Emulsifier package with quaternary ammonium surfactant for fuel emulsion

Abstract

A fuel emulsion for powering a diesel engine contains water, a fuel, and an emulsifier package containing a quaternary ammonium surfactant. A method for powering a diesel engine with the fuel emulsion involves preparing the fuel emulsion by emulsifying a fuel and water in the presence of the emulsifier package. An emulsifier package for emulsifying a fuel and water contains a quaternary ammonium surfactant and at least one nonionic surfactant, which is an alkoxylate. The quaternary ammonium surfactant is obtainable by reacting a quaternizable nitrogen compound containing at least one quaternizable, especially tertiary, amino group with a quaternizing agent, which converts the at least one quaternizable, especially tertiary, amino group to a quaternary ammonium group, where the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid.

Claims

1-15. (canceled)

16: A fuel emulsion for powering a diesel engine, comprising: water, a fuel, and an emulsifier package, which comprises a quaternary ammonium surfactant and which comprises at least two nonionic surfactants, which are alkoxylates selected from the group consisting of an ethoxylate of fatty amide, castor oil ethoxylate, and ethoxylated fatty alcohol.

17: The fuel emulsion according to claim 16, wherein the emulsifier package comprises at least 60 wt % of the at least two nonionic surfactants.

18: The fuel emulsion according to claim 16, wherein the quaternary ammonium surfactant is a reaction product obtainable by reacting a quaternizable nitrogen compound comprising at least one quaternizable amino group with a quaternizing agent, which converts the at least one quaternizable amino group to a quaternary ammonium group, wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid.

19: The fuel emulsion according to claim 16, wherein the emulsifier package comprises 1 to 40 wt % of the quaternary ammonium surfactant.

20: The fuel emulsion according to claim 16, wherein the fuel emulsion comprises the emulsifier package in an amount of 0.05 to 0.5 wt %, based on the fuel emulsion.

21: The fuel emulsion according to claim 16, wherein the fuel emulsion is an oil-in-water emulsion.

22: The fuel emulsion according to claim 16, wherein the fuel emulsion comprises 50 to 80 wt % water.

23: The fuel emulsion according to claim 16, wherein the fuel is marine fuel.

24: A method for powering a diesel engine with a fuel emulsion, the method comprising: preparing the fuel emulsion according to claim 16 by emulsifying the fuel and water in the presence of the emulsifier package.

25: An emulsifier package for emulsifying a fuel and water, comprising: a quaternary ammonium surfactant, and at least two nonionic surfactants, which are alkoxylates selected from the group consisting of an ethoxylate of fatty amide, castor oil ethoxylate, and ethoxylated fatty alcohol.

26: The emulsifier package according to claim 25, comprising 1 to 40 wt % of the quaternary ammonium surfactant.

27: The emulsifier package according to claim 25, comprising at least 60 wt % of the at least two nonionic surfactants.

28: The fuel emulsion according to claim 18, wherein the at least one quaternizable amino group is at least one quaternizable tertiary amino group.

29: The emulsifier package according to claim 25, wherein the quaternary ammonium surfactant is a reaction product obtainable by reacting a quaternizable nitrogen compound comprising at least one quaternizable amino group with a quaternizing agent, which converts the at least one quaternizable amino group to a quaternary ammonium group, wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid.

30: The emulsifier package according to claim 29, wherein the at least one quaternizable amino group is at least one quaternizable tertiary amino group.

31: The fuel emulsion according to claim 16, wherein said fuel is at least one marine fuel selected from the group consisting of Marine gas oil, Marine diesel oil, Intermediate fuel oil, Marine fuel oil, Heavy fuel oil, an Intermediate fuel oil with a maximum viscosity of 380 centistokes (<3.5% sulphur), an Intermediate fuel oil with a maximum viscosity of 180 centistokes (<3.5% sulphur), a Low-sulphur (<1.0%) intermediate fuel oil with a maximum viscosity of 380 centistokes, a Low-sulphur (<1.0%) intermediate fuel oil with a maximum viscosity of 180 centistokes, a Low-sulphur (<0.1%) Marine Gas Oil according to EU Sulphur directive 2005/33/EC, an Ultra-Low-Sulphur Marine Gas Oil, and fuels according to DIN ISO 8217.

32: The fuel emulsion according to claim 16, wherein said fuel is at least one selected from the group consisting of ISO-F-DMX, DMA, DFA, DMZ, DFZ, DFB, ISO-F RMA, RMB, RMD, RME, RMG and RMK.

33: The fuel emulsion according to claim 16, wherein said fuel has a sulfur content of less than 1 wt. %.

