EP0888421B1 - Emulgierter brennstoff und verfahren zur dessen herstellung - Google Patents

Emulgierter brennstoff und verfahren zur dessen herstellung Download PDF

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Publication number
EP0888421B1
EP0888421B1 EP97915509A EP97915509A EP0888421B1 EP 0888421 B1 EP0888421 B1 EP 0888421B1 EP 97915509 A EP97915509 A EP 97915509A EP 97915509 A EP97915509 A EP 97915509A EP 0888421 B1 EP0888421 B1 EP 0888421B1
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weight
emulsion
emulsifying system
fuel
water
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French (fr)
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EP0888421A1 (de
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Alain Haupais
Philippe Schulz
Pascal Brochette
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Elf Antar France
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Elf Antar France
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the present invention relates more specifically to new fuel compositions constituted by emulsions of water in at least one hydrocarbon and generally in a mixture of hydrocarbons, such as for example that which composes diesel. It will therefore be a question in this presentation of water / hydrocarbon stabilized emulsions , comprising surfactants capable of allowing the emulsification and stabilization of such emulsions.
  • the present invention also relates to a process for obtaining fuels (e.g. fuels) emulsified water / hydrocarbons associated with one or more several surfactants.
  • fuels e.g. fuels
  • emulsified water / hydrocarbons associated with one or more several surfactants.
  • the present invention is part of the approach, for a long time in vogue, for developing fuel compositions, in particular fuels including substitutes for petroleum derivatives, for the sake of saving and limiting pollution.
  • Water very quickly appeared as an interesting additive or partial substitute for petrol or diesel. Water is indeed an inexpensive and non-toxic liquid, which shown to be able to reduce fuel consumption, as well as emissions of visible or invisible pollutants.
  • the second apprehensible approach consists in implementing ready-made mixtures of water and fuel, but that was not to mention the considerable problems of storage stability of such mixtures in fields of temperature varying from - 20 ° C to - 70 ° C, and stability under conditions use of the emulsion in a tank.
  • phase separation phase shift / demixing
  • an emulsified fuel comprising a number of additives including an emulsifying system formed of sorbitan sesquioleate, monooleate of sorbitan and polyoxyethylene ( 6 EO) of dodecyl alcohol.
  • the total concentration of all the additives is approximately 2.1%.
  • the other additives that can be used can be: a mono- ⁇ -olefin (decene-1), methoxymethanol, toluene, an alkyl benzene and calcium hydroxide. This formulation is extremely complex, if only by the number of additives used. It is also relatively expensive.
  • the fuel emulsified according to this patent also suffers from a lack of stability, in particular at low temperature.
  • the Applicant has moreover been able to clearly demonstrate this by reproducing the preferred example of implementation of the emulsified fuel according to this US patent. It turned out that the emulsion separates (dephazes) within an hour. The phenomenon is further accentuated at low temperatures below 5 ° C. We hardly dare imagine, what could happen in vehicle tanks containing this emulsion and placed in real winter conditions of use.
  • N ° 101: 57 568 z targets an emulsified fuel comprising hydrocarbons constituted by derivatives of extremely viscous and heavy petroleum, water, ethanol and an emulsifier consisting of ethoxylated nonylphenol.
  • This emulsified fuel is intended to be used in ovens, conventional oil burners. This fuel cannot meet the expected specifications for combustion performance, limitation of pollutants and low consumption. In addition, the physicochemical stability of this emulsion is not good.
  • emulsified fuels which can be fuels, include specific quantities of hydrocarbons and a set of additives in minor quantities including in particular an emulsifying system comprising sorbitan oleate, polyalkylene glycol and alkylphenol ethoxylate. .
  • the dispersed phase of these emulsified fuels consists of water present in an amount of 5 to 35% by weight while the additives are present in an amount of 0.1 to 1.5% by weight.
  • concentration ranges for sorbitan oleate, polyalkylene glycol and alkylphenol ethoxylate are, respectively (in% by weight), from 0.20-0.26 / 0.20-0.25 / 0.20-0 , 27.
  • One of the essential objectives of the present invention is to overcome this shortcoming by providing an emulsified fuel, in particular a fuel, formed by a stable water / hydrocarbon emulsion , which remains perfectly homogeneous over long periods of time, as well in storage tanks only in elements of the circuits constituting the combustion devices, in which said fuels may be used.
  • Another essential objective of the present invention is to provide new improved emulsified fuels which provide good results in terms of reducing fuel consumption and reducing the emission of visible pollutants such as smoke and solid particles and pollutants.
