NO860669L - FUEL. - Google Patents

Description

Background for the invention

1. Field of invention

The present invention relates to a particularly efficient fuel with several desirable properties, such as very good efficiency during combustion, so that the fuel is more economical to use. More specifically, it relates to a fuel that contains small amounts of certain polyolefins or derivatives thereof. The fuel according to the invention typically comprises hydroxycarbon fuels, such as petrol or diesel fuel in combination with a suitable polyolefin additive, as well as emulsified fuels containing significant amounts of water.

2. Description of the state of the art

A large number of additives have previously been proposed for use in conventional hydrocarbon fuels such as petrol, diesel fuel etc. In many cases, additives have been proposed to remedy specific problems, such as the elimination of knocking by adding tetraethyl lead to the gasoline. Other means have also been proposed to increase the efficiency of the combustion and thereby the output per unit of fuel consumed.

Although the state of the art is full of attempts to achieve a significant increase in combustion efficiency, unfortunately few, if any, really successful additive forgings have been found.

Research in the area has also suggested the addition of significant amounts of water to liquid hydrocarbon fuels in order to obtain a flammable emulsion which could theoretically reduce the consumption of expensive hydrocarbon fuel. In fact, such proposals date back to the late nineteenth century. Here too, no really successful fuel/water emulsion has been produced before. The many problems previously experienced with such emulsified fuels include the fact that when relatively large amounts of water are present, the combustion temperature is lowered. In addition, the presence of significant amounts of water lowers the fuel's total heating value. Finally, many known fuel/water emulsions are relatively unstable and tend to separate with time. Of course, the problem of phase separation can be avoided in such emulsions if large amounts of surfactants are used, but this is a very expensive solution, and to be truly economical the amount of surfactant must be relatively small.

Patent 2,896,593 relates to a two-cycle fuel containing an unleaded pure gasoline and 6-9 vol% polyisobutylene. This combination is said to be particularly useful in two-stroke engines where the polyisobutylene prevents sooting of the engine.

Likewise, US patent 3,752,905 relates to a two-stroke fuel containing polybutylene together with mineral oil and other additives. US patent 3,085,978 is similar in certain ways to the latter patent and relates to the use of polybutylene together with a calcium salt of petroleum sulfonic acid in a fuel.

From US patents 3,909,214 and 3,782,912 it is known to use polyolefins as fuel additives together with other components, such as amine salts and the like. But none of the inventions according to the aforementioned patents relate specifically to emulsified fuels.

Other patents of interest include US Patents 4,162,143, 2,642,345, 4,339,246, 2,356,647, 4,392,865, 2,920,948, 3,163,603, 3,451,931, 4,125,382, 2,873,182, 3,410. 671, 2,959,551, 3,271,310, 3,783,131 and 3,779,922.

Summary of the Invention

According to the present invention, a very efficient fuel has been produced which overcomes many of the difficult problems discussed above. The invention lies in the observation that the use of certain types of polyoleic fine compounds, typically in relatively small quantities, gives a significantly increased combustion efficiency.

The fuel according to the invention can be largely free of lubricating oil. Fuels thereby comprise (and preferably mainly consist of) a combustible hydrocarbon material and up to approx. 2.5% by weight (eg 0.1-2.5% by weight) of a polyolefin additive. The type and amount of additive serves to increase the output power per unit of fuel obtained by using the fuel compared to the output power per unit fuel obtained under the same conditions and using the same fuel with the exception that it does not contain the polyolefin additive. The additive comprises polyolefins containing C^-C-^Q monomers, i.e. monomers containing 2-10 carbon atoms, as well as derivatives of such polyolefins.

The hydrocarbon material is preferably in liquid form

hydrocarbon, such as gasoline, diesel fuel or heavy oil of virtually any specific composition and type. The polyolefin additive, the most preferred polyolefin being polybutylene or polyisobutylene, is preferably used in a concentration of 0.1-2% by weight, and most preferably in a concentration of 0.3-0.8% by weight. However, those skilled in the art will understand that the specific amount of polyolefin additive to be used in a particular situation depends on the hydrocarbon base material used, as well as on the desired properties of the finished polyolefin supplemented fuel. When it comes to indoline, it is e.g. surprisingly observed that good results are obtained by using polybutylene in a concentration of up to 1% by weight, e.g. 0.1-1% by weight, but that substantially above this concentration the results are dramatically reduced.

