Uses and methods

Abstract

Use of a nitrogen-containing cleaning agent as an additive in a diesel fuel composition to reduce the effects of deposits in a post-combustion system of a diesel engine when combusting the diesel fuel composition.

Description

[0001] The present invention relates to methods and uses for improving the performance of diesel engines. In particular, the present invention relates to reducing the effects of deposits in the after-combustion system of a diesel engine, especially a modern diesel engine having a high pressure fuel system.

[0002] It is well known to add detergent additives to clean deposits in the combustion system of a diesel engine, such as the fuel injection system, and a variety of detergents have been developed for this purpose.

[0003] However, less research has been conducted on the removal of deposits in exhaust gas recirculation systems or afterburning systems. However, the presence of deposits in the exhaust gas recirculation system or afterburning system of a diesel engine can have a significant detrimental effect on the performance of the diesel engine, especially modern diesel engines with high pressure fuel systems.

[0004] Equip diesel vehicles with exhaust gas recirculation (EGR) systems to reduce NO x emissions. This is achieved by recirculating the exhaust gas to the combustion chamber in a controlled manner, thereby increasing the heat capacity of the gas in the combustion chamber and reducing the oxygen concentration in the gas. Several types of EGR systems have been developed. The high-pressure EGR system is arranged to divert the exhaust gas from the combustion chamber before the exhaust gas reaches any turbocharger and / or diesel particulate filter present in the engine, and supply the exhaust gas to the intake manifold downstream of the compressor. Therefore, the high-pressure EGR system operates on the high-pressure side of the intake manifold and the exhaust manifold and supplies unfiltered recirculated exhaust gas to the combustion chamber. The low-pressure EGR system is arranged to divert the exhaust gas from the combustion chamber downstream of the turbocharger and / or diesel particulate filter present in the engine, and supply the exhaust gas to the intake duct upstream of the compressor. Therefore, the low-pressure EGR system operates on the low-pressure side of the intake manifold and the exhaust manifold and supplies filtered recirculated exhaust gas to the combustion chamber. The hybrid (or combined) EGR system integrates both high-pressure EGR and low-pressure EGR on the same engine to combine the advantages of each system. A dedicated EGR (D-EGR) system is arranged to direct all exhaust gas from a subset of the power cylinders (dedicated cylinders) directly into the intake manifold.

[0005] Over time, deposits can form within the EGR system. This is a particular problem in diesel engines with high pressure EGR systems, as the recirculated exhaust gas flow is carried upstream of any turbocharger and diesel particulate filter, meaning that problematic particulate combustion products can be reintroduced into the intake manifold and combustion chamber. One area where such deposits can cause a particular problem is within the cooler assembly of the EGR system. If deposit levels become significant, the engine management system in a complex diesel engine may cause the engine to operate with reduced performance and / or enter a safe operating mode. This condition can have a significant impact on the operability of the vehicle and will need to be checked by a suitably qualified workshop.

[0006] A typical EGR system includes an intake pipe, valve, housing, cooler, and outlet pipe. Deposits can accumulate on the inner surfaces of all parts of the EGR system, but especially in the cooler.

[0007] It would be beneficial to eliminate such deposits, particularly in coolers of EGR systems, and particularly in coolers of high pressure EGR systems.

[0008] The afterburning system of a diesel engine typically includes a series of components through which the exhaust gas must flow before exiting the vehicle. The afterburning system may include a turbocharger, a diesel oxidation catalyst, a diesel particulate filter, a selective catalytic reduction unit, and an ammonia oxidation catalyst. It would be desirable to eliminate deposits in any or all of these components.

[0009] The formation of deposits in the afterburning system may involve the accumulation of soot on components of the afterburning system. Specifically, the formation of deposits in the afterburning system may involve the accumulation and / or capture of soot in a diesel particulate filter of the afterburning system.

[0010] Prevent and / or remove deposits on sensors within the post-combustion system (e.g. NO x Deposits on sensors, temperature sensors and / or pressure sensors) would also be helpful.

[0011] It would also be beneficial to prevent and / or remove soot accumulation on components of an aftercombustion system and / or prevent and / or remove soot on a diesel particulate filter of an aftercombustion system.

[0012] Surprisingly, the present inventors have discovered that the addition of certain compounds as fuel additives can counteract the effects of deposits in EGR systems and / or post-combustion systems.

[0013] According to a first aspect of the present invention there is provided the use of one or more nitrogen containing detergents as an additive in a diesel fuel composition to reduce the effect of deposits in an exhaust gas recirculation system and / or aftercombustion system of a diesel engine when the diesel fuel composition is combusted.

[0014] According to a second aspect of the invention there is provided a method of reducing the effects of deposits in an exhaust gas recirculation system and / or an aftercombustion system of a diesel engine, the method comprising combusting in the engine a diesel fuel composition comprising one or more nitrogen containing detergents as an additive.

[0015] The present invention relates to a method and use which reduces the effects of deposits in an EGR system and / or an aftercombustion system of a diesel engine.The presence of deposits on one or more components of an aftercombustion system of a diesel engine generally has a negative impact on the performance of the engine.

[0016] Reducing the effects of deposits may include reducing or preventing the formation of deposits and / or removing existing deposits and / or changing the properties of deposits.

[0017] In some embodiments, reducing the effects of deposits may include changing the properties of the deposits. This means that the structure or composition of the deposits formed is different in a way that is less detrimental to engine performance, such as by increasing the ignitability and / or thermal conductivity of the deposits.

[0018] In some preferred embodiments, reducing the effects of deposits includes reducing and / or preventing the formation of deposits and / or removing existing deposits.

[0019] In some embodiments, a first aspect of the invention provides the use of one or more nitrogen-containing detergents as an additive in a diesel fuel composition to reduce the effects of deposits in an exhaust gas recirculation system of a diesel engine when the diesel fuel composition is combusted.

[0020] Preferably, the use reduces the formation of deposits in the EGR system.

[0021] In some embodiments, a second aspect of the invention provides a method of reducing the effects of deposits in an exhaust gas recirculation system of a diesel engine, the method comprising combusting in the engine a diesel fuel composition comprising one or more nitrogen-containing detergents as an additive.

[0022] Preferably, the method reduces the formation of deposits in the EGR system.

[0023] Preferably, the first aspect of the invention provides the use of one or more nitrogen-containing detergents as an additive in a diesel fuel composition to reduce the effects of deposits in the after-combustion system of a diesel engine when the diesel fuel composition is combusted.

[0024] Preferably, a second aspect of the invention provides a method of reducing deposit formation in an aftercombustion system of a diesel engine, the method comprising combusting in the engine a diesel fuel composition comprising one or more nitrogen-containing detergents as an additive.

[0025] In a preferred embodiment, reducing the effects of deposits includes reducing and / or preventing the effects of deposits in an after-combustion system of a diesel engine.

[0026] Preferred features of the first and second aspects of the invention will now be described.

[0027] The present invention relates to the use of one or more nitrogen-containing detergents as additives in diesel fuel compositions to reduce the effects of deposits in EGR systems and / or post-combustion systems.

[0028] The present invention relates to the use of one or more nitrogen-containing cleaners as additives. This means that the present invention may include the use of one nitrogen-containing cleaner as an additive or the use of multiple nitrogen-containing cleaners as multiple additives.

[0029] For the avoidance of doubt, each additive used in the present invention may include a mixture of compounds, and reference to an additive or the additive includes a mixture unless otherwise stated. Specifically, 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 additive compounds described herein may include mixtures of isomers and / or mixtures of homologues.

[0030] The present invention relates to the use of one or more nitrogen-containing cleaning agents. Preferably, the one or more nitrogen-containing cleaning agents are selected from:

[0031] (a) quaternary ammonium salt additives;

[0032] (b) the reaction product of a carboxylic acid-derived acylating agent and an amine;

[0033] (c) products of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol;

[0034] (d) the reaction product of a carboxylic acid derived acylating agent and hydrazine;

[0035] (e) a salt formed by reacting a carboxylic acid with di-n-butylamine or tri-n-butylamine; and

[0036] (f) The reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride with an amine compound or salt, the product comprising at least one aminotriazole group.

[0037] The one or more nitrogen-containing cleaning agents are preferably selected from:

[0038] (a) quaternary ammonium salt additives;

[0039] (b) the reaction product of a carboxylic acid-derived acylating agent and an amine;

[0040] (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; and

[0041] (d) mixtures thereof.

[0042] (a) Quaternary ammonium salt additives

[0043] Component (a) may include any suitable quaternary ammonium salt additive.

[0044] Preferably, the quaternary ammonium salt additive is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent.

[0045] Any suitable quaternizing agent may be used. The quaternizing agent may suitably be selected from esters and non-esters.

[0046] 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.

[0047] In some preferred embodiments, the quaternizing agents used to form the quaternary ammonium salt additives of the present invention are esters.

[0048] Preferred ester quaternizing agents are compounds of formula (I):

[0049]

[0050] 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.

[0051] Suitable quaternizing agents include esters of carboxylic acids having a pKa of 3.5 or less.

[0052] 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.

[0053] 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.

[0054] 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 carbonyl, alkoxy, nitro, cyano, hydroxy, SR 5or NR 5 R 6 The group substituted. 5 and R 6 Each may be hydrogen or an optionally substituted alkyl, alkenyl, aryl or carbonylalkoxy 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 6 Preferably, R is one or more selected from hydroxyl, carbonyl, alkoxy, nitro, cyano and NH 2 R can be a polysubstituted aryl, such as trihydroxyphenyl. In some embodiments, R can be a hydrocarbyl substituted aryl, such as an alkyl substituted aryl. In some embodiments, R can be an aryl substituted by a hydroxyl and a hydrocarbyl (such as an alkyl), such as described in EP2631283.

[0055] Preferably, R is a monosubstituted aryl. Preferably, R is an ortho-substituted aryl. Suitably, R is selected from OH, NH 2 、NO 2 Preferably, R is OH or NH 2 Preferably, R is 2-hydroxyphenyl.

[0056] 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 an isomer thereof. 1 is benzyl or methyl. Most preferably, R 1 It is methyl.

[0057] 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.

[0058] In some embodiments, the compound of formula (I) is an ester of an α-hydroxycarboxylic acid. In such embodiments, the compound has the following structure:

[0059]

[0060] 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 EP1254889.

[0061] 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.

[0062] In some embodiments, the compound of formula (I) is an ester of a polycarboxylic acid. This definition refers to a carboxylic acid including dicarboxylic acids and having more than two acidic moieties. In this embodiment, RCOO is preferably present in the form of an ester, i.e., 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 fall within the scope of the present invention. Mixed esters of polycarboxylic acids may also be used. Preferred esters are C1 to C4 alkyl esters.

[0063] The ester quaternizing agent may be selected from the group consisting of 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.

[0064] 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 contains more than one acid group, the first dissociation constant is referred to.

[0065] The ester quaternizing agent can be selected from esters of carboxylic acids, wherein the carboxylic acids are selected from one or more of the following: oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, 2,4,6-trihydroxybenzoic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, acetylenedicarboxylic acid, glutaconic acid, muconic acid, citraconic acid, mesaconic acid, itaconic acid, tartronic acid, mesooxalic acid, tartaric acid, oxaloacetic acid, dioxosuccinic acid, α-hydroxyglutaric acid, biphenylcarboxylic acid and 2,6-naphthalene dicarboxylic acid.

[0066] The ester quaternizing agent may be selected from esters of carboxylic acids 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.

[0067] Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.

[0068] In some preferred embodiments, the quaternizing agent used to form the quaternary ammonium salt additive of the present invention is an ester selected from dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate, preferably dimethyl oxalate and methyl salicylate.

[0069] 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.

[0070] 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 salts thereof, or mixtures thereof.

[0071] 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. Such methods can be suitable for preparing hydroxides, alkoxides, nitrites or nitrates of quaternary ammonium.

[0072] Suitable alkyl halides for use herein include chlorides, bromides and iodides.

