TW201610142A - Emulsifying additive for fuel oil and emulsified fuel oil containing the same - Google Patents

Abstract

The present invention provides an emulsifying additive for fuel oil and an emulsified fuel oil prepared by adding the emulsifying additive to fuel oil, which at least comprises an ionic emulsifier (A) which is used to form the emulsified fuel oil from water and fuel oil, an oil-water coalscing agent (B) which facilitates the emulsification reaction between the fuel oil and water, an antioxidant (C), a combustion assistant (D) which enhances the ignition of the emulsified fuel oil, and an emulsion stabilizer (E) which prevents deterioration for long term storage of the emulsified fuel oil.

Description

Fuel oil emulsified additive and emulsified fuel oil containing same

The present invention relates to a fuel oil emulsifying additive and an emulsifying fuel oil, in particular to an emulsifying fuel oil or heavy oil emulsifying additive which can be used for producing high combustion efficiency, and an emulsion fuel oil produced by the same.

Heavy oil, also known as fuel oil, is a dark black liquid, which is mainly composed of atmospheric oil, crude oil residue, cracked residual oil, cracked diesel oil and catalytic diesel oil. Since heavy oil or fuel oil can be used as a fuel, the heat energy generated by the combustion can be further converted into mechanical energy or electric energy, and thus industrially, for example, a boiler or an engine.

However, the quality of fuel oil is not only good or bad, but also has a great impact on the maintenance and utilization of boilers. Poor quality fuel oil is inevitable in the accumulation of sludge in the oil storage tank, and it is easy to block the oil conveying equipment such as the oil nozzle, the oil pipeline, and the pump. It is also often used in preheaters, heat exchangers, exhaust pipes, combustion furnaces, furnaces. Walls and other scales form deposits, which lead to blockage and high and low temperature corrosion. In addition to causing damage to the combustion equipment, shortening the service life, and increasing the operation and maintenance costs, the overall production capacity will also be reduced, thus losing the industrial competitiveness.

In addition, when the quality of the fuel oil is not good or unsatisfactory, it is easy to cause thermal resistance to the combustion device, increase in exhaust gas temperature, partial combustion, excessive air combustion, black smoke, excessive pollutants, etc.; for example, often A large amount of by-products are generated due to incomplete combustion, for example, CO (carbon monoxide), HC (hydrocarbon), carbon oxide (Oxocarbon), NOx (nitrogen oxide), SOx (sulfur oxide), etc.; Harmful gases or air pollutants are emitted into the atmosphere, which can affect human health and hinder the growth of plants, causing serious pollution to the global environment.

In order to solve the above problems, an emulsified fuel oil formed by mixing fuel oil, water and appropriate additives has been widely used as a fuel in industrial furnaces, thereby improving combustion efficiency, reducing fuel oil usage, and reducing combustion process. The amount of harmful substances emitted. However, the addition of an emulsifier to a fuel oil or a heavy oil to form an emulsified fuel oil has a considerable effect in improving thermal efficiency. However, since the stability of the emulsified fuel oil is not satisfactory, oil-water separation is likely to occur even at normal temperature. Not conducive to long-term storage, long-distance transport or mass production. Furthermore, since the emulsified fuel oil is degraded due to the addition of water, it is difficult or impossible to ignite in practice. In addition, currently available additives are overpriced, extremely costly and not economical, and atomization or gasification is not easy, often resulting in a lack of complete combustion.

Therefore, in the current international awareness of environmental protection, it is urgent to study an emulsified additive that can be used to manufacture high-efficiency emulsified fuel oil or heavy oil to reduce the concentration of pollutants discharged from fuel oil combustion. With the total amount, the goal of saving fuel consumption, removing deposits in the combustion chamber, curing equipment, and reducing pollutant emissions is achieved.

<Invention Summary>

The inventors of the present invention have intensively studied in view of the problems of the above-mentioned conventional techniques, and have found that an emulsified fuel oil produced by mixing and reacting a fuel oil emulsified additive of the present invention with fuel oil has long-term storage. The characteristic that the oil and water are not separated can produce a relatively high calorific value almost equal to that of the same volume of fuel oil after combustion, and the concentration and amount of the pollutant in the exhaust gas are both low; thus the present invention has been completed.

That is, according to one aspect of the present invention, it is possible to provide a fuel oil emulsification additive comprising at least an ionic emulsifier (A) for forming water and fuel oil into an emulsified fuel oil for promoting the fuel oil and the water An emulsified oil-water fusion agent (B), an antioxidant (C), a combustion-supporting agent (D) for enhancing the ignition of the emulsified fuel oil, and an emulsified stabilizer for preventing deterioration of the emulsified fuel oil for long-term storage. (E).

