Emulsifier package containing branched surfactants for fuel emulsions

Abstract

The present invention relates to a method of powering a diesel engine with a fuel emulsion, the method comprising the step of preparing a fuel emulsion by emulsifying a fuel and water in the presence of an emulsifier package comprising a branched surfactant of formula (I) as defined below and optionally a propoxylated surfactant of formula (II) as defined below. It further relates to a fuel emulsion for powering a diesel engine.

Description

[0001] This invention relates to a method for powering a diesel engine using a fuel emulsion, the method comprising the step of preparing the fuel emulsion by emulsifying fuel and water in the presence of an emulsifier package comprising a branched surfactant of formula (I) as defined below and optionally a propoxylated surfactant of formula (II) as defined below. The invention also relates to fuel emulsions for powering diesel engines.

[0002] Water-based fuel emulsions are known to be used to power diesel engines.

[0003] The object of this invention is to find an emulsifier package for fuel emulsions that is inexpensive, easy to prepare, storage stable, based on commercially available emulsifiers, and solely based on carbon, hydrogen, nitrogen, and oxygen, and allows for rapid and easy emulsification even under low shear stress. The emulsifier package should produce a low-foaming fuel emulsion with a low cloud point, providing corrosion protection, exhibiting low foaming properties, improving emulsion filterability, and reducing sedimentation when fuel is mixed with water. The emulsifier package should stabilize the fuel emulsion at high water concentrations, varying temperatures and pressures, and with various types of water.

[0004] This objective is achieved by a method for powering a diesel engine using a fuel emulsion, the method comprising the steps of: preparing a fuel emulsion by emulsifying fuel and water in the presence of an emulsifier package, the emulsifier package comprising a branched surfactant of formula (I).

[0005] R a -O-(AO a ) m -R a' (I)

[0006] in

[0007] R a For branch C 6-32 alkyl,

[0008] AO a It is an ethylene oxide group, a propylene oxide group, a butyl oxide group, a pentylene oxide group, a styrene oxide group, or a mixture thereof.

[0009] m is a value from 1 to 100, and

[0010] R a' It is hydrogen or C 1-4 alkyl;

[0011] The emulsifier package also contains a propoxylated surfactant of formula (II).

[0012] R b -O-(AO b )nR b'(II)

[0013] in

[0014] R b C is a straight chain or a branched chain 6-32 alkyl,

[0015] AO b It is a mixture of ethylene oxide and propylene oxide groups.

[0016] n is a value from 1 to 100, and

[0017] R b' It is hydrogen or C 1-4 alkyl.

[0018] This objective is also achieved through fuel emulsions used to power diesel engines.

[0019] Fuels typically comprise hydrocarbons, such as alkanes, cycloalkanes, and aromatics. Fuels can be obtained from petroleum distillation as fractions or residues. Fuels are typically liquid fuels. Examples of fuels are gasoline, diesel, or biodiesel, or mixtures thereof, with gasoline or diesel being preferred. In particular, the fuel is diesel. Gasoline may contain primarily C4 to C12 hydrocarbons, including alkanes, alkenes, and cycloalkanes. Diesel may contain saturated hydrocarbons and aromatic hydrocarbons. Biodiesel typically comprises lower alkyl fatty acid esters, for example, prepared by transesterification of triglycerides with lower alcohols such as methanol or ethanol.

[0020] The viscosity of fuel can vary over a wide range, for example, from 1 to 10,000 mm at 40°C. 2 / s (ISO 3104) or 1 to 1000 mm at 50°C 2 / s(ISO 3104).

[0021] The fuel can be marine fuel, such as MGO (marine gas oil), MDO (marine diesel), IFO (intermediate fuel oil), MFO (marine fuel oil), or HFO (heavy fuel oil). Other examples of marine fuels include IFO 380 (intermediate fuel oil with a maximum viscosity of 380 centiliters (<3.5% sulfur)), IFO 180 (intermediate fuel oil with a maximum viscosity of 180 centiliters (<3.5% sulfur)), LS 380 (low-sulfur (<1.0%) intermediate fuel oil with a maximum viscosity of 380 centiliters), LS180 (low-sulfur (<1.0%) intermediate fuel oil with a maximum viscosity of 180 centiliters), LSMGO (low-sulfur (<0.1%) marine light diesel oil, according to the EU Sulphur Directive 2005 / 33 / EC, commonly used in European ports and anchorages), or ULSMGO (an ultra-low sulfur marine light diesel oil, also known as ultra-low sulfur diesel oil (maximum 0.0015% sulfur). Other suitable marine fuels are those according to DIN ISO. The following categories of 8217 are applicable: ISO-F-DMX, DMA, DFA, DMZ, DFZ or DFB or ISO-F RMA, RMB, RMD, RME, RMG or RMK. Other suitable marine fuels are distillate or residual marine diesel fuels.

