JPH0715105B2 - Fuel additive manufacturing method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a fuel additive containing aluminum as a main component, and more specifically, crude oil, petroleum pitch, kerosene, light oil, gasoline, regenerated oil, etc. The present invention relates to a method for producing a fuel additive which has good miscibility in fuel oil and which can maintain a low viscosity even when the content of aluminum is high.

(Conventional technology) Conventionally, fuel oil additives have been used to suppress the generation of harmful components such as sulfur oxides and nitrogen oxides, sludge dispersants, corrosion inhibitors, fuel ash deposit adhesion inhibitors, and combustion. Accelerators, smoke suppressants, ignition accelerators, cetane number improvers, freezing point depressants and the like are known.

Most of these fuel additives are mixed with fine powders of inorganic materials such as inorganic metals, metal oxides, metal hydroxides, and carbonates in a solvent or water together with a dispersant containing a surfactant as a main component to form a slurry. However, if such a slurry is added to the fuel oil by precipitating or separating inorganic substances in the components during storage of the fuel additive, it may become a pipe part or burner. Part of it may settle and block,
The burner nozzle may wear. Further, when the dispersibility is poor and the particle size is large, the effect of contacting with harmful substances present in combustion flame, exhaust gas, and the like is insufficient, and a sufficient effect as an additive cannot be expected.

Further, conventionally, a fuel oil additive in which an oil-soluble metal compound is dissolved in a petroleum solvent or the like is also known. This fuel oil additive is uniformly mixed and dissolved with the fuel oil, and therefore has good stability, but has a drawback that the content of the metal component as an active ingredient in the oil-soluble metal compound is small.

Furthermore, the oil-soluble aluminum compound has a thickening gelation property, and therefore it must be diluted in order to make it easy to handle as a fuel additive, and thus the obtained fuel additive has a content of Al component. Is actually less
As a result, only those containing about 0.1 to 0.5% can be obtained.

On the other hand, JP-A-61-152794A discloses an invention relating to a fuel additive containing an oil-soluble powder composition as an active ingredient. This is a solution of alkaline earth compounds such as magnesium, calcium and barium in NaOH, KOH, NH ₄ OH, Ca (O
H) The pH of the liquid is increased to 9 to 11 by adding an alkaline agent such as ₂ and naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate, olein are formed on the surface of the produced alkaline earth metal hydroxide. An acid, lauric acid or the like is adsorbed to produce an oil-soluble aggregate, which is further washed with water for desalting, and dehydrated and dried to obtain a powder composition, which is used as an active ingredient of a fuel additive. The powder composition obtained by this method has good dispersibility in oils, and the content of the Al component can be increased to about 3%.

(Problems to be Solved by the Invention) However, when the aluminum-containing fuel additive is produced by the above-mentioned method, the pH of the aluminum compound aqueous solution is 9 to 11
Since most of the aluminum compounds are dissolved as aluminate because it is on the alkaline side, Al (OH) with a small particle size
Only ₃ particles can be obtained, and naphthenic acid and the like are adsorbed around the small particles of Al (OH) ₃ to form an oil-soluble powder composition. Small Al
When a composition composed mainly of (OH ₃ ) particles is dispersed in oils, the viscosity of the fuel additive becomes high, so the content of Al component in the fuel additive is limited to about 3%. is there.

In addition, since most of the aluminum compounds are aluminate, many particles that are insufficiently adsorbed are present. Therefore, in the step of washing the oil-soluble aggregate with water, those particles flow out to make the washing wastewater cloudy, or the yield of the powder composition after washing and dehydration drying is reduced.

Furthermore, if particles having insufficient adsorption are contained in the powder composition,
When this powder composition is dispersed in oils, the Al component may be solidified in the form of pudding and lose its fluidity even at this low concentration.

In view of the above situation, the present invention sets the content of the Al component to, for example, 7
It is an object of the present invention to develop a method for producing a fuel additive that can maintain a low viscosity even when the content is as high as about 10% and does not solidify into a pudding.