[0073] 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.

[0074] Suitable dialkyl sulfates for use herein as quaternizing agents include those sulfates which include an alkyl group containing from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl chain. The preferred compound is dimethyl sulfate.

[0075] Suitable alkyl-substituted carbonates can include two alkyls, which can be identical or different. Each alkyl can contain 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, suitably 1 to 5 carbon atoms. Preferably, the alkyl or each alkyl is an alkyl. Preferred compounds of this type include diethyl carbonate and dimethyl carbonate.

[0076] Suitable hydrocarbyl substituted epoxides have the formula:

[0077]

[0078] Where R 1 , R 2 , R 3 and R 4 Each is independently hydrogen or a hydrocarbon group having 1 to 50 carbon atoms. Examples of suitable epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and stilbene oxide. The hydrocarbon epoxide is used in combination with an acid as a quaternizing agent.

[0079] 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.

[0080] Particularly preferred epoxide quaternizing agents are propylene oxide and styrene oxide, optionally in combination with an additional acid.

[0081] Suitable alkyl sulfonates include those having 1 to 20, preferably 1 to 10, more preferably 1 to 4 carbon atoms.

[0082] Suitable sultones include propane sultone and butane sultone.

[0083] 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.

[0084] Suitable hydrocarbyl-substituted borate groups include alkyl borates having from 1 to 12 carbon atoms.

[0085] Preferred alkyl nitrites and alkyl nitrates have 1 to 12 carbon atoms.

[0086] 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.

[0087] 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 acid is provided by a quaternized tertiary amine compound. Preferably, the acid is provided by a quaternized tertiary amine molecule.

[0088] 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).

[0089] In some embodiments, mixtures of two or more quaternizing agents may be used.

[0090] To form the quaternary ammonium salt additive, a quaternizing agent is reacted with a compound containing a tertiary amine group.

[0091] Any suitable compound containing a tertiary amine group may be used.

[0092] The compound comprising at least one tertiary amine group may be selected from:

[0093] (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;

[0094] (ii) a Mannich reaction product comprising a tertiary amine group;

[0095] (iii) a polyalkylene-substituted amine having at least one tertiary amine group; and

[0096] (iv) Simple alkylamines and alkanolamines.

[0097] 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.

[0098] The preparation of some suitable quaternary ammonium salt additives is described in WO2006 / 135881, US2020 / 0024536 and WO2011 / 095819, wherein the compound comprising at least one tertiary amine group comprises component (i).

[0099] Component (ii) is a Mannich reaction product with a tertiary amine. US 2008 / 0052985 describes the preparation of compounds containing at least one tertiary amine group, including quaternary ammonium salts of component (ii).

[0100] The preparation of compounds comprising at least one tertiary amine group including quaternary ammonium salt additives of component (iii) is described, for example, in US 2008 / 0113890.

[0101] For example, the preparation of some suitable quaternary ammonium salt additives is described in WO 2016 / 016641, wherein the compound comprising at least one tertiary amine group comprises component (i).

[0102] 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.

[0103] In some embodiments, the present invention does not encompass acid-free quaternized nitrogen compounds.In preferred embodiments, the quaternary ammonium salt additives of the present invention include a single anion and a single cation.

[0104] In some embodiments, the compound containing at least one tertiary amine group is (i) the reaction product of a hydrocarbyl-substituted acylating agent and a compound containing at least one tertiary amine group and a primary amine, secondary amine or alcohol group, the hydrocarbyl-substituted acylating agent can be provided by a fatty acid. Suitable fatty acids are compounds of the formula RCOOH, wherein R is an alkyl or alkenyl group having 6 to 36 carbon atoms, preferably 8 to 30 carbon atoms or 12 to 24 carbon atoms. A preferred fatty acid is oleic acid.

[0105] In such embodiments, the compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group is suitably provided by a compound of formula (II) or (III):

[0106]

[0107] 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 C 1 To C 22 alkyl.

[0108] According to the suitable compound of formula (II), can be 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 its combination. In some preferred embodiments, the compound comprising at least one tertiary amine group and primary amine, secondary amine or alcohol group is dimethylaminopropylamine.

[0109] Preferably, the quaternary ammonium salt additive is a quaternary ammonium reaction product of a fatty acid and a compound of formula (II), for example a fatty acid of formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, suitably in formula (II) R 2 and R 3 All C 1 To C 4 alkyl and X is an alkylene group having 2 to 5 carbon atoms.

[0110] In such an embodiment, the quaternary ammonium compound used in the present invention is a quaternary ammonium reaction product of a fatty acid (e.g., oleic acid) and dimethylaminopropylamine. The term "quaternary ammonium compound" is used interchangeably herein with "quaternary ammonium salt additive" and "quaternary ammonium salt". Therefore, in such an embodiment, the quaternary ammonium compound used in the present invention is a quaternary ammonium reaction product of a fatty acid (e.g., oleic acid) and dimethylaminopropylamine.

[0111] Preferably, the quaternary ammonium salt additive is a quaternary ammonium reaction product of oleic acid and dimethylaminopropylamine.

[0112] In such an embodiment, suitable quaternizing agents for reacting with the above reaction product are 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 salts thereof, or mixtures thereof. Preferably, the quaternizing agent is chloroacetic acid or a salt thereof, such as sodium chloroacetate.

[0113] In such embodiments, the quaternary ammonium salt additive may have formula (IV):

[0114]

[0115] (IV)

[0116] Where R 7 is an alkyl or alkenyl group having 7 to 22 carbon atoms; R 8 and R 9 are each independently an alkyl, hydroxyalkyl or carboxyalkyl group having 1 to 6 carbon atoms; m is 2 to 4; n is 0 or 1; X is an alkylene group having 1 to 6 carbon atoms optionally substituted with a hydroxyl group; and Y is -CO 2 or -SO 3 .

[0117] Preferably, the quaternary ammonium salt additive is an amido betaine having formula (V):

[0118]

[0119] Where R 7 , R 8 and R9 As defined above and wherein m is 2 or 3.

[0120] Preferably, R 7 Has 16 to 22 carbon atoms. 7 Preferred is an alkenyl group having 16 to 22 carbon atoms. 7 It can be C derived from oleic acid 17 Alkenyl. 8 and R 9 Preferred is methyl.

[0121] In a preferred embodiment, the quaternary ammonium salt additive is the quaternized reaction product of oleic acid and dimethylaminopropylamine, wherein the reaction product has been quaternized with chloroacetic acid or a salt thereof.

[0122] Other suitable quaternary ammonium salt additives suitable for use in the present invention include the quaternary ammonium salt additives described in the applicant's co-pending applications WO2011 / 095819, WO2013 / 017889, WO2015 / 011506, WO2015 / 011507, WO2016 / 016641 and WO2017 / 017454.

[0123] In some embodiments, the compound including at least one tertiary amine group is the reaction product of (i) a hydrocarbyl-substituted acylating agent, which can be provided by a hydrocarbyl-substituted succinic acid-derived acylating agent, and a compound comprising at least one tertiary amine group and a primary amine, secondary amine, or alcohol group.

[0124] In such an embodiment, the quaternary ammonium salt additive (a) is the quaternized 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.

[0125] For the avoidance of doubt, reference to a quaternized reaction product is intended to refer to a reaction product comprising a tertiary amine which has then been quaternized to form a quaternary ammonium group. The quaternary ammonium salt additive 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 the acylating agent and comprising a tertiary amine group.

[0126] 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 characteristics. Examples of hydrocarbyl groups include:

[0127] (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 in which the ring is completed by another part of the molecule (e.g., two substituents together form a ring);

[0128] (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), hydroxyl, alkoxy (e.g. C 1 To C 4 alkoxy), keto, acyl, cyano, thiol, amino, amide, nitro, nitroso, sulfoxide, nitro and carboxyl);

[0129] (iii) heterosubstituents, i.e., in the context of the present invention, substituents which, although predominantly hydrocarbon in character, contain atoms other than carbon in a ring or chain consisting of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; normally, no non-hydrocarbon substituent will be present in the hydrocarbyl group.

[0130] 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 via a chlorination route or a thermal route (the so-called "ene" reaction).

[0131] The example of hydrocarbyl substituent includes n-octyl, n-decyl, n-dodecyl, tetrapropylene, n-octadecyl, oleyl, chlorooctadecyl, triacontyl etc. Hydrocarbyl substituent 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. Alternatively, substituent can be made by other sources, for example monomer high molecular weight olefin (for example 1-tetradecene), aliphatic petroleum fractions, for example paraffin and its cracking analog, white oil, synthetic olefin (for example produced by Ziegler-Natta process) (for example poly (ethylene) grease) and other sources known to persons skilled in the art. If necessary, any unsaturation in substituent can be reduced or eliminated by hydrogenation according to methods known in the art.

[0132] Preferably, the hydrocarbyl substituent is predominantly saturated, that is, contains no more than one carbon-carbon unsaturated bond for every ten carbon-carbon single bonds present. Most preferably, contains no more than one carbon-carbon non-aromatic unsaturated bond for every 50 carbon-carbon bonds present.

[0133] 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.

[0134] Those skilled in the art will be familiar with standard techniques for measuring number average molecular weight, for example by vapor pressure osmometry, end group titration, proton NMR, boiling point elevation, freezing point depression (cryogenic methods), and GPC (gel permeation chromatography).

[0135] 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.

[0136] The preferred hydrocarbyl substituent is polyisobutylene. Such compounds are known to those skilled in the art.

[0137] 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.

[0138] Conventional polyisobutylenes and so-called "highly reactive" polyisobutylenes are suitable for use in the present invention. Highly reactive polyisobutylenes are defined herein 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 polyisobutylenes 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 (Mn) ranges as generally described above for the hydrocarbyl substituents.

[0139] Other preferred hydrocarbyl groups include those having an internal olefin, such as those described in applicant's published application WO 2007 / 015080.

[0140] 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.

[0141] Internal olefins are sometimes referred to as isomerized olefins and can be prepared from alpha olefins by isomerization processes known in the art, or can 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.

[0142] The preferred hydrocarbyl substituted succinic acid derived acylating agent for preparing the additive (a) of the present invention is polyisobutenyl 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.

[0143] 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.

[0144] The monomaleated PIBSA may have structure (A) or (B):

[0145]

[0146] 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):

[0147]

[0148] Thus, a hydrocarbyl group substituted with more than one succinic acid moiety may be provided.

[0149] Those skilled in the art will appreciate that the additive used in the present invention will typically comprise a mixture of compounds and will be prepared from a mixture of monomaleated and bismaleated PIBSA.PIBSA can be defined according to its level of bismaleation.

[0150] One way this can be determined is by calculating the average number of succinic acid moieties per molecule of acylating agent.

[0151] Monomaleylated PIBSA contains one succinic acid moiety per module.

[0152] Bismaleated PIBSA contains two succinic acid moieties per molecule.

[0153] A mixture comprising monomaleated PIBSA and bismaleated PIBSA in a 1:1 molar ratio will contain an average of 1.5 succinic acid moieties per molecule of PIBSA.

[0154] The average number of succinic acid moieties per molecule of acylating agent is sometimes referred to in the art as the "P value."

[0155] Suitably, the quaternary ammonium salt additive is prepared from a hydrocarbyl-substituted succinic acid derived acylating agent comprising an average of 1 to 2 succinic acid moieties per molecule.

[0156] In some preferred embodiments, the present invention may include the use of quaternary ammonium salts derived from hydrocarbyl-substituted acylating agents comprising an average of at least 1.2 succinic acid moieties per molecule.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] The succinic acid moiety is meant to include the succinic acid residue in either the diacid or anhydride form.

[0163] 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 provide a quaternary ammonium salt additive.

[0164] 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- 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), and the like. Other types of nitrogen- or oxygen-containing compounds having tertiary amino groups that can condense 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-dibutylamino Propylamine 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.

[0165] 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):

[0166]

[0167] 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 C 1 To C 22 alkyl.