Many different polyolefin additives can be used according to the invention. Although polyolefins of C-2~(~' 10~ monomers can be used, the most preferred polyolefins are based on C3-C8 monomers. In addition to the most preferred polybutylene additive, additives such as polyethylene, polypropylene and polypentene can also be used. the various isomers of the polyolefins find application in the invention, as well as the diolefins and mixed polymers, e.g.

In certain embodiments of the invention, certain further additives can also be used, such as an aromatic compound, e.g. toluene, and another fuel different from the base hydrocarbon, e.g. diesel fuel in connection with a petrol-based fuel.

In another embodiment of the invention, a liquid emulsified fuel has been produced which contains respective amounts of a combustible fuel based on liquid hydrocarbon, water, at least one surfactant, and an additive in the form of a polyolefin based on C2~Ciq monomer . In this case too, the combustible fuel chosen is petrol, diesel fuel and heavy oil, although other options, such as residual oil, can also be used.

Preferably, the combustible fuel component is present in a concentration of 5-99% by weight, more preferably

from 55-90% by weight. On the other hand, the water fraction is present in a concentration of 1-95% by weight, and preferably from 10-45% by weight. In the case of emulsified fuels, the polyolefin additive should be present in a concentration of up to 2.5% by weight, and more preferably in a concentration of from 0.1 to 2% by weight.

Different types of surfactants can be used according to the invention to produce stable emulsions which have good handling and combustion properties. One or more surface-active substances can be used, although in practice it has been shown that a combination of surface-active substances is best suited for the purposes according to the invention. The surfactants should be present in a concentration of up to 5% by weight, but in this case the main consideration is of an economic nature, i.e. that a high amount of surfactants may not adversely affect the properties of the fuel, but will be impractical from an economic point of view point of view.

Brief description of the drawing

The only figure shows a curve obtained during the tests described in example I and shows the increase in horsepower/unit of fuel obtained with the fuel according to the invention, and also that in the case of indoline hydrocarbon fuel the use of polybutylene in a concentration of over about. 1% by weight disadvantageous.

Description of preferred embodiments

When producing non-emulsified fuels according to the invention, the selected polyolefin additive is simply mixed with the hydrocarbon base fuel material in the desired additive concentration. The most preferred hydrocarbon bases are gasoline and diesel fuels (especially No. 2 diesel fuel), while the preferred polyolefin additive is polybutylene. The polybutylene should be dispersible in the hydrocarbon fuel used and preferably have an average molecular weight of 500-2000 and be made up of repeating isobutane monomers and a polyolefin end group. A particular commercially available polybutylene which has been used to good effect according to the invention is "Polybutene grade 24" from Chevron Chemical Co. The material is a light colored, chemically inert oily liquid of moderate to high viscosity and stickiness. The chemical and physical properties of this product are listed in a manufacturer's publication entitled "Technical Data Sheet Chevron Polybutenes" dated November 13, 1981. The material "Polybutene grade 24" has a specific gravity at 15/15°C of 0.898 (ASTM D 287 ), a density at 15/15°C of 897.6 g/l and an average molecular weight (Mechrolab Osmometer) of 950. The currently most preferred unemulsified fuel comprises approx. 99.5% base hydrocarbon fuel, particularly gasoline or No. 2 diesel oil, together with 0.5% blended polybutylene.

When it comes to emulsified fuels, the most preferred fuels contain the above-mentioned additive "Polybutene grade 24" together with water, to form a water-in-fuel emulsion. Here, too, many different fuels can be used, but the currently preferred hydrocarbon-based fuels include members from the group consisting of petrol, diesel fuels and heavy oils.

In the case of surfactants, the most preferred combination comprises respective small amounts of three emulsifiers, namely "Toximul D", an anionic/nonionic mixed emulsifier sold by Stepan Chemical Co. and which is a mixture of calcium dodecylbenzenesulfonate and alkylphenoxy-polyoxyethylene ethanol, "Ammonyx LO", sold by Onyx Chemical Co. and which is a dodecyldimethylamine oxide, as well as "Atpet-200" sold by ici Americas which is a sorbitan tolate. In addition, however, various other types of surfactants can be used, such as "Z-MAZ 90", which is sold by Mazer Chemical Co. and which is a sorbitan monothallate. As experts in the field will immediately understand, however, a large number of specific surfactants and combinations thereof can be used in the invention as long as the purpose thereof is achieved. In addition, the preferred emulsifier mixture can be used in other types of emulsified fuels which do not contain the olefin additive used according to the present invention.