[0022] The viscosity of fuels (such as marine fuels) can vary over a wide range, for example, from 1 to 10,000 mm at 40°C. 2 / s (ISO 3104) or 1 to 1000 mm at 50°C 2 / s(ISO 3104).

[0023] Fuel emulsions may contain at least 10, 20, 25, 30, 35, 40, 50, or 60% by weight of fuel. Fuel emulsions may contain up to 30, 40, 50, or 60% by weight of fuel. Fuel emulsions may contain 10 to 70%, 20 to 60%, or 30 to 50% by weight of fuel.

[0024] For ecological reasons, low-sulfur fuels are gaining increasing attention. Suitable low-sulfur fuels may contain less than 1, 0.5, 0.2, or 0.1% sulfur by weight. An example is fuel with a sulfur content of less than 0.1% by weight. ULSFO. Diesel fuels primarily used in automobiles may have sulfur contents of up to 2000 ppm, 500 ppm, 350 ppm, 50 ppm, or 10 ppm.

[0025] Any type of water can be used, such as tap water, well water, seawater, ocean water, rainwater, distilled water, wastewater, or deionized water. Water with a low chlorine concentration, such as tap water, distilled water, or rainwater, is preferred to avoid corrosion.

[0026] Water may have low hardness, for example, less than 8.4°dH as expressed in °dH (German hardness), or calcium carbonate with a concentration of less than 1.5 mmol / L.

[0027] Water can have low salinity, for example, up to 1000, 500, 100, 10 or 1 ppmw, such as in NaCl-based concentration meters.

[0028] Fuel emulsions may contain at least 10, 20, 30, 40, 50, 55, 60, 65, or 70% by weight of water. Fuel emulsions may contain up to 50, 60, 70, 75, 80, 85, or 90% by weight of water. Fuel emulsions may contain 30 to 90%, 40 to 80%, or 50 to 80% by weight of water.

[0029] The weight ratio of water to fuel can be 1:0.1 to 1:10, or 1:0.2 to 1:5, or 1:0.7 to 1:3, or preferably 1:0.1 to 1:1.

[0030] The fuel emulsion can be an oil-in-water emulsion or an oil-in-water emulsion, with an oil-in-water emulsion being preferred.

[0031] The fuel emulsion can be a crude emulsion, a fine emulsion, or a microemulsion, with a crude emulsion being preferred.

[0032] The diameter of the dispersed phase (e.g., fuel) in the fuel emulsion can be from 0.01 to 100 μm, preferably from 1 to 100 μm.

[0033] Fuel emulsions can exist at temperatures ranging from 0 to 100°C, preferably from 15 to 90°C.

[0034] The fuel emulsion can exist at a pressure of 1 to 100 bar, preferably 1 to 10 bar.

[0035] Emulsifiers include branched surfactants of formula (I).

[0036] R a -O-(AO a ) m -R a' (I)

[0037] in

[0038] R a For branch C 6-32 alkyl,

[0039] AO a It is an ethylene oxide group, a propylene oxide group, a butyl oxide group, a pentylene oxide group, a styrene oxide group, or a mixture thereof.

[0040] m is a value from 1 to 100, and

[0041] R a' It is hydrogen or C 1-4 alkyl.

[0042] R a Preferred branched C 8-22 Alkyl group. In another preferred form, R a For branch C 8-14 Alkyl group. In another preferred form, R a For branch C 10-14 Alkyl group. Suitable R a Examples include isohexyl, isooctyl (e.g., 2-ethylhexyl), isononyl, isodecyl (e.g., trimethylheptyl or 2-propylheptyl), and isostearyl. R a In particular, branched tridecyl groups, such as isotridecyl. R a It can be a technical mixture of various chain lengths and isomers. R a In another special form, it is branch C. 10 For example, C 10 Carbonyl synthesis of alcohols (oxoalcohol). R a In another special form, it is branch C. 10 Or branch C 13 .