[0168] When the compound of formula (II) is used, R 4 Preferably hydrogen or C 1 To C 16 Alkyl, preferably C 1 To C 10 Alkyl, more preferably C 1 To C 6 Alkyl. When R 4When 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.

[0169] 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.

[0170] Preferably, a hydrocarbyl-substituted acylating agent is reacted with a diamine compound of formula (II).

[0171] 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 joined 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.

[0172] Preferably, R 2 and R 3 Each independently is C 1 To C 16 Alkyl, preferably C 1 To C 10 Alkyl. 2 and R 3 R may independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or any isomer of these groups. 2 and R 3 Each independently is C 1 To C 4 Preferably, R 2 Preferably, R 3 It is methyl.

[0173] 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 within the alkylene chain, for example, X can include an ether functional group.

[0174] 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.

[0175] Examples of compounds of formula (II) suitable for use herein include 1-aminopiperidine, 1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-piperidin, 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'-triethyl 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] A particularly preferred compound of formula (II) is N,N-dimethyl-1,3-diaminopropane (dimethylaminopropylamine).

[0180] 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

[0181] In some embodiments, wherein the succinic acylating agent is combined with a compound comprising a primary amine moiety (e.g., wherein R 4 The reaction may be carried out by reacting a compound of formula (II) with hydrogen (i.e., a compound of formula (II) with hydrogen) to form an amide bond, an imide bond, or a mixture thereof. Thus, the reaction product may be succinimide or succinamide, or a mixture thereof. Whether succinimide or succinamide is formed may depend on the reaction conditions used. Those skilled in the art will be able to select appropriate reaction conditions to form a reaction product that is primarily in the form of succinimide or primarily in the form of succinamide. Succinamide suitably comprises an amide bond formed between a free carboxylic acid moiety and a succinic acylating agent and an amine compound.

[0182] In some preferred embodiments, the 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 (ie, component (i)) is a succinimide, preferably polyisobutenyl succinimide (referred to as "PIBSI").

[0183] In some preferred embodiments, the 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 (ie, component (i)) is a succinamide, preferably a polyisobutenyl succinamide.

[0184] To form the quaternary ammonium salt additive (a), a hydrocarbyl-substituted succinic acid derived acylating agent is reacted with a compound capable of reacting with the acylating agent and containing a tertiary amine group. The reaction product is then quaternized by reaction with a quaternizing agent.

[0185] 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.

[0186] 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 a 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.

[0187] 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 quaternizing agent per mole of tertiary amine groups present in the reaction product, preferably at least 2.1 molar equivalents of quaternizing agent.

[0188] In some embodiments, the reaction product of the acylating agent and the 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.

[0189] To form some of the preferred quaternary ammonium salt additives of 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).

[0190] The compound of formula (II) or formula (III) is as described above.

[0191] 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.

[0192] Suitably about one equivalent of amine is added for each 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.

[0193] 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 polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB molecular weight (Mn) of 700 to 1300. Mixtures of two or more such quaternary ammonium salts can be used.

[0194] Particularly preferred quaternary ammonium salts for use herein are formed from the reaction product of methyl salicylate or dimethyl oxalate with a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

[0195] In a preferred embodiment, the polyisobutylene-substituted succinic anhydride comprises an average of at least 1.2 succinic acid moieties per molecule.

[0196] In some preferred embodiments, the quaternary ammonium salt additive (a) is formed by reacting a quaternizing agent with a reaction product of a polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB molecular weight (Mn) of 700 to 1300, wherein the reaction product of the polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine is mainly in the form of succinimide. Preferably, the quaternizing agent is an alkylene oxide (preferably propylene oxide), chloroacetic acid or a salt thereof, methyl salicylate or dimethyl oxalate, optionally in combination with an acid. In some preferred embodiments, the quaternizing agent is methyl salicylate.

[0197] In some preferred embodiments, the quaternary ammonium salt additive (a) is formed by reacting a quaternizing agent with a reaction product of a polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB molecular weight (Mn) of 700 to 1300, wherein the reaction product of the polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine is mainly in the form of succinamide. Preferably, the quaternizing agent is an alkylene oxide (preferably propylene oxide), chloroacetic acid or a salt thereof, methyl salicylate or dimethyl oxalate, optionally in combination with an acid. In some preferred embodiments, the quaternizing agent is propylene oxide.

[0198] In some embodiments, the quaternary ammonium salt additive (a) is the reaction product of a quaternizing agent and a compound containing a tertiary amine group selected from (iv) simple alkylamines and alkanolamines.

[0199] In such embodiments, the compound comprising a tertiary amine group (iv) is of the formula R 5 R 6 R 7 N tertiary amine, where R 5 , R 6 and R 7 Each is independently an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl.

[0200] Formula R 5 R 6 R 7 The tertiary amine of N can be a small compound of low complexity and low molecular weight. In some embodiments, the tertiary amine can be a complex molecule and / or a high molecular weight molecule comprising a tertiary amine group.

[0201] Formula R 5 R 6 R 7 The tertiary amine compounds of N preferably do not include any primary or secondary amine groups. In some embodiments, they may be derived from compounds containing these groups, but preferably these compounds are subsequently reacted to form additional tertiary amine species. 5 R 6 R 7 The tertiary amine compound of N may contain more than one tertiary amine group. However, tertiary amine compounds including primary or secondary amine groups are also within the scope of the present invention, as long as these groups do not interfere with the quaternization of the tertiary amine species.

[0202] In formula R 5 R 6 R 7 In some embodiments of the N compound, R 5 , R 6 and R 7 Each is independently an optionally substituted alkyl, alkenyl, aryl, aralkyl or alkaryl group.

[0203] R 5 , R 6 and R 7 Can be the same or different. In some preferred embodiments, R 5 and R 6 Same and R 7 different.

[0204] Preferably, R 5 and R 6 Each is independently an optionally substituted alkyl, alkenyl, aryl, aralkyl or alkaryl group having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms.

[0205] R 5 and R 6Each may be optionally substituted by one or more groups selected from halogen (especially chlorine and fluorine), hydroxyl, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, dialkylamino, nitro, nitroso and sulfoxide. The alkyl groups of these substituents may be further substituted.

[0206] Preferably, R 5 and R 6 Each is independently an optionally substituted alkyl or alkenyl. 5 and R 6 Each is independently an optionally substituted alkyl. 5 and R 6 Each is independently an optionally substituted alkyl or alkenyl group having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, suitably 1 to 8 carbon atoms, for example 1 to 6 carbon atoms.

[0207] In some preferred embodiments, R 5 is an optionally substituted alkyl or alkenyl group, preferably having 1 to 10, preferably 1 to 4, carbon atoms. 5 is an alkyl group. It may be a substituted alkyl group, such as a hydroxy-substituted alkyl group. Preferably, R 5 is an unsubstituted alkyl group. The alkyl chain may be straight or branched. Preferably, R 5 is selected from methyl, ethyl, propyl and butyl, including isomers thereof. Most preferably, R 5 It is methyl.

[0208] In some preferred embodiments, R 6 is an optionally substituted alkyl or alkenyl group, preferably having 1 to 10, preferably 1 to 4, carbon atoms. 6 is an alkyl group. It may be a substituted alkyl group, such as a hydroxy-substituted alkyl group. Preferably, R 6 is an unsubstituted alkyl group. The alkyl chain may be straight or branched. Preferably, R 6 is selected from methyl, ethyl, propyl and butyl, including isomers thereof. Most preferably, R 6 It is methyl.

[0209] In some embodiments, R 7For the optionally substituted alkyl or alkenyl, it has 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, suitably 1 to 8 carbon atoms, for example 1 to 6 carbon atoms. Suitable substituents include halogen (especially chlorine and fluorine), hydroxyl, alkoxy, keto, acyl, cyano, sulfydryl, alkylthiol, amino, alkylamino, nitro, nitroso, sulfoxide, amide, alkylamide, imide and alkylimide. The alkyl of these substituents can be further substituted.

[0210] In some embodiments, R 7 is an optionally substituted alkyl or alkenyl group, preferably having 1 to 10, preferably 1 to 4 carbon atoms. Suitably, R 7 is an optionally substituted alkyl group. 7 is a substituted alkyl group. Preferred substituents include alkoxy and hydroxy.

[0211] In some preferred embodiments, R 7 is a hydroxy-substituted alkyl group. The alkyl chain may be straight or branched. Most preferably, R 7 It is hydroxyethyl.

[0212] Suitable formula R 5 R 6 R 7 The tertiary amine compounds of N include simple alkylamino and hydroxyalkylamino compounds; trialkylamino compounds having high molecular weight substituents; Mannich reaction products of tertiary amines and substituted acylated amines or alcohols including tertiary amines.

[0213] Simple alkylamino and hydroxyalkylamino compounds are preferably of the formula R 5 R 6 R 7 N compound, wherein R 5 , R 6 and R 7 Each is an alkyl group or a hydroxyalkyl group. 5 , R 6 and R 7 Each may be the same or different. In some embodiments, R 5 , R 6 and R 7 Each is independently selected from an alkyl or hydroxyalkyl group having 1 to 10, preferably 1 to 6, for example 1 to 4 carbon atoms. 5 , R 6 and R 7 Each may be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl and hydroxyhexyl. 5R 6 R 7 The amine of N may be a trialkylamine, a dialkylhydroxyalkylamine, a dihydroxyalkylalkylamine or a trihydroxyalkylamine. There are many compounds of this type and these will be well known to those skilled in the art.

[0214] In some embodiments, the group R 5 , R 6 and R 7 One or two of the groups are short-chain alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms, and the other one or two groups are long-chain alkyl groups or groups having 6 to 30, preferably 10 to 24 carbon atoms.

[0215] In some embodiments, R 5 and R 6 Each is C 1 To C 4 Alkyl, preferably methyl, and R 7 It is an alkyl or alkenyl group having 6 to 36 carbon atoms, preferably 10 to 30 carbon atoms, for example 12 to 24 carbon atoms.

[0216] Compounds of this type include, for example, dimethyloctadecylamine and hexadecyldimethylamine.

[0217] To provide a quaternary ammonium salt additive, hexadecyldimethylamine can be quaternized by reaction with propylene oxide (e.g., 1 to 3 molar equivalents of propylene oxide) and polyisobutylene succinic acid (e.g., 1 molar equivalent of polyisobutylene succinic acid).

[0218] For example, in some embodiments, R 5 C 1 To C 4 alkyl, preferably methyl, and R 6 and R 7 Each is an alkyl or alkenyl group having 6 to 36 carbon atoms, preferably 8 to 30 carbon atoms, for example 10 to 24 carbon atoms.

[0219] Compounds of this type include, for example, hexadecyl dimethylamine, N-methyl NN-ditallowamine and dicocomethylamine.

[0220] Particularly preferred is formula R 5 R 6 R 7 The tertiary amine compounds containing N include N,N-dimethylethanolamine, dimethyloctadecylamine and N-methylNN-ditallowamine.

[0221] In some preferred embodiments, the quaternary ammonium salt additive (a) is a reaction product of a compound containing a tertiary amine group and a quaternizing agent, wherein the compound containing a tertiary amine group is selected from one or more of the following:

[0222] (ia) the reaction product of a fatty acid of the formula RCOOH with a compound of the formula (II), wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, and wherein R 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms;

[0223] (ib) the reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms; and

[0224] (iv-a) Formula R 5 R 6 R 7 N tertiary amine, where R 5 , R 6 and R 7 Each is independently an alkyl group or a hydroxyalkyl group.

[0225] The quaternizing agent is preferably selected from alkylene oxides, preferably propylene oxide, optionally in combination with an acid, chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate.

