KR20030040692A - Composition for combustion improver additive of heavy fuel oil and its use - Google Patents

Abstract

PURPOSE: An additive composition for improved combustion of heavy fuel oil is provided, which can reduce generation of incombustible carbon and dust while increasing thermal efficiency. CONSTITUTION: The additive composition for improved combustion of heavy fuel oil comprises 30 to 84 wt.% of hydrocarbon based solvent, 10 to 30 wt.% of barium based organic metal compounds selected from the group consisting of barium stearate, barium oleate and their mixtures, 5 to 20 wt.% of dispersant selected from the group consisting of oleic acid, polyisobutylene succinimide, liposoluble polyoxyethylene nonylphenyl ester and their mixtures, and the additive composition further comprises at least one solvents selected from the group consisting of methylethylbenzene with a carbon number of nine, trimethylbenzene, dimethylethyl benzene and its isomer; methylpropylbenzene with a carbon number of ten, dimethylethylbenzene, tetramethylbenzene and its isomer; aromatic compound with a carbon number of 11 to 12 and its isomer; and their mixtures.

Description

Composition for combustion improver additive of heavy fuel oil and its use}

The present invention relates to a combustion promoting additive composition of heavy fuel oil and a method of using the same. More particularly, the amount of unburned carbon and dust by adding a supporting material including a barium-based organometallic compound and a dispersant during combustion of petroleum heavy fuel oil. The present invention relates to a combustion promoting additive composition of heavy fuel oil and a method of using the same, which can reduce fuel consumption by improving thermal efficiency.

The residue fraction obtained from atmospheric distillation process of crude oil is called atmospheric residue oil. The residue oil is classified as a heavy oil A, B, C (bunker A, B, C) products by the difference in kinematic viscosity according to the diesel oil and its blending amount. Commercially produced heavy oil is mainly used in industrial boilers or furnaces and is selected as fuel according to burner / boiler characteristics and user's purpose.

Combustion is a series of physicochemical reactions in which fuel vaporizes to vaporize and vaporized particles are pyrolyzed and oxidized. The better the vaporization, pyrolysis and oxidation, the better the combustibility.

On the other hand, the complete combustion of heavy oil content requires first of all the spraying and mixing of the combustion gas, that is, the ability to make the fuel thinner and the combustion gas mixing ability to bring the fuel into good contact with oxygen. Good evaporative and oxygen contact atmospheres are key requirements for combustibility.

Next, the combustibility of the heavy oil fraction depends on the combustion residence time. In other words, the combustion time varies depending on the size of the boiler, and the longer the combustion time, the better the combustion.

Finally, the combustibility of the heavy oil fraction is highly dependent on the combustion temperature. Combustion temperature can lead to complete combustion as the firebox structure provides an oxygen atmosphere and a temperature sufficient to evaporate and pyrolyze the fuel.

Corresponding to the combustibility improvement function of the boiler, the kinematic viscosity that determines the spray characteristics in terms of the performance of the fuel itself is managed as an important standard under the Petroleum Business Law. However, since kinematic viscosity is a physical property that can promote vaporization in the combustion step, and is not related to subsequent pyrolysis and oxidation, it is not possible to expect complete combustion of heavy fuel oil only by managing the kinematic viscosity.

As described above, the combustibility of the heavy oil is dependent on the characteristics of the combustion apparatus and the physicochemical characteristics of the heavy oil, but due to the limitation of the combustion time and combustion temperature of the boiler combustion apparatus and the high molecular weight and chemical stability of the heavy oil itself. It is difficult to expect complete combustion.

On the other hand, unburned carbon powder (soot) as an incomplete combustion product is a coke and carbonized material due to incomplete thermal decomposition and oxidation of heavy fuel oil, a hydrocarbon compound, and its properties are determined according to the molecular weight and chemical structure of the fuel.

In addition, molecular weight is a factor influencing the evaporation of fuel, and thermal decomposition after evaporation is determined by the chemical structure of each fuel molecule, that is, the intermolecular bonding force. Increasingly, from the single bond material to the aromatic structure and the resonance structure, the thermal decomposition property becomes disadvantageous. That is, the more constituents of heavy oil than the paraffin group, the more aromatic compounds become disadvantageous in thermal decomposition. This determines the oxidation rate, which is the final reaction stage, and determines the combustibility. For example, asphaltenes and resin compounds, which are high molecular aromatic compounds, are typically aromatic compounds which are disadvantageous for combustion in heavy oil.