[0043] AO a It can be an ethylene oxide group, a propylene oxide group, a butyl oxide group, or a mixture thereof. AO a Preferably, it contains an ethylene oxide group. AO a The alkoxy units (e.g., EO and PO units) can be in block or statistical sequence, preferably in diblock sequence. AO a The molar ratio of the ethylene oxide group to other alkyl oxide groups (e.g., propylene oxide group) present in the mixture can be 50:1 to 1:2, or 10:1 to 1:1, or 5:1 to 1:1.

[0044] m can be a value from 1 to 80, 2 to 80, or 3 to 60. In another form, m can be a value from 1 to 30, 1 to 25, 1 to 20, 1 to 15, or 1 to 10. In another form, m can be a value from 2 to 25, 2 to 15, 3 to 15, or 3 to 10. In another form, m can be a value from 15 to 100, 20 to 70, or 25 to 60. In another form, m is at least 1, 2, 3, 5, 10, 15, 20, 25, or 30. In another form, m is at most 80, 70, 60, 50, 40, 30, 20, 15, 10, or 5.

[0045] R a' It can be hydrogen or methyl, with hydrogen being preferred.

[0046] In a preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It can be hydrogen or methyl.

[0047] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 15, and R a' It is hydrogen.

[0048] In a preferred form, R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It can be hydrogen or methyl.

[0049] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 80, and R a' It can be hydrogen or methyl.

[0050] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 70, and R a' It is hydrogen.

[0051] In another preferred form, R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 20 to 60, and R a' It can be hydrogen or methyl.

[0052] In a preferred form, the emulsifier package further comprises a propoxylated surfactant of formula (II).

[0053] R b -O-(AO b ) n -R b' (II)

[0054] in

[0055] R b For straight or branched C 6-32 alkyl,

[0056] AO b It is a mixture of ethylene oxide and propylene oxide groups.

[0057] n is a value from 1 to 100, and

[0058] R b' It is hydrogen or C 1-4 alkyl.

[0059] In another preferred form, the emulsifier comprises a branched surfactant of formula (I) and a propoxylated surfactant of formula (II).

[0060] R b Preferably, straight-chain C 8-22 Alkyl group. In another preferred form, R b For straight chain C 10-20 Alkyl group. In another preferred form, R b For straight chain C 12-18 Alkyl group. In another preferred form, R b For straight chain C 14-18 Alkyl group. In another preferred form, R b For straight chain C 16-18 Alkyl group. In another preferred form, R b For straight or branched C 8-22 Alkyl group. In another preferred form, R b For straight or branched C 10-20 Alkyl group. In another preferred form, R b For straight or branched C 12-18 Alkyl group. In another preferred form, R b For straight or branched C 14-18 Alkyl group. In another preferred form, R b For straight or branched C 16-18 Alkyl group. R b It can be a technical mixture of various chain lengths and isomers.

[0061] AO b It is a mixture of ethylene oxide and propylene oxide groups, preferably without other alkylene oxide groups. AO b The alkoxy units (e.g., EO and PO units) can be in block or statistical sequence, preferably in diblock sequence. AO b The molar ratio of the ethylene oxide group to other alkyl oxide groups (e.g., propylene oxide group) present in the mixture can be 50:1 to 1:2, or 10:1 to 1:1, or 5:1 to 1:1.

[0062] n can be a value from 1 to 80, 2 to 80, or 3 to 60. In another form, n can be a value from 1 to 30, 1 to 25, 1 to 20, 1 to 15, or 1 to 10. In another form, n can be a value from 2 to 25, 2 to 15, 3 to 15, or 3 to 10. In another form, n can be a value from 15 to 100, 20 to 70, or 25 to 60. In another form, n is at least 1, 2, 3, 5, 10, 15, 20, 25, or 30. In another form, n can be up to 80, 70, 60, 50, 40, 30, 20, 15, 10, or 5.

[0063] R b' It can be hydrogen or methyl, preferably hydrogen. Preferably, R a' and R b' It is hydrogen.

[0064] In a preferred form, R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 25, and R b' It can be hydrogen or methyl.

[0065] In another preferred form, R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 15, and R b' It is hydrogen.

[0066] In another preferred form, R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 80, and R b' It can be hydrogen or methyl.

