JPS62167393A - Fuel additive - Google Patents

Abstract

PURPOSE:An additive having an inorganic substance such as metallic compound, etc., and improved compatibility with fuel oil, containing a composition as an active ingredient obtained by subjecting the surface of fine particles of iron oxide(hydroxide) to adsorption treatment with a specific compound. CONSTITUTION:The aimed fuel additive comprising a composition as an active ingredient obtained by subjecting the surface of fine particles comprising one or more of iron oxide(hydroxide) having 50-500Angstrom particle diameter to adsorption treatment with one or more of naphthenic acid, tall oil fatty acid, alkylphosphoric acid ester, oleic acid, lauric acid and euric acid.

Description

Detailed Description of the Invention (Field of Industrial Application) This invention is directed to crude oil and heavy oil containing a high concentration of total flex compounds and used in combustion engines such as diesel engines, boilers, heating furnaces, and gas turbines. The present invention relates to a fuel additive that has good miscibility with fuel oils such as petroleum coke, petroleum pitch, kerosene, and gasoline.

(Prior art) Conventional fuel additives have been used to suppress the generation of harmful components such as sulfur oxides and nitrogen oxides, to inhibit the generation of harmful components such as sulfur oxides and nitrogen oxides, to suppress the generation of harmful components such as sludge dispersants, emulsion breakers, corrosion inhibitors, and to deposit fuel ash. Vegetation inhibitor, combustion accelerator, soot inhibitor.

These fuel additives are known as ignition accelerators, sedan value improvers, freezing point depressants, etc., but these fuel additives are in the form of inorganic full-strength,
It is made into a slurry by mixing fine powders of metal oxides, metal hydroxides, carbonates, etc. with water together with a dispersant whose main component is a surfactant.

(Problem to be solved by the invention) However, in this type of fuel additive, the inorganic substances contained in the composition may precipitate or separate during storage, or when added to fuel oil, may cause damage to piping parts or It may precipitate and block the burner, or it may wear out the burner nozzle.

Furthermore, in such fuel additives, the particle size of the inorganic substances contained in the composition is large and the dispersibility is poor. So, I can't expect it to have a partial effect as an additive.

On the other hand, fuel additives in which oil-soluble metal compounds are dissolved in petroleum-based solvents have also been known.

These fuel additives uniformly mix and dissolve with fuel oil, and therefore have good stability and good contact efficiency with harmful components present in exhaust gas and other substances during combustion. The drawback is that it has a low content of metal components, which are the active ingredients, and is expensive.

Therefore, this invention aims to provide crude oil, heavy oil, petroleum coke, petroleum pitch, kerosene, and gasoline that contain high concentrations of inorganic substances such as metal compounds and are used in combustion engines such as diesel engines, boilers, heating furnaces, and gas turbines. The aim is to develop fuel additives that have good miscibility with fuel oils such as

(Means for Solving the Problems) In order to solve the following problems, the present invention uses one or two iron oxides or hydroxides whose particle size is 50 to 500.
The surface of fine particles consisting of seeds or more is coated with naphthenic acid, tall oil fatty acid, and petroleum sulfonic acid.

The present invention proposes a fuel additive containing as an active ingredient Group IJi, which has been adsorbed with one or more of alkyl phosphates, oleic acid, lauric acid, and erucic acid.

That is, in this invention, a composition obtained by adsorbing the surfaces of fine particles having a particle size of 50 to 500 and consisting of one or more types of iron oxides or hydroxides with naphthene m or the like is used as a fuel additive. This fuel additive is prepared, for example, as follows.

Na OII, KOJI, former LOII,
Add an alkaline agent such as Ca(011)2 to adjust the pH of the liquid.
9 to II, and then add one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphoric acid ester, oleic acid, lauric acid, and erucic acid. The aggregates are filtered, further washed with water for the purpose of desalting, and dehydrated and dried to obtain the desired powder composition consisting of fine particles.

To explain in more detail the manufacturing method of this powder composition,
Generally, when an alkali agent is added to an aqueous solution of an iron compound to raise the pH, iron hydroxide is generated. Generated Fe(011)
t, Fe(Otl):+, Fe0O11 particles are aggregated to form coarse particles.

In this invention, Fe(Oll)2, Fe(0+l)z, F
Before fine particles of e0OH aggregate and become coarse, naphthenic acid,
The surface is coated with tall oil fatty acids, petroleum sulfonic acid, alkyl phosphate esters, oleic acid, lauric acid, erucic acid, etc. to prevent the particles from becoming coarser and to make them lipophilic (oil-soluble).