(Means for Solving Problems) In order to solve the above problems, as a result of earnest research, Al
Since (OH) ₃ is ultrafine particles called hydrosol, it is possible to maintain a low viscosity even with a high content of Al component as described above, and to produce a fuel additive that does not solidify into a purine form. , Al (OH) _{3 has} a particle size of several tens to several hundreds of Å, and it is necessary to completely adsorb naphthenic acid and the like to each of the particles.

Therefore, in the present invention, ammonia water is added to an aqueous solution of a water-soluble salt of aluminum to adjust the pH of the solution to 6 to 9 and the resulting aqueous suspension of aluminum hydroxide is sufficiently heated before naphthenic acid or tall oil is added. O / consisting of an adsorbing substance consisting of one or more of fatty acids, petroleum sulfonic acids, unsaturated fatty acids and saturated fatty acids, an oily non-polar solvent, water and ammonia
w An emulsion is added to agglomerate the particles in the suspension, and the agglomerate is filtered, washed, dried, and dispersed in oil to prepare a method for producing a fuel additive.

The present invention will be described in detail. As the water-soluble salt of aluminum used here, chloride is particularly preferable, but in addition, water-soluble salts of aluminum such as sulfate, nitrate and acetate can be used. .

NH ₄ OH is added to such an aqueous solution of a water-soluble salt of aluminum to raise the pH of the solution to 6 to 9 to produce aluminum hydroxide. After raising the temperature of this liquid to about 80 to 95 ° C and heating it sufficiently, add an o / w emulsion consisting of an adsorbent, an oily non-polar solvent, water and ammonia water to agglomerate the particles in suspension. Excuse me.

As the oily non-polar solvent, kerosene, normal paraffin, liquid paraffin, spindle oil, or other general petroleum solvent can be used, and the ratio of the adsorbent and the non-polar solvent is 1: 0.3 to A range of 1: 2 is preferred.

Further, the amount of the adsorbed substance is preferably added in an amount not less than the amount required to form a monomolecular adsorption layer around the Al particles.

Further, the o / w emulsion composed of the adsorbed substance, the oily non-polar solvent, water and ammonia water is preferably a uniform emulsion having a pH of 7-9.

The oil-soluble aggregate produced as described above is filtered, washed with water for the purpose of desalting, and then dehydrated and dried to obtain an oil-soluble aluminum powder.

The drying conditions are, for example, 1 to 5 m of water-containing powder (water content around 30%) pelletized into φ10 mm or 5 to 10 mm x 30 mm.
Dry for 1 hour at about 100 ℃ under hot air of / sec.

The powder of the oil-soluble aggregate obtained in this manner was treated with kerosene,
Petroleum solvent such as spindle oil, liquid paraffin, light oil, heavy oil, vegetable oil such as castor oil and olive oil, oleic acid,
Higher fatty acids such as linoleic acid, higher fatty acid esters such as ethyl oleate, animal oils such as squalene and squalane, oils such as aromatic solvents such as methylnaphthalene and alkylbenzene, and evenly dispersed at high concentration. A low concentration of colloidal fuel additive is produced.

The oil-soluble aggregate produced as described above is completely adsorbed by one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, unsaturated fatty acid, and saturated fatty acid on all surfaces of aluminum hydroxide particles. Since it is coated, even if it is mixed in the above-mentioned oils, it is uniformly dispersed in the same state as it was dissolved to form a colloidal solution.

(Effect of the invention) As described above, in the present invention, ammonia water is added to an aqueous solution of a water-soluble salt of aluminum to adjust the pH of the solution to 6 to 9 to produce an aqueous suspension of aluminum hydroxide. After sufficiently heating the water suspension of aluminum hydroxide, add an adsorbent, an oily non-polar solvent, and an O / w emulsion consisting of water and ammonia.
Since the pH is set to around 6 to 9 neutral,
Unlike the method disclosed in Japanese Patent No. 15274, there is no formation of aluminate, and only aluminum hydroxide is formed. Furthermore, excess ammonia gradually evaporates with heating,
The pH of the liquid is kept near neutral, and the growth of Al (OH) ₃ particles produced by the coexisting action of ammonium salts is promoted.

