived acylating agent and comprising a tertiary amine group is an amine of formula (II) or (III):

[0152]

[0153] Where R 2 and R 3 are the same or different alkyl, alkenyl, aryl, alkaryl or aralkyl groups having 1 to 22 carbon atoms; X is a bond or an optionally substituted alkylene group having 1 to 20 carbon atoms; n is 0 to 20; m is 1 to 5; and R 4 is hydrogen or C1 to C 22 alkyl.

[0154] When the compound of formula (II) is used, R 4 Preferably hydrogen or C1 to C 16 Alkyl, preferably C1 to C 10 alkyl, more preferably C1 to C6 alkyl. 4 When R is an alkyl group, it may be straight chain or branched. For example, it may be substituted with hydroxyl or alkoxy substituents. Preferably, R 4 More preferably, R 4 is selected from hydrogen, methyl, ethyl, propyl, butyl and isomers thereof. Most preferably, R 4 For hydrogen.

[0155] When a compound of formula (III) is employed, m is preferably 2 or 3, most preferably 2; n is preferably 0 to 15, preferably 0 to 10, more preferably 0 to 5. Most preferably, n is 0 and the compound of formula (III) is an alcohol.

[0156] Preferably, a hydrocarbyl-substituted acylating agent is reacted with a diamine compound of formula (II).

[0157] R 2 and R 3 are the same or different alkyl, alkenyl, aryl, alkaryl or aralkyl groups having 1 to 22 carbon atoms. 2 and R 3 can be linked together to form a ring structure, such as a piperidine, imidazole or morpholine moiety. 2 and R 3 Together they may form an aromatic and / or heterocyclic moiety. 2 and R 3 It may be a branched alkyl or alkenyl group. Each may be substituted, for example, with hydroxy or alkoxy substituents.

[0158] Preferably, R 2 and R 3 Each independently is C1 to C 16 Alkyl, preferably C1 to C 10 Alkyl. 2 and R 3R may independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or any isomer of these groups. 2 and R 3 Each is independently a C1 to C4 alkyl group. 2 Preferably, R 3 It is methyl.

[0159] X is a bond or an optionally substituted alkylene group with 1 to 20 carbon atoms. In a preferred embodiment, when X is an alkylene group, the group can be straight chain or branched. The alkylene group can contain a cyclic structure therein. It can be optionally substituted, for example, by a hydroxyl or alkoxy substituent. In some embodiments, X can include heteroatoms in the alkylene chain, for example, X can include an ether functional group.

[0160] X is preferably an alkylene group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example 2 to 6 carbon atoms or 2 to 5 carbon atoms. In some preferred embodiments, X is an unsubstituted alkylene group. Most preferably, X is ethylene, propylene or butylene, especially propylene.

[0161] Examples of compounds of formula (II) suitable for use herein include 1-aminopiperidine, 1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-piperidinol, 1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolidinyl)piperidine, 1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N'- triethylethylenediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, N,N,N'-trimethyl-1,3-propylenediamine, N,N,2,2-tetramethyl-1,3-propylenediamine, 2-amino-5-diethylaminopentane, N,N,N',N'-tetraethyldiethylenetriamine, 3,3'-diamino-N-methyldipropylamine, 3,3'-iminobis(N,N-dimethylpropylamine), 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, 3,3-aminobis(N,N-dimethylpropylamine), 3-(2-(dimethylamino)ethoxy)propylamine, or a combination thereof.

[0162] In some preferred embodiments, the compound of formula (II) is selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine or a combination thereof.

[0163] Examples of compounds of formula (III) suitable for use herein include alkanolamines, including but not limited to triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol , 2-dimethylamino-2-methyl-1-propanol, N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol and N,N,N'-trimethylaminoethylethanolamine.

[0164] In some preferred embodiments, the compound of formula (III) is selected from triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol or a combination thereof.

[0165] A particularly preferred compound of formula (II) is N,N-dimethyl-1,3-diaminopropane (dimethylaminopropylamine).

[0166] When the compound of formula (III) reacts with a succinic acylating agent, the resulting product is a succinic ester. 4 When the succinic acid acylating agent reacts with the compound of formula (II) (wherein R 4 When the reaction is carried out with 2-H-butyl 2-nitropropene (not hydrogen), the product obtained is an amide

[0167] To form the quaternary ammonium salt (a), a hydrocarbyl-substituted succinic acid-derived acylating agent is reacted with a compound capable of reacting with the acylating agent and comprising a tertiary amine group. The reaction product is then reacted with a quaternizing agent for quaternization.