That is, Fe(Off)2 suspended in water, Fe(Oil
), ll, Fe0011 fine particles are positively charged, and when water-insoluble negatively charged organic substances such as naphthenic acid, petroleum sulfonic acid, tall oil fatty acid, oleic acid, lauric acid, and erucic acid are added to them. The above-mentioned oil-soluble aggregates are produced by an adsorption reaction due to positive and negative charges.

Specifically, as described above, an alkali agent is added to an aqueous solution of an iron compound to raise Pl+ to 9 to 11.

After generating fine particles of Fc(Oll)z, Fe(Off)i, and Fc0011, the liquid temperature was raised to 80 to 85°C, and the organic matter of the naphthenic acid rod was added, and the mixture was sufficiently heated and stirred. Fe(Oil)z, Fe(Off),, Fe00
As a result, the surface of the fine particles becomes lipophilic (insoluble in water) and aggregates.

In this case, naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphoric acid ester, oleic acid, erucic acid, etc. are added as they are to prepare Fe(011)t, Fc.
(011)z, Fe0OII may be adsorbed on the surface of the fine particles, but in the above case, in order to improve the cohesiveness and filterability of the powder, and to facilitate washing with water, it is adsorbed in the suspension of the fine particles. When neutralized by adding an acidic agent such as lIc1 at high temperature, the generated Fe(Oll)2, FC(Kano)3, F
There is a possibility that e0OII particles may become unstable.

At this time, the above organic substances such as naphthenic acid, tall oil fatty acids, petroleum sulfones, alkyl phosphate esters, oleic acid, erucic acid, etc. are dissolved in a solvent such as kerosene, normal paraffin, isoparaffin, liquid paraffin, animal and vegetable oil, and then fine particles are formed. When added to a suspension, the fine particles have good agglomeration and filterability, and washing with water is extremely easy, and filtration can be performed without neutralization with lIc1 or the like.

Furthermore, in this case, drying of the powder after filtration becomes easy, and the dispersibility of the powder in various oils is very good, resulting in a uniform colloidal solution with good stability.

In this case, the dissolution ratio of the organic substance and solvent is 1:0.5~
A range of l:3 is suitable.

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

The drying conditions for the powder include, for example, a water-containing powder (containing about 30% moisture), which is made into pellets with a diameter of about 10 m or 5 to 30 mm, spread on a wire mesh, and dried with hot air at 1 to 5 m/sec. In this case, 30 minutes at 95-100℃
It is best to dehydrate and dry for about 1 hour, at 10°C.
If the temperature is higher than 90°C, the adsorbed organic substances such as naphthenic acid will decompose, and if the temperature is lower than 90°C, dehydration will be insufficient. Further, drying for a long time of one hour or more is also not good because it causes deterioration and decomposition of the organic substances.

(Effect of the invention) The fuel additive according to the present invention has a particle size of 50 to 500.
The surface of fine particles consisting of one or more types of human iron oxides or hydroxides is coated with naphthenic acid, tall oil fatty acid sulfonic acid, alkyl phosphate ester, oleic acid,
Since the active ingredient is a composition adsorbed and coated with 1m or more of lauric acid and erucic acid, petroleum solvents such as kerosene, spindle oil, liquid paraffin, light oil and heavy oil, vegetable oils such as castor oil and olive oil, and olein When mixed with acids, higher fatty acids such as linoleic acid, higher fatty acid esters such as ethyl oleate, animal oils such as squalene and squalane, and aromatic solvents such as methylnaphthalene and alkylbenzene, they are dispersed in the same state as the dissolved state. It becomes a colloidal solution.

Therefore, even if the above-mentioned composition is added as it is or a solution obtained by dispersing it in an appropriate solvent is added to fuel oil, it will be uniformly dispersed in the fuel oil, and therefore will not precipitate, and will be used in fuel oil piping and other areas. Will not block or wear out the burner.

In addition, the fuel additive according to the present invention contains iron oxides or iron hydroxides in high concentration. It has a higher iron content than iron compounds, and FeO
There are 50 to 601 of them. Moreover, since the above-mentioned iron oxide or iron hydroxide is composed of fine particles with a particle size of 50 to 500 particles, it has a large surface area, high physical and chemical activity, and has no effect on contact with harmful components. In good condition.