  • invisible gases such as CO, NO x and / or SO 2 , unburnt hydrocarbons and CO 2 .
  • Another essential objective of the present invention is to provide new low-cost emulsified fuels so that not to annihilate the gain obtained by the partial replacement of expensive hydrocarbons with water.
  • Another object of the present invention is to provide a method of preparation of stable, non-polluting and economical emulsified fuels, which process should also be inexpensive and also easy to implement work, without sophisticated operating protocol and device.
  • the improved emulsified fuels which have these characteristics benefit from great storage stability over long periods of time. They do not phase-shift (phase separation), both in tanks and in the various elements constituting the supply circuits of devices suitable for serving as a seat for combusion, namely: internal combustion engines, burners ...
  • the emulsion according to the invention remains perfectly homogeneous so that the risks of malfunction of the combustion devices are extremely limited.
  • This absence of phase shift (phase separation) and coalescence, whether by gravity or by any other means of separation (filtration, centrifugal effect, etc.) constitutes major technical progress, which makes it possible to concretely envisage industrial applications and serious business.
  • the stability of the emulsion is understood to mean maintenance of the latter in its initial physicochemical state of homogeneous emulsion (no phase shift, no coalescence of the dispersed phase droplets), during a storage for at least 3 months at room temperature.
  • the fuels emulsified according to the invention provide at the same time quite interesting and satisfactory performances, as far as concerns the reduction of polluting emissions and consumption, and this for a reasonable cost price.
  • the mean value in diameter of droplets of aqueous phase fixed at 3 ⁇ m, preferably 2 ⁇ m and more preferably still at 1 ⁇ m, and accompanied by a standard deviation of 1 ⁇ m maximum appeared to be one of the determining factors for guarantee the stability of the emulsion and in particular the limitation of coalescence and phase shift phenomena.
  • a “monodisperse” particle size profile is therefore provided around 1 ⁇ m in practice (see curve in FIG. 5 ). This means that the droplet population is homogeneous in size, the latter also being low enough to contribute to stability.
  • HLB Hydrophilic-Lipophilic-Balance
  • This is a well-known parameter for characterizing emulsifiers.
  • the qualitative and quantitative composition of the emulsifying system is also an essential element of the invention, which contributes to the results obtained especially with regard to stability.
  • the emulsion comprises at least 5% by weight of water and the emulsifier system concentration relative to the total mass of the fuel is less than or equal to 3% by weight, preferably 2% by weight.
  • the fatty acid ester of sorbitan ( I ) preferably consists essentially of one or more C 18 sorbitan oleates, optionally combined with one or more esters of C 18 fatty acid (linoleic, stearic) and in C 16 (palmitic).
  • the ester ( I ) is not limited to monoesters of fatty acids and of sorbitan but extends to di and / or tri-esters and their mixtures.
  • one of the selection criteria for this ester ( I ) is advantageously belonging to the range of HLB between 1 and 9, which gives it a marked lipophilic tendency.
  • the HLB more particularly preferred for the ester ( I ) is between 2.5 and 5.5.
  • esters essentially consisting of oleates and, in smaller quantities, of palmitate, stearate and sorbitan linoleate. It may, for example, thus be sorbitan sesquioleate, of the type of those sold under the brand SPAN 83® or ARLACEL 83® (HERE).
  • sorbitan esters ( I ) As other examples of sorbitan esters ( I ), mention may be made of sorbitan laurates, of the type sold under the brand SPAN 20® or ARLACEL 20® (ICI), ALKAMULS SML (RHONE POULENC), sorbitan stearates of the type sold under the ARLACEL 60® brand (HERE) or ALKAMULS SMS (RHONE POULENC), without this list being exhaustive. It goes without saying that, within the meaning of the present invention, the esters ( I ) extend to all analogs and derivatives of fatty acid and sorbitan esters.
  • compound ( II ) is chosen from oleates and / or stearates and / or ricinoleates of polyalkyleneglycol and preferably of polyethylene glycol (PEG), preferably from those whose PEG has a molecular weight less than or equal to 450, preferably of the order of 300. It may, for example, thus be a PEG 300 monooleate of the type of those sold under the brand TILOL 163® (UNION DERIVAN SA), EMULSOGEN A® (HOECHST).
  • PEG 300 monooleate of the type of those sold under the brand TILOL 163® (UNION DERIVAN SA), EMULSOGEN A® (HOECHST).
  • the alkylphenol ( III ) alkoxylate is preferably chosen from nonylphenols and / or polyethoxylated octylphenols, polyethoxylated nonylphenols being particularly preferred.