[0067] In another preferred form, R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 2 to 60, and R b' It is hydrogen.

[0068] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It is hydrogen or methyl, and

[0069] R bFor straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 25, and R b' It can be hydrogen or methyl.

[0070] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 15, and R a' It is hydrogen, and

[0071] R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 25, and R b' It can be hydrogen or methyl.

[0072] In another preferred form, R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It is hydrogen or methyl, and

[0073] R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 15, and R b' It is hydrogen.

[0074] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It is hydrogen or methyl, and

[0075] R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 25, and R b' It is hydrogen or methyl, and

[0076] The emulsifier package contains branched surfactants and propoxylated surfactants in weight ratios of 10:1 to 1:10, 4:1 to 1:4, or 2:1 to 1:2.

[0077] In another preferred form, R a For branch C 8-14Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 15, and R a' It is hydrogen, and

[0078] R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 25, and R b' It is hydrogen or methyl, and

[0079] The emulsifier package contains branched surfactants and propoxylated surfactants in weight ratios of 10:1 to 1:10, 4:1 to 1:4, or 2:1 to 1:2.

[0080] In another preferred form, R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It is hydrogen or methyl, and

[0081] R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 15, and R b' It is hydrogen, and

[0082] The emulsifier package contains branched surfactants and propoxylated surfactants in weight ratios of 10:1 to 1:10, 4:1 to 1:4, or 2:1 to 1:2.

[0083] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 1 to 80, and R a' It is hydrogen or methyl, and

[0084] R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 80, and R b' It can be hydrogen or methyl.

[0085] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 80, and Ra' is hydrogen, and

[0086] R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 80, and R b' It can be hydrogen or methyl.

[0087] In another preferred form, R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 15 to 80, and R a' It is hydrogen or methyl, and

[0088] R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 30, and R b' It is hydrogen.

[0089] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 1 to 80, and R a' It is hydrogen or methyl, and

[0090] R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 80, and R b' It is hydrogen or methyl, and

[0091] The emulsifier package contains branched surfactants and propoxylated surfactants in weight ratios of 10:1 to 1:10, 4:1 to 1:4, or 2:1 to 1:2.

[0092] In another preferred form, R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 80, and Ra' is hydrogen, and

[0093] R b For straight chain C 14-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 80, and R b' It is hydrogen or methyl, and

[0094] The emulsifier package contains branched surfactants and propoxylated surfactants in weight ratios of 10:1 to 1:10, 4:1 to 1:4, or 2:1 to 1:2.

[0095] In another preferred form, R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 20 to 70, and R a' It is hydrogen or methyl, and

[0096] R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 20, and R b' It is hydrogen, and

[0097] The emulsifier package contains branched surfactants and propoxylated surfactants in weight ratios of 10:1 to 1:10, 4:1 to 1:4, or 2:1 to 1:2.

[0098] The emulsifier package may contain branched surfactants and propoxylated surfactants in weight ratios of 20:1 to 1:20, or 10:1 to 1:10, 4:1 to 1:4, 3:1 to 1:3 or 2:1 to 1:2.

[0099] In another form, the emulsifier package may contain branched surfactants and propoxylated surfactants in a weight ratio of 20:1 to 1:3, or 10:1 to 1:2, 4:1 to 1:1, or 4:1 to 2:1.

[0100] In another form, the emulsifier package may contain propoxylated surfactants and branched surfactants in a weight ratio of 20:1 to 1:3, or 10:1 to 1:2, 4:1 to 1:1, or 4:1 to 2:1.

[0101] The emulsifier package may contain a certain weight percentage of branched surfactants or propoxylated surfactants, which can be calculated based on the total amount of surfactants (e.g., branched surfactants and propoxylated surfactants) present in the emulsifier package.

[0102] The emulsifier package may contain at least 0.1, 0.5, 1, 2, 5, 10, 20, 30 or 40% by weight of branched surfactant.

[0103] The emulsifier package may contain up to 100, 90, 80, 70, 60, 50, 40, 30, 20, 10 or 5% by weight of branched surfactants.

[0104] The emulsifier package may contain 0.1 to 20% by weight, or 0.5 to 10% by weight, or 1 to 5% by weight of branched surfactant. In another form, the emulsifier package may contain 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of branched surfactant.

