CS267777B1 - Emulsion fuel from the oil shares - Google Patents

Abstract

The fuel is prepared from very viscous petroleum fractions, primarily from residues after vacuum distillation of crude oil. Since the fuel is in the form of an oil-in-water emulsion, its viscosity is low, it is very fluid even at a temperature of 20 C, it disperses well in burners at low temperatures and pressures, and its combustion is more complete even at lower excess air in the combustion chamber. The formation of the emulsion is conditioned, in addition to the presence of emulsifiers, by a co-emulsifier based on ammonia-neutralized distillation residue from a by-product of catalytic oxidation of cyclohexane.

Description

CS 267.777 D1 1

SUMMARY OF THE INVENTION The present invention relates to an emulsion fuel of petroleum podium drawers in the form of an oil-type emulsion emulsion suitable for the use of liquid fuel, and has a high viscosity, often a high solidification point, which can be used. They are hungry for storage, transportation and combustion by heating to a higher temperature in order to achieve their desired fluidity, thus allowing them to be transported through pipes and sufficient spray in the furnace burners. Many resistive portions, such as distillation residues from vacuum oil alobo oils, have such a high viscosity that, in order to reduce it to the burner nozzle demand, alobo must be reduced in proportion to reduce viscosity by stiffening proesters. However, such a conversion to a viscous product is associated with both energy losses and material losses and is costly. In the combustion of heavy-duty oils, good atomization and / or use of steam is required. Combustion excellence is achieved with relatively large air surpluses. As a result, the combustion temperature or the heating temperature is reduced. in the case of an excessive excess of air, the fume and the additional surface area increase. With the exces- sive value of the excess air coefficient, the parameters from which the total heat resistance of the quarry depends depends substantially. Currently, these improvements are achieved by emulsifying water into fuel oils. Podlá čsl. No. 2,665,778, heating oil having modified coating properties comprises 0.5 to 20 wt. water-emulsified water with a kva-pi-below-20 yura diameter. When such fuel is injected into the carton, the water is rapidly evaporated and the subsequent subsequent separation of the fuel droplets into the tank, as a result of which the fuel is sprayed more intensively, intensified with the air, all of which allows the lower air coefficient coefficient to be treated in the incinerators. In this case, it is a stable water-in-oil (v / o) emulsion, where the viscosity of the resulting emulsion is determined by the flow properties! the outer phase, the dispersion medium, that is, the oil sub-emulsion. Such a type of emulsion as well as allowing a more complete combustion of the edible oils does not reduce the viscosity of the fuel. Yeah, we know that lowering the viscosity of the oil-based oil can also be achieved by creating an emulsion! oil-in-water (o / v) type, which viscosity is close to the long-water environment. These emulsions can be pumped at temperatures well below the freezing point of the petroleum fraction, have a good fluidity at 20 ° C, therefore higher temperatures do not need to be heated during storage, transport and combustion. It can be perfectly scattered in burners. Despite these uses, it is dependent on the availability and cost of the surfactant needed to form and stabilize the emulsion. Cationic, anionic or non-ionic types of surfactants are used, allobo and their balanced blends in which the desired type of o / w emulsion is achieved and the stability of the emulsion is satisfactory. in which the o / v type emulsions are formed. heavy petroleum products or heavy petroleum by natural bacterial eystems that produce the necessary bio-emulsifiers. Biopolymers, bioemulsifiers and classical surface-active substances are used in the emulsifier system to prepare an emulsion fuel known as "premixed fuel". The horsebacks for energy shavings require large amounts of heating oils, while preparing the ioh emulsion! The o / v type is confronted with the problem of the availability of a relative large number of orifiers and their cost, so that the resulting price of fuel for production and consumers is switching on an economic indicator.

