CS267777B1 - Emulsion fuel from heavier oil fractions - Google Patents

Abstract

The fuel is prepared from a very visoznyoh oil shares, especially from residuals after vacuum distillation of oil. In that the fuel is in the form of a type emulsion oil in water its viscosity is low it is very fluid at temperature 20 C, goodness bursts into flames low temperature and pressures a its burning is more perfect even with the lower eater prebytkooh air in peoiaoh, Vmik the emulsion is conditioned in addition to the presence emulsifiers, and a co-emulsifier based on ammonia neutralized distillation residue from the next product from the catalyst cyclohexane oxidase.

Description

The present invention relates to an emulsion fuel of heavy petroleum fractions in the form of an oil-in-water type, suitable for equipment using liquid fuels.

Heavier petroleum materials are characterized by high viscosity, often high freezing point, which weighs even more. They must be heated to a higher temperature during storage, transport and before incineration in order to achieve the required fluidity and thus allow their economical transport by pipeline and sufficient atomization in the burners of the furnace. Many heavier oil shares such as Distillation residues from the vacuum feed of oils or from fission processes have such a high viscosity that in order to reduce it to the value required in the burner nozzles, they must be controlled with lighter fractions or a reduction in viscosity is achieved by fission processes. However, token conversion to less viscous products is associated with energy and mass losses and is economically expensive. When burning heavy fuel oils, good atomization is required by pressure burners or using steam. Combustion perfection is achieved with relatively large excess air. As a result, the combustion temperature decreases, or with a small excess of air, smoke and clogging of additional surfaces increase. As the value of the excess air coefficient increases, the parameters on which the overall thermal efficiency of the furnace depends significantly deteriorate. At present, for these reasons, improvements are achieved by emulsifying water in heating oils. According to Czechoslovakia. 20 2'1'1578 heating oil with modified combustion properties contains 0.5 to 20 .mu.m, of emulsified water with a droplet diameter of less than 20 .mu.m. When injecting this fuel into the furnace, the water evaporates quickly and causes further subsequent division of fuel droplets into monaio, as a result of which there is a more perfect atomization of fuel, its more intensive contact with air, all allowing to work in combustion plants with lower air excess coefficient. it is a stable water-in-oil / w / o emulsion, where the viscosity of the resulting emulsion is given by the flow properties of the external phase, the dispersion medium, i.e. the petroleum fraction of the emulsion. This type of combustion does not reduce the viscosity of the fuel, although it allows better combustion of heating oils. It is known that a reduction in the viscosity of heavier oil fractions can also be achieved by forming an emulsion! of the oil-in-water (o / w) type, whose viscosity approaches the dispersion medium - water. These compounds can be pumped even at temperatures well below the freezing point of the oil fraction, and have a good flowability at 20 DEG C., so they do not need to be heated to a higher temperature during storage, transport and incineration. They can be perfectly sprayed in carbide burners. Despite these advantages, their use depends on the availability and cost of the surfactants needed to form and stabilize the emulsions. Cationic, anionic or nonionic surfactant types or balanced mixtures thereof are used in which the desired type of o / v emulsion is achieved and satisfactory stability of the etulinum. Another solution is described in U.S. Pat. No. 4,618,348, where o / w emulsions are formed in heavy petroleum products or heavy oils using natural bacterial crystals that produce the necessary bioemulsifiers. Biopolymers, bioemulsifiers and conventional surfactants are used in the emulsification system for the preparation of emulsion fuel, referred to as preatomized fuel. Kenya for energy aces large amounts of heating oils are required, when preparing ioh emulsion! The o / w type also encounters the problem of the availability of a relatively large number of hydraulics and their price, so that the resulting price of fuel before production and consumption meets the economic indicator.

