BRANCHED PRIMARY ALKYL AMINES AS ADDITIVES FOR GASOLINE FUELS

Abstract

Certain branched amines are useful as additives for gasoline fuels, especially for reducing injector nozzle fouling in direct injection spark ignition engines.

Claims

1-16. (canceled)

17: A method for reducing injector nozzle fouling in a direct injection spark ignition engine, the method comprising: adding a fuel additive to an unleaded gasoline composition comprising a major proportion of a gasoline suitable for the spark ignition engine, wherein the fuel additive is a branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by .sup.1H-NMR spectroscopy.

18: A method for improving storage stability and/or formulability of a fuel additive package for gasoline, the method comprising: adding an additive to the fuel additive package, wherein the additive is a branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by .sup.1H-NMR spectroscopy.

19: The method according to claim 17, wherein the gasoline composition further comprises at least one deposit control agent selected from the group consisting of quaternary ammonium compounds, Mannich adducts, and polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range of 300 to 5000.

20: The method according to claim 17, wherein the branched primary alkyl amine is selected from the group consisting of 2-propyl heptyl amine, branched nonyl amine, branched tridecyl amine, and branched heptadecyl amine.

21: An unleaded gasoline composition, comprising: a major proportion of a gasoline suitable for a spark ignition engine, and 10 to 3000 ppmw, based on the unleaded gasoline composition, of a branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by .sup.1H-NMR spectroscopy.

22: The unleaded gasoline composition according to claim 21, further comprising: at least one deposit control agent selected from the group consisting of from 10 to 100 ppm by weight of a quaternary ammonium compound, from 10 to 1000 ppm by weight of a Mannich adduct, and from 10 to 1000 ppm by weight of a polyalkenemono- or polyalkenepolyamine having a number average molecular weight in the range of 300 to 5000.

23: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is of the formula
.sup.+NR.sup.1R.sup.2R.sup.3R.sup.4A.sup.? in which A.sup.? stands for an anion, a carboxylate R.sup.5COO.sup.?, or a carbonate R.sup.5OCOO.sup.?, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an organic residue with from 1 to 100 carbon atoms, substituted or unsubstituted, and R.sup.5 additionally may be a substituted or unsubstituted cycloalkyl or aryl residue bearing 5 to 20 carbon atoms.

24: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is obtainable by addition of a compound which comprises at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group, onto a polycarboxylic anhydride compound, and subsequent quaternization in the presence of an acid or in an acid-free manner.

25: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is of formula ##STR00011## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, R stands for a C.sub.1- to C.sub.4-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup.? stands for an anion.

26: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is of formula ##STR00012## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, and R stands for a hydroxy-C.sub.1- to C.sub.4-alkyl.

27: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is of formula ##STR00013## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, R stands for an C.sub.1- to C.sub.4-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup.? stands for an anion.

28: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is of formula ##STR00014## wherein in this formula R.sup.a stands for C.sub.1-C.sub.20-alkyl, R.sup.b stands for a hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup.? stands for an anion.

29: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is of formula ##STR00015## wherein in this formula X.sub.i for i=1 to n and 1 to m, are independently of another selected from the group consisting of CH.sub.2CH.sub.2O, CH.sub.2CH(CH.sub.3)O, CH(CH.sub.3)CH.sub.2O, CH.sub.2C(CH.sub.3).sub.2O, C(CH.sub.3).sub.2CH.sub.2O, CH.sub.2CH(C.sub.2H.sub.5)O, CH(C.sub.2H.sub.5)CH.sub.2O, and CH(CH.sub.3)CH(CH.sub.3)O, m and n independently of another are positive integers, with the proviso that the sum (m+n) is from 2 to 50, R stands for an C.sub.1- to C.sub.4-alkyl, and A.sup.? stands for an anion.

30: The unleaded gasoline composition according to claim 22, wherein the at least one deposit control agent is of formula ##STR00016## wherein in this formula R.sup.a and R.sup.b independently of another stand for C.sub.1-C.sub.20-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup.? stands for an anion.

31: A fuel additive package for gasoline fuels, comprising: at least one branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by .sup.1H-NMR spectroscopy, at least one deposit control agent selected from the group consisting of quaternary ammonium compounds, Mannich adducts, and polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, and optionally, at least one further gasoline fuel additive selected from the group consisting of corrosion inhibitors, carrier oils, and solvents.

32: The unleaded gasoline composition according to claim 21, wherein the alkyl group has 13 carbon atoms.

33: The unleaded gasoline composition according to claim 21, wherein the branching is from at least 1.5 to 7.0 as determined by .sup.1H-NMR spectroscopy.

34: The unleaded gasoline composition according to claim 23, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are unsubstituted, linear or branched alkyl, alkenyl or hydroalkyl residues with 1 to 100 carbon atoms.

35: The unleaded gasoline composition according to claim 24, wherein the quaternization is with an epoxide in the absence of free acid, or with a carboxylic ester.

36: The unleaded gasoline composition according to claim 35, wherein the epoxide is styrene or propylene oxide, or wherein the carboxylic ester is dimethyl oxalate or methyl salicylate.