On the other hand, in the water suspension of grown Al (OH) ₃ particles, as described above, the adsorbent, the non-polar solvent and the ammonia water are used.
w When an emulsion is added, the emulsion disperses very uniformly in the water suspension, and eventually the adsorbent substance is chemically adsorbed on the surface of all Al (OH) ₃ particles to form an active monomolecular adsorption layer. The non-polar solvent and the remaining adsorbent are physically adsorbed around the adsorbent to form a bimolecular adsorption layer. And
By adding a non-polar solvent to the Al (OH) ₃ particles, the surface becomes more lipophilic, and eventually large oil-soluble aggregates having a diameter of about 1 to 2 mm are obtained. As a result, the steps of filtering and washing the aggregates are greatly facilitated.

Further, in the present invention, most of aluminum water-soluble salts are Al
It becomes (OH) ₃ particles, and the adsorbent is surely adsorbed on the surface. That is, unlike the method disclosed in Japanese Patent Application Laid-Open No. 61-152794, a large amount of insufficiently adsorbed particles exist around aluminum particles due to the formation of aluminate. Therefore, particles are not adsorbed insufficiently even in the washing step for desalting, the yield of aggregates can be increased, and the washing waste water becomes colorless and transparent without white turbidity.

Furthermore, since the monomolecular adsorption layer composed of the adsorbed substance of the agglomerates is covered with the bimolecular adsorption layer mainly composed of a non-polar solvent, which prevents direct contact with the air, the ignition phenomenon during drying occurs. High temperature drying is possible.

On the other hand, since the agglomerate powder obtained by drying is coated with a bimolecular adsorption layer mainly composed of a non-polar solvent on the surface, it is extremely difficult to produce a fuel additive in addition to oils. It can be easily dispersed, the time required for the dispersion step can be shortened, and the fuel additive can be manufactured at low cost.

Further, in the present invention, most of aluminum water-soluble salts are Al
Since it becomes (OH) ₃ particles and is aged, the particle size of Al (OH) ₃ particles becomes extremely large as compared with the particle size disclosed in the above-mentioned JP-A-61-152794. Therefore, even if the aluminum content in the fuel additive is increased, the increase in viscosity of the fuel additive can be suppressed.

Further, since the aggregate powder obtained by the present invention does not contain particles that are not sufficiently adsorbed, it is possible to prevent the phenomenon of solidification into a pudding even when mixed and dispersed in oils.

(Example) Hereinafter, the Example of this invention is shown.

Production Example 1 Solution A: 10% Al ₂ (SO ₄ ) ₃ aqueous solution 300 parts Solution B: NH ₄ OH aqueous solution 50 parts Solution C: naphthenic acid 15 parts, isoparaffin 15 parts, water 50
Part, and o / w type emulsion consisting of 10 parts of NH ₄ OH aqueous solution, add solution B and raise pH to 7.5 to generate fine particles of Al (OH) ₃ and then raise liquid temperature to 80 ℃ ( Crystallization and aging process). When the fine particles have grown to an appropriate particle size, C liquid is added and sufficiently heated and stirred, and naphthenic acid is gradually adsorbed on the surface of the fine particles, isoparaffin is surrounded further, and eventually the oil-soluble powder containing aluminum aggregates. The liquid becomes transparent (adsorption process).

Next, filtration and washing are performed to remove the contained inorganic salt (filtration and washing step). The powder after filtration and water washing contains 50% of water, but this is made into a spherical pellet of φ10 mm, and 200
Spread on a mesh wire mesh and dry with hot air at 110 ° C for 40 minutes at a wind speed of 3 m / sec to reduce the water content to 2.1% (drying process).

The dried powder is mixed with an equal weight mixture of heavy oil A and alkylbenze and stirred with a disper to obtain a dispersion (dispersion step).

Production Example 2 Solution A: 10% AlCl ₃ aqueous solution 200 parts Solution B: NH ₄ OH aqueous solution 40 parts Solution C: Petroleum sulfonic acid 10 parts, kerosene 15 parts, water 40
Part, and o / w type emulsion consisting of 10 parts of NH ₄ OH aqueous solution, add solution B and raise pH to 8.5 to generate fine particles of Al (OH) ₃ and then raise liquid temperature to 80 ℃ ( Crystallization / aging reaction step), and when solution C is added and sufficiently heated and stirred at 80 to 85 ° C, the aluminum-containing oil-soluble powder aggregates and the solution becomes transparent (adsorption reaction step).