  • alkylphenol ethoxylate In practice, it is eg nonylphenol ethoxylate. It can advantageously be replaced or combined with one or more other alkylphenol alkoxylates. It is thus interesting to retain the alkoxylates of alkylphenol ( III ) in which the alkyl radical substituting the phenol contains approximately from 1 to 20 carbon atoms, preferably from 5 to 20. In addition, it is also preferable to select the alkoxylates (eg ethoxylate) of alkylphenol in which the alkoxyl chain preferably comprises from 8 to 20 and, more preferably still, from 8 to 15 groups of alkylene oxide (eg ethylene oxide) per molecule.
  • alkylene oxide eg ethylene oxide
  • polyethoxylated nonylphenol C 9 H 19 -C 6 H 4 - (OCH 2 CH 2 ) m -OH, with 8 ⁇ m ⁇ 15. It appeared essential in the context of the invention to use polyethoxylated nonylphenols, characterized not only by their hydrophilic nature, but also by cloud points, defined within the meaning of standard DIN 53917 with an aqueous solution at 1% by mass greater than 30 ° C. A combination of these characteristics has indeed made it possible to obtain not only efficient emulsifying systems for the preparation of a water-fuel emulsion within the meaning of the invention, but, moreover, to obtain quite remarkable temperature resistance properties and capable of making this emulsion stable in a wide range of temperature.
  • compounds (III) include octylphenol polyethoxylated particularly those marketed under the brand OCTAROX® (SEPPIC) and OP n SINNOPAL ® (SIDOBRE-SINNOVA).
  • the compound ( III ) of the emulsifying system is a mixture of polyethoxylated nonylphenols, preferably two polyethoxylated nonylphenols having 9 and 12 ethylene oxide residues respectively
  • the fuels more specifically targeted by the present invention are those in which the hydrocarbon or the mixture of hydrocarbons entering into their constitution is (are) chosen from the following group of products: diesel fuels , gasolines, kerosene, fuel oils, synthetic fuels, vegetable or animal oils, esterified or not, and their mixtures. Even more preferably, the present invention relates to a particular group of fuels that are fuels (gas oils, gasolines, kerosene, synthetic fuels, vegetable or animal oils whether or not esterified) used as fuels in internal combustion engines or heat engines.
  • the fuel or fuel according to the invention can be added using a number of products having various functionalities.
  • one of the main advantages of the hydrocarbon / water emulsions according to the present invention is to offer two different types of support for the additives, namely: a lipophilic support constituted by the continuous hydrocarbon phase and a hydrophilic support constituted by the aqueous phase.
  • only the oil-soluble compounds could be incorporated easily into fuels.
  • This constraint is now eliminated thanks to the present invention, all the more since the solubility in water is a property offered to a number of products far greater than that of products soluble in fuels within the meaning of the invention.
  • additives soluble or miscible in water or even in hydrocarbons may therefore consist of one or more selected procetane products, preferably among the peroxides and / or nitrates and their mixtures.
  • Nitrates are examples of procetanes which can be incorporated into the emulsion via the hydrocarbon phase.
  • the nitrate salts are the hydrophilic pendants of alkyl nitrates. Their quality of salts allows them to be supported by the aqueous phase.
  • the anti-soot function is another function which it is possible to provide in the emulsified fuels of the invention.
  • the promoters of such a function are advantageously additives consisting of at least one metallic catalyst or alkaline earth, capable of promoting the post-combustion reaction of soot, said catalyst preferably based on magnesium, calcium, barium, cerium, copper, iron or their mixtures.
  • These catalytic soot destruction promoters are all the easier to introduce since they are generally compounds whose salts are soluble in water, which makes them compatible with the aqueous phase of emulsions according to the invention. The same is not true for conventional fuels of the prior art exclusively consisting of hydrophobic hydrocarbons.
  • biocidal or even bactericidal properties to emulsified fuels.
  • biocide preferably a bactericide.
  • the detergent function can also be useful for emulsions according to the invention. It is therefore advisable to consider the case where these include one or more detergent agents or additives.
  • the nitrogen dioxide (NO x ) function which can be provided by ammonia compounds (of the urea or ammonia type), is also valued in fuels and more particularly in fuels.
  • the present invention is perfectly in step with the current trend of using "green oil” as a partial substitute for fuel, in particular diesel.
  • "green oil” as a partial substitute for fuel, in particular diesel.
  • They can be, for example, rapeseed, soybean or sunflower oils, esterified or not, which can enter the fuel composition up to 5%, 30% or even 50% by mass for example.