Description

EXAMPLES

Example 1: Determination of Injector Cleanliness with a Direct Injection Spark Ignition Engine

[0353] 1. Injector Cleanliness in Direct Injecting Gasoline Engines (Direct Injection Spark Ignition (DISI) or Gasoline Direct Injection (GDI)): Keep-Dean Performance

[0354] The test method is a preliminary version of the upcoming CEC test for injector fouling in DISI engines (TDG-F-113) and was published by D. Weissenberger, J. Pilbeam, Characterisation of Gasoline Fuels in a DISI Engine, lecture held at Technische Akademie Esslingen, Jun. 27, 2017. The test engine is a VW EA111 1.4L TSI engine with 125 kW. The test procedure is a steady state test at an engine speed of 2000 rpm and a constant torque of 56 Nm.

[0355] The test procedure is performed with the following injectors: Magneti Marelli 03C 906 036 E. Reference oil RL-271 from Haltermann Carless was used as engine oil.

[0356] 2. Injector Cleanliness in Direct Injecting Gasoline Engines (Direct Injection Spark Ignition (DISI) or Gasoline Direct Injection (GDI)): Clean-Up Performance

[0357] In the dirty-up-clean-up sequence dirty-up is achieved by running the engine over 48 hours as described for the keep-clean procedure (see above) with base fuel. The relative change of activation time is determined as described above for the keep-clean test. The subsequent clean-up run is done with additized base fuel over 10 h. At the end of the test 3 data points are determined within 15 minutes, which mean value gives the activation time at end of clean-up test. The test result for the clean-up is the relative change of activation time of the injectors relative to the aver-age activation time determined at the end of the dirty-up phase

[0358] The test was run with an EN 228 compliant low sulfur Haltermann DISI TSI fuel according to CEC RF-83 mod complying with EN 228.

[0359] The dirty-up phase used fuel without additive and was run for 48 hours, the clean-up phase using additized fuel for 10 hours.

[0360] In Run 1 the fuel contained 300 mg/kg PIBA* and 30 mg/kg linear dodecylamin

[0361] In Run 2 the fuel contained 300 mg/kg PIBA* and 30 mg/kg branched tridecylamin obtained by amination from the corresponding tridecanol isomeric mixture with a branching index of 2.2 determined following the above-mentioned procedure. [0362] Kerocom? PIBA (65% by weight solution of polyisobutylene amine based on high-reactivity polyisobutene (after hydroformylation and amination), Mn=1000, in an aliphatic hydrocarbon mixture)

[0363] Nozzle coking is measured as change of activation time of the injector (ti_I), which is measured periodically within the test procedure. Due to nozzle coking, the hole diameters of the injector holes are reduced, and the activation time adjusted by the Engine Control Unit (ECU) accordingly. The activation time in milliseconds is a direct readout from the ECU via ECU control software. A prolongation of activation time is an indicator for nozzle coking. The test duration was 48 h.

[0364] After a run-in period of 30 minutes 3 data points for ti_I were determined within 15 minutes, which mean value gives the activation time at start of test. At the end of the test 3 data points were determined within 15 minutes, which mean value gives the activation time at end of test. The test result is the relative change of activation time ti_I of the injectors.

TABLE-US-00001 Run 1 (for comparison) dirty-up: 14.14% clean-up: 92.3% Run 2 (according to the dirty-up: 11.32% clean-up: 104.25% invention)

[0365] It can easily be seen that the additive package comprising the branched alkyl amine according to the invention shows at least the same activity in reducing injector nozzle fouling as the linear dodecyl amine according to the prior art, if not even an improved activity.

Example 2: Determination of Storage Stability of a Fully Formulated Gasoline Additive Package

[0366] Three gasoline performance packages were formulated according to the following table. The carrier fluid used is a propoxylated tridecanol derived from trimerbutene (after hydroformylation and hydrogenation). Clear formulations were obtained in both cases.

TABLE-US-00002 Formulation 2 Formulation 3 Formulation 1 [wt %] [wt %] [wt %] (Comparative) (Comparative) Kerocom PIBA* 38.01 38.01 31.35 Carrier fluid** 13.37 13.37 11.03 Corrosion inhibitor*** 0.85 0.85 0.7 branched tridecylamin 5.31 linear dodecylamin 5.31 4.38 Solvent Naphtha 42.46 42.46 52.54 heavy**** Sum 100 100 100 *Kerocom(R) PIBA (65% by weight solution of polyisobutylene amine based on high-reactivity polyisobutene (after hydroformylation and amination), Mn = 1000, in an aliphatic hydrocarbon mixture) **propoxylated tridecanol derived from trimerbutene (after hydroformylation and hydrogenation) ***copolymer of maleic anhydride and C.sub.20- to C.sub.24-olefin according to synthetic example 2 of WO 15/114029 ****solvent

[0367] All three formulations were stored at 40? C., room temperature and ?20? C. for one week to evaluate their storage stability.

TABLE-US-00003 Formulation 2 Formulation 3 Formulation 1 (Comparative) (Comparative) +40? C. liquid, liquid, liquid, homogeneous homogeneous homogeneous Room liquid, sediment liquid, temperature homogeneous homogeneous ?20? C. liquid, nearly solid liquid, homogeneous homogeneous

[0368] It can easily be seen that Comparative Formulation 2 using the same weight composition of the components as Formulation 1 according to the invention exhibits a much worse storage stability than Formulation 1.

[0369] In order to yield a comparable storage stability the amount of solvent has to be significantly increased (Comparative Formulation 3).