JPS61152794A - Fuel additive - Google Patents

Abstract

PURPOSE:An additive having improved miscibility with fuel oil such as crude oil, petroleum coke, kerosine, gas, oil, etc., having a high concentration of metallic compound, comprising a composition obtained by adsorbing naphthenic acid, etc., on fine particles of bivalent - tetravalent metallic oxide(hydroxide) as an active ingredient. CONSTITUTION:(B) One or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkylphosphoric ester, olefinic acid, lauric acid is adsorbed on (A) fine particles consisting of one or more of oxides(hydroxide) having 200-400Angstrom particle diameter, consisting of Mg, Ca, Al, Ba, Mn, Cu, Zn, Cr, Ti, or Sn, to give a composition which is used as an active ingredient, to give the aimed additive. EFFECT:Suppressing evolution of SOX, NOX, soot and smoke, sources of air pollution, and corrosion of boiler caused by evolution of SO2 and SO3.

Description

Detailed Description of the Invention (Industrial Field of Application) This invention is characterized by a high concentration of metal compounds and miscibility with fuel oils such as crude oil, heavy oil, petroleum coke, petroleum pitch, kerosene, and gasoline. is concerned with good fuel oil additives.

(Prior art) Conventional fuel oil additives are used to suppress the generation of harmful components such as sulfur oxides and nitrogen oxides, to suppress 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, fuel ash deposition inhibitors,
It is known as a combustion accelerator, soot inhibitor, ignition accelerator, cetane number improver, freezing point depressant, etc., but these forms are inorganic substances such as inorganic metals, metal oxides, metal hydroxides, and carbonates. The fine powder is mixed with a solvent or water together with a dispersant mainly composed of a surfactant to form a slurry.

(Problem to be solved by the invention) However, in these fuel oil additives, the inorganic substances in the ingredients may precipitate or separate during storage, or may precipitate in piping or burner parts when added to fuel oil. If the burner nozzle is blocked, the burner nozzle may be worn out.

Furthermore, because of poor dispersibility and large particle size, the effect of contact with harmful substances present in combustion flames, exhaust gas, and other sources is insufficient, and a sufficient effect as an additive cannot be expected.

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

These fuel oil additives uniformly mix and dissolve with fuel oil, and therefore have good stability and good contact efficiency with harmful components present in the combustion flame, exhaust gas, etc. The drawbacks are that the content of the metal component, which is an active ingredient in the soluble metal compound, is low and the price is high.

(Means for Solving the Problems) In order to solve the above problems, in this invention, Mg,
Ca, At, Ha, hliy+, Cm,
2 represented by Zn, Cr, Ti, Ss
- Fine particles consisting of one or more oxides or hydroxides of tetravalent metals and having a particle size of 200 to 400X,
The present invention proposes a fuel additive whose active ingredient is a composition adsorbed with one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate ester, oleic acid, and lauric acid.

The present invention is characterized in that fine particles having a particle size of 200 to 400x are adsorbed with 1-naphthenic acid, etc., and used as an active ingredient of a fuel additive, and the manufacturing method thereof is as follows.

The above di- to tetravalent metal water-soluble salts, such as chlorides, nitrates,
Nα0H1KOH%NH, in aqueous solution of sulfate, acetate, etc.
Add an alkaline agent such as OH%Cα(OH) to adjust the pH of the liquid.
Oil-soluble aggregates produced by raising H to 9 to 11 and then adding one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate, oleic acid, and lauric acid. is passed through the mouth, further washed with water for the purpose of desalting, and dehydrated and dried to obtain the desired powder composition consisting of fine particles.

The method for producing this powder composition will be explained in more detail by taking magnesium as an example. Generally, when an alkali agent is added to an aqueous solution of a magnesium compound to raise the pH, magnesium hydroxide is produced. The generated My (OH) t particles are aggregated to form coarse particles.

In this invention, the generated Mg(OH)! Before the fine particles aggregate and become coarse, the particle surface is coated with naphthenic acid, petroleum sulfonic acid, tall oil fatty acid, oleic acid, lauric acid, etc. to prevent the coarsening of the particles and to make the particles lipophilic (oil-soluble). )K change.

That is, suspended in water, 9Mσ(OH)! The fine particles are positively charged, and when water-insoluble organic substances with negative charges such as naphthenic acid, petroleum sulfonic acid, tall oil fatty acids, oleic acid, and lauric acid are added to these, the particles are charged with positive and negative charges. The adsorption reaction produces oil-soluble aggregates as described above.