  • the process according to the invention can therefore be summarized as a training of emulsion and a fractionation of this emulsion, so as to reduce the size of the droplets of dispersed aqueous phase until obtaining and maintaining a monodisperse particle size of 1 ⁇ m with a standard deviation of less than 1 ⁇ m.
  • the method according to the invention can be one of those usable for prepare the improved emulsified fuel (e.g. fuel) described above. he It follows that by extension, the characteristics and observations given in the description above about the products used in the emulsion, can be fully transposed in this part of the presentation on the process.
  • the fractionation of the emulsion is a mechanical or thermomechanical treatment aimed at breaking the cohesive force of the droplets, so as to promote their subdivision.
  • the fractionation means preferably used during step (c) are of the static mixer, centrifugal or other pump type, colloidal mill or other, rotor mixer, ultrasonic mixer and other method of fragmenting a liquid in another immiscible liquid.
  • static mixers can be used as fractionation means. These static mixers are bodies through which the emulsion is passed at high speed and in which it undergoes sudden changes in direction and / or in diameter of the pipes which make up the interior of the mixers. This leads to a pressure drop, which is a factor in obtaining a correct emulsion in finesse and stability.
  • a rotor mixer of the type of those marketed under the ULTRA-TURRAX® brand a high homogenizer pressure of the type of those sold by APV-BAKER or any known process for those skilled in the art and allowing an easy extrapolation of scale.
  • the steps b and c of mixing / fractionation are, for example, sequential, that is to say that the procedure consists of first mixing the hydrocarbon (s) and the emulsifying system and any additives, the premix being in a second time mixed and emulsified with water.
  • Steps - a - to c - of the method according to the invention take place at ambient temperature, which is also that of the fluids and raw materials used.
  • the emulsified fuel conforms to the invention and / or obtained by the process according to the invention, is dedicated to multiple industrial and commercial applications.
  • thermal engines e.g. diesel
  • the engines will be able to operate efficiently, economically and in a low-pollution manner, with emulsified fuels comprising from 35 to 45% by weight of water.
  • emulsified fuels comprising from 35 to 45% by weight of water.
  • FIG. 1 represents a photograph under an optical microscope with a given magnification of a water / diesel emulsion according to the invention, with droplets of dispersed aqueous phase, of size less than or equal to 1 ⁇ m.
  • FIG. 2 represents a photograph under an optical microscope with the same magnification as that of FIG. 1 of a water / diesel emulsion according to the closest prior art, with droplets of dispersed aqueous phase, of size greater than or equal to 10 ⁇ m.
  • FIG. 3 represents a diagram of an example of an emulsion fractionation device, capable of being used in the method of the invention.
  • FIG. 4 represents a graph of a cyclic engine speed (revolution / minute) as a function of time t (second), imposed on buses equipped with a diesel engine, for carrying out functional characterization tests of fuels emulsified according to l invention and according to the prior art. ( Example II ).
  • FIG. 5 represents a graph of the monodisperse particle size distribution of an emulsified fuel according to the invention, in which the mean diameter is plotted on the abscissa d droplets of the aqueous phase and on the ordinate ⁇ N / N, N being the total number of droplets and ⁇ N the number of droplets d given.
  • Figure 6 represents the cycles of temperature variations and agitation applied to the summer formulations ( fig. 6.1 ) and winter ( fig. 6.2 ) to determine their stability in use.
  • compositions of the emulsifying systems tested are given in Table 2.
  • Table 2 the compositions have been presented in the form of the proportions by weight of each of the constituents of the emulsifying system, it being specified that this represents 1.86% by weight of the final emulsion formulation.
  • This criterion is twofold and targets stability under conditions of use (character dynamic) as well as storage stability at different temperatures.
  • Figure 6 For each “summer” and “winter” formulation, the profile of the temperature variation cycle is illustrated in Figure 6 . Note that the system must be agitated (gentle mechanical agitation, approximately 60 rpm), or at rest depending on the phase of the cycle.
  • Figure 6.1 illustrates the summer formulation cycle and Figure 6.2 . that of the winter formulation.
  • Storage stability is assessed by the more or less long time for the formulation presents the phenomenon of demixing.
  • This emulsifying system has an HLB of 7.2.
  • the 4 kg of emulsifier system is incorporated into the 164 kg of diesel fuel and homogenize this mixture using the propeller agitator rotating at a speed of a few hundred revolutions / min for a few minutes.
  • the propeller agitator rotating at a speed of a few hundred revolutions / min for a few minutes.
  • Container 1 is a conventional container, which is supplied continuously or discontinuously with a diesel / emulsifier / adiitf premix.
