EP0961822A1

EP0961822A1 - Fuel-water emulsions

Info

Publication number: EP0961822A1
Application number: EP98907932A
Authority: EP
Inventors: Guido Dessauer; Ute Horn; Helmut Berenbold; Gerhard Crass
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 1997-01-16
Filing date: 1998-01-09
Publication date: 1999-12-08
Also published as: AR010103A1; US6280486B1; AU6613598A; JP2001508117A; WO1998031773A1

Abstract

The invention concerns fuel-water emulsions substantially comprising between 60 and 80 wt % of a fuel, between 0.5 and 5 wt % of one or a plurality of water-soluble and petrol-insoluble emulsifiers of formulae A) R-O-(CH2CH2O)x-H, in which R means alkyl or alkenyl, each with between 8 and 18 carbon atoms, or C9-C14 alkyl phenyl, and x is a number from 8 to 30, or B) HO-(C2H4O)x-(C3H6O)y-(C2H4O)z-H, in which the portion of ethylene oxide units is between 40 and 80 wt % of the molecular mass, or C) (i), in which x is a number from 8 to 30, and between 1 and 10 wt % of a water-soluble and petrol-insoluble polyalkylene glycol as stabilizer, as well as water and optionally further additives up to 100 wt %. The emulsions according to the invention can be used to operate internal combustion engines.

Description

Fuel-water emulsions

It is already known to use large diesel engines, e.g. in shipbuilding or in high-performance internal combustion engines, e.g. for racing cars to specifically inject water into the combustion chamber. This achieves better efficiency and increased knock resistance. The main advantage of such a water injection is that the emission of nitrogen oxides is reduced in this way.

The use of water-containing fuels is disclosed, for example, in GB-A-0669037, GB-A-0205582, EP-A-0 095 823 and WO-88/04311. The cited documents teach the use of mixtures of a hydrocarbon, an alcohol and water as a fuel for internal combustion engines.

EP-A-0 431 357 discloses a method for operating

Internal combustion engines with water-containing fuels, wherein a catalyst is used in the combustion chamber.

EP-A-0 372 353 discloses the production of a fuel-water mixture by means of an electromagnetic device.

The task now is to avoid a separate injection of water and the use of catalysts and to develop alcohol-free emulsions which simultaneously contain the fuel and the water in a uniform form. This problem was solved by using a special emulsifier and a stabilizer.

The invention relates to fuel-water emulsions consisting essentially of 60 to 80% by weight of a fuel, 0.5 to 5% by weight of one or more water-soluble and gasoline-insoluble emulsifiers of the formulas (A) R - 0 - (CH ₂ CH ₂ 0) _x - H

wherein R is alkyl or alkenyl each having 8 to 18 carbon atoms or C ₉ -C ₁₄ alkylphenyl and x is a number from 8 to 30, and / or

(B) ethylene oxide / propylene oxide block polymers in which the proportion of ethylene oxide units is between 40 and 80% by weight of the molecular weight, and / or

wherein x is a number between 10 and 30, and 1 to 10 wt .-% of a water-soluble and gasoline-insoluble polyalkylene glycol as a stabilizer, and water and optionally other additives ad 100 wt .-%.

Preferably 0.5 to 1 wt .-%, in particular 0.65 to 0.75 wt .-% emulsifier is used. In the compounds mentioned under A), R is preferably alkyl or alkenyl having 12 to 16 carbon atoms or C ₉ alkylphenyl. x is preferably a number between 9 and 13. In the compounds mentioned under C), x is preferably a number between 9 and 13. The emulsifier is generally a commercially available oxethylation product: (A) are oxyethylated fatty alcohols, preferably oxyethylated alkylphenols (®Arkopal, manufacturer Hoechst AG) and (B) are EO / PO copolymers of the general formula

HO - (C ₂ H ₄ 0) _a - (C ₃ H ₆ 0) _b - (C ₂ H ₄ 0) _c - H. In these block polymers, indices a, b and c are such that the weight fraction of EO is 40 to 80%. The numerical values of a, b and c therefore depend on the molecular weight of the block polymers, which is preferably between 2000 and 10,000 units. These copolymers of ethylene oxide (EO) and propylene oxide (PO) are commercially available under the name ®Genapol PF (Hoechst AG). The butylphenol oxyethylates described under C) are sold under the name ®Sapogenat T (Hoechst AG). C ₄ H ₉ here stands for an n-, iso- or tert-butyl radical. The preferred emulsifiers are the ethoxylated alkylphenols, of which the ethoxylated nonylphenols are preferred.