The following table indicates the components in particularly preferred emulsified fuels according to the invention together with the most preferred concentrations and suitable concentration ranges:

To prepare emulsions according to the invention, it is preferred to first mix the surfactants to be used, after which these surfactants are added to the hydrocarbon-based material with sufficient stirring to ensure homogeneity. At this point, the water is added, also while stirring to ensure a relatively even dispersion. The above-described mixture of surfactants makes the mixing process much easier, and no special equipment etc. is required. In the case of petrol-based emulsions, the mean particle diameter of the water in the emulsion is estimated to be up to approx. 0.5 [am.

The following examples will illustrate specific fuels according to the invention and conspicuously desirable properties for these. However, it should be understood that these examples are given for illustrative purposes only.

Example I

To determine the degree of combustion enhancement using polyolefin-supplemented distillate hydrocarbon fuels containing a major proportion of a hydrocarbon-based fuel that distills in the gasoline's destination region, engine tests were performed under load simulated using a dynamometer in the laboratories of the University of California at Los Angeles, Los Angeles, California. A 132-horsepower (3600 rpm) 6-cylinder Ford engine with a bore of approx. 10.2 cm, a stroke length of approx. 10.1 cm, a displacement of 4.9 1, a compression ratio of 7.9 and torque of 33.25 m-kg at 1800 rpm. was used in conjunction with a dyno torquer that was equipped with automatic control at constant speed or constant load in the tests. Reference fuel was 91 octane indolin test fuel from Amoco Oil Company.

The test program included the addition of polybutylene ("Polybutene grade 24" from Chevron Chemicals Co. of San Francisco, California) in concentrations of from 0.25-2% by weight to the indolin test fuel to achieve the ratio of output power to fuel consumed at standard engine rpm and torque loads . The engine speed was measured and determined using a digital pulse counter from 700 rev/min. to a maximum of 3000 rpm. The torque was kept at 7.24 m-kg. In one test, a concentration of 0.3% by weight of polymethylene was chosen for testing at three revolutions (1500, 2000, 2500) and a torque of 7.24 m-kg. As a comparison, unmixed indoline was also used at the same number of revolutions and torques, whereby the following results were obtained: at 1500 rpm. and 7.24 m-kg, a given effect per kg was recorded. unmixed indoline fuel of 91.5 HP/kg, at 200 rpm, 7.24 m-kg 91.1 HP/kg and at 2,500 rpm. and 7.24 m-kg 89.3 HP/kg. Table II shows the results of this test.

As will be seen, in all cases the presence of polybutylene increased the emitted power per kg. fuel compared to the unblended indolin test fuel. The percentage increase in combustion effect is significant and thereby confirms the value of adding polyolefin.

In a second series of tests, polybutylene was added to the indoline test fuel in varying concentrations from 0.25-2% by weight. These fuels, which were supplemented with additives, were tested as described above to determine the output per kg. fuel. In all cases the engine test was carried out at 2000 rpm. and 7.24 m-kg.

The results of this series of tests are graphically shown in the accompanying drawing. As you will see, the emitted power per kg increases. fuel quickly (compared to the unsupplemented indoline) up to an additive concentration of approx. 1.0% by weight has been achieved. Between 1.0 and 1.25% by weight, however, the emitted power per kg decreases. fuel dramatically to a point below the unmixed indoline. This was a very surprising result and shows that, at least in connection with the specific indolin test fuel used and under the conditions indicated, a relatively critical concentration of polybutylene addition is required to obtain optimal results.

Example 2

To confirm the results obtained in Example 1 quantitatively and to more fully determine the feasibility of the additive-supplemented distillate hydrocarbon fuels containing a major proportion of hydrocarbon-based fuel that is distillable in the gasoline's destination area, consumption tests were conducted at the Jarama race track in Madrid, Spain. The tests were carried out by and all drivers approved by the Real Automobil Club de Espana.

