The present invention relates to an emulsion of fuel oil in water, and in particular, to an emulsion of marine fuel oil in water.

Within the marine industry, both distillate and residual fuel oils are employed.

Such fuels tend to be stored on board the vessel and pumped to a diesel engine or boiler, where combustion takes place.

At low temperatures, marine fuels become relatively viscous, making them difficult to pump on board and around the vessel. One method of reducing the viscosity is by adding a diluent to the residual fuel oil. Typically, a light hydrocarbon cutter stock is employed. This thins the fuel sufficiently for it to be mobilised at low temperature to meet the requirements of the use. Cutter stocks, however, are of variable composition in terms of aromatic versus paraffinic character, and also contain insoluble contaminants, which have to be removed before the fuel is burnt. Conventionally, this removal is carried out on board the vessel, for example, using a complex arrangement of settling tanks, filters and centrifuges. Furthermore, a marine vessel fuelled by a conventional marine fuel can only be re-fuelled with a different marine fuel, if steps are taken to segregate the two fuels in the storage tanks owing to differences in solvent character. If such steps are not taken, sludging, resulting from asphaltene precipitation, can occur.

The use of emulsions to improve the transportation of heavy hydrocarbons is described in US 5863301 and CA 2145030. The preparation and use of emulsions is also described in EP0156486A and EP0162591 A.

WO 99/54426 relates to aqueous macroemulsions based upon vacuum resid, visbroken vacuum resid, liquified coke, and fuel oils Nos. 4,5 and 6 which are said to- be a useful substitute for non-emulsified fuel oil. However, since fuel oils no. s 4,5 and

6 also contain hydrocarbon cutter stocks the potential still exists for incompatibility problems.

It has now been found that emulsions made using fuel oil in the substantial absence of hydrocarbon cutter stock may be mixed without the potential incompatibility problems. This is particularly advantageous for marine vessels, since it obviates the need for the complex arrangement of settling tanks, filters and/or centrifuges.

Thus, according to the present invention there is provided a process for fuelling a marine vessel having a diesel engine and/or a boiler, which process comprises: (a) providing said marine vessel with a storage tank operably connected to said diesel engine and/or boiler; (b) introducing into said storage tank a first high internal phase ratio (HIPR) emulsion (A) comprising 10-40 % by weight water and a fuel oil comprising at least one member selected from the group consisting of atmospheric residues, vacuum distillate residues, visbreaker residues and other heavy refinery streams in the substantial absence of hydrocarbon cutter stock; and (c) introducing into said storage tank optionally containing emulsion (A), a second high internal phase ratio (HIPR) emulsion (B) comprising 10-40 % by weight water and a fuel oil comprising at least one member selected from the group consisting of atmospheric residues, vacuum distillate residues, visbreaker residues and other heavy refinery streams in the substantial absence of hydrocarbon cutter stock; and in which the emulsions (A) and (B) are different from each other.

The emulsions of the present invention, have reduced viscosity.

The phase ratio of the emulsions may be independently 10 to 60% water, preferably 30 to 50% water, more preferably, 30 to 40% water.

The emulsions, which are typically, highly concentrated, preferably comprise fuel oil droplets having a mean diameter of 2 to 50 microns, preferably, 10 to 30 microns. At very low concentrations of water, typically less than 25 %, the fuel oil will be distributed as distorted droplets separated by thin films of water and may, as a consequence, be too viscous for the application.

Preferably, the emulsions are pumpable without the application of heat, even at ambient temperature (eg 5 °C). The viscosity of the emulsions at 25°C may be 100 to 1000 cSt, preferably, 100 to 500 cSt and most preferably, 100 to 300 cSt.

Preferably, the emulsions independently comprise 20 to 50 vol % water, more preferably, 30 to 40 vol %.

Preferably, the emulsions independently comprise 50 to 80 vol % fuel oil, more preferably, 60 to 70 vol %.

Suitable fuel oils include residual oils from refinery processing such as atmospheric residues, vacuum distillation residues, visbreaker residues and other heavy refinery streams. The initial viscosity of the fuel oil at 50°C maybe 1000 to 100,000cSt, preferably, 500 to 1, OOOcSt.

The emulsions may independently further comprise a surfactant. Suitable surfactants include non-ionic surfactants, anionic surfactants, cationic surfactants and mixtures thereof.

Suitable non-ionic surfactants include ethoxylated alkyl phenols, ethoxylated alcohols and ethoxylated sorbitan esters.

Suitable anionic surfactants include the salts of long (eg hydrocarbon) chain carboxylic and sulphonic acids, and long (eg hydrocarbon) chain sulphates.

Suitable cationic surfactants include the hydrochlorides of fatty diamines, imidazoles, ethoxylated amines, amido-amides and quaternary ammonium compounds.

When a surfactant is employed, it may be present in an amount of 0.1 to 5 wt % based on the total weight of the emulsion.

The emulsions of the present invention may also independently comprise conventional fuel additives. Suitable additives may include ignition improvers, combustion improvers, corrosion inhibiters, biocides, SOx reducing agents, NOx reducing agents, ash modifiers and soot release agents.