[0168] The reaction product of the acylating agent and the compound comprising a tertiary amine group is preferably reacted with at least one molar equivalent of quaternizing agent per mole of tertiary amine groups present in the reaction product.

[0169] In some embodiments, the reaction product of the acylating agent and the compound comprising a tertiary amine group may be reacted with more than one molar equivalent of quaternizing agent per mole of tertiary amine groups present in the reaction product, preferably at least 1.2 molar equivalents of quaternizing agent per mole of tertiary amine groups, more preferably at least 1.5 molar equivalents of quaternizing agent, suitably at least 1.7 molar equivalents of quaternizing agent, for example at least 1.9 molar equivalents of quaternizing agent.

[0170] In some embodiments, the reaction product of the acylating agent and the compound containing a tertiary amine group may be reacted with two or more molar equivalents of the quaternizing agent per mole of tertiary amine groups present in the reaction product, preferably at least 2.1 molar equivalents of the quaternizing agent.

[0171] In some embodiments, the reaction product of an acylating agent and a compound comprising a tertiary amine group is reacted with more than 2.2 molar equivalents of quaternizing agent per mole of tertiary amine groups present in the reaction product, e.g., 2.3 to 4 molar equivalents, 2.3 to 3 molar equivalents, or 2.3 to 2.7 or 2.5 to 3 molar equivalents.

[0172] To form some preferred quaternary ammonium salts for use in the present invention, a compound of formula (I) is reacted with a compound formed by the reaction of a hydrocarbyl-substituted acylating agent and an amine of formula (II) or (III).

[0173] The compound of formula (II) or formula (III) is as described above.

[0174] Preferably, the amine of formula (II) or (III) is reacted with a hydrocarbyl-substituted succinic acid derived acylating agent such as succinic acid or succinic anhydride.

[0175] Suitably about one equivalent of amine is added per succinic acid moiety present in the acylating agent.Thus, the proportion of amine used will generally depend on the average number of succinic acid moieties present per molecule of the acylating agent.

[0176] Preferred quaternary ammonium salts for use herein can be formed by reacting methyl salicylate, dimethyl oxalate or propylene oxide (optionally in combination with an acid) with the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight of 700 to 1300 and dimethylaminopropylamine.

[0177] Preferred quaternary ammonium salts for use herein can be formed by reacting chloroacetic acid or a salt thereof with the reaction product of oleic acid or a reactive derivative thereof and dimethylaminopropylamine.

[0178] Particularly preferred quaternary ammonium salts for use herein are formed by reacting methyl salicylate or dimethyl oxalate with the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight of 700 to 1300 and dimethylaminopropylamine.

[0179] In a preferred embodiment, the polyisobutylene-substituted succinic anhydride comprises an average of at least 1.2 succinic acid moieties per molecule.

[0180] In some embodiments, the present invention involves using (b) the reaction product of a carboxylic acid-derived acylating agent and an amine as an additive.

[0181] These compounds may also be collectively referred to herein as acylated nitrogen-containing compounds.

[0182] Suitable acylated nitrogen compounds can be prepared by reacting a carboxylic acid acylating agent with an amine and are known to those skilled in the art.

[0183] The preferred hydrocarbyl substituted acylating agent is polyisobutenyl succinic anhydride.These compounds are commonly referred to as "PIBSA" and are well known to those skilled in the art.

[0184] Conventional polyisobutylenes and so-called "highly reactive" polyisobutylenes are suitable for use in the present invention. These are suitably as described herein previously in relation to the preparation of some preferred quaternary ammonium detergents.

[0185] Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

[0186] In a preferred embodiment, the reaction product of a carboxylic acid derived acylating agent and an amine includes at least one primary or secondary amine group.

[0187] Preferred acylated nitrogen compounds for use herein are prepared by reacting a polyisobutylene-substituted succinic acid derived acylating agent (e.g., anhydrides, acids, esters, etc.) with a mixture of ethylene polyamines having from 2 to about 9 amino nitrogen atoms, preferably from about 2 to about 8 nitrogen atoms and from about 1 to about 8 ethylene groups per ethylene polyamine, wherein the number average molecular weight (Mn) of the polyisobutylene substituent is from 170 to 2800. These acylated nitrogen compounds are suitably formed by reacting an acylating agent:amino compound molar ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 2:1 to 1:2, and most preferably from 2:1 to 1:1. In a particularly preferred embodiment, the acylated nitrogen compound is formed by reacting an acylating agent to an amino compound in a molar ratio of from 1.8:1 to 1:1.2, preferably from 1.6:1 to 1:1.2, more preferably from 1.4:1 to 1:1.1, and most preferably from 1.2:1 to 1:1. Acylated amino compounds of this type and their preparation are well known to the person skilled in the art and are described, for example, in EP 0 565 285 and US Pat. No. 5,925,151.