  • the fractionation means 3 comprise a static mixer 5 of the type of those of the SMV - 4DM 20 type (5 mixing elements in series) sold by the company SULZER.
  • This mixer consists of a hollow cylinder having a fluid inlet and outlet and defining, inside the cylinder, a zig-zag path for the fluid, using several stages of transverse partitions provided with oblique slots forming fluid passage pipes.
  • the outlet of the static mixer 5 is connected to a conduit 6 opening into the interior of the container 1 (means of conveying 6 the effluent into the container 1 ), while its inlet is connected to a conduit 7 equipped with a pump 8 .
  • the free end 9 of this pipe 7 plunges into the premix or emulsion bath 2 contained in the container 1 .
  • This device is also connected upstream and in the vicinity of the pump inlet 8 to a pipe 10 for water supply, which forms with the valve 11 , the circuit 4 mentioned above.
  • This device is capable of ensuring a large pressure drop, at nominal flow rate, so as to cause the dispersion of the emulsion.
  • the fractionation using this device takes place as follows: after filling the container 1 with the diesel / SE / additives premix, the pump 8 is put into operation so as to establish a circulation of fluid through the mixer static 5 .
  • the solenoid valve 11 is then opened to supply water and mix it with the premix G / SE / A within the pump 8 , this mixture then being conveyed to the static mixer for undergoing fractionation. wish.
  • the pressure of the fluid at the outlet of pump 8 is 5 MPa.
  • the 30 kg of water are introduced in approximately 1 min.
  • the system works in a loop to ensure fractionation for 30 min.
  • 200 kg of emulsion corresponding to the characteristics of the invention are thus obtained.
  • This emulsion has a whitish color and a kinematic viscosity of 6.2 mm 2 / s at 20 ° C.
  • 200 kg of emulsion are also prepared with 164 kg of diesel, 4 kg of emulsifying system, 2 kg of additives consisting of magnesium oxide and toluene and 30 kg of water.
  • the proportions of SORBITHOM® S06: TILOL 163®: NONILFENOL® 9 M OXIETHIL® are 1: 1: 1 and not 3: 2: 1 as provided in paragraph II.1. above.
  • This emulsifying system has an HLB of 8.7.
  • the operating protocol used is that described in PCT patent application WO 93/18 117.
  • Figures 1 and 2 attached clearly show the difference in dimensional profile of the droplets of aqueous dispersed phase.
  • emulsion II.1 A homogeneity in diameter of the droplets can be observed, with a maximum value of the order of ⁇ m, which establishes the monodispersion of the droplets.
  • the water droplets of the emulsion II.2 known ones show a very large dimensional disparity, with a majority of droplets of size greater than 5 ⁇ m and a non-negligible proportion of droplets of size greater than 10 ⁇ m.
  • the buses used for these tests are R enault V éhicules I ndustriels® type R312 vehicles, with a diesel tank fitted with a low point draw-off, so as to avoid defusing the injection pump in the event of braking, turn, or hill.
  • a first bus is supplied with 300 liters of the emulsion according to II.1. and a second comparative bus also with 300 liters of the emulsion according to II.2 .
  • the two buses cover a 100 km urban route. They are then stopped for 48 hours. The two buses are then restarted. Both start. However, after 15 to 30 seconds of idling, the comparative bus stalls, which is not the case for the bus whose fuel is formed by the emulsion according to the invention.
  • the timing of the comparative bus is explained by the lack of stability of the emulsion II.2. , which underwent a phase shift by gravity settling during the 48-hour outage. It follows that during the withdrawal of fuel from the tank base, large amounts of phase-shifted water were brought by the injection pump to the combustion chamber. These excessively high water contents cause the engine to stall irreparably.
  • a series of tests is carried out on the RVI R312 vehicles mentioned above by subjecting them to an operating cycle as shown in FIG. 4 and comprising a phase R of idling, a phase A of acceleration, a phase P of full speed (plateau) and a deceleration phase D.
  • the speeds vary from 500 rpm in phase R to 2,200 rpm in phase P.
  • the duration of the RAPD phases of the cycle is given on the graph. In test conditions, this cycle is repeated a few tens of times on RVI 312 vehicles.
  • This measurement is carried out using a full-flow (online) opacimeter of the type technotest 490.
  • the maximum opacity, expressed in m -1 , is on average 3.51 for pure diesel and 1.22 for the emulsion according to the invention.
  • the measurements of solid particles are carried out using a minitunnel of dilution according to the ISO 8178 standardized method.
  • Tests are carried out using the Peugeot 106 vehicles referred to above, according to protocols standardized in the European Union for the approval of vehicles, namely: ECE (urban route) and EUDC (peri-urban route - hot engine).