Moreover, according to another aspect of the present invention, an emulsified fuel oil may be provided, comprising: fuel oil, water, and the fuel oil emulsification additive; wherein the fuel oil emulsification additive comprises at least an ionic emulsifier (A), oil-water fusion The agent (B), the antioxidant (C), the combustion improver (D), and the emulsion stabilizer (E) are composed.

Hereinafter, the fuel oil emulsion additive of the present invention will be described.

According to the present invention, there is provided a fuel oil emulsification additive comprising at least an ionic emulsifier (A) for forming an emulsified fuel oil with water and fuel oil, and an oily water for enhancing emulsification between the fuel oil and the water. The fusion agent (B), the antioxidant (C), the combustion improver (D) for enhancing the ignition of the emulsified fuel oil, and the emulsion stabilizer (E) for preventing deterioration of the emulsion fuel oil for long-term storage.

The ionic emulsifier (A) used in the fuel oil emulsified additive of the present invention is not particularly limited as long as it has an effect of forming water and fuel oil into an emulsified fuel oil. For example, it may be a cationic emulsifier or an anionic emulsifier. In the ionic emulsifier (A) of the present invention, a cationic emulsifier is preferably used.

The cationic emulsifier which can be used as the ionic emulsifier (A) in the present invention may, for example, be at least a carboxylate, a sulfonate, a sulfate, or a phosphate At least one selected from the group consisting of salts, alkylamines, amides, imidazolines, quaternary ammonium salts, ethylene oxide bisamines, aminated lignin, and the like. The alkylamines which can be used as the ionic emulsifier (A) in the present invention may specifically be, for example, C ₁₂ to C ₂₂ monoalkylamines, 2 to 4 methylene groups. - alkyl polymethylene diamine salts, C ₁₆ ~ C ₂₀ aliphatic hydrocarbyl-substituted ethylene or propylene diamine, alkyl halides reacted with ethylene diamine, N-alkyl ethylene diamine, halogenated alkane and A methylene polyamine, for example, an N-alkyl polyamine obtained by reacting dimethylenetriamine or trimethylenetetramine.

The quaternary ammonium salt used in the present invention as the ionic emulsifier (A) may specifically be, for example, an alkyl quaternary ammonium salt 1831, an alkyl quaternary ammonium salt 18331 or an alkyl quaternary ammonium salt 1621. Or a quaternary ammonium salt having a heterocyclic structure, a quaternary ammonium salt linked via a group such as an amide, an ester or an ether, a C ₈ -C ₂₂ chain aryl group or a cycloalkyl quaternary ammonium salt.

Oil-water fusion used in the fuel oil emulsification additive of the present invention The agent (B) is not particularly limited as long as it has an effect of enhancing the emulsification between the fuel oil and the water. For example, it may be at least one selected from the group consisting of polyoxyalkylphenols, ethanolamines, glycerides, and lower alcohols.

Specific examples of polyoxyalkylphenols, for example, It may be an alkylphenol ethoxylate, a nonylphenol ethoxylate, a polyoxyethylene nonylphenol, an octylphenol ethoxylate, a dodecyl ethoxylate, a polyoxyethylene octylphenol or Dinonylphenol ethoxylate.

Specific examples of ethanolamines, for example, they can It is monoethanolamine, diethanolamine and triethanolamine. As an example of a specific glyceride, for example, it may be a monoacid, a diacid or a triglyceride. Examples of specific lower carbon alcohols, for example, may be methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, isopropanol , neopentyl alcohol, hexanol, heptanol, octanol, ethylene glycol, propylene glycol, glycerol, isovaerythritol and or a compound or mixture thereof.

Relative to 100 parts by weight of the ionic emulsifier (A), in the present hair The content of the oil-water fusion agent (B) in the fuel oil emulsion additive is not particularly limited, and is generally in the range of 0.01 to 30 parts by weight; preferably in the range of 0.01 to 28 parts by weight; more preferably It is in the range of 0.01 to 25 parts by weight; more preferably in the range of 0.01 to 22 parts by weight; particularly preferably in the range of 0.01 to 20 parts by weight.

Antioxidant used in the fuel oil emulsion additive of the present invention (C), as long as it can, anti-oxidation, delay oil oxidation and prolong the service life; it can be an anti-oxidant anti-corrosion agent or an anti-oxidation additive, and is not particularly limited. For example, a phenol such as zinc dithiophosphate, 2,6-di-t-butyl-p-cresol or the like, a thiophosphonium octyl zinc salt, a thiophosphonium dioctyl zinc salt, or the like may be used. A compound selected from the group consisting of thiophosphonium octyl alkyl zinc salt, thiophosphonium second primary alkyl zinc salt, thiophosphorus third alkyl zinc salt, or aromatic amine.