For this reason, the fuel additive according to the present invention can be expected to have a sufficient effect even when added in small amounts to fuel oil. Without, V, Na, S
High-temperature corrosion of super heaters, etc. due to SO□, SO
, corrosion in the boiler's low-temperature parts can be suppressed.

(Example) Examples of this invention will be shown below.

Production example 1 Liquid A...15! FeC 1g aqueous solution 620 parts Liquid B
--20XN11. OI amount aqueous solution 375 parts C liquid...
・Add solution B to solution A of a mixed solution of 10 parts of naphthenic acid and 13 parts of isoparaffin to raise the pH to 9.5 to 10. After fine particles of Fe(Oll)z are generated, the temperature of the solution is lowered to 80.
When the temperature is raised to C, add liquid C, and heat and stir sufficiently at 80 to 85°C, the iron-containing oil-soluble powder will collect and the liquid will become transparent.

Next, filtering and washing with water are performed to remove the a-free salts contained therein. The powder obtained after filtering and washing with water contains about 50% water, or it is made into spherical pellets of φlosm and spread on a wire mesh of 200 mesh at a wind speed of 3 cm/sec 9
Dry with hot air at 5°C for 40 minutes to reduce the moisture content to Z, tX.

Add to the same weight mixture of dry VKA heavy oil and alkylbenzene, stir and mix with a desaber, and make 4oz (Wt$)
A dispersion was obtained.

Production Example 2 Liquid A...15$ FCCI3 aqueous solution 300 parts Liquid B...
... 20% leaf aqueous solution 150 parts Solution C... A mixed solution of 4 parts tall oil fatty acid and 8 parts kerosene Solution B was added to Solution A, the pH was raised to 9.5 to IO, and Fe (Oll. ): After generating 1 of fine particles, the liquid temperature was reduced to 80
When the temperature is increased to 80-85°C and the mixture is sufficiently heated and stirred, the barium-containing oil-soluble powder aggregates and becomes transparent.

Next, filter and wash with water. The powder obtained after filtration and washing with water contains 5 oz of water or
A rectangular parallelepiped pellet of 30 mm was spread on a wire mesh of 300 mesh and dried with hot air at a wind speed of 5 s/sec at 95°C for 30 minutes to obtain a powder with a moisture content of 3z. After drying, it was dispersed in kerosene using a powder disperser to obtain a sox (wt%) dispersion.

Production Example 3 Solution A...15zFeC12 aqueous solution 350 parts Solution B
--200 parts of Na0tl aqueous solution oxidize to Fc0
After forming fine particles of 011, raise the liquid temperature to 80℃, add liquid C, and heat and stir thoroughly at 80-85℃, the iron-containing oil-soluble powder will aggregate and the liquid will become transparent. come.

Next, filtering and washing with water are performed to remove the ammonium contained therein. The powder obtained after filtering and washing with water contains about 60% of water, but it is made into spherical pellets with a diameter of 10 mm and spread on a wire mesh of 200 mesh at a wind speed of 1 ml sec 9
Hot air drying was performed at 0°C for 1 hour to obtain a powder with a moisture content of 2z.

In addition to the dried powder alkylbenzene, the mixture was stirred and mixed with a disper to obtain a 40°C 4-dispersion liquid.

Usage Example The 6 liquid obtained in Production Example 1.2.3 is forcibly mixed into the boiler's fuel piping at a rate of 1/1000 of the fuel using a plunger pump, and mixed with the fuel into the boiler's flame. The amount of nitrogen oxide, SO□, and dust generated at the outlet of the air heater of the boiler was determined by ΔI4, and the economizer
The SO3 was measured at the outlet, and the super heater (JIS
G]462 material 5TBA-24) and test piece with air heater (JIS G:1101 material 5S-41)
The amount of corrosion was measured and compared with that without additives. The results are shown in table f.

The boiler used is a Mitsubishi CE natural circulation type with maximum continuous evaporation capacity of 150T/11 and maximum working pressure of 125Kg.
/c+s2 Maximum operating temperature or 540°C2 Fuel usage fee or 2
1:1Kg/II.

Tewa Cne 13 Orthography (Spontaneous) September 26, 1986

Claims (1)

[Claims] 1 of iron oxide or hydroxide whose particle size is 50 to 500 Å
A composition in which the surface of seeds or fine particles consisting of two or more types is adsorbed with one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate, oleic acid, lauric acid, and erucic acid. A fuel additive characterized by containing as an active ingredient.