The above mentioned deficiencies are eliminated emulsion fuel of lažěích oil shares as an oil-in-water, which is characterized in that it comprises 50 to 75 wt. Parts of the oil units having a viscosity at 100 DEG C. vačšoj than 20 mm ^2, p ~ ^1, 25 to 50 parts by weight of water and 1.5 to 15 parts by weight of a mixed emulsifier consisting of ammonium salts of a by-product of the catalytic oxidation of cyclohexane to cyclohoxonol α / or cyclohexonane, isolated as a distillation residue from a hydrolysis stage with an acid number of 100 to 35 ° C. mg KOH / g and a dilution number of 25Ο to 500 mg KOH / g and 0.03 to 1 part of ammonium salts of higher fatty acids and / or an emulsifier with an HLB value higher than 3,

CS 267 777 Bl

According to the invention, a buffered emulsifier is used for the preparation of the o / w emulsion and its stabilization, the basic component of which is the ammonium salts of the by-product of the oxidation of cyclohoxane. Individual fatty acids, technical products containing several fatty and bituminous acids or their esters, distillation residues from the production of fatty acids or their mixtures can be used for the preparation of ammonium salts of higher fatty acids. Synthetic emulsifiers or mixtures of emulsifiers are also used in the mixed emulsifier. with an HLB value higher than 3. The advantage of a mixed emulsifier is that the ammonium salts of the by-product of the catalytic oxidation of cyclohexane in combination with a smaller amount of other oxidizers allow to produce fuel from heavier petroleum fractions with good pumpability, without having to heat them to higher storage temperatures. , transport and combustion to achieve the required viscosity for burners by pressurizing or steam spraying fuel through the burner nozzles. Another advantage of the mixed emulsifier is in its higher effect, i. that the formation of an o / w emulsion from heavier petroleum fractions is achieved with a lower amount of components in the mixed emulsifier compared to the amounts required to form an o / w emulsion using the emulsifier alone. The preparation of an o / w emulsion is also simplified. The atmospheric emulsifier can also be formed in the emulsification process, for example by using ammonium salts of the cyclohexane oxidation by-product dissolved in water together with a stoichiometric or overstoichiometric amount of ammonia calculated on fatty acids and the fatty acids being dissolved directly in oil. then, with vigorous stirring at a temperature when the oil fractions are sufficiently liquid, an o / w emulsion is formed. The advantage of the solution according to the invention is also that , to reduce the low-temperature and high-temperature corrosion of the plant, water-freezing additives, combustion-improving compounds, water- and oil-phase-inhibiting microbial growth compounds, iron-emulsion-suppressing rust-forming compounds and saucer additives, each of which may be added especially if only one treatment is monitored but or in a mixture if a complex effect is to be deoielled, the compounds being chosen so that no reactions take place between them which would cause a loss of water solubility of any of the additives or a disturbance of the stability of the emulsion. The fuel according to the invention also has the further advantage that, due to the presence of water in the fuel, its combustion temperature decreases and thus the formation of nitrogen oxides is also reduced. Emissions of sulfur exides from the fuel according to the invention depend on the sulfur content of the starting oil bed, and mixtures of oil fractions with different sulfur contents can also be used for the preparation, which makes it possible to prepare the fuel to meet local sulfur exide emission standards. The amount of water in the fuel can vary within wide limits. By using a smaller amount, a higher calorific value of the fuel is achieved, but at the expense of a higher viscosity. When using a larger amount of water, the opposite is true and the limit of the maximum amount of water is given by the required viscosity for operational purposes. It is also not negligible that the ammonium salts in the mixed emulsifier act as a flame retardant.

The properties of the fuel from the stiffer petroleum fractions are set out in more detail in the examples, which do not limit but only illustrate the possibilities described in the invention.