In order to overcome the above physicochemical properties, oil refineries have implemented quality control by adjusting the blending amount of crude oil, which is a raw material of heavy oil, and also lowering the flash point and continuing to improve initial ignition and combustibility. Quality control, such as lowering the amount of residual carbon, is carried out for combustion.

However, efforts to improve combustibility by improving the properties of the fuel itself have limitations due to the disadvantages of limited production of crude oil in ships, shortage of high-quality crude oil, and increase in introduction cost.

As a technique to solve the above-mentioned problems, the performance limit of the fuel is reduced by injecting various fuels that act as an oxidant directly during combustion, reburn the unburned carbon after combustion, or improve injection property in the injection stage. It is effective in overcoming.

For example, Korean Patent No. 227965 discloses a flame retardant composition in which a lower alcohol and polybutene polypropyl glycol or butylated hydroxy toluene and an organo iron compound having a ferrocene base skeleton are added. However, the oxidation-catalyzed crude combustion additive composition containing ferrocene-based aromatic organoferrous compounds may not only cause process instability due to phase instability, but also have limited compatibility with fuel oils containing a large amount of wax. There is a disadvantage that is used as input.

Korean Patent Laid-Open Publication No. 2000-42107 discloses a crude product obtained by dissolving a fatty acid organic iron compound and a fatty acid organic magnesium compound in an aromatic organic solvent. Korean Patent No. 3363 discloses a metal hydroxide or metal hydroxide in an oxide obtained by oxidizing heavy oil in air. Disclosed is a composition comprising a mixture of metal salts (Cu, Co) and partial oxides obtained by directly dissolving and dispersing oxide powders. However, when dispersing a compound such as iron magnesium and alkali in fuel oil, precipitation may occur due to the polarity difference between the fuel and the metal compound, and when an alkali is used, anionic and cationic surfactants have a common ion effect and an acid-base. There is a problem causing precipitation due to the effect of neutralization reaction.

In order to solve the above problems, the present inventors have conducted extensive research to remove unburned carbon by adding a crude material using a barium-based organometallic compound and a dispersant during combustion of petroleum heavy fuel oil, and remove asphaltenes and polymer precipitates. It was possible to obtain a combustion promoting additive composition of heavy fuel oil by dispersing to suppress the production of unburned carbon during combustion, and the present invention was completed based on this.

Accordingly, it is an object of the present invention to provide a combustion promoting additive composition of heavy fuel oil that can maximize the amount of fuel consumption and equipment conservation through improved thermal efficiency by reducing the amount of unburned carbon and dust during combustion of petroleum heavy fuel oil.

Still another object of the present invention is to provide a method of using the combustion promoting additive composition.

The composition of the present invention for achieving the above object comprises 30 to 84% by weight hydrocarbon solvent, 10 to 30% by weight barium-based organometallic compound and 5 to 20% by weight dispersant.

The method of the present invention for achieving the above another object is used by adding 200 to 2000 ppm of the composition of the present invention to heavy fuel oil.

Hereinafter, the present invention will be described in more detail.

As described above, the present invention relates to a combustion-promoting additive composition of heavy fuel oil and a method of using the same, more specifically, 30 to 84% by weight of a hydrocarbon solvent, 10 to 30% by weight of a barium organometallic compound, and a dispersant 5 The present invention relates to a combustion promoting additive composition of heavy fuel oil and a method of using the same.

According to the present invention, when the petroleum-based heavy fuel oil is burned, by adding the combustion-promoting additive of the present invention, firstly, polymer unburned polymers generated during combustion by dispersing precipitates due to precipitation and condensation of asphaltenes, waxes and resins in heavy oil are dispersed. Production of carbon is suppressed, and secondly, unburned carbon generated after combustion in the presence of an organometallic compound as a metal cocatalyst is reburned, and finally, as a medium for dispersing the metal cocatalyst material and dispersant in heavy oil. By further using the aromatic solvent, the unburned carbon powder can be effectively removed.

Hydrocarbon solvents of the present invention are all materials obtainable from feed materials and residues of the bottom of the heavy aromatic column produced in oil refining and petrochemical processes, kerosene fraction, diesel Powder and mixtures thereof. Since the hydrocarbon solvent has the same chemical structure and average molecular weight as the fuel oil, it is preferable to be the same as the fuel used in each boiler because it is excellent in dispersibility when added to the fuel. In this case, the amount of the hydrocarbon-based solvent is preferably 30 to 84% by weight. If the amount of the hydrocarbon-based solvent is less than 30%, the dissolution and dispersion of the barium-based organic metal are uneven, and the supporting effect is canceled. The amount of organometallic addition and dispersant addition is limited to reduce the supporting effect.