A specific example, for example, it may be N, N'-di-second butyl P-phenylenediamine, N, N'-di-second butyl p-phenylenediamine, 2,6 di-t-butyl-p-cresol, 2,6 di-butanol, 2,4-dimethyl-6 - phenols such as tert-butylphenol and 2,6 di-t-butyl-α-dimethylamino-p-cresol, zinc dithiophosphate, 2,6-di-t-butyl-p-cresol, Thiofosyl zinc salt, thiophosphonium dioctyl zinc salt, thiophosphonium dioctyl zinc salt, thiophosphonium second alkyl zinc salt, thiophosphorus second alkyl zinc salt, and aromatic amine The class constitutes at least one selected from the group.

Relative to 100 parts by weight of the ionic emulsifier (A), in the present hair The content of the antioxidant (C) in the fuel oil emulsified additive of the present invention is not particularly limited as long as it can achieve an antioxidant function, and is generally 0.01 to 30% by weight. Within the range of parts; preferably in the range of 0.01 to 28 parts by weight; more preferably in the range of 0.01 to 25 parts by weight; more desirably in the range of 0.01 to 22 parts by weight; It is in the range of 20 parts by weight.

A combustion improver used in the fuel oil emulsion additive of the present invention (D) is not particularly limited as long as it has an effect of improving the ignition of the emulsified fuel oil. For example, it may be formed of at least one selected from the group consisting of organic peroxides, boron organic compounds, inorganic peroxides, organic acid salts, organic acid metal salts, and metal salts. a compound or mixture.

Used in the combustion improver (D) of the fuel oil emulsion additive of the present invention An example of a specific organic peroxide, for example, it may be at least a third butyl peroxybenzoate, dibutyl butyl peroxide, 2-ethylperoxyhexanoate And at least one selected compound or mixture selected from the group consisting of tributyl methacrylate.

An example of a specific combustion improver (D), for example, Therefore, it contains trimethyl (toluate) isopropyl sulfide phosphate, boron organic compound, acetate, acetate oxalate, succinate, fatty acid salt, alkylbenzenesulfonate, sulfamate, horse Organic acid salts of acid salts, fumarates, citrates, tartrates, citrates, lactates, hydroxy acid salts, benzoates, naphthenates, isooctanoates, etc.; fatty acid copper salts a metal salt of a copper naphthenate, a copper trimethyl sulfonate, a methylcyclopentadienyl tricarboxy manganese, or the like; a potassium permanganate, a sodium permanganate or a potassium dichromate Oxide; and its compound or mixture At least one selected from the group.

Relative to 100 parts by weight of the ionic emulsifier (A), in the present hair The content of the combustion improver (D) in the fuel oil emulsion additive of the present invention is not particularly limited as long as it can achieve the combustion-supporting function, and is generally in the range of 0.01 to 65 parts by weight; preferably 0.01 to 62. It is preferably in the range of 0.01 to 30 parts by weight; more preferably in the range of 0.01 to 58 parts by weight; more preferably in the range of 0.01 to 55 parts by weight.

The emulsion stabilizer (E) of the fuel oil emulsion additive of the present invention is not particularly limited as long as it has an effect of being able to stabilize the emulsification. For example, it may be a compound or a mixture formed of at least one selected from the group consisting of a polyol compound, a phenol compound, and a low carbon number alcohol.

Specific examples of the polyol compound, for example, may be ethylene glycol, propylene glycol, glycerin, isovaerythritol or the like. Specific examples of the phenolic compound may, for example, be cresol, xylenol, butanol, octylphenol, second octylphenol, indophenol or the like.

The content of the emulsion stabilizer (E) in the fuel oil emulsion additive of the present invention is not particularly limited, and is generally 0.01 to 30 parts by weight with respect to 100 parts by weight of the ionic emulsifier (A). Within the range; preferably in the range of 0.01 to 28 parts by weight; more preferably in the range of 0.01 to 25 parts by weight; more desirably in the range of 0.01 to 22 parts by weight; particularly preferably 0.01 to 20 parts by weight Within the range of parts by weight.

The solvent suitable for the fuel oil emulsion additive of the present invention is as long as it is The fuel oil emulsified additive of the present invention can be dissolved, and is not particularly limited. For example, a preferred specific example of the solvent, for example, may be selected from the group consisting of diethylene glycol dibutyl ether, dibutyl phthalate, butyl acetate, and methyl isobutyl ketone. At least one compound or mixture formed.

The fuel oil emulsion additive of the present invention is suitably used for fuel oils such as emulsified diesel heavy oil or a mixture thereof.

"Embodiment" <Example 1-5> (Preparation of fuel oil emulsion additive)

The ionic emulsifier (A), the oil-water fusion agent (B), the antioxidant (C), the combustion improver (D), and the emulsion stabilizer (E) are added to the 1 liter container according to the dosage ratio shown in Table 1. The mixture is stirred and mixed to prepare fuel oil emulsion additives A1 to A5.