[0105] The emulsifier package may contain 0.1 to 20% by weight, or 0.5 to 10% by weight, or 1 to 5% by weight of branched surfactants, wherein R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It can be hydrogen or methyl.

[0106] The emulsifier package may contain 0.1 to 20% by weight, or 0.5 to 10% by weight, or 1 to 5% by weight of branched surfactants, wherein R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 2 to 25, R a' It can be hydrogen or methyl.

[0107] In another form, the emulsifier package may contain 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of a branched surfactant, wherein R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It can be hydrogen or methyl.

[0108] In another form, the emulsifier package may contain 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of a branched surfactant, wherein R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 2 to 25, and R a' It can be hydrogen or methyl.

[0109] The emulsifier package may contain 0.1 to 20% by weight, or 0.5 to 10% by weight, or 1 to 5% by weight of branched surfactants, wherein R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 2 to 80, and R a' It can be hydrogen or methyl.

[0110] The emulsifier package may contain 0.1 to 20% by weight, or 0.5 to 10% by weight, or 1 to 5% by weight of branched surfactants, wherein R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 2 to 60, and R a' It can be hydrogen or methyl.

[0111] In another form, the emulsifier package may contain 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of a branched surfactant, wherein R a For branch C 8-14 Alkyl, AO a It is an ethylene oxide group, m is a value from 15 to 80, and R a' It can be hydrogen or methyl.

[0112] In another form, the emulsifier package may contain 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of a branched surfactant, wherein R a For branch C 10-14 Alkyl groups (e.g., isotriadecyl), AO a It is an ethylene oxide group, m is a value from 20 to 60, and R a' It can be hydrogen or methyl.

[0113] The emulsifier package may contain at least 0.1, 0.5, 2, 5, 10, 20, 30 or 40% by weight of propoxylated surfactant.

[0114] The emulsifier package may contain up to 90, 80, 70, 60, 50, 40, 30, 20, 10 or 5% by weight of propoxylated surfactant.

[0115] The emulsifier package may contain 0.1 to 20% by weight, or 0.5 to 10% by weight, or 1 to 5% by weight of a propoxylated surfactant. In another form, the emulsifier package may contain 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of a propoxylated surfactant.

[0116] The emulsifier package may contain at least 0.1, 0.5, or 2% by weight of a propoxylated surfactant, wherein R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, n is a value from 1 to 15, and Ra' is hydrogen or methyl.

[0117] The emulsifier package may contain up to 40, 30, 20, 10, or 5% by weight of a propoxylated surfactant, wherein Rb For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 15, and R a' It is hydrogen.

[0118] In another form, the emulsifier package may contain 1 to 99 wt%, 5 to 90 wt%, 10 to 80 wt%, or 20 to 70 wt% of a propoxylated surfactant, wherein R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 15, and R a' It can be hydrogen or methyl.

[0119] In another form, the emulsifier package may contain 1 to 99 wt%, 5 to 90 wt%, 10 to 80 wt%, or 20 to 70 wt% of a propoxylated surfactant, wherein R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 15, and R a' It is hydrogen.

[0120] The emulsifier package may contain at least 0.1, 0.5, or 2% by weight of a propoxylated surfactant, wherein R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 80, and R a' It can be hydrogen or methyl.

[0121] The emulsifier package may contain up to 40, 30, 20, 10, or 5% by weight of a propoxylated surfactant, wherein R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 1 to 80, and R a' It is hydrogen.

[0122] In another form, the emulsifier package may contain 1 to 99 wt%, 5 to 90 wt%, 10 to 80 wt%, or 20 to 70 wt% of a propoxylated surfactant, wherein R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 2 to 70, and R a' It can be hydrogen or methyl.

[0123] In another form, the emulsifier package may contain 1 to 99 wt%, 5 to 90 wt%, 10 to 80 wt%, or 20 to 70 wt% of a propoxylated surfactant, wherein R b For straight chain C 16-18 Alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups, where n is a value from 2 to 60, and R a' It is hydrogen.

[0124] The emulsifier package may contain at least 0.5, 2, or 5% by weight of the sum of branched surfactants and propoxylated surfactants.

[0125] The emulsifier package may contain up to 100, 90, 80, 70, 60, 50, 40, 30, 20, 15 or 10% by weight of branched surfactants and propoxylated surfactants.