Next, filtration and washing are performed to remove the contained inorganic salt (filtration and washing step). 55% water content after washing with water
It is included, but this is made into a spherical pellet of φ10 mm and 200
The powder is spread on a mesh wire net and dried with hot air at a wind speed of 1 m / sec at 105 ° C for 1 hour to obtain a powder having a water content of 2% (drying step).

The dried powder is mixed with alkylbenzene and stirred with a disper to obtain a dispersion (dispersion step).

Next, as a comparative production example, the one disclosed in JP-A-61-152794 is shown below.

Comparative Production Example 1 Solution A: 10% AlCl ₃ aqueous solution 620 parts Solution B: 20% NaOH aqueous solution 375 parts Solution C: mixed solution of 10 parts naphthenic acid and 13 parts isoparaffin Add solution B to solution A After raising the pH to 10 and forming fine particles of Al (OH) ₃ , the liquid temperature is raised to 80 ° C. and the liquid C is added. When heated and stirred sufficiently at 80 to 85 ° C, the aluminum-containing oil-soluble powder aggregates and the liquid becomes transparent.

Then, filtration and washing are performed to remove the contained inorganic salt. After washing the filtrate with water, the powder contains 50% water, but this is made into a spherical pellet with a diameter of 10 mm, spread on a 200 mesh wire mesh, and dried with hot air for 40 minutes at a wind speed of about 3 m / sec 95 ° C to reduce the water content.
Lower to 2.1%. The dried powder is mixed with an equal weight mixture of heavy oil A and alkylbenzene and stirred with a disper to obtain a dispersion liquid.

Comparative Production Example 2 After adding solution B to solution A to raise pH to 10 and producing fine particles of Al (OH) ₃ , raise the solution temperature to 80 ° C, add solution C, and heat and stir at 80-85 ° C. When it is carried out, the oil-soluble powder containing aluminum aggregates and the liquid becomes transparent.

Then, filtration and washing are carried out to remove the inorganic salt contained in the powder. After filtering and washing, the granules contain 50% of water, and this is made into rectangular parallelepiped pellets of 5 mm × 10 mm × 30 mm, spread on a 300 mesh wire mesh, and dried with hot air at a wind speed of 5 m / sec 95 ° C for 30 minutes to obtain a water content. 3% powder is obtained. The dried powder is dispersed in alkylbenzene with a disper to obtain a dispersion liquid.

The accompanying drawings show the relationship between the aluminum concentration and the viscosity of the dispersions of Production Examples 1 and 2 and the dispersions of Comparative Production Examples 1 and 2 obtained as described above. In Comparative Production Examples 1 and 2, even if the aluminum concentration was set to about 3%, the viscosity still increased, so that the aluminum concentration could not be further increased.
The viscosity could be kept low even if the aluminum concentration was about 11-12%.

[Brief description of drawings]

The drawing shows the relationship between the aluminum concentration and the viscosity of the dispersions of Production Examples 1 and 2 and the dispersions of Comparative Production Examples 1 and 2.

Claims (2)

[Claims] 1. A naphthenic acid, tall oil fatty acid after sufficiently heating an aqueous suspension of aluminum hydroxide produced by adding ammonia water to an aqueous solution of a water-soluble salt of aluminum to adjust the pH of the solution to 6-9. , Petroleum sulfonic acid, unsaturated fatty acid,
An adsorbent consisting of one or more saturated fatty acids, an oily non-polar solvent, and an O / w emulsion consisting of water and ammonia are added to agglomerate the particles in the suspension, and the agglomerate is filtered, A method for producing a fuel additive, which comprises washing, drying and dispersing in oils. 2. One or more kinds of kerosene, normal paraffin, isoparaffin, liquid paraffin and spindle oil are used as an oily non-polar solvent, and the ratio of the adsorbent to the solvent is 1: 0.3 to 1: 2. The manufacturing method according to claim 1, wherein the amount is adjusted to a range and added to the water suspension.