  • the preparation protocol is the same as that given in Example II.1.
  • the emulsion prepared in IV.1 is stable and has substantially the same dimensional profile of aqueous droplets as the emulsion obtained according to Example II.1.
  • the speed imposed on the engine during the tests is 2,250 rpm with a average effective pressure of 8.4 MPa (full load).

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Claims (15)

  1. Verbesserter Brennstoff, umfassend eine Emulsion von Wasser in wenigstens einem Kohlenwasserstoff, dadurch gekennzeichnet, daß
    → diese Emulsion ein Emulgatorsystem beinhaltet, welches umfaßt:
    Δ (I) wenigstens einen Sorbitester der allgemeinen Formel:
    Figure 00350001
    worin:
    die Reste X untereinander gleich oder verschieden sind und jeder OH, R1COO- entspricht, wobei R1 einen gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls durch einen Hydroxylrest substituierten aliphatischen Kohlenwasserstoffrest mit 7 bis 22 Kohlenstoffatomen darstellt, wobei R1 vorzugsweise ein Fettsäurerest ist, der mit einer endständigen Carboxylgruppe endet,
    wobei dieser Ester (I) einen HLB-Wert (Hydrophil/Lipophil-Gleichgewicht) zeigt, der zwischen 1 und 9 enthalten ist;
    Δ (II) wenigstens einen Fettsäureester der allgemeinen Formel:
    Figure 00360001
    worin:
    R2 einen gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls durch eine Hydroxylfunktion substituierten aliphatischen Kohlenwasserstoffrest mit 7 bis 22 Kohlenstoffatomen darstellt, wobei R2 vorzugsweise ein Fettsäurerest ist, der durch eine endständige Carboxylgruppe abgeschlossen ist,
    R3 eine lineare oder verzweigte C1-C10-, vorzugsweise C2-C3-Alkylengruppe ist,
    n eine ganze Zahl größer oder gleich 6, vorzugsweise zwischen 6 und 30, enthalten ist,
    R4 H, einem linearen oder verzweigten C1-C10-Alkylrest,
    Figure 00360002
    entspricht,
    wobei R5 die gleiche Definition aufweist wie R3 oben;
    wobei der Ester (II) vorzugsweise einen HLB-Wert von größer oder gleich 9 aufweist;
    Δ (III) wenigstens einen Alkylphenolpolyalkoxyl-Rest der allgemeinen Formel:
    Figure 00370001
    worin:
    R6 einen linearen oder verzweigten C1-C20-, vorzugsweise C5-C20-Alkylrest darstellt;
    m eine ganze Zahl von größer oder gleich 8, vorzugsweise zwischen 8 und 15, ist,
    R7 und R8 jeweils der gleichen Definition entsprechen, welche oben für R3 und R4 der Formel (II) angegeben ist,
    wobei dieser Ester (III) vorzugsweise einen HLB-Wert aufweist, welcher zwischen 10 und 15 enthalten ist;
    dadurch, daß das Emulgatorsystem einen Gesamt-HLB-Wert aufweist, welcher zwischen 6 und 8, vorzugsweise zwischen 6,5 und 7,5 liegt,
    dadurch, daß die Emulsion derart verwirklicht wird, daß die mittlere Größe der Tröpfchen der wäßrigen dispergierten Phase kleiner oder gleich 3 µm, vorzugsweise 2 µm und bevorzugter 1 µm mit einer Standardabweichung von kleiner 1 µm ist.
  2. Brennstoff nach Anspruch 1, dadurch gekennzeichnet, daß die Emulsion wenigstens 5 Gew.-% Wasser umfaßt und dadurch, daß die Konzentration an Emulgatorsystem im Verhältnis zur Gesamtmasse des Brennstoffes kleiner oder gleich 3 Gew.-%, vorzugsweise 2 Gew.-%, beträgt.
  3. Brennstoff nach Anspruch 1 oder nach Anspruch 2, dadurch gekennzeichnet, daß das Emulgatorsystem die Verbindungen (I), (II) und (III) umfaßt und dadurch, daß die Verhältnisse an diesen Verbindungen die folgenden sind:
    (I) 2,5 bis 3,5 Gewichtsteile, vorzugsweise 3 Gewichtsteile,
    (II) 1,5 bis 2,5 Gewichtsteile, vorzugsweise 1,5 bis 2 Gewichtsteile,
    (III) 0,5 bis 1,9 Gewichtsteile, vorzugsweise 0,5 bis 1,5 Gewichtsteile.