[0126] The emulsifier package may contain 1 to 90 wt%, 1 to 60 wt%, 1 to 35 wt%, or 2 to 20 wt%, or 5 to 12 wt% of branched surfactants and propoxylated surfactants.

[0127] The emulsifier package may contain other nonionic surfactants, such as alkoxylates, alkyl glucosides and alkyl polyglucosides, or fatty acids with glycerol or sorbitol (e.g., monoesters, diesters and triesters) (e.g., glyceryl monostearate, sorbitol monooleate, sorbitol tristearate).

[0128] A suitable alkoxylated compound, unlike the branched surfactants and propoxylated surfactants, is...

[0129] Alkoxylated alkylphenols, such as ethoxylated nonylphenyl, ethoxylated dodecylphenyl, ethoxylated isotridecylphenol and their esters, such as acetates.

[0130] -A block copolymer of ethylene oxide and propylene oxide,

[0131] -Ethoxylated alkyl glucosides and alkyl polyglucosides

[0132] -Ethoxylated fatty amines,

[0133] -Ethoxylated fatty acids,

[0134] - Ethoxylated fatty acids with glycerol or dehydrated sorbitol, such as ethoxylated glyceryl monostearate

[0135] - Ethoxylated compounds of vegetable oils or animal fats, such as corn oil ethoxylated compounds, castor oil ethoxylated compounds, and butter ethoxylated compounds.

[0136] - Ethoxylated fatty amines or fatty amides.

[0137] Emulsifier packets typically contain up to 50, 40, 30, 20, 10, 5, or 1% by weight of other nonionic surfactants. Emulsifier packets typically contain at least 1, 5, 10, 20, 30, or 40% by weight of other nonionic surfactants.

[0138] In another form, the emulsifier package is free of ethoxylated fatty acids. In another form, the emulsifier package is free of fatty acid amides. In another form, the emulsifier package is free of ethoxylated castor oil. In another form, the emulsifier package is free of fatty acid amides, ethoxylated fatty acids, and ethoxylated castor oil.

[0139] Emulsifier packets typically contain up to 10, 8, 5, 4, 3, 2, or 1% by weight of all ionic surfactants, such as anionic or cationic surfactants. In another form, the emulsifier packet contains no ionic surfactants. The total weight of all ionic surfactants in the emulsifier packet is typically less than the total weight of branched surfactants and propoxylated surfactants. The total weight of branched surfactants and propoxylated surfactants is typically in excess of 1, 1.5, or 2 times the total weight of all ionic surfactants.

[0140] Emulsifier packets are typically aqueous emulsifier packets, which generally contain water. Emulsifier packets may contain at least 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90% by weight of water, typically based on the total weight of the emulsifier packet.

[0141] In another form, the emulsifier packet is essentially water-free and contains, for example, less than 10, 8, 6, 4, 2, 1 or 0.2% by weight of water.

[0142] The emulsifier package is typically liquid, solid, or gel at 20°C, preferably liquid.

[0143] The emulsifier package may contain an organic solvent, which is preferably miscible with water (e.g., at 20°C in an amount of at least 10% by weight). Suitable organic solvents are ethers (e.g., ethylene glycol ethers), ketones, or alcohols, with ethers (especially ethylene glycol ethers) being preferred.

[0144] Preferred organic solvents are glycol ethers, such as methyl diethylene glycol, methyl triethylene glycol, methyl tetraethylene glycol, butyl triethylene glycol, butyl ethylene glycol, butyl diethylene glycol, and hexyl diethylene glycol.

[0145] The emulsifier package may contain up to 90, 80, 70, 60, 50, 40, 30, 20, 15 or 10% by weight of an organic solvent, such as glycol ether.

[0146] Emulsifier packets may contain at least 1, 5, 10, 20, 30, 40, 50, 60, 70, 80 or 90% by weight of organic solvents, typically based on the total weight of the emulsifier packet.

[0147] The emulsifier package may contain 0.5 to 30% by weight or 1 to 15% by weight of an organic solvent, such as glycol ether.

[0148] In another form, the emulsifier package may contain water, an organic solvent, or a mixture of water and an organic solvent. In yet another form, the emulsifier package may contain at least 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90% by weight of water, an organic solvent, or a mixture of water and an organic solvent.