Description

EXAMPLES

[0141] Quat A: N,N-dimethyl-N-hexydecylamine quaternized with propylene oxide and polyisobutylenesuccinic acid obtained from succinic acid and polyisobutylene (Mn about 1000 g/mol); 50 wt % in 2-ethylhexanol. [0142] Nonionic A: ethoxylate of fatty amide from fatty acid and ethanolamine, clear liquid, hydroxyl value about 150 mg KOH/g. [0143] Nonionic B: castor oil ethoxylate, clear liquid, hydroxyl value about 150 mg KOH/g. [0144] Nonionic C: fatty alcohol alkoxylate, solidification temperature about 18 C., kinematic viscosity 30 mm.sup.2/s (40 C., ASTM D445). [0145] Additive D: Commercial fuel additive, amines, polyethylenepoly-, reaction products with succinic anhydride polyisobutenyl (40-60 wt %) in C10 hydrocarbons, aromatics (40-60 wt %). [0146] Additive E: Commercial fuel additive, polyisobutylene succinimide of dimethylaminopropylamine in 25-50 wt % hydrocarbon solvent. [0147] Additive F: Commercial fuel additive, polyisobutylene succinamide of dimethylaminopropylamine. [0148] Additive G: Commercial diesel additive, propoxylated polyisobutylene succinamide of dimethylaminopropylamine [0149] Solvent A: C11-14 Hydrocarbons (n-alkanes, isoalkanes, cyclics and up to 25% aromatics) mixed with nearly 50% C14-18 hydrocarbons (n-alkanes, isoalkanes, cyclics and up to 25% aromatics), clear liquid, boiling range 178-285 C., freeze point below 30 C.

Example 1Emulsion Stability

[0150] The emulsifier packages were prepared by mixing the emulsifiers as indicated in Table 1 and a liquid mixture of emulsifiers was obtained. The samples for testing the emulsion stability contained diesel fuel and distilled water in a ratio of each 40 ml and the emulsifier package in the given treat rate (cf Table 1). The diesel fuel was a clear liquid, free of additive packages and had a density of about 0.83 to 0.85.

[0151] An emulsion was prepared by shaking the samples in a graduated cylinder on a shaker with a lift of 125 mm and a lift speed of 10 lifts for five seconds at 20 C. After the shaking stopped the graduated cylinders were allowed to stand for up to 30 min. The amount of separated water phase was determined. For example, if 8 ml separated water phase was detected in the 80 ml total volume sample, it corresponded to an emulsion stability of 90%. If no separated water phase was detected this corresponded to 100% emulsion stability.

TABLE-US-00001 TABLE 1 Emulsion Stability (concentrations in wt %, treat rate in relation to diesel) F Test A B C D E Comparative Nonionic A 0.06 0.09 0.15 0.065 0.065 0.067 Nonionic B 0.03 0.045 0.075 0.03 0.033 Nonionic C 0.03 Quat A 0.01 0.015 0.025 0.005 0.005 Treat Rate 0.1 wt % 0.15 wt % 0.25 wt % 0.1 wt % 0.1 wt % 0.1 wt % 1 min 100% 100% 100% 100% 100% 100% 2 min 100% 100% 100% 100% 100% 99% 4 min 100% 100% 100% 100% 100% 91% 6 min 100% 100% 100% 98% 100% 88% 8 min 100% 100% 98% 90% 100% 83% 10 min 100% 100% 94% 88% 99% 78% 15 min 100% 100% 91% 81% 94% 68% 20 min 100% 100% 88% 75% 89% 63% 30 min 100% 100% 70% 70% 95% 58%

Example 2Corrosion Protection on Steel

[0152] An emulsifier package EP-1 was prepared by mixing 10 wt % Quat A, 60 wt % Nonionic A. and 30 wt % Nonionic C.

[0153] The corrosion protection properties of the emulsifier package EP-1 on steel was tested according to DIN ISO 7120 A. The marine diesel had a density at 15 C. of about 890 kg/m.sup.3, viscosity of about 7 mm2/s (ISO 3104 at 40 C.) and sulphur content of about 0.2 wt %. The samples contained marine diesel and distilled water in a weight ratio of 50:50 and optionally the emulsifier package EP-1 in a treat rate of 0.1 wt % based on the marine diesel. A cylindrical steel finger was immersed for 24 h at 60 C. and then observed for of rusting.

[0154] The steel finger immersed in the emulsion without EP-1 showed clear signs of rusting. The steel finger immersed in the emulsion with the EP-1 showed no signs of rusting. Thus, the emulsifier package reduced the corrosion.

Example 3Corrosion Protection on Copper

[0155] The corrosion protection properties of the emulsifier package EP-1 on copper was tested according to DIN ISO 2160 A. The samples contained marine diesel as in Example 2 and destilled water in a weight ratio of 50:50 and optionally the emulsifier package EP-1 in a treat rate of 0.1 wt % based on the marine diesel. A copper plate was immersed for 3 h at 80 C. and then observed for of rusting.