[0226] In some preferred embodiments, the quaternary ammonium salt additive (a) is a reaction product of a compound containing a tertiary amine group and a quaternizing agent, wherein the compound containing a tertiary amine group is selected from one or more of the following:

[0227] (ia) the reaction product of a fatty acid of formula RCOOH with a compound selected from the group consisting of 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, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms;

[0228] (ib) the reaction product of a hydrocarbyl-substituted succinic acid derived acylating agent and a compound selected from the group consisting of 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; and

[0229] (iv-a) Formula R 5 R 6 R 7 N tertiary amine, where R 5 , R 6 and R 7 Each is independently an alkyl group or a hydroxyalkyl group.

[0230] In some preferred embodiments, the quaternary ammonium salt additive (a) is the reaction product of a compound containing a tertiary amine group and a quaternizing agent;

[0231] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0232] The compound containing a tertiary amine group is selected from one or more of the following:

[0233] (ia) the reaction product of a fatty acid of formula RCOOH with a compound selected from the group consisting of 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, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms;

[0234] (ib) the reaction product of a hydrocarbyl-substituted succinic acid derived acylating agent and a compound selected from the group consisting of 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; and

[0235] (iv-a) Formula R 5 R 6 R 7 N tertiary amine, where R 5 , R 6 and R 7 Each is independently an alkyl group or a hydroxyalkyl group.

[0236] In some particularly preferred embodiments, the quaternary ammonium salt additive (a) is the reaction product of a compound containing a tertiary amine group and a quaternizing agent;

[0237] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0238] The compound containing a tertiary amine group is selected from one or more of the following:

[0239] (ia) the reaction products of fatty acids of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with N,N-dimethyl-1,3-diaminopropane (DMAPA);

[0240] (ib) the reaction product of a polyisobutylene-substituted succinic anhydride having a molecular weight (Mn) of 700 to 1300 and N,N-dimethyl-1,3-diaminopropane; and

[0241] (iv-a) Formula R 5 R 6 R 7 N tertiary amine, where R 5 and R 6 Each is C 1 To C 4 Alkyl, preferably methyl, and R 7 is an alkyl or alkenyl group having 12 to 24 carbon atoms.

[0242] (b) Reaction product of a carboxylic acid-derived acylating agent and an amine

[0243] In some embodiments, the present invention relates to the use of (b) a reaction product of a carboxylic acid-derived acylating agent and an amine as an additive.

[0244] These compounds may also be collectively referred to herein as acylated nitrogen-containing compounds.

[0245] 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.

[0246] 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.

[0247] Conventional polyisobutylenes and so-called "highly reactive" polyisobutylenes are suitable for use in the present invention. These are suitable as described previously herein with respect to the preparation of some preferred quaternary ammonium cleaners.

[0248] Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

[0249] 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.

[0250] 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 between 170 and 2800. These acylated nitrogen compounds are suitably formed by reacting an acylating agent: amino compound molar ratio of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 2:1 to 1:2, and most preferably 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 1.8:1 to 1:1.2, preferably 1.6:1 to 1:1.2, more preferably 1.4:1 to 1:1.1, and most preferably 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.

[0251] In some preferred embodiments, the composition comprises a detergent of the type formed by the reaction of an acylating agent derived from a polyisobutylene-substituted succinic acid and a polyethylene polyamine. Suitable compounds are described, for example, in WO2009 / 040583.

[0252] 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 between 500 and 2000, preferably between 600 and 1200.

[0253] (c) Products of the Mannich reaction between an aldehyde, an amine and an optionally substituted phenol

[0254] In some embodiments, the present invention may involve the use of (c) the product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol.

[0255] Preferably, component (c) comprises the product of a Mannich reaction between:

[0256] (x) aldehydes;

[0257] (y) amines; and

[0258] (z) Optionally substituted phenol.

[0259] Preferably, the aldehyde component used to prepare the Mannich additive is an aliphatic aldehyde. Preferably, the aldehyde has 1 to 10 carbon atoms. The most preferred aldehyde is formaldehyde.

[0260] Amines suitable for preparing Mannich additives include monoamines and polyamines. One suitable monoamine is butylamine.

[0261] The amine used to prepare the Mannich additive 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 tetraethylenepentamine or ethylenediamine.

[0262] 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.

[0263] 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).

[0264] Suitable Mannich reaction products and methods of preparing such additives will be known to those skilled in the art and include, for example, the compounds described in applicant's publications WO2009040582 and WO2013017887.

[0265] A preferred Mannich reaction product additive is the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol.

[0266] A particularly preferred Mannich reaction product additive for use herein is the reaction product of dodecylphenol, formaldehyde and ethylenediamine.

[0267] The appropriate treat rate of one or more nitrogen-containing detergents may depend on the type of fuel used, and different levels of additives may be required to achieve different performance levels.

[0268] In a preferred embodiment, the diesel fuel composition comprises one or more of the following:

[0269] (a) quaternary ammonium salt additives;

[0270] (b) the reaction product of a carboxylic acid derived acylating agent and an amine; and

[0271] (c) Products of the Mannich reaction between aldehydes, amines and optionally substituted phenols.

[0272] In some embodiments, the diesel fuel composition comprises 0.1 to 10000 ppm, preferably 1 to 1000 ppm, preferably 5 to 250 ppm, for example 5 to 100 ppm of (a) quaternary ammonium salt additive.

[0273] In some embodiments, the diesel fuel composition comprises from 0.1 to 10000 ppm, preferably from 1 to 1000 ppm, preferably from 5 to 500 ppm, for example from 5 to 250 ppm of (b) the reaction product of a carboxylic acid derived acylating agent and an amine.

[0274] In some embodiments, the diesel fuel composition comprises 0.1 to 10000 ppm, preferably 1 to 1000 ppm, preferably 5 to 500 ppm, for example 5 to 100 ppm of (c) the product of the Mannich reaction between an aldehyde, an amine and an optionally substituted phenol.

[0275] Each of additives (a), (b) and (c) may be provided as a mixture of compounds. The above amounts refer to the total amount of all such compounds present in the composition.

[0276] For the avoidance of doubt, the above amounts refer to the amount of active additive compound present in the composition and disregard any impurities, solvents or diluents that may be present.

[0277] In some embodiments, a diesel fuel composition comprises (a) a quaternary ammonium salt additive and (b) the reaction product of a carboxylic acid derived acylating agent and an amine.

[0278] In some embodiments, a diesel fuel composition comprises the product of a Mannich reaction between (a) a quaternary ammonium salt additive and (c) an aldehyde, an amine, and an optionally substituted phenol.

[0279] In some embodiments, the diesel fuel composition comprises (b) the reaction product of a carboxylic acid derived acylating agent and an amine, and (c) the product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol.

[0280] In some embodiments, a diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid derived acylating agent and an amine, and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol.

[0281] In some embodiments, the diesel fuel composition comprises (b) the reaction product of a carboxylic acid derived acylating agent and an amine and (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; wherein component (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 1200; and component (c) comprises the reaction product of formaldehyde, a polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0282] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; 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 a polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB molecular weight (Mn) of 700 to 1300; and component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol (preferably dodecylphenol).

[0283] In some embodiments, a diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol; 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 a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and a reaction product of dimethylaminopropylamine; component (b) comprises the reaction product of polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200; and component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0284] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; wherein component (a) comprises a quaternary ammonium salt formed by the reaction of a compound comprising a tertiary amine group with a quaternizing agent;

[0285] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0286] The compound containing a tertiary amine group is selected from:

[0287] (ia) the reaction products of fatty acids of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with N,N-dimethyl-1,3-diaminopropane (DMAPA);

[0288] (ib) the reaction product of a polyisobutylene-substituted succinic anhydride having a molecular weight (Mn) of 700 to 1300 and N,N-dimethyl-1,3-diaminopropane; and

[0289] (iv-a) Formula R 5 R 6 R 7 N tertiary amine, where R 5 and R 6 Each is C 1 To C 4 alkyl, preferably methyl, and R 7 is an alkyl or alkenyl group having 12 to 24 carbon atoms; and

[0290] Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0291] In some embodiments, a diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound comprising a tertiary amine group with a quaternizing agent;

[0292] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0293] The compound containing a tertiary amine group is selected from:

[0294] (ia) the reaction products of fatty acids of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with N,N-dimethyl-1,3-diaminopropane (DMAPA);

[0295] (ib) the reaction product of a polyisobutylene-substituted succinic anhydride having a molecular weight (Mn) of 700 to 1300 and N,N-dimethyl-1,3-diaminopropane; and

[0296] (iv-a) Formula R5 R 6 R 7 N tertiary amine, where R 5 and R 6 Each is C 1 To C 4 alkyl, preferably methyl, and R 7 is an alkyl or alkenyl group having 12 to 24 carbon atoms;

[0297] Component (b) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200; and

[0298] Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0299] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; wherein component (a) comprises a quaternary ammonium salt formed by the reaction of a compound comprising a tertiary amine group with a quaternizing agent;

[0300] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0301] wherein the compound containing a tertiary amine group is the reaction product of a fatty acid of the formula (ia) RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, and N,N-dimethyl-1,3-diaminopropane (DMAPA); and

[0302] Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0303] In some embodiments, a diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound comprising a tertiary amine group with a quaternizing agent;

[0304] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0305] The compound containing a tertiary amine group is (ia) the reaction product of a fatty acid of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, and N,N-dimethyl-1,3-diaminopropane (DMAPA);

[0306] Component (b) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200; and

[0307] Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0308] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; wherein component (a) comprises a quaternary ammonium salt formed by the reaction of a compound comprising a tertiary amine group with a quaternizing agent;

[0309] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0310] The compound containing a tertiary amine group is (iv-a) of formula R 5 R 6 R 7 N tertiary amine, where R 5 and R 6 Each is C 1 To C 4 alkyl, preferably methyl, and R 7 is an alkyl or alkenyl group having 12 to 24 carbon atoms; and

[0311] Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0312] In some embodiments, a diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound comprising a tertiary amine group with a quaternizing agent;

[0313] wherein the quaternizing agent is selected from alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid;

[0314] The compound containing a tertiary amine group is (iv-a) of formula R 5 R 6 R 7 N tertiary amine, where R 5 and R 6 Each is C 1 To C 4 alkyl, preferably methyl, and R 7 is an alkyl or alkenyl group having 12 to 24 carbon atoms;

[0315] Component (b) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200; and

[0316] Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0317] One or more nitrogen-containing detergents may be added to diesel fuel at any convenient point in the supply chain. For example, the additive may be added to the fuel at a refinery, at a distribution terminal, or after the fuel leaves a distribution terminal. If the additive is added to the fuel after the fuel leaves a distribution terminal, this is referred to as an aftermarket application. Aftermarket applications include situations such as adding the additive 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 fuel additive in a vial suitable for direct addition to a fuel storage tank or vehicle tank.

[0318] Diesel fuel includes any fuel suitable for use in a diesel engine, whether for on-road or off-road use. This includes, but is not limited to, fuels described as diesel, marine diesel, heavy fuel oil, industrial fuel oil, and the like.

[0319] The diesel fuel composition used in the present invention may include petroleum-based fuel oils, especially middle distillate fuel oils. Such distillate fuel oils generally have a boiling point in the range of 110° C. to 500° C., for example 150° C. to 400° C. The diesel fuel may include a blend of atmospheric or vacuum distillates, cracked gas oil, or straight run oil and refinery fractions (e.g., thermal and / or catalytic cracking and hydrocracking fractions) in any proportion.

[0320] The diesel fuel composition may include non-renewable Fischer-Tropsch fuels, such as those described as GTL (gas-to-liquids) fuels, CTL (coal-to-liquids) fuels, and OTL (oil sands-to-liquids) fuels.

[0321] The diesel fuel composition may include a renewable fuel, such as a biofuel composition or a biodiesel composition.

[0322] Diesel fuel compositions may include first generation biodiesel. First generation biodiesel contains esters such as vegetable oil, animal fat and waste edible fat or oil. This form of biodiesel can be obtained by the transesterification of oil and alcohol (normally monohydric alcohol) usually carried out in the presence of a catalyst, such as rapeseed oil, soybean oil, canola oil, safflower oil, palm oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, jatropha oil (jatropha oil), sunflower oil, waste edible oil, hydrogenated vegetable oil or any mixture thereof.