Test A was conducted by driving a 1978 Daimler Jaguar with a six-cylinder engine (the engine had been installed and had been in use for less than six months) which had a bore of 92.06 mm, a stroke of 106 mm and a displacement of 4 ,2 1, with a duration of approx. 10 1 fuel consumption. The Jaguar was first tested using unblended 98 octane petrol and then compared against 90 octane petrol containing 0.5% polybutylene. Data are given in Table III, and in the opinion of the test driver the results obtained with additive supplemented fuels were "remarkable".

Test B was conducted driving a 1982 Datsun, model 280 ZX with an engine having a bore of 3.386 mm, a stroke of 79 mm and a displacement of 2.8 L and which was equipped with 5 gears and electronic fuel delivery. The car was driven at the highest possible speed for a duration of approx. 10 1 fuel consumption. The Datsun was first tested with standard 98 octane petrol and then compared with 90 octane petrol supplemented with additive (0.5% by weight polybutylene). Data are given in Table III. It should be noted that both cars will not function on standard 90 octane gasoline without additive due to detonation ("knocking" or "ignition knocking").

Another test involved a qualitative comparison of detonating combustion effects between 98 octane gasoline and additive-supplemented (0.5% by weight polybutylene) 90 octane gasoline using a new Honda, model VF-1000, 1.0 1, four-stroke test engine at the Jarama racetrack in Madrid, Spain. It was found that the motorcycle has detonating combustion when using 98 octane gasoline at high temperatures, while no detonating combustion occurred at high temperatures with 90 octane gasoline containing the additive.

Example 3

To demonstrate the advantages of emulsions according to the invention containing water and distillate hydrocarbon fuels having a major proportion of a hydrocarbon-based fuel which distills in the destination area of diesel fuel, two engine tests were carried out in the province of Andalucia in Spain. The comparison tests were carried out using unmixed Gas-Oil A, a known reference fuel, and alternatively an emulsion which was prepared as stated above and which contained 77% by weight standard Gas-Oil A, 0.75% by weight "Atpet-200", 0.50% by weight "Ammonyx-LO", 0.50% by weight "Polybutene 24" from Ashland Chemical Company and 20% by weight water. During each test, observations were made without quantitative measurements regarding soot reduction, how easy hot and cold starting and stopping were and regarding general driving characteristics. In all cases, the emulsions were judged to be better than the unmixed fuel.

In engine test 1, fuel consumption for unmixed Gas-Oil A was measured compared to emulsified Gas-Oil A in a Diter D302.1 16 HP single-cylinder diesel engine with a displacement of 12.2 1, which was used to drive a water pump with constant load at 2,300 rpm In test 2, fuel consumption for unmixed Gas-Oil A was compared to emulsified Gas-Oil A with operation of a four-cylinder Mercedes 200D diesel engine. It was clear during test 2 that the Mercedes produced more energy when burning emulsified Gas-Oil A as opposed to Gas-Oil A without emulsion, although the amount was not measured quantitatively. The results of the consumption are indicated below.

"^Corrected for water content in emulsified fuels to

achieve comparable results in terms of the amounts of hydrocarbon in both mixed and emulsified fuels.

Example 4

Tests were conducted to determine the general properties of emulsified distillate fuels in a conventional fuel treatment system, such as a boiler or furnace. Factors investigated were pumpability, filterability, ignitability and flare stability. Equipment used was a Centurty Type Jl oil burner with a Sundstrand fuel pump and Marathon engine model T2742. The burner was changed to a superstructure with a horizontal, approx. 0.9 m long pipe which had a diameter of 12.7 cm and which was equipped with a 0.6 m long vertical chamber with a diameter of 20.33 cm, and an approx. 1.5 m long cobblestone with a diameter of 12.7 cm, at the outlet end of the horizontal pipe. A 1.27 cm diameter horizontal water pipe was installed through the vertical to allow water to flow through the pipe without the flame directly hitting the water pipe, and to measure water inlet and outlet temperatures.

Different emulsified fuels were tested under the same conditions and compared with diesel fuel No. 2 as a reference. Fuel flow was measured on a weight/time basis (simulated load cell) to obtain the amount of calories added when water condenses, for measuring the output power. Efficiency was not assessed as the purpose was to determine the relative increase in combustion chemistry.