[0188] Preferred nitrogen-containing detergents are of the type formed by the reaction of an acylating agent derived from a polyisobutylene-substituted succinic acid with a polyethylene polyamine. Suitable compounds are described, for example, in WO2009 / 040583.

[0189] In a preferred embodiment, the reaction product of a carboxylic acid-derived acylating agent and an amine (b) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is from 500 to 2000, preferably from 600 to 1000.

[0190] In some embodiments, the present invention may involve the use of (c) a Mannich reaction product between an aldehyde, an amine, and an optionally substituted phenol.

[0191] Preferably, component (c) comprises the product of a Mannich reaction between:

[0192] (x) aldehydes;

[0193] (y) amines; and

[0194] (z) Optionally substituted phenol.

[0195] Preferably, the aldehyde component used to prepare the Mannich reaction product is an aliphatic aldehyde. Preferably, the aldehyde has 1 to 10 carbon atoms. The most preferred aldehyde is formaldehyde.

[0196] Amines suitable for preparing the Mannich reaction product include monoamines and polyamines. One suitable monoamine is butylamine.

[0197] The amine used to prepare the Mannich reaction product is preferably a polyamine. This can be selected from any compound comprising two or more amine groups. Preferably, the polyamine is a polyalkylene polyamine, preferably a polyethylene polyamine. Most preferably, the polyamine comprises tetraethylene pentamine or ethylenediamine.

[0198] The optionally substituted phenol component used to prepare the Mannich additive may be substituted on the aromatic ring by 0 to 4 groups (in addition to the phenolic OH). For example, it can be a hydrocarbyl-substituted cresol. Most preferably, the phenol component is a monosubstituted phenol. Preferably, it is a hydrocarbyl-substituted phenol. Preferred hydrocarbyl substituents are alkyl substituents having 4 to 28 carbon atoms, especially 10 to 14 carbon atoms. Other preferred hydrocarbyl substituents are polyalkenyl substituents. The number average molecular weight of such polyisobutylene substituents is 400 to 2500, for example 500 to 1500.

[0199] The preferred Mannich reaction product used in the present invention is generally formed by reacting components (x), (y) and (z) in a molar ratio of 1.1 to 5 parts (x): 1 part (y): 1.1 to 2 parts (z).

[0200] Suitable Mannich reaction products and methods of preparing such Mannich reaction products are known to those skilled in the art and include, for example, the compounds described in applicant's publications WO2009040582 and WO2013017887.

[0201] The preferred Mannich reaction product is the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol.

[0202] A particularly preferred Mannich reaction product for use herein is the reaction product of dodecylphenol, formaldehyde and ethylenediamine.

[0203] The appropriate treat rate of the at least one nitrogen-containing detergent may depend on the type of fuel used, and different levels of nitrogen-containing detergent may be required to achieve different performance levels.

[0204] The at least one nitrogen-containing detergent may be added to the fuel at any convenient point in the supply chain. For example, the at least one nitrogen-containing detergent may be added to the fuel at a refinery, a distribution terminal, or after the fuel leaves the distribution terminal. The at least one nitrogen-containing detergent may be added to the renewable diesel component and / or the biodiesel component before it is mixed; and / or the at least one nitrogen-containing detergent may be added to the mixed fuel after the components are mixed. If the at least one nitrogen-containing detergent is added to the fuel after the fuel leaves the distribution terminal, this is referred to as an aftermarket application. Aftermarket applications include situations where the at least one nitrogen-containing detergent is 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 the at least one nitrogen-containing detergent in a vial suitable for direct addition to a fuel storage tank or a vehicle tank.

[0205] The at least one nitrogen-containing detergent 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.

[0206] The at least one nitrogen-containing detergent may be present in the fuel composition in an amount of up to 1000 ppm, suitably up to 750 ppm, for example up to 600 ppm.

[0207] The at least one nitrogen-containing detergent is preferably 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 350 ppm.