The following were used to prepare the fuels listed in the examples:

(a) heavy oil fractions with characteristics according to the following table:

Heavy oil podiol 1 2 3 Viscosity at 100, the RAM ² .e "^ 47 70 105 Flash point according to Marousson, C ISO 205 263 Freezing point, ° C 4o - - Softening point, ° C - 35 4o Sulfur content, mass. 2.8 3.1 3.7

CS 267 777 B1

b) a by-product from the catalytic oxidation of cyclohexane to cyclohexanol and / or cyclohexanone isolated as a distillation residue from the hydrolysis step characterized by the following compounds;

Acid number 256.3 mgKOH / g

Saponification number 4 12.8 mgKOH / g

Flash point 20 ^ 4 ° C

Water content 6.9 wt.

Bromine number 23.1 g Br / 100 g

Example 1

Fuels from other petroleum fractions in the form of an o / w emulsion were prepared using a different content of emulsifier, which formed the ammonium salt of oleic acid, and poured the following composition:

Fuel

ABC

Heavy petroleum fraction / 0 viscosity at 100 ° C 2 ~ 1 ύ? ΠΠΉ, S ’/, $ wt. 03.5 5955

Water, $ wt. 35 3535

Ammonium salt of oleic acid, wt. 1.5 610

The obtained fuels were stored at 80 ° C for 30 days. Fuels B, C with a high content of emulsifiers during storage were stable> no water separation. During storage, 20% by weight of fuel A was separated from the total emulsified water.

Example 2

Fuels were prepared in the form of an o / w emulsion with the following composition:

Fuel

ABC

Heavy petroleum product / 0 viscosity at 100 ° C 2 1 1.

mm. s /,% wt. 62 5945

Water, $ wt. 35 3535

Ammonium salt of the by-product of the catalytic oxidation of cyclohexane to cyclohexanol, mass, 3,620

The obtained fuels were stored at 80 ° C for 30 days. Fuel A and B extracted water during storage. Fuel C was stable, no water separation.

Example 3

Fuels were prepared in the form of an o / w emulsion with the following composition;

CS 267 777 B1

Fuel

Λ B C Heavy oil podiol / 0 viscosity at 100 ⁰ C o ·, 70 mm, s /, Jo wt. 57.5 55.5 53.5 Water, yes mass. 35 35 35 The ammonium salt of the aqueous product from the catalytic oxidation of cyclohoxane to cyclohoxanol, wt. 6 8 10 Ammonium salt of oleic acid, m.p. ’» 5 ’, 5 1.5

The prepared fuels did not emit water when stored at 80 DEG C. for 30 days. Fuels show good flow properties at / 2—1 September 20 to 25 ™ .s.

° C, the viscosity of the fuel is in the range of Example h

The fuel was prepared in the form of an o / w omulsion with the following composition:

Fuel Heavy petroleum 0 viscosity at 100 ° C; A B C 70 mm ^ .s ”^,% wt. 62.5 - - 2 - 1 _f 105 mm. s, Jo mass. - 57.5 51 Water, J »wt. The ammonium salt of the catalytic by-product 30 35 '»0 oxidation of cyclohexane to cyclohoxanol, wt. 6 7 8 Ammonium salt of a mixture of fatty acids, i wt. Synthetic emulsifier - oxyethylated nonyl- 1.5 - - phonol with 12 moles of ethylene oxide, J> wt. - 0.5 Prepared fuels for storage at the laboratory temperature and at 80 ° C for 30 days

not exclude water »Veíkoeí particles of the emulsified oil íažkóho interest in omulzii was between 1.5 and gentian, um, and the fuel viscosity at 50 ° C, the nan 36» s ^- "and the viscosity of the stump IV / 2-1

B and C in the range of 12 to 20 mm .s.

Example 5

The fuel was prepared in the form of an o / w emulsion as in Example 3 β with the difference that water-soluble substances dissolved in water were added as additives. V fuel A 1 per cent of the amount of water distillation residues from the production of tri- and tetraethylene glycols, V fuel B 0.8 per cent of the amount of water magnesium nitrate as an additive of high temperature vanadium corrosion, V fuel C 3 per cent of the amount of water ammonium nitrate as a combustion promoting additive by carbon black formation.

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.