Advantageously water-soluble additives are compatible with the emulsions of the present invention, as they can dissolve in the continuous water phase surrounding the fuel oil droplets of the emulsion. These may optionally be added to the prepared emulsion, or to the aqueous phase prior to emulsification.

The emulsions of the present invention may be prepared using any suitable method. For example, the emulsions may be prepared by mixing the fuel oil directly with water. The mixing may be carried out under low shear conditions in the range of 10 to 1000, preferably, 50 to 250 s-l. The mixing may be carried out in the presence of a suitable surfactant. Alternatively, the fuel oil may be mixed directly with an aqueous solution of a suitable surfactant.

The emulsions of the present invention is particularly useful for diesel engines designed to operate with heavy fuel oils, more preferably, marine heavy fuel diesel engines. Accordingly, the present invention also provides a method of fuelling a heavy fuel diesel engine, which method comprises introducing an emulsion of the present invention into said engine.

Advantageously, the emulsions of the present invention are of sufficiently low viscosity, allowing them to be mobilised from the storage tanks to the fuel engine in a convenient manner. Thus, although the emulsions may be pre-heated to enhance their mobility to or around the vessel, pre-heating is not essential.

Because of their relatively low viscosity, the emulsions of the present invention need not contain hydrocarbon cutter stocks. In fact, hydrocarbon cutter stocks are substantially absent from the emulsions of the present invention. This is advantageous because cutter stocks are often aromatic, and have a detrimental effect on the combustion and ignition quality of the fuel. Moreover, cutter stocks tend to contain significant amounts of insoluble contaminants. Thus, in the substantial absence of such stocks, the levels of insoluble contaminants in the emulsions may be relatively low, for example, less than 20ppm, preferably, below lppm based on the total weight of the emulsion.

When the amount of insoluble contaminants in the emulsion is below 20ppm, it may not be necessary to rid the emulsion of such contaminants prior to use. This is particularly advantageous on marine vessels, because the equipment conventionally employed to remove solid contaminants from marine fuel tends to be complex and bulky. When an emulsion of the present invention is employed as a marine fuel, the emulsion may be pumped from the storage tank of the vessel to the fuel engine, without the need for processing the emulsion through the various settling, filtering and/or centrifugation steps. Indeed, in many circumstances, it is undesirable to subject the emulsion to, eg centrifugation, which may tend to cause separation of the emulsion into its components. In one embodiment of the invention, the emulsion is mobilised directly from the storage tank to the fuel engine.

Another advantage that the emulsion of the present invention has over a conventional fuel oil is that, whereas a mixture of two different fuel oils may be too unstable for storage, a mixture of two different emulsions of the present invention may not be. This increased miscibility is related to the presence of a common water phase

and surfactant type surrounding the fuel oil droplets of each emulsion. Because of this miscibility and enhanced compatibility, a marine vessel fuelled by an emulsion of the present invention may be re-fuelled with a different emulsion, without problems (incompatibility) arising from the second emulsion coming into contact with any residual first emulsion in the storage tank. In contrast, a marine vessel fuelled by a conventional marine fuel can only be re-fuelled with a different marine fuel, if steps are taken to segregate the two fuels in the storage tanks. If such steps are not taken, "sludging", resulting from asphaltene precipitation, can occur.

The invention will now be described by way of example only by reference to the following experiments.

Separate emulsions were prepared from two uncut vacuum residue feedstocks from BP's Coryton and Grangemouth refineries in the UK were prepared based on the "High Internal Phase Ratio (HIPR)"method described in EP-A-0156486 and EP-A- 0162591. These are called emulsions C and G, respectively.

Each residue was heated to 70°C. 5 parts by weight of each residue were added to one part by weight of a 2wt% solution of Igepal CA-630 (octylphenol 9-ethoxylate) in deionised water, originally at ambient temperature. The components were then mixed using a hand-held low speed (1200 rpm) domestic mixer for one minute to produce an HIPR emulsion, exhibiting a smooth texture. Owing to the relative densities of the components, the use of parts by volume and parts by weight can be considered to be interchangeable. After the initial mixing stage, further quantities of deionised water can be added as a dilution stage. In this way, 65% by weight residue emulsions C and G, stabilized by approximately 0.25 wt% surfactant were produced.

Droplet size distributions were determined for emulsions C and G using a Galai CIS-1 instrument, and these exhibited droplet diameters in the range 5 to 40 microns, with volume mean statistical diameters of approximately 20 microns. Modification of the emulsification conditions (for example, surfactant type, surfactant concentration, first stage mixing time and speed) allows emulsions with mean diameters between 5 and 30 microns to be produced.

Storage stability tests on each of emulsions C, G and 50: 50 binary combinations made therefrom were conducted, and their droplet size distributions monitored as a function of time at 40°C. This method is common practice when attempting to identify signs of instability in emulsions. No evidence of time-dependent instability could be found. This shows that these two emulsions are compatible and can be mixed with each other in these tests.