Search

EP-4739755-A1 - METHODS AND USES RELATING TO THE COMBUSTION OF GASOLINE FUEL COMPOSITIONS IN A DIRECT INJECTION SPARK IGNITION ENGINE

EP4739755A1EP 4739755 A1EP4739755 A1EP 4739755A1EP-4739755-A1

Abstract

A method of agglomerating nanoparticles in the exhaust stream from the combustion of a gasoline fuel composition in a direct injection spark ignition engine, the method comprising adding to the gasoline fuel composition as an agglomeration additive one or more quaternary ammonium compounds.

Inventors

  • KNIGHT, PETER
  • BROOM, NIGEL

Assignees

  • Innospec Limited

Dates

Publication Date
20260513
Application Date
20240705

Claims (20)

  1. 1 . A method of agglomerating nanoparticles in the exhaust stream from the combustion of a gasoline fuel composition in a direct injection spark ignition engine, the method comprising adding to the gasoline fuel composition as an agglomeration additive one or more quaternary ammonium compounds.
  2. 2. The use of one or more quaternary ammonium compounds as an agglomeration additive in a gasoline fuel composition to agglomerate nanoparticles in the exhaust stream from the combustion of the gasoline fuel composition in a direct injection spark ignition engine.
  3. 3. A method or use according to claim 1 or 2 wherein the or each quaternary ammonium compound is the reaction product of a nitrogen-containing species having at least one tertiary amine group and a quaternising agent wherein the nitrogen-containing species having at least one tertiary amine group may be selected from: (i) the reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group; (ii) a Mannich reaction product comprising a tertiary amine group; (iii) a polyalkylene substituted amine having at least one tertiary amine group; (iv) a tertiary amine of formula R 5 R 6 R 7 N, wherein each of R 5 , R 6 and R 7 is independently an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group; (v) a cyclic tertiary amine; and (vi) a polyetheramine compound.
  4. 4. A method or use according to claim 3 wherein the nitrogen-containing species having at least one tertiary amine group is the reaction product of an alcohol or amine including a tertiary amino group and an optionally substituted succinic acid or anhydride thereof.
  5. 5. A method or use according to claim 4 wherein the succinic acid or anhydride thereof is substituted with a hydrocarbyl group and the hydrocarbyl substituted acylating agent includes an average of at least 1 .2 succinic acid moieties per molecule.
  6. 6. A method or use according to claim 4 or claim 5 wherein the succinic acid or anhydride thereof is substituted with a polyisobutenyl group having a number average molecular weight of from 170 to 2800, preferably 450 to 1500.
  7. 7. A method or use according to any of claims 3 to 6 wherein the alcohol or amine including a tertiary amino group is selected from dimethylaminopropanol, dimethylaminopropylamine, N,N-diethyl-1 ,3- diaminopropane, N,N-dimethylethylenediamine, N,N- diethylethylenediamine, N,N-dibutylethylenediamine, or combinations thereof.
  8. 8. A method or use according to any of claims 3 to 7 wherein the quaternising agent is selected from esters of a carboxylic acid, dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides optionally in combination with an acid, alkyl halides, alkyl sulfonates, sulfones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.
  9. 9. A method or use according to claim 8 wherein the quaternising agent is an ester of formula R 18 COOR 19 wherein R 19 is a Ci to C7 alkyl group and R 18 is the residue of a carboxylic acid selected from a substituted aromatic carboxylic acid, an a-hydroxycarboxylic acid and a polycarboxylic acid.
  10. 10. A method or use according to claim 9 wherein the quaternising agent is an ester of a carboxylic acid 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.
  11. 11. A method or use according to claim 10 wherein the quaternising agent is selected from dimethyl oxalate, methyl 2-nitrobenzoate, dimethylphthalate, dimethyltartrate and methyl salicylate
  12. 12. A method or use according to claim 8 wherein the quaternising agent is selected from epoxides, optionally in combination with an acid, wherein the epoxide has the formula: wherein each of R 25 , R 26 , R 27 , R 28/ is independently selected from hydrogen or an optionally substituted alkyl, alkenyl or aryl group, provided at least one of R 25 , R 26 , R 27 and R 28 is hydrogen.
  13. 13. A method or use according to claim 12 wherein each of R 25 , R 26 and R 27 is hydrogen and R 28 is selected from phenyl, an optionally substituted alkyl or alkenyl group having 1 to 20 carbon atoms, hydrogen, CH2OR 29 or CH2OCOR 30 wherein each of R 29 and R 30 is an optionally substituted alkyl or aryl group having from 1 to 20 carbon atoms.
  14. 14. A method or use according to claim 13 or claim 14 wherein the epoxide is selected from styrene oxide, ethylene oxide, propylene oxide, butylene oxide, stilbene oxide and isopropyl glycidyl ether.
  15. 15. A method or use according to any of claims 8, 12, 13 or 14 wherein the epoxide quaternising agents are used in combination with an acid.
  16. 16. A method or use according to claim 15 wherein the acid is selected from: - a small simple acid selected from formic acid, acetic acid, propionic acid and butyric acid; - a fatty acid compound; and - a hydrocarbyl substituted phthalic acid or succinic acid derivative.
  17. 17. A method or use according to any preceding claim wherein the gasoline composition further comprises one or more additional components selected from: a) carrier oils b) acylated nitrogen compounds which are the reaction product of a carboxylic acid-derived acylating agent and an amine c) hydrocarbyl-substituted amines wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms d) Mannich base additives comprising nitrogen-containing condensates of a phenol, aldehyde and primary or secondary amine; and e) polyether amines.
  18. 18. A method or use according to any preceding claim which reduces the number of particulates emitted per unit volume of exhaust gas and /or the total mass of particulates emitted per unit volume of exhaust gas.
  19. 19. A method or use according to any preceding claim which reduces the number of particulates emitted per unit volume of exhaust gas and /or the total mass of particulates emitted per unit volume of exhaust gas by at least 50%.
  20. 20. A method or use according to any preceding claim wherein the agglomeration additive is present in the gasoline composition in an amount of from 0.5 to 50 ppm.