[0323] Diesel fuel compositions may include second generation biodiesel. Second generation biodiesel is derived from renewable resources such as vegetable oils and animal fats, and is typically processed in a refinery, for example using hydroprocessing, such as the H-Bio process developed by Petrobras. Second generation biodiesel may be similar in properties and quality to petroleum-based fuel oil streams, such as renewable diesel produced from vegetable oils, animal fats, etc. and sold under the name Renewable Diesel by ConocoPhillips and sold under the name NExBTL by Neste.

[0324] The diesel fuel composition may include third generation biodiesel. Third generation biodiesel utilizes gasification and Fischer-Tropsch technologies, including technologies known as BTL (biomass-to-liquid) fuels. Third generation biodiesel is not much different from some second generation biodiesels, but is designed to utilize whole plants (biomass), thereby expanding the feedstock base.

[0325] In some embodiments, the diesel fuel composition may comprise a pyrolysis oil, such as a plastic pyrolysis oil or a biomass (wood, vegetable oil, algae) pyrolysis oil.

[0326] The diesel fuel composition may contain a blend of any or all of the above diesel fuel compositions.

[0327] In some embodiments, the diesel fuel composition can be a mixed diesel fuel comprising biodiesel. In such blends, biodiesel can exist in an amount of, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 99% at the most.

[0328] In some embodiments, the fuel composition may comprise pure biodiesel.

[0329] In some preferred embodiments, the fuel composition comprises at least 5 wt. % biodiesel.

[0330] In some embodiments, the fuel composition may include a GTL fuel or be pure GTL fuel.

[0331] In some embodiments, the diesel fuel composition may contain a secondary fuel, such as ethanol. Preferably, however, the diesel fuel composition does not contain ethanol.

[0332] The diesel fuel composition used in the present invention may contain a relatively high sulphur content, for example greater than 0.05% by weight, such as 0.1% or 0.2%.

[0333] However, in a preferred embodiment, the sulphur content of the diesel fuel composition is at most 0.05 wt%, more preferably at most 0.035 wt%, in particular at most 0.015%. Fuels with even lower sulphur contents are also suitable, for example fuels with a sulphur content by weight of less than 50 ppm, preferably less than 20 ppm, for example 10 ppm or less.

[0334] The diesel fuel composition used in the present invention preferably comprises at least 5 wt% biodiesel and less than 50 ppm sulphur.

[0335] Various metal species may be present in diesel fuel compositions. This may be due to contamination of the fuel during manufacture, storage, transportation or use, or due to contamination of fuel additives. Metal species may also be intentionally added to the fuel. For example, transition metals are sometimes added as fuel-borne catalysts, for example to improve the performance of diesel particulate filters.

[0336] Other metal-containing species may also be present as contaminants, for example, by acidic species present in the fuel or from lubricating oils that corrode metal and metal oxide surfaces. During use, fuels (e.g., diesel fuels) often come into contact with metal surfaces, such as in vehicle refueling systems, fuel tanks, fuel transportation devices, etc. Typically, metal-containing contaminants may include transition metals, such as zinc, iron, and copper; Group I or Group II metals and other metals, such as lead.

[0337] In addition to the metal-containing contaminants that may be present in diesel fuel, metal-containing species are sometimes intentionally added to the fuel. For example, as is known in the art, metal-containing fuel-borne catalyst species may be added to aid in the regeneration of a particulate trap. The presence of such catalysts may also lead to injector deposits when the fuel is used in a diesel engine having a high-pressure fuel system.

[0338] Metal-containing contaminants may be present in the form of insoluble particles or soluble compounds or complexes, depending on their source. Metal-containing fuel-borne catalysts are usually soluble compounds or complexes or colloidal species.

[0339] In some embodiments, the diesel fuel may include a metal-containing species comprising a fuel-borne catalyst. Preferably, the fuel-borne catalyst comprises one or more metals selected from iron, cerium, platinum, manganese, Group I and Group II metals (e.g., calcium and strontium). Most preferably, the fuel-borne catalyst comprises a metal selected from iron and cerium.

[0340] Typically, the total amount of all metal-containing species in the diesel fuel, expressed as the total weight of metals in that species, is between 0.1 and 50 ppm by weight, such as between 0.1 and 20 ppm by weight, preferably between 0.1 and 10 ppm by weight, based on the weight of the diesel fuel.

[0341] The diesel fuel composition used in the present invention may include one or more other additives, such as those common in the diesel fuel. These include, for example, antioxidants, dispersants, detergents, metal deactivation compounds, wax anti-settling agents, cold flow improvers, cetane number improvers, demisters, stabilizers, demulsifiers, defoamers, corrosion inhibitors, lubricity improvers, dyes, markers, combustion improvers, metal deactivators, odor masking agents, drag reducers and conductivity improvers. The examples of the appropriate amounts of these types of additives will be known to those skilled in the art.

[0342] Suitable cetane number improvers can be selected from C2-24 alkyl nitrates and dialkyl peroxides, preferably decyl nitrate, 2-ethylhexyl nitrate and di-tert-butyl peroxide. Such cetane number improvers are suitably used in a concentration of 50-6,000 ppm, preferably 50-750 ppm, based on the diesel fuel composition.

[0343] The present invention reduces the impact of deposits in the EGR system and / or after-combustion system of a diesel engine.

[0344] The diesel engine may be a direct injection diesel engine or an indirect injection diesel engine.

[0345] In some embodiments, the engine may be a non-road engine, such as a marine, railroad, or stationary engine. Stationary engines include engines for power generation and engines for pumping.

[0346] Most preferably, the engine is a direct injection diesel engine.

[0347] The post combustion deposit control additives used in the present invention have been found to be particularly effective in modern diesel engines having high pressure fuel systems.

[0348] Suitably, the present invention may be used to reduce the formation of deposits in the afterburning system of a diesel engine having a high pressure fuel system. The fuel pressure of the diesel engine is suitably in excess of 1350 bar (1.35 x 10 8 Pa). Its pressure can be up to 2000 bar (2x10 8 Pa) or higher.

[0349] Such diesel engines can have a variety of features.

[0350] Such engines are typically equipped with fuel injection equipment that meets or exceeds "Euro 5" emissions regulations or equivalent regulations in the United States or other countries.

[0351] Such engines are typically equipped with a fuel injector having a plurality of holes, each hole having an inlet and an outlet.

[0352] Such engines are characterized in that the hole is tapered so that the inlet diameter of the injection hole is larger than the outlet diameter.

[0353] Such modern engines are characterised in that the outlet diameter of the orifices is less than 500 μm, preferably less than 200 μm, more preferably less than 150 μm, preferably less than 100 μm, most preferably less than 80 μm or less.

[0354] A characteristic feature of modern diesel engines of this type is that the hole is rounded at the inner edge of the inlet.

[0355] Such modern diesel engines are characterised in that the injector has more than one hole, suitably more than 2 holes, preferably more than 4 holes, for example 6 holes or more.

[0356] Such modern diesel engines are characterized by operating tip temperatures exceeding 250°C.

[0357] Such modern diesel engines are characterized in that the fuel injection system provides a fuel pressure greater than 1350 bar, preferably greater than 1500 bar, more preferably greater than 2000 bar.

[0358] Two non-limiting examples of such high pressure fuel systems are: common rail injection systems, in which the fuel is compressed by a high pressure pump to supply it to the fuel injection valves via a common rail; and unit injection systems, which integrate the high pressure pump and the fuel injection valves in one assembly, achieving pressures in excess of 2000 bar (2x10 8 In both systems, as the fuel is pressurized, it heats up, typically to temperatures of about 100°C or more.

[0359] Preferably, the diesel engine has a fuel injection system which comprises a common rail injection system.

[0360] In a common rail system, the fuel is stored at high pressure in a central accumulator rail or in separate accumulators before being delivered to the injectors. Typically, some of the heated fuel is returned to the low-pressure side of the fuel system or to the fuel tank. In a unit injection system, the fuel is compressed within the injector to create a high injection pressure. This in turn increases the temperature of the fuel.

[0361] In both systems, the fuel resides within the injector body prior to injection where it is further heated due to the heat of the combustion chamber. The fuel temperature at the injector tip can be as high as 250-350°C.

[0362] Therefore, the pressure of the fuel before injection is 1350 bar (1.35x10 8 Pa) to 2000 bar (2x10 8 Pa) and temperatures of about 100°C to 350°C are sometimes recirculated back into the fuel system, increasing the time the fuel experiences these conditions.

[0363] The EGR system recirculates exhaust gas to reduce the oxygen concentration in the combustion chamber. This reduces NO x Gas production.

[0364] The EGR system includes a cooler. This component reduces the temperature of the recirculated exhaust gases.

[0365] Exhaust gas enters the EGR system after passing through or being generated in the combustion chamber. Exhaust gas may contain substances from incomplete combustion. These substances may be deposited in the EGR system. One component where deposits often accumulate is the cooler of the EGR system.

[0366] Previously, these deposits have not received the same level of research as other fuel system or combustion deposits. In fact, the discovery of such deposits appears to be a relatively new phenomenon. A particularly thorough review of the work done to elucidate how they form and why they are a problem can be found in Lance et al. International Journal of Heat and Mass Transfer 126, (2018), 509-520 and SAE 2014-01-0629.

[0367] The present inventors have investigated the nature of deposits found in EGR systems and in particular in coolers. It has surprisingly been found that the formation of these deposits can be particularly reduced by adding one or more nitrogen-containing detergents to the diesel fuel combusted in the engine.

[0368] The use of the first aspect and / or the method of the second aspect may relate to reducing the effects of deposits in an exhaust gas recirculation system of a diesel engine, the exhaust gas recirculation system being a high pressure, low pressure, hybrid or dedicated EGR system. Suitably, the exhaust gas recirculation system is a high pressure, hybrid or dedicated EGR system. Preferably, the exhaust gas recirculation system is a high pressure or hybrid EGR system. Most preferably, the exhaust gas recirculation system is a high pressure EGR system.

[0369] Preferably, the use or method of the invention reduces the formation of deposits in a high pressure EGR system of a diesel engine.

[0370] Reducing the formation of deposits in an EGR system means that when a fuel including the EGR deposit reducing additive is combusted in an engine, reduced deposit levels are obtained compared to combusting an otherwise identical fuel except for the inclusion of the EGR deposit reducing additive under the same conditions.

[0371] Suitably adding one or more nitrogen-containing detergents to a diesel fuel combusted in an engine may reduce the formation of deposits in the EGR system by at least 5%, preferably at least 10%, such as at least 15% or at least 20%.

[0372] In some embodiments, adding one or more nitrogen-containing detergents to a diesel fuel combusted in an engine can reduce the formation of deposits in the EGR system by at least 30%, such as at least 40% or at least 50%.

[0373] The reduction of deposits in the EGR system may be measured by any suitable method.

[0374] One simple way in which deposit levels in an EGR system can be determined is by weighing the system before and after use. One or more components of the system may be weighed.

[0375] Preferably, the present invention reduces the total amount of deposits formed in the EGR system by at least 5%, preferably at least 10%, more preferably at least 15%, for example at least 20% or at least 30%.

[0376] Suitably, the present invention reduces the amount of deposits that form within the cooler of an EGR system.

[0377] Preferably, the present invention reduces the total amount of deposits formed in the cooler of the EGR system by at least 5%, preferably at least 10%, more preferably at least 15%, such as at least 20% or at least 30%.

[0378] The deposits formed in the EGR system can be analyzed. This can be achieved, for example, by extracting the deposits or a portion thereof into a solvent. The sample can be separated into a soluble and an insoluble portion; these portions can then be analyzed separately by methods known to those skilled in the art, such as elemental analysis, thermogravimetric analysis, and / or gas chromatography mass spectrometry.