[0149] Fuel or emulsifier packages may contain other additives, such as carrier oils, cold flow improvers, lubrication improvers, corrosion inhibitors, demisting agents, defoamers, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal passivators, and / or dyes. Fuel or emulsifier packages may contain up to 50, 30, 10, 5, or 1% by weight of other additives. In another form, the emulsifier package may be free of other additives.

[0150] The fuel emulsion contains up to 5, 3, 2, 1, 0.8, 0.6, 0.4 or 0.3% by weight of emulsifier packets, based on diesel fuel.

[0151] The fuel emulsion contains an amount of emulsifier packet of 0.001 to 1.0 wt%, 0.01 to 0.5 wt%, 0.01 to 0.4 wt%, or 0.05 to 0.3 wt%, based on diesel fuel.

[0152] The fuel emulsion contains up to 2, 1, 0.5, 0.2, 0.1, or 0.08% by weight of an emulsifier packet, based on the fuel emulsion.

[0153] The fuel emulsion contains an amount of emulsifier packet of 0.001 to 0.5, 0.005 to 0.4, 0.005 to 0.15, or 0.02 to 0.08% by weight, based on the fuel emulsion.

[0154] Powering diesel engines with fuel emulsions is known. Suitable diesel engines are, for example, large turbocharged two-stroke diesel engines (e.g., described in WO 2010 / 145652 or WO 2010 / 105620) or two-stroke diesel engines (e.g., described in DE 19747247 or DE19747240). Diesel engines can be used in stationary land engines (generators), railway locomotives, automobiles, trucks, inland waterway vessels, or ocean-going vessels. Large two-stroke diesel engines can be used as prime movers in power plants or ocean-going vessels.

[0155] Emulsification of fuel and water can be achieved by applying mechanical shear energy, such as in stirred vessels, grinding aggregates (e.g., ball mills or stirred ball mills), shaking, rotor-stator mixing, turbulence in pipes conveyed by pumps or gravity, static mixers, and countercurrent mixers. Fuel and water emulsification can also be achieved by circulating the fuel and water through a loop, for example, by pumping them from the bottom to the top of the tank and then pouring them onto the surface of the tank contents. Pre-stirring may be performed before fuel and water circulation, but is not required.

[0156] The emulsifier package may contain different components. To emulsify the fuel and water, some components may be added to the fuel and some components may be added to the water prior to emulsification. Therefore, the different components of the emulsifier package can be combined during the preparation of the fuel emulsion. Preferably, all components of the emulsifier package are premixed prior to emulsification. Preferably, all components of the emulsifier package are added simultaneously to the fuel or water prior to emulsification. The invention also relates to fuels that power diesel engines using fuel emulsions, wherein the water contains the emulsifier package.

[0157] Emulsification can be carried out at temperatures ranging from 0 to 100°C, or from 10 to 90°C, or from 20 to 50°C.

[0158] Emulsification can be carried out at pressures of 0.5 to 20 bar or 1 to 10 bar.

[0159] The time between the preparation of the fuel emulsion and its combustion in the diesel engine can be less than 24 hours, 6 hours, 1 hour, 45 minutes, 30 minutes, 15 minutes, 10 minutes, 5 minutes or 1 minute.

[0160] Various devices for emulsifying fuel and water in a diesel engine are known, for example, by WO 2016 / 064722, WO 90 / 12959, US 4,388,893 or WO 00 / 53916. Example

[0161] An emulsifier package was prepared by mixing the emulsifiers shown in Table 1 with distilled water, and an aqueous solution of the emulsifiers was obtained.

[0162] Samples for testing emulsion stability were prepared by mixing the additive package with diesel fuel. For all experiments in Table 1, the amount of emulsifier used was 0.05%, based on the total volume of the emulsion (including fuel and water).

[0163] The diesel fuel used is DMA marine diesel fuel according to DIN ISO 8217, which is a clarified liquid diesel fuel without additives and has a density of about 0.83 to 0.85.

[0164] The emulsion was prepared in 10 seconds at 7500 rpm at room temperature using a Silverson L5 high-shear laboratory emulsifier based on the rotor-stator principle.

[0165] The emulsified sample is then placed in a graduated cylinder and allowed to stand for up to 30 minutes. The amount of separated aqueous phase is determined. For example, if 8 ml of separated aqueous phase is detected in an 80 ml total volume sample, this corresponds to 90% emulsion stability. If no separated aqueous phase is detected, this corresponds to 100% emulsion stability. These values ​​are given in Table 1.