[0208] For the avoidance of doubt, where the fuel composition comprises a mixture of two or more nitrogen-containing detergents, the above amounts refer to the total amount of all nitrogen-containing detergents present in the composition. Unless otherwise stated, all references to ppm in this specification are parts per million by weight.

[0209] In preferred embodiments, the fuel composition comprises one or more of the following:

[0210] (a) quaternary ammonium salts;

[0211] (b) the reaction product of a carboxylic acid derived acylating agent and an amine; and

[0212] (c) Products of the Mannich reaction between aldehydes, amines and optionally substituted phenols.

[0213] 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) the quaternary ammonium salt.

[0214] 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 carboxylic acid derived acylating agent and an amine.

[0215] 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 product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol.

[0216] Each of the nitrogen-containing detergents (a), (b) and (c) can be provided as a mixture of compounds. Each of the nitrogen-containing detergents (a), (b) and (c) can be provided as 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.

[0217] For the avoidance of doubt, the above amounts refer to the amount of active nitrogen-containing detergent compound present in the composition and disregard any impurities, solvents or diluents that may be present.

[0218] In some preferred embodiments, the fuel composition comprises the product of a Mannich reaction between (a) a quaternary ammonium salt and (c) an aldehyde, an amine, and an optionally substituted phenol.

[0219] Preferably, the fuel composition comprises 5 to 500 ppm, preferably 10 to 250 ppm of (a) a quaternary ammonium salt, and 5 to 500 ppm, preferably 10 to 250 ppm of (c) a product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol.

[0220] In some embodiments, the fuel composition comprises (a) a quaternary ammonium salt and (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol, suitably in a weight ratio of 3:1 to 1:3, preferably about 1:1; wherein component (a) comprises a quaternary ammonium salt formed by reacting methyl salicylate, dimethyl oxalate or propylene oxide (optionally in combination with an acid) with the reaction product of polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB molecular weight of 700 to 1300; and component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol (preferably dodecylphenol).

[0221] Fuel composition of the present invention can comprise one or more other additives, for example those additives common in the diesel fuel.These comprise for example antioxidant, dispersant, detergent, 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 is known to those skilled in the art.

[0222] The present invention relates to reducing the filter plugging tendency of a fuel composition having a tendency to plug filters.

[0223] A fuel composition having a tendency to block a filter refers to a fuel composition that will cause the filter to block if not handled with at least one nitrogenous detergent as described herein. The tendency of the fuel composition to block a filter can be measured by a series of standard industrial tests. A fuel composition that is suitable for handling according to the present invention is a fuel composition that does not meet the requirements of such standard tests without adding at least one nitrogenous detergent claimed. The reduction in the tendency of the filter blockage of the fuel composition can be demonstrated by obtaining improved performance in one of these tests.

[0224] Standard test methods for determining filter blocking 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 blocking tendency is specified in IP618. One of these tests can be used to evaluate the present invention.

[0225] A preferred method by which the clogging tendency of the filters of the present invention can be determined is the Canadian Cold Soak Filter Clogging Tendency Test (CSFBT). In this test, the fuel is stored at 1°C for 16 hours and then evaluated for 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.

[0226] In a preferred embodiment, the present invention reduces the filter plugging tendency of the fuel composition, as measured by the method of the CSFBT test. 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.

[0227] Preferably, the present invention reduces the filter plugging tendency of a fuel composition which, prior to treatment with at least one nitrogen-containing detergent 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.

[0228] 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%.

[0229] The invention will now be further described by way of the following non-limiting examples.

[0230] Embodiment 1:

[0231] Additive A, a nitrogen-containing detergent which is a Mannich reaction product, was prepared as follows:

[0232] 4-Dodecylphenol (129.6 g, 0.494 mole, 1.7 eq) was transferred to a 1 L jacketed glass reactor. Aromatic A150 solvent (95.2 g) was added and heated to 75°C. Ethylenediamine (17.5 g, 0.291 mole, 1 eq) was added and the mixture was heated to 90°C. A 37% aqueous formaldehyde solution (94.3 g, 1.16 mole, 4 eq) was then added, maintaining the reaction mixture temperature in the range of 90-96°C. The reactor was sealed and the temperature was raised to 120°C over 3 hours. At the same time, the pressure was increased to 0.8 barg. The reaction mixture was maintained at 120-122°C for 3 hours with a pressure of up to 1.1 barg. The reaction temperature was then reduced to about 95°C and the pressure to <0.5 bar, at which point the reactor was opened to atmosphere. Stirring was stopped and the contents were allowed to separate. The amber organic phase was washed twice with water at 90-90°C. Finally, any remaining water was removed from the organic phase under reduced pressure to yield a clear bright amber liquid (235 g).