  4. Brennstoff nach jedem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß:
    (I) aus den Sorbitoleaten ausgewählt ist, wobei die Sorbit-Sesquioleate bevorzugt sind,
    (II) aus den Oleaten und/oder Stearaten und/oder den Ricinoleaten von Polyethylenglycol (PEG) ausgewählt ist, vorzugsweise aus jenen, bei denen das PEG ein Molgewicht von kleiner oder gleich 450, vorzugsweise in der Größenordnung von 300 aufweist,
    (III) aus den Nonylphenolen und/oder den polyethoxylierten Octylphenolen ausgewählt ist, wobei die polyethoxylierten Nonylphenole besonders bevorzugt sind.
  5. Brennstoff nach Anspruch 4, dadurch gekennzeichnet, daß die Verbindung (II) des Emulgatorsystemes eine Mischung von polyethoxylierten Nonylphenolen, vorzugsweise von zwei polyethoxylierten Nonylphenolen, welche jeweils 9 bis 12 Ethylenoxidreste aufweisen, ist.
  6. Emulgierter Brennstoff nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Kohlenwasserstoff aus der Gruppe der folgenden Produkte ausgewählt ist: Gasöle, Benzine, Kerosine, schwere Heizöle, synthetische Treibstoffe, veresterte oder nicht-veresterte pflanzliche oder tierische Öle und deren Mischungen.
  7. Emulgierter Brennstoff nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß er außer dem Emulgatorsystem Additive umfaßt, welche aus einer oder mehreren ProcetanVerbindungen ausgewählt sind, welche vorzugsweise aus den Peroxiden und/oder den Nitraten oder ihren Mischungen ausgewählt sind.
  8. Emulgierter Brennstoff nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß er als Additiv umfaßt:
    wenigstens einen metallischen oder erdalkalischen Katalysator der Nachverbrennungs-Reaktion von Ruß, wobei der Katalysator vorzugsweise auf Basis von Magnesium, Calcium, Barium, Cer, Kupfer, Eisen oder deren Mischungen vorliegt;
    gegebenenfalls ein Biozid, vorzugsweise ein Bakterizid,
    und gegebenenfalls wenigstens ein Antigelierungsmittel, ausgewählt aus den Glycolen.
  9. Emulgierter Brennstoff nach einem der Ansprüche 1 bis 8, gekennzeichnet durch die folgende Zusammensetzung:
    Kohlenwasserstoff(e)    50 bis 99 %, vorzugsweise 65 bis 99 %
    Wasser    0,1 bis 50 %, vorzugsweise 1 bis 35 %
    Emulgatorsystem    0,05 bis 5 %, vorzugsweise 0,1 bis 3 %
    Additive    0,01 bis 5 %, vorzugsweise 0,05 bis 2 %.
  10. Brennstoff nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß er wenigstens ein verestertes oder nichtverestertes pflanzliches Öl und/oder wenigstens ein Extrakt davon, vorzugsweise im Verhältnis von 1 bis 60 Gew.-% umfaßt.
  11. Additivzusammensetzung für Brennstoff, insbesondere Treibstoff auf Kohlenwasserstoffbasis, dadurch gekennzeichnet, daß sie im wesentlichen umfaßt:
    das Emulgatorsystem, wie es in einem der Ansprüche 1 bis 10 definiert ist,
    und gegebenenfalls wenigstens ein weiteres Additiv, vorzugsweise aus den folgenden Produkten: Procetane, katalytischer Promotor der Verbrennung und Ruß, Biozide, Detergenzien, ammoniakalische Verbindungen, Antigelierungsmittel, veresterte oder nicht-veresterte pflanzliche Öle und deren Mischungen.