The aforementioned drawbacks are eliminated by the emulsion fuel from these petroleum subioles in the form of an oil-in-water emulsion which essentially contains 50 to 75 wt. oil fraction with a viscosity at 100 ° C of more than 20 mm 2, with 1, 25 to 50 wt. ducts and 1.5 to 15 wt. parts of a mixed emulsifier, which consists of ammonium salts of aqueous product from the cyclohexane to cyclohoxanol and / or cyclohexonone oxidation isolated from the "hydrolysis" stage of acidity of 100 to 350 mg KOH / g and 250 to 500 mg KOH / g and 0.03 to 1 diol ammonium salts of SSi fatty acids and / or allobo emulsifier with HLB value greater than 3.2 CS 267 777 Bi

According to the invention, a mixed emulsifier is used for the preparation of the o / v emulsion and its stabilization, the basic component of which is the ammonium and by-products of the oxidation of cycloxane. For the preparation of amine salts of higher fatty acids, individual fatty acids, thickening products containing several fatty and bituminous acids or esters, distillation residues from fatty acid production or mixtures thereof can also be used. Synthetic emulsifiers or mixtures of amulgators are also used in the mixed emulsifier. with an HLB value greater than 3, the advantage of the blend emulsifier Jo in that the ammonium salts of the byproducts of the catalytic oxidol cyclohexane in combination and the smaller amount of emulsifiers allow the fuel from the oil blend to be drilled 3 with good pumpability, no heating to higher temperatures during storage, transport and incineration to achieve the required viscosity for the burners at the pressurized or vaporized fuel through the burner nozzles. Further, the advantage of the mixed emulsifier is in its higher effect, that is, the formation of an o / v emulsion of oil blends is achieved at a lower amount of components in the blend emulsifier compared to the amounts required to form an o / w emulsion using a separate emulsifier. Also, the preparation of the o / w emulsion is simplified, the mixed emulsifier may also be produced in the emulsification process, for example by using an ammonium salt product of the cyclohexane oxidation dissolved in water together with the stoichiometric or supra-stoichiometric amount of ammonia calculated on fatty acids and fatty acids they are dissolved directly in the petroleum fraction and then form an O / W emulsion with vigorous stirring at a temperature where the petroleum fractions are sufficiently liquid. It is also an advantage of the invention that a water-soluble additive may be used in the o / v-type emulsion in the oil-based fuel composition to reduce the low temperature high temperature corrosion of the device, the freezing temperature-reducing additives, the combustion-improving compounds. , compounds inhibiting microbial proliferation in aqueous and petroleum phases, antifouling compounds in contact with an emulsion with salves, and coarse additives, wherein the additives may be added separately if only one refining is observed or in the mixture if it is to be distilled a complex effect, wherein the compound is chosen so that it does not react reactively to cause loss of water solubility of any of the ingredients or disruption of the emulsion stability. The fuel according to the invention has the additional advantage that in the presence of water in the fuel, its temperature is reduced and thus the formation of nitrogen oxides is reduced. Emissions of sulfur sulfur exides of the present invention depend on the sulfur content of the starting oil fraction, and a mixture of petroleum portions with different sulfur content may also be used to prepare the fuel to meet local standards for sulfur exide emissions. The amount of water in the fuel can change to a wide range. By using a smaller amount, a higher fuel load is achieved but at the expense of higher viscosity. By using a larger amount of jet jet water on the contrary, and a maximum amount of water being given the desired viscosity for the pre-operating purposes, it is also important that the ammonium salts in the mixed emulsifier act as a flame intensifier.

The properties of the fuel from the oil-based portions are described in more detail in the Examples, which are not limiting, but merely illustrate the possibilities described herein.

For the preparation of the fuels mentioned in the example, the following were used: a) oil bed with a characteristic of the table: heavy petroleum subiol 1 2 3 viscosity at 100 ° C, 47 70 105 flash point according to Harousson, ° C 15Ο 205 263 pour point, ° C 4o - - Point of snapping, ° C - 35 4o Sulfur content, mass. B) lead the product from the catalytic oxidation of cyclohexane to cyclohaxanol and / or cyclohexanone isolated from the distillation residue from "hydrolyzate" characterized by the following data: Acid number zmydolnoniaBottom pointWater contentBrom number

256.3 mgKOH / g412.8 mgKOH / g204 ° C 6.9 wt. 23.1 g Br / 100 g Example 1 O / O fluxes from the crude oil-based emulsions were prepared using a varying emulsifier content consisting of the ammonium salt of oleic acid and nasal composition:

Fuel Heavy petroleum fraction / 0 viscosity at 100 ° C47 wt.