The barium-based organometallic compound of the present invention is added to heavy oil as a metal cocatalyst to reburn the incompletely burned carbon in the combustion process to remove unburned carbon and additionally reduce sulfur oxides (SOx). The organic barium compound is converted into barium oxide (BaO) by oxidation in the combustion process, and then converted into barium sulfate (BaSO ₄ ) by reacting with sulfur oxides in the combustion gas. Barium sulfate is sparingly toxic / nontoxic and is currently used as a dosage for clinical imaging with radiation.

The combustion process of the fuel and the combustion promoting action of the retardant are estimated as follows.

(1) Combustion Process:

Fuel injection ⇒ Fuel vaporization ⇒ Fuel pyrolysis (produces hydrocarbon radicals) ⇒ Fuel oxidation ⇒ Carbon dioxide, water, unburned hydrocarbons, carbon, sulfur oxides, nitrogen oxides and metal ash (ASH) generation.

(2) combustion promoting action of the supporting catalyst:

Oxidation of organobarium compounds ⇒ Barium oxide formation ⇒ Barium oxide and sulfur oxide reaction ⇒ Barium sulfate formation ⇒ Barium sulfate and unburned carbon (oxidation & reduction) ⇒ Barium sulfide and carbon monoxide production.

For example, BaSO ₄ + 4C ⇒ BaS + 4CO as a reaction for promoting combustion of the organic barium compound, and the temperature condition for the reaction to occur is preferably 1000 to 1250 ℃.

In addition, barium is known to have an ability to prevent high temperature corrosion of metals in a boiler by performing an anti-scaling action with alkaline earth metals.

The barium-based organometallic compound of the present invention is particularly preferably selected from the group consisting of barium stearate, barium oleate and mixtures thereof. At this time, the amount of the barium-based organometallic compound is preferably 10 to 30% by weight, if the amount is less than 10%, can not effectively perform the supporting action, if it exceeds 30% the viscosity of the saturated solution increases handling This is hard.

The dispersant of the present invention disperses deposits due to precipitation and condensation of asphaltenes, waxes and resins, thereby suppressing the generation of unburned carbon and preventing fuel agglomeration in the fuel storage tank, thereby achieving atomization of the fuel injection particles and burning them. The conditions are further improved. The dispersing agent includes oleic acid, which is a fatty acid surfactant, polyisobutylene succinimide, which is a succinic amide series, a fat-soluble polyoxyethylene nonylphenyl ether in a petroleum surfactant, and mixtures thereof. In particular, the oleic acid increases the solubility of the barium-based organometal and promotes combustion by acting as an oxygenate during combustion, and the mixed composition of the polyisobutylene succinimide and the fat-soluble polyoxyethylene nonyl phenyl ether It improves combustibility by dispersing sludge including paltenes and resins. At this time, the amount of the dispersant is preferably 5 to 20% by weight. If the amount is less than 5%, the flocculation prevention and dispersion of precipitates such as asphaltenes, waxes and resins are insignificant. The amount of the solvent and the barium-based organometallic compound is limited to reduce the effect.

Meanwhile, an aromatic solvent may be further used as a medium for dispersing the metal cocatalyst material and the dispersant of the present invention in heavy oil. The aromatic solvent may be methylethylbenzene, trimethylbenzene, dimethylethylbenzene and isomers thereof having 9 carbon atoms; Methylpropylbenzene, dimethylethylbenzene, tetramethylbenzene and isomers thereof having 10 carbon atoms; Aromatic compounds having 11 to 12 carbon atoms and isomers thereof; And mixtures thereof.

The combustion promoting additive composition of the present invention is preferably used to add 200 to 2000ppm to the fuel oil during the combustion of heavy fuel oil, and if the addition amount is less than 200ppm, the dust reduction rate is small due to the influence of the combustibility of the heavy oil and the characteristics of the boiler. It is not effective, and if it exceeds 2000 ppm, dust can be reduced to the maximum without being affected by fuel and boiler characteristics, but it can reduce the efficiency of additive operation by reducing the input economic efficiency.