[0156] The copper plate immersed in the emulsion without the emulsifer package showed clear signs of rusting. The copper plate immersed in the emulsion with the emulsifer package showed no signs of rusting. Thus, the emulsifier package reduced the corrosion.

Example 4Prevention of Precipitate

[0157] 40 ml Marine diesel as used in Example 2 was mixed with 40 ml destilled water and optionally mixed with the emulsifier package EP-1. A black precipitate formed immediately in the samples, which was filtered off through a paper filter (Macherey-Nagel MN 126/70, thickness 0.2 mm, weight 70 g/m.sup.2). After 24 h the amount of residue on the paper filter was determined.

[0158] The sample without the emulsifer package resulted in 36.8 g wet filter residue filtration. The sample with the emulsifer package resulted in only 5.5 g wet filter residue. Thus, the emulsifier package reduced the amount of precipitate and improved the filterability.

Example 5Additive Packages

[0159] The emulsifier packages were prepared by mixing the emulsifiers as indicated in Table 2 and a liquid mixture of emulsifiers was obtained.

[0160] The samples for testing the emulsion stability were prepared by mixing the additive package with diesel fuel. The amount of emulsifier used was 0.05% based on total volume of emulsion, including fuel and water, for all experiments in table 2.

[0161] The used diesel fuel was a marine diesel oil of the type DMA according to DIN ISO 8217 a clear liquid diesel, free of additive packages and had a density of about 0.83 to 0.85.

[0162] The emulsion was prepared with a Silverson L5 high shear lab emulsifier based on rotor-stator principle within 10 sec at 7500 rpm at room temperature.

[0163] Then the emulsified samples were put in a graduated cylinder which was allowed to stand for up to 30 min. The amount of separated water phase was determined. For example, if 8 ml separated water phase was detected in the 80 ml total volume sample, it corresponded to an emulsion stability of 90%. If no separated water phase was detected this corresponded to 100% emulsion stability. The values are given in Table 2.

TABLE-US-00002 TABLE 2 Additive Packages (all amounts in wt %) and Emulsion stability A B C D E F G H I J K Nonionic C 30 24 12 6 3 15 7.5 15 24 15 7.5 Nonionic A 60 48 24 12 6 30 15 30 48 30 15 Quat A 10 8 4 2 1 5 2.5 5 8 5 2.5 Additive D 20 10 80 40 50 25 Additive E 50 Additive F 50 25 Additive G 20 Solvent A 50 50 50 50 Ratio Fuel:Water 1:1 1:1.4 1:1.4 1:1.4 1:1.4 1:1.4 1:1.4 1:1.4 1:1.4 1:1.4 1:1.4 1 min. 99% 99% 99% 99% 99% 99% 99% 99% 94% 96% 100% 2 min. 99% 98% 99% 99% 99% 99% 99% 99% 86% 94% 100% 5 min. 98% 98% 95% 97% 97% 97% 97% 99% 84% 93% 98% 10 min. 93% 96% 90% 95% 94% 95% 95% 98% 82% 89% 93% 20 min. 82% 95% 82% 92% 91% 94% 93% 96% 73% 84% 88% 30 min. 76% 93% 80% 86% 88% 91% 90% 95% 68% 80% 77%

Example 6Diesel Types

[0164] The additive packages were prepared and tested for emulsion stability as in Example 5 with various DMA Diesel types. The results are summarized in Table 3. Tested DMA Marine Diesel Types were: [0165] DMA-1: dark brown, density (15 C.) about 885 kg/m3, kinetic viscosity 4.9 cSt at 40 C., pour point 9 C. [0166] DMA-2: clear, homogenous with colour marker, density (15 C.) about 888 kg/m3, kinetic viscosity 5.1 cSt at 40 C., pour point 21 C. [0167] DMA-3: clear, homogenous with colour marker, density (15 C.) about 865 kg/m3, kinetic viscosity 4.2 cSt at 40 C., pour point 9 C. [0168] DMA-4: light brown, clear, density (15 C.) about 887 kg/m3, kinetic viscosity 6.0 cSt at 40 C., pour point 12 C.

TABLE-US-00003 TABLE 3 Additive Packages (all amounts in wt %) and Emulsion stability A B C D Nonionic C 15 15 15 15 Nonionic A 30 30 30 30 Quat A 5 5 5 5 Additive E 50 50 50 50 Diesel Type DMA-1 DMA-2 DMA-3 DMA-4 Ratio Fuel: 1:1.4 1:1.4 1:1.4 1:1.4 Water 1 min. 99% 99% 99% 99% 2 min. 99% 99% 99% 99% 5 min. 99% 98% 98% 97% 10 min. 98% 96% 96% 92% 20 min. 96% 90% 94% 88% 30 min. 95% 84% 89% 81%