[0379] For example, the deposits formed in the EGR system can be analyzed by thermogravimetric analysis (TGA). When performing thermogravimetric analysis (TGA), it was found that most of the deposits that occur on the EGR system cooler are carbonaceous deposits, which degrade at temperatures between 400 and 540°C.

[0380] Thermogravimetric analysis (TGA) involves measuring the mass of a sample over time during heating. The technique is well known to those skilled in the art, and the selection of appropriate methods and suitable equipment will be within the capabilities of those skilled in the art.

[0381] Aftercombustion systems for diesel engines are provided in order to reduce the emission of pollutants such as particulate matter and noxious gases into the environment. The formation of deposits on aftercombustion system components can reduce the efficiency of the system and lead to increased emissions of particulate deposits and / or noxious gases.

[0382] In some embodiments, the effects of the deposits may be reduced by changing the properties of the deposits.

[0383] Preferably, the present invention reduces the formation of deposits in the post-combustion system.

[0384] Reducing the formation of deposits in an aftercombustion system means that when a fuel comprising one or more nitrogen-containing detergents is combusted in an engine, reduced deposit levels are obtained compared to combusting an otherwise identical fuel under the same conditions except for the inclusion of the aftercombustion deposit reducing additive.

[0385] Suitably adding one or more nitrogen-containing detergents to diesel fuel combusted in an engine can reduce deposit formation in one or more components of the afterburner system by at least 0.01%, preferably at least 0.1%, for example at least 1% or at least 2%.

[0386] In some embodiments, adding one or more nitrogen-containing detergents to a diesel fuel combusted in an engine can reduce the formation of deposits in one or more components of the post-combustion system by at least 3%, such as at least 4% or at least 5%.

[0387] The after-combustion system of a diesel engine refers to any part of the engine through which the exhaust gases pass after they finally leave the combustion system.

[0388] The afterburning system may include one or more components selected from a turbocharger, a diesel oxidation catalyst, a diesel particulate filter, a selective catalytic reduction unit, and an ammonia oxidation unit. The afterburning system may include these components in any order, and the order may vary from vehicle to vehicle. The present invention may reduce the effects of deposits in or on one or more of these components.

[0389] In some embodiments, adding one or more nitrogen-containing detergents to diesel fuel combusted in an engine can suitably reduce deposit formation in a turbocharger by at least 0.01%, preferably at least 0.1%, such as at least 1% or at least 2%.

[0390] The present invention can reduce deposits on fixed geometry turbochargers or variable geometry turbochargers. Variable geometry turbochargers have moving parts that are controlled by the engine management system. This allows the aspect ratio of the turbocharger to be changed to optimize performance at different speeds. The formation of deposits can cause the components to stick. As a result, the turbocharger will not be able to provide the correct level of boost and may eventually fail. Therefore, reducing deposits on the turbocharger is very beneficial.

[0391] Preferably, the present invention reduces deposits on a turbine wheel of a turbocharger.

[0392] In some embodiments, adding a nitrogen-containing detergent to a diesel fuel combusted in an engine can reduce deposit formation in a turbocharger by at least 3%, such as at least 4% or at least 5%.

[0393] In some embodiments, the addition of one or more nitrogen-containing detergents to diesel fuel combusted in an engine may suitably reduce deposit formation in a diesel oxidation catalyst by at least 0.01%, preferably at least 0.1%, such as at least 1% or at least 2%.

[0394] Diesel oxidation catalysts typically include a ceramic support structure coated with a metal such as palladium, platinum and / or rhodium. The formation of deposits in a diesel oxidation catalyst can result in reduced flow through the catalyst and / or poisoning of the catalyst.

[0395] In some embodiments, adding one or more nitrogen-containing detergents to a diesel fuel combusted in an engine can reduce the formation of deposits in a diesel oxidation catalyst by at least 3%, such as at least 4% or at least 5%.

[0396] Suitably, the addition of one or more nitrogen containing detergents to diesel fuel combusted in an engine may suitably reduce deposit formation in a diesel particulate filter by at least 0.01%, preferably at least 0.1%, for example at least 1% or at least 2%.

[0397] Suitably, the addition of one or more nitrogen containing detergents to diesel fuel combusted in an engine may suitably reduce soot accumulation in a diesel particulate filter by at least 0.01%, preferably by at least 0.1%, for example at least 1% or at least 2%.

[0398] The diesel particulate filter is designed to capture particles such as soot formed in the combustion chamber from the exhaust gas. These particles accumulate on the filter and are intermittently burned off by increasing the exhaust gas temperature and injecting additional fuel. This process is called filter regeneration.

[0399] The present invention can extend the interval between regenerations. This can improve the fuel economy of the engine and reduce emissions. The reduction in regeneration refers to reducing active, passive or parked regeneration of the diesel particulate filter. For example, the number of regeneration events per 1000 kilometers can be reduced.

[0400] In some embodiments, adding one or more nitrogen-containing detergents to a diesel fuel combusted in an engine can reduce the formation of deposits in a diesel particulate filter by at least 3%, such as at least 4% or at least 5%.

[0401] In some embodiments, adding one or more nitrogen-containing detergents to diesel fuel combusted in an engine may suitably reduce deposit formation in the selective catalytic reduction unit by at least 0.01%, preferably at least 0.1%, such as at least 1% or at least 2%.

[0402] Selective catalytic reduction for removal of NO from exhaust gas x and other harmful gases, and involves the use of ammonia as a reducing agent in the presence of a catalyst. The selective catalytic reduction unit comprises a porous ceramic support and a catalyst, typically comprising a metal or a zeolite.

[0403] The formation of deposits on the selective catalytic reduction unit may result in reduced flow rate through the unit and / or poisoning of the catalyst.

[0404] In some embodiments, adding a nitrogen-containing detergent to diesel fuel combusted in an engine can reduce the formation of deposits in the selective catalytic reduction unit by at least 3%, such as at least 4% or at least 5%.

[0405] In some embodiments, the addition of one or more nitrogen-containing detergents to diesel fuel combusted in an engine may suitably reduce deposit formation in the ammonia oxidation catalyst by at least 0.01%, preferably at least 0.1%, such as at least 1% or at least 2%.

[0406] The ammonia oxidation catalyst is used to oxidize any ammonia present in the exhaust gas after passing through the selective catalytic reduction unit.

[0407] The formation of deposits on the ammonia oxidation catalyst may result in reduced flow rate through the catalyst and / or poisoning of the catalyst.

[0408] In some embodiments, adding one or more nitrogen-containing detergents to a diesel fuel combusted in an engine can reduce the formation of deposits in the ammonia oxidation catalyst by at least 3%, such as at least 4% or at least 5%.

[0409] In some embodiments, adding one or more nitrogen-containing detergents to diesel fuel combusted in an engine can suitably reduce deposit formation on sensors within the post-combustion system by at least 0.01%, preferably at least 0.1%, such as at least 1% or at least 2%.

[0410] Sensors may be present in the post-combustion to measure temperature, pressure and / or gases in the exhaust such as NO x If deposits are present on or around the sensors, they may not function properly or may make inaccurate measurements, resulting in incorrect information being provided to the engine management system. This can result in poor engine performance.

[0411] In some embodiments, adding one or more nitrogen-containing detergents to diesel fuel combusted in an engine can reduce the formation of deposits on sensors within a post-combustion system by at least 3%, such as at least 4% or at least 5%.

[0412] The reduction of deposits in the post-combustion system may be measured by any suitable method.

[0413] One simple method of determining the deposit level of a post-combustion system component may be by weighing that component of the system before and after use.One or more components of the system may be weighed.

[0414] Other less direct methods may also be used. For example, an improvement in fuel economy may indicate longer intervals between regenerations of the diesel particulate filter.

[0415] Preferably the invention provides an improvement in fuel economy of at least 0.1%, preferably at least 0.5%, suitably at least 1%, for example at least 2%.

[0416] The vehicle's engine management system can be queried to evaluate the performance of components such as the turbocharger, diesel particulate filter, diesel oxidation catalyst and selective catalytic reduction unit.

[0417] The present invention may result in fewer error messages being provided to the driver by the engine management system.

[0418] An increase in the maintenance interval required for the catalytic components may also indicate improved performance due to reduced deposits.

[0419] The deposits formed in the post-combustion system can be analyzed. This can be achieved, for example, by extracting the deposits or a portion thereof into a solvent. The sample can be separated into soluble and insoluble fractions; these fractions can then be analyzed separately by methods known to those skilled in the art, such as elemental analysis, thermogravimetric analysis and / or gas chromatography mass spectrometry.

[0420] Thermogravimetric analysis (TGA) involves measuring the mass of a sample over time during heating. The technique is well known to those skilled in the art, and the selection of appropriate methods and suitable equipment will be within the capabilities of those skilled in the art.

[0421] When the post-composite deposit contains soot, the soot density can be measured, for example using the AVL483 micro-soot sensor.

[0422] The particle size of the soot can be measured by techniques known to those skilled in the art.

[0423] Reducing deposits in the aftercombustion system of a diesel engine in accordance with the present invention has significant benefits.

[0424] These include, but are not limited to: increased power generation; increased torque; improved fuel economy; reduced emissions; reduced combustion chamber deposits; improved acceleration; improved drivability; reduced cold start issues; reduced soot formation; reduced lubricant degradation and / or performance loss; reduced diesel exhaust fluid and consumption, such as urea consumption; reduced wear on all aftercombustion components (including but not limited to turbochargers, oxidation catalysts, DPFs, SCR CATs, sensors and injectors within the aftercombustion system); increased service life of exhaust components; increased maintenance intervals for the engine and / or aftercombustion components; and protection of intake components downstream of the EGR, such as swirl flaps, throttle bodies and intake manifolds (due to reduced likelihood of clogging, etc.).

[0425] In some embodiments of the present invention, one or more of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent with an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol preferably reduces the formation of deposits in the EGR system by at least 5%, e.g., at least 20% or at least 50%.

[0426] In some embodiments of the present invention, one or more of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent with an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol reduces the impact of deposits on one or more of a turbocharger, a diesel oxidation catalyst, a diesel particulate filter, a selective catalytic reduction unit, and an ammonia oxidation catalyst.

[0427] In some embodiments of the present invention, one or more of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent with an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol can prevent and / or remove post-combustion system sensors, such as NO x Deposits on sensors, temperature sensors and / or pressure sensors.

[0428] In some embodiments of the present invention, the combination of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent and an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol preferably reduces the formation of deposits in the EGR system by at least 5%, e.g., at least 20% or at least 50%.

[0429] In some embodiments of the present invention, the combination of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent with an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol reduces the impact of deposits on one or more of a turbocharger, a diesel oxidation catalyst, a diesel particulate filter, a selective catalytic reduction unit, and an ammonia oxidation catalyst.

[0430] In some embodiments of the present invention, the combination of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent and an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol can prevent and / or remove post-combustion system sensors, such as NO x Deposits on sensors, temperature sensors and / or pressure sensors.

[0431] In some embodiments of the present invention, the combination of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid derived acylating agent and an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol suitably reduces the formation of deposits on a diesel particulate filter by at least 0.01%, preferably at least 2%.

[0432] In some embodiments of the present invention, the combination of (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid derived acylating agent and an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine, and an optionally substituted phenol extends the regeneration interval of a diesel particulate filter.

[0433] In some embodiments of the present invention, the combination of (a) a quaternary ammonium salt additive; and (b) a reaction product of a carboxylic acid derived acylating agent and an amine reduces the effect of deposits on one or more of a turbocharger, a diesel oxidation catalyst, a diesel particulate filter, a selective catalytic reduction unit, and an ammonia oxidation catalyst; wherein component (a) comprises a quaternary ammonium salt formed by the reaction of 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 (Mn) of 700 to 1300 and dimethylaminopropylamine; and component (b) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride with 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 between 500 and 2000, preferably between 600 and 1200.

[0434] Any feature of the invention may be combined with any other feature as appropriate.