Water, wt.

Ammonium salt of oleic acid, wt. C B C 63.5 59 55 35 35 35 1.5 6 to. The obtained spirits were stored at 80 ° C for 30 days. Hot B, Chomulgulators during storage were stable> 20% w / w was separated from water. from total emulsified water. with a high fuel content Λ for Example 2 Spices were prepared in the form of an o / w emulsion with the following composition: A Fuel B c Heavy petroleum product / 0 viscosity at 100 ° C 47 µm -1 / 1% w / w. 62 59 45 Water, 9 wt. Ammonium salt of the byproduct from the catalytic oxidation of cyclohexane to oyclohexonol, wt. 3 6 20

The recovered flames were stored at 80 ° C for 30 days. Fuel A and B dug water during storage. Fuel C was stable, water was not removed. EXAMPLE 3 Hot O / W emulsion formulations were prepared with the following ingredients:

I CS 2Ó7 777 D1

Fuel A B C Heavy Petroleum Subiol / O Viscosity at 100 ° C 70 nNn ^, s ~ 1 / wt. 57,5 55,5 53,5 Water, "6% by weight 35 35 35 Ammonium salt of the water-based product of the catalytic cyclohexane oxide nn cyclohoxanol, mass 6 8 10 Ammonium salt of olojovoj, 5,5 1,5 1,5 Prepared spirits stored at 80 ° C for 30 days did not exclude water, the skewers of emulsified heavy petroleum fraction in omulsion were in the range of 1.5 to 10 µm, The fuels show good flow properties at 35 ° C, the viscosity of the fuel is in the range EXAMPLE h Fuel was prepared in the form of an emulsion of the type " in the "

Fuel A B C Heavy petroleum fraction 0 Viscosity at 100 ° C: 70% w / w 62.5 - - 2 - 1, 105 mm, s, J mass - 57.5 51 Water,? Ammonium salt by-product of catalytic oxidation of cyclohexane to cyclohexanol, wt. 6 7 8 Ammonium salt of fatty acid mixtures, w / w. 1,5 - - Synthetic emulsifier - oxyethylated nonylphenol with 12 moles of ethylene oxide. - 0.5 - Prepared hot at room temperature and at 80 ° C for 30 days did not exclude water, The size of emulsified heavy oil particles in omulsion ranged from 1.5 to 16, um, Fuel viscosity at 50 ° C was 36 mm .3 "'and viscosity pn iv2 - 1 B and C in the range of 12 to 20 mm., Example 5 A fuel in the form of an o / v emulsion was prepared as in Example 3 with the difference in water solubility. as a additive, in the A 1 per cent of the amount of the distillation residue from the production of tri- and tetraethylene glycols, V B B a percentage of the amount of water of magnesium nitrate as an additive of high temperature vanadium corrosion, V fuel C 3 of the amount of water of ammonium nitrate as an additive by combustion and by the formation of soot.

Claims (2)

1. The emulsion fuel oil of íažších units in the form of an oil-in-water characterized in that it comprises up to 75 wt 5θ, oil components share a viscosity at 100 _{C> T} 2-1 are greater than 20 mm and, 25 to 50 weight , parts of water and 1.5 to 15 parts by weight of a mixed emulsifier consisting of 1 part of ammonium salts of a by-product from the catalytic oxidation of cyclohexane to cyclohexanol and / or cyclohexanone, isolated as a distillation residue from a hydrolysis step having an acid number of 100 to 35. ° mgKOH / g and a saponification number of 250 to 5θθ mg KOH / g and 0.03 to 1 part of ammonium salts of higher fatty acids and / or emulsifiers with an IILB value higher than 3.