[0166] Use the following surfactants:

[0167] Branched surfactants of formula (I):

[0168] Nonionic A: Pure ethoxylated C 10 Carbonyl synthesis alcohol, hydroxyl value approximately 150mg

[0169] KOH / g.

[0170] Nonionic B: Isotridecyl alcohol ethoxylate, with an active ingredient content of 70% in water, and a pour point of approximately 0°C according to ISO 3016.

[0171] Nonionic C: Isotridecyl ethoxylate, with an active ingredient content of 70% in water and an HLB content of approximately 18%.

[0172] Propoxylated surfactants of formula (II):

[0173] Nonionic D: Alkoxylated C 16 / 18 Fatty alcohol, pour point approximately 15°C (ASTM D7346).

[0174] Table 1: Additive Packaging (all amounts are in wt%) and Emulsion Stability (bottom half)

[0175] Example 1 2 3 4 5 water 87.5 87.5 Nonionic A 100 Nonionic B 100 Nonionic C 12.5 100 10 Nonionic D 2.5 fuel:water ratio 1:1.4 1:1.4 1:1.4 1:1.4 1:1.4 1 minute 99％ 99％ 99％ 99％ 99％ 2 minutes 97％ 99％ 99％ 99％ 99％ 5 minutes 82％ 99％ 99％ 99％ 96％ 10 minutes 80％ 99％ 99％ 99％ 91％ 20 minutes 70％ 98％ 99％ 99％ 83％ 30 minutes 64％ 97％ 98％ 99％ 73％

Claims

1. A method for powering a diesel engine with a fuel emulsion, comprising the step of preparing the fuel emulsion by emulsifying fuel and water in the presence of an emulsifier package, said emulsifier package comprising a branched surfactant of formula (I). R a -O-(AO a ) m -R a' (I) in R a For branch C 8-22 alkyl, AO a It has an ethylene oxide group. m is a value between 3 and 60, and R a' It is hydrogen or C 1-4 alkyl; The emulsifier package also contains a propoxylated surfactant of formula (II). R b -O-(AO b ) n -R b' (II) in R b For straight chain C 8-22 alkyl, AO b It is a mixture of ethylene oxide and propylene oxide groups. n is a value between 3 and 60, and R b' It is hydrogen or C 1-4 alkyl.

2. The method according to claim 1, wherein R a For branch C 8-14 alkyl.

3. The method according to any one of claims 1 to 2, wherein R a It is a branched tridecyl group.

4. The method according to any one of claims 1 to 2, wherein R b For straight chain C 10-22 alkyl.

5. The method according to any one of claims 1 to 2, wherein R b For straight chain C 16-18 alkyl.

6. The method according to any one of claims 1 to 2, wherein R a' and R b' It is hydrogen.

7. The method according to any one of claims 1 to 2, wherein the emulsifier comprises a branched surfactant and a propoxylated surfactant in a weight ratio of 10:1 to 1:

10.

8. The method according to any one of claims 1 to 2, wherein the emulsifier comprises a branched surfactant and a propoxylated surfactant in a weight ratio of 4:1 to 1:

4.

9. The method according to any one of claims 1 to 2, wherein the emulsifier comprises 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of a branched surfactant.

10. The method according to any one of claims 1 to 2, wherein the emulsifier comprises 1 to 99% by weight, 5 to 90% by weight, 10 to 80% by weight, or 20 to 70% by weight of a propoxylated surfactant.

11. The method according to any one of claims 1 to 2, wherein the emulsifier package contains up to 10% by weight of an ionic surfactant.

12. The method according to any one of claims 1 to 2, wherein the emulsifier package contains up to 1% by weight of an ionic surfactant.

13. The method according to any one of claims 1 to 2, wherein the emulsifier package comprises at least 10, 30, or 50% by weight of water, an organic solvent, or a mixture of water and an organic solvent.

14. The method according to any one of claims 1 to 2, wherein the fuel emulsion comprises 0.05 to 0.4% by weight of an emulsifier packet, based on diesel fuel.

15. The method according to any one of claims 1 to 2, wherein the fuel emulsion comprises 40 to 80% by weight of water.

16. The method according to any one of claims 1 to 2, wherein the fuel is marine fuel.

17. A fuel emulsion used to power a diesel engine by the method described in any one of claims 1 to 16.