[0435] In some preferred embodiments of the use of the first aspect or the method of the second aspect for reducing the effects of deposits in the after-combustion system of a diesel engine when burning a diesel fuel composition, the nitrogen-containing detergent is a quaternary ammonium salt additive formed by the reaction of (a) a quaternizing agent and a compound containing a tertiary amine group; wherein the compound containing a tertiary amine group is (ib) a reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4 An alkyl group is an alkyl group, and X is an alkylene group having 2 to 5 carbon atoms.

[0436] In such embodiments, the compound of formula (II) is preferably selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, or a combination thereof.

[0437] In some preferred embodiments of the use of the first aspect or the method of the second aspect for reducing the effects of deposits in the after-combustion system of a diesel engine when burning a diesel fuel composition, the nitrogen-containing detergent is (a) a quaternary ammonium salt additive formed by reacting a quaternizing agent with a compound comprising a tertiary amine group; wherein the compound comprising a tertiary amine group is (iv-a) of formula R 5 R 6 R 7 N tertiary amine, where R 5 , R 6 and R 7 Each is independently an alkyl group or a hydroxyalkyl group.

[0438] In such embodiments, preferably R 5 and R 6 Each is C 1 To C 4 alkyl, preferably methyl, and R 7 is an alkyl or alkenyl group having 12 to 24 carbon atoms.

[0439] In some preferred embodiments of the use of the first aspect or the method of the second aspect for reducing the effects of deposits in the after-combustion system of a diesel engine when burning a diesel fuel composition, the nitrogen-containing detergent is (a) a quaternary ammonium salt additive formed by the reaction of a quaternizing agent with an acylating agent derived from a hydrocarbyl-substituted succinic acid and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms, which is mainly in the succinamide form (ie, a half-acid half-amide compound).

[0440] In such embodiments, the hydrocarbyl-substituted succinic acid-derived acylating agent is preferably a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300, and the compound of formula (II) is preferably selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, or a combination thereof; preferably dimethylaminopropylamine.

[0441] In some preferred embodiments of the use of the first aspect or the method of the second aspect, the nitrogen-containing detergent is selected from one or more of the following: (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent with an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; and the use or method reduces the formation of deposits on a turbocharger of a post-combustion system.

[0442] In such embodiments, the nitrogen-containing cleaner is preferably selected from one or more of the following:

[0443] (a) a quaternary ammonium salt additive which is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent, wherein the quaternizing agent is preferably selected from alkylene oxides (preferably propylene oxide), chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate, optionally in combination with an acid; and wherein the compound comprising a tertiary amine group is selected from:

[0444] (ia) the reaction product of a fatty acid of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with a compound of the formula (II) 2 and R 3Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms;

[0445] (ib) the reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms; and

[0446] (iv-a) Formula R 5 R 6 R 7 N tertiary amine, where R 5 , R 6 and R 7 are each independently alkyl or hydroxyalkyl;

[0447] (b) the reaction products of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200; and

[0448] (c) The reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0449] In such embodiments, the nitrogen-containing cleaner is preferably selected from:

[0450] (a) a quaternary ammonium salt additive which is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent, wherein the quaternizing agent is preferably selected from alkylene oxides (preferably propylene oxide), chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate, optionally in combination with an acid; and wherein the compound comprising a tertiary amine group is selected from:

[0451] (ia) the reaction product of a fatty acid of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with a compound of the formula (II) 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms;

[0452] (ib) the reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4alkyl, and X is an alkylene group having 2 to 5 carbon atoms; and

[0453] (b) the reaction products of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200.

[0454] In such embodiments, the nitrogen-containing cleaning agent is preferably (a) a quaternary ammonium salt additive, which is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent, wherein the quaternizing agent is preferably selected from an alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid; and wherein the compound comprising a tertiary amine group is selected from:

[0455] (ia) the reaction product of a fatty acid of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with a compound of the formula (II) 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms;

[0456] (ib) the reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4 An alkyl group is an alkyl group, and X is an alkylene group having 2 to 5 carbon atoms.

[0457] In such embodiments, the nitrogen-containing detergent is preferably the reaction product of (b) 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 between 500 and 2000, preferably between 600 and 1200.

[0458] In such embodiments, the nitrogen-containing cleaner is preferably the product of a Mannich reaction between (c) an aldehyde, an amine, and an optionally substituted phenol.

[0459] In some preferred embodiments of the use of the first aspect or the method of the second aspect, the nitrogen-containing detergent is selected from one or more of the following: (a) a quaternary ammonium salt additive; (b) a reaction product of a carboxylic acid-derived acylating agent with an amine; and (c) a product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; and the use or method reduces the formation of deposits in a diesel particulate filter of an afterburning system. Suitably, the use or method reduces the accumulation of soot in a diesel particulate filter.

[0460] In such embodiments, the nitrogen-containing cleaner is preferably selected from one or more of the following:

[0461] (a) a quaternary ammonium salt additive which is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent, wherein the quaternizing agent is preferably selected from alkylene oxides (preferably propylene oxide), chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate, optionally in combination with an acid; and wherein the compound comprising a tertiary amine group is selected from:

[0462] (ia) the reaction product of a fatty acid of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with a compound of the formula (II) 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms;

[0463] (ib) the reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms; and

[0464] (iv-a) Formula R 5 R 6 R 7 N tertiary amine, where R 5 , R 6 and R 7 are each independently alkyl or hydroxyalkyl;

[0465] (b) the reaction products of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200; and

[0466] (c) The reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

[0467] In such embodiments, the nitrogen-containing cleaner is preferably selected from:

[0468] (a) a quaternary ammonium salt additive which is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent, wherein the quaternizing agent is preferably selected from alkylene oxides (preferably propylene oxide), chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate, optionally in combination with an acid; and wherein the compound comprising a tertiary amine group is selected from:

[0469] (ia) the reaction product of a fatty acid of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with a compound of the formula (II) 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms;

[0470] (ib) the reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms; and

[0471] (b) the reaction products of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200.

[0472] In such embodiments, the nitrogen-containing cleaning agent is preferably (a) a quaternary ammonium salt additive, which is the reaction product of a compound comprising a tertiary amine group and a quaternizing agent, wherein the quaternizing agent is preferably selected from an alkylene oxide (preferably propylene oxide), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate, optionally in combination with an acid; and wherein the compound comprising a tertiary amine group is selected from:

[0473] (ia) the reaction product of a fatty acid of the formula RCOOH, wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, with a compound of the formula (II) 2 and R 3 Both C 1 To C 4 alkyl, and X is an alkylene group having 2 to 5 carbon atoms;

[0474] (ib) the reaction product of a hydrocarbyl-substituted succinic acid-derived acylating agent and a compound of formula (II), wherein R 2 and R 3Both C 1 To C 4 An alkyl group is an alkyl group, and X is an alkylene group having 2 to 5 carbon atoms.

[0475] In such embodiments, the nitrogen-containing detergent is preferably the reaction product of (b) 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 between 500 and 2000, preferably between 600 and 1200.

[0476] In such embodiments, the nitrogen-containing cleaner is preferably the product of a Mannich reaction between (c) an aldehyde, an amine, and an optionally substituted phenol.

[0477] The present invention will now be further described with reference to the following non-limiting examples. In the following examples, the treatment rate values ​​given in parts per million (ppm) represent the active dose, rather than the amount of the formulation added and containing the active agent. All parts per million are by weight.

[0478] Embodiment 1:

[0479] Additive A is a Mannich reaction product and is prepared as follows:

[0480] 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, keeping 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 raised to 0.8 barg. The reaction mixture was maintained at 120-122°C at a pressure of up to 1.1 barg for 3 hours. The reaction temperature was then reduced to ~95°C and the pressure was reduced to <0.5 bar, at which point the reactor was opened to the atmosphere. Stirring was stopped and the contents separated. The amber organic phase was washed twice with 90-90°C water. Finally, any remaining water was removed from the organic phase under reduced pressure, leaving Additive A (235 g) as a clear, bright amber liquid.

[0481] Embodiment 2:

[0482] Additive B is a quaternary ammonium salt additive, which is prepared as follows:

[0483] 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 maintained 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, maintaining the reaction temperature within the range of 120°C-130°C. The reaction 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 reactants were diluted with solvent, then cooled and discharged to obtain product Additive B (271.2 g).

[0484] Embodiment 3:

[0485] Additive C is a polyisobutylene-substituted succinimide additive, which is prepared as follows:

[0486] A reaction apparatus using a 1L jacketed glass reactor was equipped with a Dean Stark condenser, an overhead stirrer, a dropping funnel, and a nitrogen input. 600 g of PIBSA (HR 750MW PIB, 0.768 mole) and 483.33 g of Aromatic A150 solvent were transferred to the reactor. The mixture was stirred and heated to 65 ° C to form a uniform liquid. Tetraethylenepentamine (138.12 g, 0.729 mol) was then added to the reactor via a dropping funnel within 1 hour. The temperature of the mixture was raised to 135 ° C and maintained for 1 hour to distill out water. The temperature of the mixture was then raised to 165 ° C and maintained for 3 hours. After the distillation was complete, the product additive C was cooled and transferred to a reservoir (1208.32 g).

[0487] Embodiment 4:

[0488] Additives A, B and C were added to a diesel fuel composition comprising 7 vol% RME in mineral diesel fuel in the amounts specified in Table 1. The specifications of the mineral diesel fuel are shown in Table 2.

[0489] Table 1.

[0490] additive ppm active ingredient A 36.4 B 33.6 C 120

[0491] Table 2.

[0492]

[0493]

[0494] Embodiment 5:

[0495] The diesel fuel composition of Example 3 was evaluated for its ability to reduce deposit formation in a diesel particulate filter according to the following procedure:

[0496] A Mercedes Sprinter 314CDI equipped with a 2.1 liter direct injection OM651 DE 22LA engine was purchased from the market and mounted on a state-of-the-art four-wheel chassis hub dynamometer. For testing purposes, the vehicle's fuel tank was bypassed by the test cell fuel supply. This ensured minimal cross-influence between the test fuels and accurate consumption measurements.

[0497] After initial setup, two baseline runs were completed using EN590 compliant additive-free diesel (RME content 7% v / v). DPF saturation was monitored via the vehicle CAN network from the state immediately after regeneration to the reported 100% load. For ease of comparison, the data is aligned to ~10% load. The time to reach 100% load was consistent, averaging 2.76 hours.

[0498] The baseline fuel was added with the additives specified in Table 1 and the DPF load cycle was repeated four more times.

[0499] Once the Sprinter switched to the additive-fortified fuel, an immediate 13% increase in regeneration time compared to the baseline average was observed.

[0500] Subsequent test runs with the additive-added fuel consistently showed improved performance compared to the previous ones. The fourth and final treatment run extended the regeneration time to 4.90 hours, equivalent to an increase of 77%.

[0501] These results are Figure 1 shown.

[0502] Embodiment 6:

[0503] Additive D is a quaternary ammonium salt additive, which is prepared as follows:

[0504] 700g (0.7mol) of polyisobutylene (Mn 1000) is loaded into a jacketed reactor flushed with nitrogen equipped with an overhead stirrer. The starting material is heated to 120°C under stirring and nitrogen inerting is repeated. The reaction temperature is raised to 190°C, and maleic anhydride (82.4g, 0.84mol, 1.2 equivalents) is added within 1 hour. After the temperature is maintained at 190°C for another 1 hour, the temperature is raised to 200-208°C and maintained within this range for 8 hours. Then vacuum (<30mbar) is applied for 2.5 hours while maintaining the reaction temperature, which reduces the content of residual maleic anhydride to ≤0.05 weight %. The reaction mass is cooled to ≤80°C and then discharged from the reactor.