  12. Verfahren zum Erhalten eines emulgierten Brennstoffes, dadurch gekennzeichnet, daß es im wesentlichen in gleichzeitiger oder nicht gleichzeitiger Weise umfaßt:
    -a- Einsetzen wenigstens eines Kohlenwasserstoffes, von Wasser und einem Emulgatorsystem, welches umfaßt:
    Δ (I) wenigstens einen Sorbitester der allgemeinen Formel:
    Figure 00400001
    worin:
    die Reste X gleich oder verschieden voneinander sind und jeweils OH, R1COO- entsprechen, wobei R1 einen gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls durch einen Hydroxylrest substituierten aliphatischen Kohlenwasserstoff mit 7 bis 22 Kohlenstoffatomen darstellt, wobei R1 vorzugsweise ein Fettsäurerest ist, welcher von einer endständigen Carboxylgruppe abgeschlossen ist,
    wobei der Ester (I) einen HLB-Wert zeigt, der gleich oder 1 bis 9 ist;
    Δ (II) wenigstens einen Fettsäureester der allgemeinen Formel:
    Figure 00410001
    worin:
    R2 einen gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls durch Hydroxylfunktionen substituierten aliphatischen Kohlenwasserstoffrest mit 7 bis 22 Kohlenstoffatomen darstellt, R2 vorzugsweise ein Fettsäurerest ist, wlecher von einer endständigen Carboxylgruppe abgeschlossen ist,
    R3 einen linearen oder verzweigten C1-C10-, vorzugsweise C2-C3-Alkylenrest darstellt,
    n eine ganze Zahl größer oder gleich 6, vorzugsweise zwischen 6 und 30, ist,
    R4 H, einem linearen oder verzweigten C1-C10-Alkylrest,
    Figure 00410002
    entspricht, wobei R5 die gleiche Definition aufweist, welche oben für R2 gegeben ist;
    wobei der Ester (II) vorzugsweise einen HLB-Wert von größer oder gleich 9 aufweist;
    Δ (III) wenigstens einen polyalkoxylierten Alkylphenolrest der allgemeinen Formel:
    Figure 00420001
    worin:
    R6 einen linearen oder verzweigten C1-C20-, vorzugsweise C5-C20-Alkylrest darstellt;
    m eine ganze Zahl von größer oder gleich 8, vorzugsweise von 8 bis 15, ist,
    R7 und R8 jeweils der gleichen Definition entsprechen, welche oben für R3 und R4 der Formel (II) angegeben ist,
    wobei der Ester (III) vorzugsweise einen HLB-Wert aufweist, welcher zwischen 10 und 15 enthalten ist;
    das Emulgatorsystem einen HLB-Wert zwischen 6 und 8, vorzugsweise zwischen 6,5 und 7,5 aufweist,
    und gegebenenfalls weitere Additive;
    b- Vermischen dieser Bestandteile, so daß eine Wasser-in-Öl-Emulsion erzeugt wird;
    c- und Fraktionieren der Emulsion um die Tröpfchengröße der wäßrigen dispergierten Phase auf eine mittlere Größe kleiner oder gleich 3 µm, vorzugsweise 2 µm und bevorzugter 1 µm mit einer Abweichung unter 1 µm zu reduzieren.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, daß das Emulgatorsystem die folgende Zusammensetzung aufweist:
    (I) 2,5 bis 3,5 Gewichtsteile, vorzugsweise 3 Gewichtsteile,
    (II) 1,5 bis 2,5 Gewichtsteile, vorzugsweise 1,5 bis 2 Gewichtsteile,
    (III) 0,5 bis 1,9 Gewichtsteile, vorzugsweise 0,5 bis 1,5 Gewichtsteile.
  14. Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, daß man während der Stufe -c- Fraktionierungsmittel vom Typ Sieb, statische Mischer, Rotormischer, Ultraschallmischer einsetzt.
  15. Vorrichtung zur Durchführung des Verfahrens nach einem der Ansprüche 10 bis 14, dadurch gekennzeichnet, daß sie im wesentlichen umfaßt:
    wenigstens eine Aufnahme(1), geeignet um eine Vormischung (2) aus Kohlenwasserstoff bzw. kohlenwasserstoffhaltigem System/Emulgator/Additiv(en) und/oder die Emulsion aufzunehmen, welche alles oder einen Teil des Wassers umfaßt, das in seine Konstitution eingeht,
    Mittel (3) zum Fraktionieren der Emulsion, umfassend vorzugsweise wenigstens einen statischen Mischer (5), dessen Eingang mit einer Leitung (7), welche wenigstens mit einer Pumpe (8) verbunden ist, und deren freie Extremitäten (9) dazu bestimmt sind, in den Behälter (2) der Aufnahme (1) einzutauchen, wobei der Ausgang des Mischers (5) mit wahlweisen Ableitmitteln (6) des Abstromes in der Aufnahme (1) verbunden ist,
    und einen Kreislauf (4) zum Einspeisen von Wasser, welcher vorzugsweise wenigstens ein Kanalisierungssystem (10) aufweist, das mit einem Ventil (11) ausgerüstet ist und mit der Leitung (7) stromaufwärts der Pumpe (8) verbunden ist.
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FR2746106B1 (fr) 1998-08-28
AU2296397A (en) 1997-10-10
AU711348B2 (en) 1999-10-14
JP3236024B2 (ja) 2001-12-04
PL328827A1 (en) 1999-02-15

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