Wherein, the ionic emulsifier (A) is a mixture of N-alkyl polymethylene diamine salts, alkyl quaternary ammonium salts 1831 and N-alkyl polyamines; and the oil-water fusion agent (B) is C III a mixture of an alcohol, a polyoxyethylene nonylphenol, and the like; an antioxidant (C) is a 2,6-di-t-butyl group Cresol; the combustion improver (D) is a mixture of an alkylbenzenesulfonate, a copper naphthenate, a potassium permanganate and a copper trimethylglycolide; the emulsion stabilizer (E) is octylphenol, A mixture of isoprene and the like.

<Example 6-20> (Preparation of emulsion fuel oil)

In the vessel, 1750 g of water and 3250 g of fuel oil preheated to 85 ° C were respectively charged, and the fuel oil emulsion additives A1 to A5 obtained in the above Examples 1-5 were added as shown in Table 2, and the temperature was slow. The fuel oil and water were emulsified by stirring at a rapid rate, and then the emulsified fuel oils S1 to S15 were formed by rapid agitation (see Examples 6 to 20).

The obtained emulsified fuel oils S1 to S15 were stored in a space at a constant temperature of 50 ° C, and the emulsified state was observed, and the storage period until the oil-water separation phenomenon occurred was recorded. The results are shown in Table 2. The calorific value of the emulsified fuel oils S1 to S15 obtained in the above Examples 6 to 20 was measured by a microcomputer calorie meter and recorded, as shown in Table 2.

It can be seen from the results of Examples 6 to 20 shown in Table 2: The emulsified fuel oils S1~S15 made by the fuel oil emulsification additive of the invention can be stored for more than 171 days without being separated by oil and water even if kept at a high temperature of 50 ° C, and the calorific value is also 9.89 仟 / More than gram.

Thus, the fuel oil emulsified additive according to the present invention is ignited The oil and water mixing and reaction can obtain a characteristic that the oil and water are not separated for a long time, and after burning, a heat value which is almost equal to that of the same volume of fuel oil can be obtained, and the concentration and quantity of the pollutants in the exhaust gas are generated. Emulsified fuel oil with low characteristics; thus, it can reduce the concentration and total amount of pollutants discharged from fuel oil combustion, and achieve the effects of saving fuel consumption, removing deposits in the combustion chamber, curing equipment, and reducing pollutant emissions.

In addition, the enumerated persons in the above embodiments are used for illustration and description. It should be noted that the embodiments of the present invention are not limited thereto. also, The present invention is not limited to the above description, and all changes, and equivalents and modifications of the scope of the claims, and other combinations of the embodiments as described above, are included in the scope of the invention. Modification.

Claims (7)

A fuel oil emulsification additive comprising the following components: 100 parts by weight of an ionic emulsifier (A); 0.01 to 30 parts by weight of an oil-water fusion agent (B); 0.01 to 30 parts by weight of an antioxidant (C); 0.01 to 65 parts by weight of the combustion improver (D); and 0.01 to 20 parts by weight of the emulsion stabilizer (E). The fuel oil emulsion additive according to claim 1, wherein the ionic emulsifier (A) contains at least a carboxylate, a sulfonate, a sulfate salt, a phosphate salt, an alkylamine, or an amide. a mixture of at least one selected from the group consisting of imidazolines, quaternary ammonium salts, ethylene oxide bisamines, aminated lignin, and the like. The fuel oil emulsion additive according to claim 1, wherein the oil-water fusion agent (B) is at least contained in a group consisting of polyoxyalkylphenols, ethanolamines, glycerides, and low carbon alcohols. Select at least one of them. The fuel oil emulsification additive according to claim 1, wherein the antioxidant (C) contains at least a peroxide, a boron organic compound, an inorganic peroxide, an organic acid salt, an organic acid metal salt, and a metal salt. At least one of the selected mixtures selected from the group consisting of. The fuel oil emulsification additive according to claim 1, wherein the combustion improver (D) contains at least benzotriene peroxide, dibutyl butyl peroxide, and tert-butyl 2-ethylperoxyhexanoate, And a mixture of at least one selected from the group consisting of tributyl methacrylate. The fuel oil emulsion additive according to claim 1, wherein the emulsion stabilizer (E) is at least one selected from the group consisting of a polyol compound, a phenol compound, and a low carbon alcohol. a compound or mixture. An emulsified fuel oil comprising the fuel oil emulsification additive, water and fuel oil according to any one of claims 1 to 6, wherein the ratio of water to fuel oil is 25 to 45%: 55~ In the range of 75%, the fuel oil emulsification additive is added in the range of 1% to 25%.