[0233] Embodiment 2:

[0234] Additive B, a nitrogen-containing detergent which is a quaternary ammonium salt, is prepared as follows:

[0235] HR 1000MW polyisobutylene (126.37 g, 126 mmol, 1.0 equiv) was heated to 190°C and maleic anhydride (12.47 g, 127 mmol, 1.0 equiv) was then added over 1 hour. The reaction was heated to 205°C and then held for eight hours. Unreacted maleic anhydride was removed by vacuum distillation. The resulting PIBSA was cooled to 120°C and DMAPA (11.9 g, 116 mmol, 0.9 equiv) was added, keeping the reaction temperature within the range of 120°C-130°C. The reaction mixture was stirred and the temperature was then raised to 140°C to distill off water. After the distillation was complete, methyl salicylate (17.36 g, 114 mmol, 0.9 equiv) was added and the reaction was heated at 140°C until the reaction was complete. The reaction mixture was diluted with solvent, then cooled and discharged (271.2 g).

[0236] Embodiment 3:

[0237] A commercially derived fuel composition comprising a mixture of 80 vol% renewable diesel and 20 vol% biodiesel was treated with 1000 ppm of an additive composition comprising Aromatic solvent, 15 wt% Additive A and 14 wt% Additive B (Additive Composition G below).

[0238] Untreated fuel blends have the following characteristics:

[0239]

[0240] Embodiment 4:

[0241] The unsupplemented and spiked fuel compositions described in Example 3 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.

[0242] The revised test method is summarized as follows:

[0243] 1. The fuel composition sample is first conditioned to eliminate its thermal history.

[0244] 2. The fuel composition was then maintained at 1°C for 16 hours.

[0245] 3. The fuel composition was then warmed to 25°C for 2-4 hours.

[0246] 4. After warming, 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).

[0247] 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

[0248] 4.2. If a pressure drop of 105 kPa is reached before 300 mL of the fuel composition is filtered, use the volume filtered when 105 kPa is reached to calculate the CSFBT result.

[0249] 5. The results of the CSFBT test can 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).

[0250] The results are shown in Table 1.

[0251] Table 1.

[0252] fuel FBT Base fuel 3.88 Added fuel 1.56

[0253] Embodiment 5:

[0254] A mixed fuel composition was prepared, comprising 80 vol% renewable diesel fuel (R100) and 20 vol% biodiesel fuel (B100).

[0255] Unmixed fuel components have the following characteristics:

[0256]

[0257] The fuel composition is prepared by dosing the following additives into the mixed fuel composition:

[0258] Additive C comprises a Mannich reaction product prepared by reacting dodecylphenol, ethylenediamine and formaldehyde, using a method similar to that described in Comparative Example 2 of WO2013017886A1. After the reaction is complete, the active substance content of Additive C is adjusted to 29 wt% by dilution with Aromatic 150 solvent.

[0259] Additive D is a solution of polyisobutenyl succinimide (in Aromatic solvent) obtained by condensation of polyisobutenyl succinic anhydride derived from polyisobutene having an Mn of about 750 with a mixture of polyethylene polyamines having an average composition close to that of tetraethylene pentamine. The product is obtained by mixing polyisobutenyl succinic anhydride and tetraethylene pentamine at 50° C. under nitrogen and heating at 160° C. for 5 hours to remove water. After the reaction is complete, the active matter content of Additive D is adjusted to 29% by weight by diluting with Aromatic 150 solvent.

[0260] Additive E was prepared by quaternization of succinamide with propylene oxide in the absence of additional acid, using a procedure similar to that described in Preparation Example 1 of US9255236B2. Propylene oxide was used instead of styrene oxide for the quaternization reaction. The succinamide precursor was prepared by reacting polyisobutylene succinic anhydride (PIBSA) with a PIB number average molecular weight of 1000 with dimethylaminopropylamine (DMAPA) at 20-25°C. After the reaction was completed, the active substance content of Additive E was adjusted to 29% by weight by diluting with Aromatic 150 solvent.