[0505] The PIBSA prepared as described above was charged into a nitrogen flushed jacketed reactor equipped with an overhead stirrer and heated to 120°C. 3-(Dimethylamino)propylamine (DMAPA) (1 equivalent relative to the anhydride groups) was slowly added, maintaining the reaction temperature between 120-130°C. After stirring at 120°C for an additional hour, the reaction temperature was raised to 140°C and maintained for 3 hours while distilling off water. Methyl salicylate (2.1 equivalents relative to the anhydride groups) was added in one portion and heating was continued at 140°C for 10 hours. The reaction mass was diluted with Aromatic 150 solvent to provide a total solids content of 60% by weight and then discharged from the reactor to provide Additive D.

[0506] Embodiment 7:

[0507] Additive E is an oleamidopropyl betaine additive, which is prepared as follows:

[0508] 183.5 g (0.5 mole) of oleamidopropyl dimethylamine (N-[3-(dimethylamino)propyl]oleamide), 68 ml of isopropanol, 25.5 g (1.42 moles) of water and 56.5 g (0.48 moles) of sodium chloroacetate were charged into a Lenz jacket reactor. The reaction mixture was heated to 80° C. and then heated at 80-85° C. for about 6 hours, then cooled and heated at N 2 The reaction mixture was then reheated to 60°C and charged with 300 ml of isopropyl alcohol (IPA) and 67.5 g of 2-ethylhexanol. The heating was then further increased to 90°C. This allowed H 2 O and IPA were removed azeotropically and NaCl was precipitated. A vacuum of 100 mbar was applied to remove the remaining water and some solvents, and the resulting suspension was filtered through a glass microfiber filter at 75-80° C. 275.6 g of Additive E were collected, containing 53% by weight of active ingredient.

[0509] Embodiment 8:

[0510] Additive F is a quaternary ammonium salt of a polyisobutylene-substituted succinic acid half-acid half-amide, which is prepared as follows:

[0511] Equipped with N 2A Lenz jacketed reactor with an inlet and reflux condenser was charged with 123.2 g (0.105 mole, 1.0 equivalent) of polyisobutylene-substituted succinic anhydride (1000 MW PIB) and 123.0 g of A150 solvent. 8.9 g (0.087 mole, 0.83 equivalent) of N,N-dimethylaminopropylamine (DMAPA) was added via a dropping funnel over a period of about 30 minutes. During the addition, the reaction temperature was maintained at 20°C-25°C, and after the addition, the mixture was stirred for 1 hour. The reaction mixture temperature was reduced to 17°C, and propylene oxide (12.2 g) was added over a period of about 25 minutes. After the addition, the temperature was maintained at 20-22°C while stirring. This was maintained for 4 hours. The reactor was opened and stirred for 2 hours to discharge excess propylene oxide gas. 264.4 g of dark orange liquid additive F was collected. The active ingredient content was 50% by weight.

[0512] Embodiment 9:

[0513] Additive G is a polyisobutylene-substituted quaternary ammonium succinate salt of hexadecyldimethylamine, which is prepared as follows:

[0514] 251.1g (0.20 mole) of polyisobutenyl-substituted succinic acid (1000MW PIB) was loaded into a 1L pressure reactor and preheated because it was a viscous liquid. Then 207g of 2-ethylhexanol was added. Then 48.7g (0.181 mole) of N,N-dimethylhexadecylamine was added under stirring at 30°C. 21.0g (0.362 mole, 2 equivalents) of propylene oxide were added and the reactor was sealed. Using nitrogen, the pressure in the reactor was increased to 2.0 bar, and the temperature was increased to 43-48°C. It was maintained overnight for a total of 17 hours, at which time the pressure in the reactor was reduced to 1.2 bar and the temperature was 43°C. When the pressure in the reactor was further reduced to 1.0 bar, the reactor was opened and the pressure was released. Excess PO was allowed to escape. This provided 610.5g of a clear orange liquid additive G. The conversion rate was 93.4% as determined by analysis. The active ingredient content was 60% by weight.

[0515] Embodiment 10:

[0516] Additives A, D and C were added in the amounts specified in Table 3 to the diesel fuel composition described in Example 11 below.

[0517] Table 3.

[0518] additive ppm active ingredient A 36.4 D 33.6 C 120

[0519] Example 11 - Engine Testing

[0520] Engine testing was performed as described below to evaluate the performance of the nitrogen-containing additives of the present invention in reducing deposits in diesel engine after-combustion systems.

[0521] Engine Details

[0522] A 2.0-liter HSDI engine that complies with the Euro 6 standard is connected to a test automation system and test bench equipped with an engine dynamometer. The engine is controlled by an ECU provided by the engine manufacturer. Before the first test, the engine had been used for more than 1,100 hours. Before the first test, the engine oil was changed.

[0523] Improve / Test Settings

[0524] 1. There is no SCR catalyst or related components in the exhaust system.

[0525] 2. The high pressure EGR cooler was artificially controlled at 40°C during the test.

[0526] The base fuel was RF-06-03 diesel fuel (Haltermann Carless, UK) with the following specifications:

[0527]

[0528] Test additives, treatment rate:

[0529] The exemplary nitrogen-containing detergents were added to the above base diesel fuel at a dosage of 100 mg / kg. Nitrogen-containing detergent A was added to the base fuel to provide Test Fuel 1, nitrogen-containing detergent C was added to the base fuel to provide Test Fuel 2, and the nitrogen-containing detergent mixture described in Example 10 was added to the base fuel to provide Test Fuel 3.

[0530] Soot Deposition Measurement Method (DPF & EGR Soot Weight)

[0531] The amount of soot deposited in the DPF was determined by weighing both assemblies before and after each test.

[0532] Prior to the initial weighing, the DPF was passively regenerated on a test bench to remove any residual soot. Once regeneration was complete, the DPF was placed in an oven, preheated to 185°C, and mounted on a set of scales. After the scales had stabilized, the weight measurements were averaged over a 15-minute period. This weighing process was repeated at the end of the test. The difference between the weights measured before and after the test represents the change in mass due to soot deposition.

[0533] Testing Procedure

[0534] -[D] EGR cleaning and weighing

[0535] -[D]DPF+Slave EGR Installation

[0536] -Engine start + warm up

[0537] - Passive DPF regeneration is performed by varying engine speed and load until regeneration is complete. The differential pressure across the DPF is used to monitor the progress of regeneration.

[0538] - Engine stop

[0539] -Change the test fuel

[0540] -[C]DPF+slave EGR removed

[0541] -[C]DPF Start of Test (SOT) weighing

[0542] -[C]DPF+[C]EGR installation

[0543] -Engine start + warm up

[0544] -8 hours steady state test cycle

[0545] - 1200RPM

[0546] - 60Nm

[0547] - Engine stop

[0548] -[D]DPF removal and end-of-test (EOT) weighing

[0549] -[D] EGR removal and EGR test end weighing

[0550] [C] indicates a clean component

[0551] [D] indicates fouling component

[0552] result

[0553]

[0554] These results demonstrate that the use of the nitrogen-containing detergents described herein as additives in diesel fuel compositions can significantly reduce deposits in the aftercombustion system of a diesel engine combusting the fuel, and in particular reduce soot deposited on a diesel particulate filter of the aftercombustion system.

Claims

1. Use of one or more nitrogen-containing detergents as an additive in a diesel fuel composition to reduce the effects of deposits in the after-combustion system of a diesel engine when the diesel fuel composition is combusted.

2. A method of reducing the effects of deposits in an after-combustion system of a diesel engine, the method comprising combusting in the engine a diesel fuel composition comprising one or more nitrogen-containing detergents as an additive.

3. Use or method according to claim 1 or claim 2, which reduces the formation of deposits in the aftercombustion system of a diesel engine.

4. The use or method according to any one of the preceding claims, wherein the additive is selected from: (a) quaternary ammonium salt additives; (b) products of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; (c) the reaction product of a carboxylic acid derived acylating agent and an amine; and (d) mixtures thereof.

5. The use or method according to any one of the preceding claims, wherein the diesel fuel composition comprises (a) a quaternary ammonium salt additive.

6. Use or method according to any one of the preceding claims, wherein the diesel fuel composition comprises (b) the reaction product of a hydrocarbyl-substituted acylating agent and an amine.

7. Use or method according to any one of the preceding claims, wherein the diesel fuel composition comprises (c) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol.

8. The use or process according to any one of the preceding claims, wherein component (a) comprises a quaternary ammonium salt formed by the reaction of 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 (Mn) of 700 to 1300 and dimethylaminopropylamine.

9. The use or method according to any one of the preceding claims, wherein component (a) comprises a quaternary ammonium salt formed by the reaction of methyl salicylate, dimethyl oxalate or propylene oxide (optionally in combination with an acid) with a reaction product of a fatty acid of the formula RCOOH with a compound of the formula (II), wherein R is an alkyl or alkenyl group having 12 to 24 carbon atoms, and wherein R 2 and R 3 Each is a C1 to C4 alkyl group and X is an alkylene group having 2 to 5 carbon atoms.

10. The use or method according to any one of the preceding claims, wherein component (a) comprises a mixture of methyl salicylate, dimethyl oxalate or propylene oxide (optionally in combination with an acid) and a hydroxyl radical of formula R 5 R 6 R 7 N tertiary amine reaction to form a quaternary ammonium salt, where R 5 , R 6 and R 7 Each is independently an alkyl group or a hydroxyalkyl group.

11. The use or process according to any one of the preceding claims, wherein component (b) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and mixtures and isomers thereof; wherein the number average molecular weight of the polyisobutylene substituent is between 500 and 2000, preferably between 600 and 1200.

12. Use or process according to any one of the preceding claims, wherein component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and a para-substituted monoalkylphenol, preferably dodecylphenol.

13. Use or method according to any one of the preceding claims, wherein the diesel fuel composition comprises 1 to 1000 ppm, preferably 5 to 100 ppm of (a) a quaternary ammonium salt additive; and / or 1 to 1000 ppm, preferably 5 to 250 ppm of (b) a reaction product of a carboxylic acid derived acylating agent with an amine; and / or 1 to 1000 ppm, preferably 5 to 100 ppm of (c) a product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol.

14. Use or method according to any one of the preceding claims, which reduces the formation of deposits on a turbocharger of a post-combustion system.

15. Use or method according to any one of the preceding claims, which reduces the formation of deposits on a diesel oxidation catalyst of a post-combustion system.

16. Use or method according to any one of the preceding claims, which reduces the formation of deposits on a diesel particle filter of a post-combustion system.

17. Use or method according to any one of the preceding claims to reduce the accumulation of soot in a diesel particulate filter.

18. Use or method according to any one of the preceding claims, which reduces the formation of deposits on a selective catalytic reduction unit of a post-combustion system.

19. Use or method according to any one of the preceding claims, which reduces the formation of deposits on an ammonia oxidation catalyst of a post-combustion system.

20. Use or method according to any one of the preceding claims to reduce the formation of deposits on sensors in post combustion systems.

21. Use or method according to any one of the preceding claims, which reduces the formation of deposits in one or more components of a post-combustion system by at least 5%.

22. The use or method according to any one of the preceding claims, wherein the diesel fuel composition comprises one or more nitrogen-containing detergents.

23. Use or method according to any preceding claim, wherein the diesel engine is a non-road engine, such as a marine, railway or stationary engine.

24. The use or method according to any of the preceding claims, providing one or more benefits selected from the following: increased power generation; increased torque; improved fuel economy; reduced emissions; reduced combustion chamber deposits; improved acceleration; improved drivability; reduced cold start problems; reduced soot formation; reduced lubricant degradation and / or performance loss; reduced diesel exhaust treatment fluid and consumption, such as urea consumption; reduced wear of all aftercombustion components (including but not limited to turbochargers, oxidation catalysts, DPFs, SCR CATs, sensors and injectors within the aftercombustion system); increased service life of exhaust components; increased maintenance intervals for the engine and / or aftercombustion components; and protection of intake components downstream of the EGR, such as swirl flaps, throttles and intake manifolds (due to reduced likelihood of clogging, etc.).

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