Description

METHODS AND USES RELATING TO THE COMBUSTION OF GASOLINE FUEL COMPOSITIONS IN A DIRECT INJECTION SPARK IGNITION ENGINE The present invention relates to the use of additives in fuel compositions, and especially for use in spark ignition engines. In particularthe invention provides compositions which address issues relating to the emission of nanoparticles from direct injection spark injection engines. With over a hundred years of development the spark ignition (SI) engine has become a highly tuned piece of engineering. Engine designers have developed high performance engines which include injection systems where the fuel is injected directly into the cylinder. Such engines are alternatively known as direct injection spark ignition (DISI), direct injection gasoline (DIG), gasoline direct injection (GDI), etc. It is common to include catalytic converters in the exhaust system of a direct injection gasoline engine. These typically include three way catalytic converters which reduce the concentrations of hydrocarbons, carbon monoxide and NOX species released into the atmosphere. However, unlike in diesel engines where diesel particulate filters are commonly fitted in the exhaust system, the emission of particulates from direct injection gasoline engines has not been routinely monitored. Nevertheless the emission of particulates from direct injection spark ignition engines is a serious problem. There is increasing evidence that the emission of nanoparticles in particular represents a significant risk to human health and an environmental hazard. Whilst it is desirable to reduce the overall emission of particulate matters from exhaust systems, it is especially important to reduce the concentration of nanoparticles emitted. Nanoparticles pose a particular problem because not only are they more harmful than larger particles, they are also more difficult to trap as they may pass through a filter. The present inventors have surprisingly found that the addition of certain additives into a fuel can lead to the agglomeration of nanoparticles to form larger particles that may be more easily captured by a filter. According to a first aspect of the present invention there is provided a method of agglomerating nanoparticles in the exhaust stream from the combustion of a gasoline fuel composition in a direct injection spark ignition engine; the method comprising adding to the gasoline fuel composition as an agglomeration additive one or more quaternary ammonium compounds. According to a second aspect of the present invention there is provided the use of one or more quaternary ammonium compounds as an agglomeration additive in a gasoline fuel composition to agglomerate nanoparticles in the exhaust stream from the combustion of the fuel composition gasoline in a direct injection spark ignition engine. Preferred features of the first and second aspects of the invention will now be described. Any feature of any aspect may be combined with any feature of any other aspect as appropriate. The present invention relates to a method and a use involving one or more quaternary ammonium compounds as a fuel additive. The additive may be referred to herein as “the additive of the present invention”, or as “the agglomeration additive”. The agglomeration additive may comprise a single quaternary ammonium compound. In some embodiments mixtures containing more than one quaternary ammonium compound may be used. Thus the present invention may involve the use of one quaternary ammonium compound, or a mixture of two or more quaternary ammonium compounds. Unless otherwise specified, references herein to “an additive” or “an agglomeration additive” of the invention or “the additive” or “the agglomeration additive” include embodiments in which mixtures of two or more quaternary ammonium compounds are used. The or each quaternary ammonium compound is suitably the reaction product of a nitrogencontaining species having at least one tertiary amine group and a quaternising agent. The nitrogen-containing species having at least one tertiary amine group may be selected from any compound including a tertiary amine functional group. Suitably the nitrogen-containing species having at least one tertiary amine group may be selected from: (i) the reaction product of a hydrocarbyl-substituted acylating agent and a compound having at least one tertiary amine group and a primary amine, secondary amine or alcohol group; (ii) a Mannich reaction product comprising a tertiary amine group; (iii) a polyalkylene substituted amine having at least one tertiary amine group; (iv) a tertiary amine of formula R5R6R7N, wherein each of R5, R6 and R7 is independently an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group; (v) a cyclic tertiary amine; and (vi) a polyetheramine compound. The nitrogen-containing species having at least one tertiary amine group is reacted with a quaternising agent. Any suitable quaternising agent may be used. In some embodiments the