The polyalkylene glycol used as stabilizer is preferably added in amounts of 1.5 to 5, in particular 2.5 to 3.5,% by weight. Preferred polyalkylene glycols are those which contain both ethylene oxide and propylene oxide groups, such as the polyglycol B11 types from Hoechst AG. It is further preferred to use polyalkylene glycols which have molecular weights between 1000 and 10000 units.

The emulsions according to the invention can also contain, as a further additive, 0.5 to 8, preferably 1.5 to 2.5% by weight of hydrogen peroxide as a biostatic agent. Hydrogen peroxide has the advantage that it provides additional oxygen for the combustion of the fuel, but other bactericidal, algicidal and fungicidal compositions which burn without residue can also be used. All percentages by weight relate to the entire emulsion.

The preferred fuel is gasoline for internal combustion engines - (for example normal or super), as well as other types of fuel such as diesel oil, naphtha or kerosene. Fuel-water emulsions which contain 70-75% by weight of normal or super gasoline are preferred.

The fuel-water emulsions according to the invention can be produced in various ways. One possibility is to dissolve the emulsifier and polyalkylene glycol in warm water and stir this solution into the fuel. Stir for a short while and then turn off the stirrer, whereupon the mixture separates into two phases. Then the mixture is stirred again until the emulsion is homogeneous and sufficiently thin. It is essential in this variant of the process that stirring is dispensed with in the meantime and the emulsion is left to stand briefly.

In the second process variant, the emulsifier and polyalkylene glycol are also clearly dissolved in water. The fuel is then added to this solution with stirring and stirring is continued until the emulsion is homogeneous and thin. The water required for the preparation of these emulsions is preferably completely desalinated so that no solid residues form when these emulsions are burnt. Suitable aggregates for producing the emulsions according to the invention are all aggregates known to those skilled in the art, for example high-shear dispersing aggregates (Ultraturrax), ultrasonic dispersers or dispersing disks of the Cowls mixer type or a Caddy-Mill.

The fuel-water emulsions according to the invention are suitable for operating internal combustion engines, in particular direct injection engines.

Examples

example 1

3 ml of an oxyethylated nonylphenol (content of ethylene oxide 11 mol) and 7 ml of an ethylene oxide / propylene oxide polyalkylene glycol with an ethylene oxide / propylene oxide ratio of 1: 1 and a molar mass of 3100 were in -84 ml double-distilled water at 40-45 ° C solved. After cooling to room temperature, 20 ml of H ₂ 0 ₂ (30%) were added. 300 ml of normal gasoline were stirred into this solution and sheared intensively for 15 minutes. A stable emulsion was obtained.

Example 2

3 ml of the oxalkylated nonylphenol according to Example 1 and 15 ml of the

Polyalkylene glycol according to Example 1 was double distilled at 40 ° C in 90 ml Water dissolved. 300 ml of normal gasoline were mixed into this solution at approx. 45 ° C using a mixer that supplied high shear forces (type Caddy-Mill) until the viscosity visibly decreased. The temperature rises to about 50 ° C. After cooling, 20 ml of H ₂ O ₂ (30% strength) were added, which results in a further reduction in the viscosity.

The emulsions according to the invention according to Examples 1 and 2 have the compositions and properties given in Table 1:

Table 1: (all data in% by weight)

Ingredient / property Example 1 Example 2

Water 30.5% 31%

H ₂ O ₂ 2.1% 2%

Emulsifier (ethoxyl. Nonylphenol) 1% 0.9%

Polyalkylene glycol 2.2% 4.6%

Petrol 64.2% 61.5%

Viscosity at 48 ° C 440 mPas. 330 mPas.

Viscosity at 22 ° C 750 mPas. 650 mPas.