All emulsified fuels (up to 40% water) functioned satisfactorily. There was no sign of water splitting or filter clogging. The emulsions burned well at all the pump pressures at which No. 2 diesel would burn. Atomization proved to be good, and no corrosion tendencies were observed. The subsequent table V indicates the results of these tests, where: fuel (1) is an emulsion containing 20% by weight water, 0.5% by weight "polybutene 24" (Ashland Chemical), 75% by weight "Toximul D" (Stephan Chemical Co.), 0.75 wt% "Atpet-200"

(I.CI. Americas), 0.50% "Ammoyx-LO" (Onyx Chemical Co.) and 77.5% diesel fuel No. 2, fuel (2) is an emulsion containing 15% by weight water, 0, 5% by weight polybutylene, same

emulsifiers and quantities as fuel (1), as well as 82.5% diesel fuel f no. 2, fuel (3) is unmixed diesel fuel no. 2 and fuel (4) is the same as fuel (1) with the exception that the polybutylene is omitted so that it contains 78% by weight of No. 2 diesel fuel.

As can be seen from a comparison of the fuels (1) and (4), the presence of polybutylene gives a very significant increase in the emitted power per kg. fuel. Moreover, the results show that in most cases the emulsified fuels are advantageous compared to unmixed diesel fuel no. 2.

Temperature measurements at the inlet and outlet respectively for the water pipe with a diameter of 1.2 7 cm.

In addition to the foregoing, limited comparative testing was conducted in a small boiler in Kansas City, Missouri. The boiler was a 75 HP Kewanee steam boiler set at approx. 0.52 kg/cm 2 high pressure shear and 0.28 kg low pressure shear. The load consisted of 5 fan ovens (fans with approx. 51 cm diameter). Fuel samples in barrels with a diameter of approx.

54.1 cm was measured volumetrically. Water measurement by carried out by passing what is fed through the boiler's filling line through a flow sensor Signet MK 515 with flow meter MK575R.

The boiler was brought up to pressure with minimal firing with the fuel bypass modulator valve locked in the minimum position. About. 6 min. after high pressure shutdown, the boiler was filled with water until the pump was shut down using a high level switch. The water flow meter was then reset to 0 and the fuel level measured. The boiler was fired automatically using the high and low steam switches through four complete cycles. About. 6 min. after depressurization in the fourth firing cycle, the boiler was filled again and final measurements were made of fuel level and water meter reading.

CC>2 increased from 11%, firing with diesel fuel engine (reference fuel) to 12.5% firing with emulsified diesel fuel (same as fuel (1), Table IV), suggesting an increased combustion efficiency. The firing became unstable when switching to emulsified fuel due to that according to the test engineer, there was insufficient excess air (oxygen) to sustain combustion. Excess air was opened to about maximum (sustained more than 3MM 0.75MM kcal/h combustion), and the fuel flow rate was lowered to a minimum (about 0.3 MM kcal/h), and there was still insufficient air to sustain the combustion. This indicates that the emulsified fuel according to the invention has a combustion efficiency that is far higher than that of diesel fuel no. 2.

Example 5

Various tests were conducted and confirmed under the direction of the Ministerio de Defensa at the Instituto Nacional de Tecnica Aerospacial in Madrid, Spain. The results were recorded in certificate no. 40180 as follows in the case of 4 emulsions produced according to the present invention:

Emulsion No. 1 -

20 wt% water, 0.5 wt% polybutylene, 2 wt% emulsifiers (0.75 wt% "T-Mulz-D", 0.75 wt% "Atpet-200" and 0.5 ect% "Ammonyx-LO " as well as 77.5% by weight Gas-Oil A,

pH - 7.8

viscosity at 37.8°C - 6.2 cSt (centistoke) filtration - passes unhindered

stability - stable

Emulsion No. 2 -

20% by weight water, 0.5% by weight polybutylene, 2.0% by weight emulsifiers (same as in emulsion no. 1) and 77.5% by weight Gas-Oil B

pH - 7.5

viscosity at 37.8°C - 5.4 cSt

filtering - passes unhindered

stability - stable

Emulsion No. 3 -

20% by weight water, 0.5% by weight polybutylene, 2.0% by weight emulsifiers (same as in emulsion no. 1) and 77.5% by weight Gas-Oil C

pH - 7.7

viscosity at 37.8°C - 5.7 cSt

filtering - passes unhindered

stability - stable

Emulsion No. 4 -

20% by weight water, 0.5% by weight polybutylene, 2.0% by weight emulsifiers (same as in emulsion no. ) and 77.5% by weight residual fuel oil

viscosity at 37.8°C - 580.4 cSt

viscosity at 50.0°C - 331E

The emulsions were stable and remained stable for more than two months of storage time.