[0261] Additive F was prepared according to the following procedure:

[0262] Oleamidopropyl dimethylamine (183.5 g, 0.5 mol), isopropanol (68 mL), water (25.5 mL) and sodium chloroacetate (56.5 g, 0.48 mol) were added to a 1 L reactor and heated to 80° C. and stirred for 6 hours. After cooling to 60° C., isopropanol (300 mL) and 2-ethylhexanol (67.5 g) were added and the reaction temperature was raised to 90° C. The volatile liquids were evaporated over a 2 hour period. Residual isopropanol and water were then removed by applying a vacuum (about 50 mbar) while maintaining heating. The reaction mass was cooled to about 75° C. and then filtered through a glass microfiber filter under vacuum. The filtrate was then diluted with Aromatic 150 solvent to obtain Additive F, a 29 wt % solution of the quaternized reaction product.

[0263] Additive Composition G contained Aromatic solvent, 15 wt% Additive A and 14 wt% Additive B.

[0264] The additive was dosed into the mixed fuel and tested according to a modified version of the procedure of the standard CSFBT test method specified in CAN / CGSB 3.0, No. 142-2019 and described in Example 4.

[0265] The results are shown in Table 2.

[0266] Table 2.

[0267]

[0268]

Claims

1. Use of at least one nitrogen-containing detergent 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.

2. A method of reducing the filter plugging tendency of a fuel composition having a tendency to plug filters and comprising a biodiesel component and a renewable diesel component, the method comprising dosing at least one nitrogen-containing detergent into the fuel.

3. A fuel composition comprising a renewable diesel component, a biodiesel component and at least one nitrogen-containing detergent; wherein: The fuel composition has a reduced tendency to plug filters compared to an otherwise identical fuel composition that does not contain a nitrogen-containing detergent and that has a tendency to plug filters.

4. The use, method or composition according to any one of the preceding claims, 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.

5. The use, method or composition according to any one of the preceding claims, wherein the at least one nitrogen-containing cleaning agent is selected from one or more of the following: (a) quaternary ammonium salts; (b) the reaction product of a carboxylic acid-derived acylating agent and an amine; (c) products of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; (d) the reaction product of a carboxylic acid derived acylating agent and hydrazine; (e) salts formed by the reaction of carboxylic acids with di-n-butylamine or tri-n-butylamine; and (f) The reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride with an amine compound or salt, said product comprising at least one aminotriazole group.

6. The use, method or composition of claim 5, wherein the at least one nitrogen-containing cleaning agent comprises a quaternary ammonium salt.

7. The use, method or composition of claim 6, wherein the quaternary ammonium salt is the reaction product of a compound comprising at least one tertiary amine group and a quaternizing agent.

8. The use, method or composition of claim 7, wherein the quaternizing agent is selected from esters of carboxylic acids, dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides (optionally in combination with an acid), alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.

9. The use, method or composition according to claim 6 or claim 7, wherein the compound comprising at least one tertiary amine group is selected from: (i) the reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group; (ii) a Mannich reaction product comprising a tertiary amine group; (iii) a polyalkylene-substituted amine having at least one tertiary amine group; and (iv) Alkylamines (eg tertiary alkylamines), alkylalkanolamines (eg dimethylethanolamine) and alkanolamines.

10. The use, method or composition of any one of claims 6 to 9, wherein the quaternary ammonium salt is the quaternization reaction product of a hydrocarbyl-substituted succinic acid derived acylating agent and a compound capable of reacting with the acylating agent and comprising a tertiary amine group.

11. The use, method or composition of any one of claims 6 to 10, wherein the quaternary ammonium salt is formed by the reaction of methyl salicylate, dimethyl oxalate or propylene oxide, optionally in combination with an acid, with the reaction product of polyisobutylene-substituted succinic anhydride having a PIB molecular weight of 700 to 1300 and dimethylaminopropylamine.

12. The use, method or composition of any one of claims 6 to 9, wherein the quaternary ammonium salt is formed by reacting chloroacetic acid or a salt thereof with the reaction product of oleic acid or a reactive derivative thereof and dimethylaminopropylamine.

13. The use, method or composition of claim 5, wherein the at least one nitrogen-containing cleaning agent comprises the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol.

14. The use, method or composition of claim 13, wherein the Mannich reaction product is the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol.

15. The use, method or composition according to any one of the preceding claims, which provides improved filter blocking tendency as measured by the Canadian Cold Soak Filter Blocking Tendency Test CAN / CGSB-3.0 No.142.0-2019.

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