Evaporation residue mg / 100 ml 2440 4165

Chlorine content <30 ppm <30 ppm

Example 3

10 ml of an ethylene oxide / propylene oxide with an ethylene oxide / propylene oxide ratio of 4: 1 and a molar mass of 1000 were mixed with 90 ml of softened water (pH 5.0). 3 ml of the oxyalkylated nonylphenol according to Example 1 were added to this mixture and the mixture was briefly heated to approximately 50 ° C. for better homogenization. 300 ml of regular gasoline were introduced separately and the water was slowly Emulsifier mixture stirred into the gasoline. A white emulsion of water-in-gasoline was obtained, which was further stirred for about 3 to 5 minutes. The emulsion thus obtained was then left to stand until the white water-containing layer which formed on standing had settled to about 50% of the total volume. The phase was reversed by vigorous stirring and a stable, low-viscosity emulsion was obtained.

An equally good emulsion was obtained by using 4 ml instead of 3 ml of the oxyethylated nonylphenol.

Example 4

In succession, ethoxylated nonylphenol and polyalkylene glycol, both according to Example 1, were clearly dissolved in electrolyte-free water at approx. 45 ° C. This solution was then stirred into the petrol presented. After stirring for 5 minutes, the mixture was allowed to settle, two distinct phases clearly forming. After 5 minutes, stirring was continued until the emulsion became thin. The emulsion warmed to about 48 ° C. while stirring.

Example 5

Water and additives were mixed and heated as in Example 3. Then the gasoline was stirred into the aqueous solution with the aid of an Ultraturrax. The stirring was continued until the emulsion became thin, without letting the emulsion settle in the meantime.

The emulsions according to Examples 4 and 5 have the compositions and properties given in Table 2: Table 2

Ingredient / property Example 4 Example 5

E-water 60 g 60 g oxyethylated nonylphenol 2 g 2 g

Polyalkylene glycol 3 g 3 g

Regular gasoline 135 g 135 g

Viscosity at 46 ° C (in mPas) 440 330

Viscosity at 22 ° C (in mPas) 750 650

Claims

claims

1. Fuel-water emulsions consisting essentially of 60 to 80 wt .-% of a fuel, 0.5 to 5 wt .-% of one or more water-soluble and gasoline-insoluble emulsifiers of the formulas

(A) R - 0 - (CH ₂ CH ₂ 0) _x - H

2. Fuel-water emulsion according to claim 1, characterized in that the content of emulsifier 0.5 to 1 wt .-%, in particular 0.65 to

0.75% by weight.

3. Fuel-water emulsion according to claim 1 and / or 2, characterized in that the emulsifier is a nonylphenol oxyethylate with 8 to 30 units of ethylene oxide.

4. Fuel-water emulsion according to one or more of claims 1 to

3, characterized in that the emulsifier is a nonylphenol oxyethylate with 9 to 13 units of ethylene oxide.

5. Fuel-water emulsion according to one or more of claims 1 to

4, characterized in that the emulsion contains 1, 5 to 5, in particular 2.5 to 3.5 wt .-% of a polyalkylene glycol.

6. Fuel-water emulsion according to one or more of claims 1 to

5, characterized in that the emulsion contains 0.5 to 8, preferably 1, 5 to 2.5 wt .-% hydrogen peroxide as a further additive.

7. -Fuel-water emulsion according to one or more of claims 1 to

6, characterized in that the emulsion contains a bactericide, algicide or fungicide as a further additive.

8. Fuel-water emulsion according to one or more of claims 1 to

7, characterized in that the emulsion contains 70 to 75% by weight of normal or super gasoline.

9. Fuel-water emulsion according to one or more of claims 1 to

8, characterized in that the ethylene oxide / propylene oxide block polymers used as emulsifiers have molecular weights between 2000 and 10000 units.

10. Fuel-water emulsion according to one or more of claims 1 to

9, characterized in that the polyalkylene glycols used as stabilizers have molecular weights between 1000 and 10000 units.

11. Use of the fuel-water emulsions according to one or more of claims 1 to 10 for the operation of internal combustion engines, in particular direct-injection internal combustion engines.

12. A process for the preparation of fuel-water emulsions, characterized in that a solution of emulsifier and stabilizer is initially introduced and the fuel is emulsified therein.

13. The method according to claim 12, characterized in that the emulsification of the fuel takes place in at least 2 temporally separate steps.