Example 6

To determine the ability of emulsified distillate fuels of the present invention to pass through a coalescing filter without separating water, various emulsified distillate fuels were pumped through a Caterpillar 6M7617 water separator element. Emulsions were pumped at an air pressure of o 0.35 kg/m 2 through the coalescing filter mounted in a glass bowl. No free water was observed during more than four months of testing.

A qualitative comparison of the amount of sulfur in combustion gases from emulsified and non-emulsified fuel oils was carried out by sequentially burning different grades of fuel oil in a bowl. A pipe with a diameter of 12.7 cm and a length of 45 cm was placed over the flame to function as a chimney pipe. Porous filter paper soaked in potassium permanganate solution was placed over the tube for one minute. Bleaching of these papers would indicate the presence of sulfur in the combustion gases.

Both destallate and residual fuel oil samples that burned showed marked color change (bleaching). Emulsified residual fuel oil samples that did not contain polyolefins or emulsifiers showed similar color change to non-emulsified samples of the same fuels, although somewhat darker. Fuel oil samples emulsified with water and the preferred emulsifiers and added polybutylene showed no color change when using distillate fuel (diesel No. 2) and only slight color change with residual fuels (No. 5 and No. 6).

Although the inventors do not wish to be bound by any particular theory as to why polyolefin derivatives according to the invention give such excellent results, it is a hypothesis that these additives in a way initiate or promote reactions analogous to cracking during the combustion of the polyolefin-containing fuel. Based on this way of reasoning, such reactions will produce smaller hydrocarbons with a lower molecular weight, which are known to be more easily combustible. In addition, the exothermic reaction heaters will theoretically significantly increase the heating value obtained from the fuels.

Although the above description is primarily aimed at the use of liquid hydrocarbon-based materials, it is believed that the combustibility of solid hydrocarbon materials, such as coal, can also be increased with the use of polyolefin additives according to the invention. In such an application, the polyolefin material can be simply sprayed onto crushed coal to provide better combustion characteristics, or alternatively, the polyolefin additives can be added to coal/liquid suspensions

Claims (12)

1. Liquid motor fuel largely free of butter oil, characterized in that it contains a combustible, liquid hydrocarbon material selected from petrol, diesel fuel and heavy fuel oil, 0.3-0.8% by weight of an additive in the form of a polyolefin based on C ^ -Cg monomers, which have a relatively low molecular weight and which are in the form of a liquid at normal environments. 2. Fuel in accordance with claim 1, characterized in that it mainly consists of the hydrocarbon material and the additive. 3. Fuel in accordance with claim 1, characterized in that the additive is polybutylene. 4. Fuel for four-stroke engines, largely free of butter oil, characterized in that it contains petrol and 0.3-0.8% by weight polybutylene. 5. Fuel in accordance with claim 4, characterized in that it mainly consists of petrol and polybutylene. 6. Liquid, emulsified fuel, characterized in that it contains 5-99% by weight of combustible hydrocarbon fuel selected from gasoline, diesel fuel and heavy fuel oil, 1-90% by weight of water, at least one surface-active substance to achieve a stable emulsion of the fuel and the water, and up to approx. 2.5% by weight of an additive in the form of a polyolefin based on G, -(\ q -monomers. 7. Emulsified fuel in accordance with claim 6, characterized in that the concentration is from 0.1-2% by weight. 8. Emulsified fuel in accordance with claim 6, characterized in that the surfactant is present in a concentration of up to 5% by weight. 9. Emulsified fuel in accordance with claim 6, characterized in that it contains a number of surfactants. 10. Emulsified fuel in accordance with claim 6, characterized in that the additive is selected from among polyolefins on the basis of C1 -C1 monomers. j b 11. Emulsified fuel in accordance with claim 6, characterized in that the additive is polybutylene. 12. Emulsified fuel, characterized in that it contains respective quantities of a liquid, flammable petroleum fuel, water and up to approx. 5% by weight of a system of surfactants comprising (a) a mixture of alkaline earth decylbenzene sulfonate and alkyl-phenoxypolyoxyethylene ethanol, (b) dodecyldimethylamine oxide and (c) sorbitan allate.