According to the present invention, when the petroleum-based heavy fuel oil is burned, by adding the fuel retardant of the present invention, the amount of pollutants emitted by oxidizing carbon and unburned carbon in soot reduces the volume of dust and removes carbon. Can be reduced. In addition, by removing the unburned carbon attached to the boiler, the heat exchange rate can be improved to save fuel by increasing the thermal efficiency, and the amount of excess oxygen required when operating the boiler can be reduced due to the supporting effect of oxygenated additives. Additional fuel savings can be achieved. In addition, an excellent solubility of the solvent according to the present invention can provide a supporting additive composition having economy in the adoption and application of the catalyst material.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Example 1

53% by weight of the heavy aromatic separation column feed material (solvent) and the remaining residual solvent at the bottom of 25% by weight of barium stearate, 5% by weight of oleic acid, 15% by weight of polyisobutylenesuccinimide and 2% by weight of polyoxyethylene nonylphenyl ether 2M Was added and stirred for 30 minutes with a mixing stirrer to prepare an additive for promoting combustion.

As shown in Table 1 below, 500 ppm of the additive for promoting combustion was added to the heavy oil C, followed by stirring, and after combustion operation in each oil boiler, the amount of unburned carbon was measured and the results are shown in Table 1 below. .

division Measurement company Boiler Capacity Standard Burner type Unburned carbon generation amount (generation amount / collection time) Dust reduction rate Before adding additive After adding additive Example 1 A chemical company 4 tons Rotary 3 bags * / day * bag: 80kg 2.2bag * / day * bag: 80kg 30% Example 2 B food company 5 tons Rotary 6 kg / 8 hours 1.6 kg / 8 hours 70% Example 3 C food company 10 tons Atomizer 7 bags * / day * bag: 80kg 3 bags * / day * bag: 80kg 60% Example 4 D Food Company 50 tons Atomizer 0.9 sachet * / day * sachet: 300kg 0.3 sachet * / day * sachet: 300kg 66%

The measurement company classification of the embodiment shown in Table 1 is classified by the boiler capacity criteria / burner type as the experiment / evaluation was carried out, which is to classify the performance of the supporting additives in various ways.

As shown in Table 1 above, by adding the additive for promoting combustion of the present invention during the combustion of petroleum-based heavy fuel oil, it was possible to reduce the amount of unburned carbon by up to 70%. However, there may be a slight difference in unburned carbon reduction rate and thermal efficiency improvement depending on the characteristics of the fuel as a combustion material and the characteristics of the boiler as a combustion device.

As described above, the additive for promoting combustion according to the present invention is added to the fuel during the combustion of petroleum-based heavy fuel oil, thereby suppressing the production of unburned carbon and dust, and redispersing the pre-produced unburned carbon and dust. It is possible to reduce the amount of heat, thereby improving fuel efficiency and maximizing equipment conservation. In addition, by using the composition according to the present invention, domestic raw and subsidiary materials have been overcome to overcome the performance limitations of low-cost domestic products with respect to petroleum-based fuels using the prior art and to raise the cost due to high dependency on imports of raw materials. It can be solved by lowering the manufacturing cost by using it as a raw material.

Claims (6)

A combustion fuel additive composition for heavy fuel oil, comprising 30 to 84% by weight of a hydrocarbon solvent, 10 to 30% by weight of a barium organometallic compound, and 5 to 20% by weight of a dispersant. The method of claim 1, wherein the hydrocarbon solvent is promoted the combustion of heavy fuel oil, characterized in that selected from the group consisting of a heavy aromatics separation tower feed material (solvent) of the petrochemical process and the residual solvent and kerosene diesel oil and mixtures thereof at the bottom. Additive composition. The additive composition of claim 1, wherein the barium-based organometallic compound is selected from the group consisting of barium stearate, barium oleate, and mixtures thereof. The composition of claim 1, wherein the dispersant is selected from the group consisting of oleic acid, polyisobutylenesuccinimide, fat-soluble polyoxyethylene nonylphenyl ether, and mixtures thereof. The composition of claim 1, wherein the composition comprises methylethylbenzene, trimethylbenzene, dimethylethylbenzene, and isomers thereof having 9 carbon atoms; Methylpropylbenzene, dimethylethylbenzene, tetramethylbenzene and isomers thereof having 10 carbon atoms; Aromatic compounds having 11 to 12 carbon atoms and isomers thereof; And at least one solvent selected from the group consisting of a mixture thereof. A method for using a combustion-promoting additive composition for heavy fuel oil, wherein 200 to 2000 ppm of the composition according to any one of claims 1 to 5 is added to the heavy fuel oil.