Specifically, as mentioned above, an alkaline agent is added to an aqueous solution of a magnesium compound to raise the pH to 9 to 11, and the M
After generating fine particles of g(OH)*, the liquid temperature was lowered to 80-8
Raise the temperature to 5°C, add an organic substance such as the above-mentioned 7thenic acid, and sufficiently heat and stir to adsorb MlF (OH) on the surface of the fine particles. As a result, the surface of the fine particles becomes lipophilic (water-insoluble) and aggregates. .

Note that naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphoric acid ester, oleic acid, lauric acid, etc. may be added as they are and adsorbed to the surface of Mg(OH)* fine particles, but in particular, the above organic substances may be added to kerosene, If a solution dissolved in noral paraffin, isoparaffin, liquid paraffin, animal or vegetable oil, etc. is used, the dispersibility in various oils will be very good, and a uniform colloidal solution will be obtained and its stability will be good. The dissolution ratio of the above-mentioned organic substance and solvent is suitably in the range of 1:0.5 to 1:5.

The oil-soluble aggregates produced as described above are collected, washed with water for the purpose of desalination, and further dehydrated and dried to obtain an oil-soluble magnesium-containing powder.

When dispersing the oil-soluble magnesium-containing powder in an organic solvent, the dispersibility of the magnesium-containing powder differs depending on the drying conditions described above.

As for the drying conditions, for example, a water-containing powder (containing about 30 grams of moisture) is made into a pellet of diameter 10 m or about 5 to 101 wI x 5011I11, spread on gold copper, and dried with hot air at a wind speed of 1 to 5 W'yg. In this case, 50°C at 95-100°C
It is best to dehydrate and dry for about 10 minutes to 1 hour.
If the temperature is higher than 0°C, the adsorbed organic substances such as naphthenic acid will decompose, and if the temperature is lower than 95°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 above powder composition has a particle surface of 200 to 400A particle size containing 1m or more of 7thenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate, oleic acid and lauric acid. Because it is adsorbed and coated, it cannot be used with petroleum solvents such as kerosene, spindle oil, liquid paraffin, light oil, heavy oil, etc.
Even when mixed with vegetable oils such as castor oil and olive oil, higher fatty acids such as oleic acid and linoleic acid, higher fatty acid esters such as ethyl oleate, animal oils such as squalene and squalane, and aromatic solvents such as methylnaphthane and alkylbenzene. In the same state as it was dissolved, it is dispersed to form a colloidal solution.

Therefore, even if the above composition is added to fuel oil as it is or as a solution dispersed in an appropriate solvent, the composition will be uniformly dispersed and will not precipitate. Therefore, the fuel oil piping and burner will not be clogged or worn out.

Furthermore, since the composition is composed of fine particles with a particle size of 200 to 400X, it has a large surface area and high physical and chemical activity. Therefore, it has a good contact effect with harmful components, and is not a fool to suppress the generation of 80X1 NOx and soot, which are sources of air pollution. , S03 can be suppressed from boiler corrosion.

Furthermore, the composition contains a high concentration of metal oxide or metal hydroxide. For example, looking at magnesium, it has a higher magnesium content than general organic magnesium compounds such as petroleum magnesium sulfonate, naphthenic magnesium, magnesium oleate, and magnesium octylate, with 50% MgO present.

Therefore, sufficient effects can be expected with addition of small portions.

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

Production example 1 A liquid...15 gct, aqueous solution 620 parts B liquid...
・201NαOH aqueous solution 575 parts Solution C... Add Solution B to Solution A, a mixed solution of 10 parts of naphthenic acid and 15 parts of isoparaffin, and raise the pH to 9.5 to 10 M
After fine particles of σ(on)* are generated, the liquid temperature is raised to 80°C, and liquid C is added. When sufficiently heated and stirred at 80 to 85°C, the magnesium-containing oil-soluble powder aggregates and the liquid becomes transparent.

Next, the mouth is rinsed with water to remove the contained inorganic salts. The powder after rinsing with water contains 50% water, but this was made into spherical pellets with a diameter of 10 m, spread on 200 meshes of gilt copper, and dried with hot air at -95°C for 40 minutes at a wind speed of about 6 mm to reduce the water content to 2. Lower it to .1%. The dried powder is mixed with a mixture of the same weight of heavy oil A and alkylbenzene and stirred with a disper to obtain a 40%<wt%) dispersion.

Production Example 2 Liquid A-151BaC1, aqueous solution 500 parts Liquid B...2
150 parts of 0% KOH solution
When heated and stirred sufficiently at ~85°C, the barium-containing oil-soluble powder aggregates and the liquid becomes transparent.

Next, the powder is rinsed with water to remove inorganic salts contained in the powder. The granules after rinsing with water contain 50% water, and are made into rectangular parallelepiped pellets of 5 x 10 m x 50 IIIll and spread on a 500 mesh gilt copper plate with a wind speed of 5.
”/see Hot air drying is performed at 95° C. for 50 minutes to obtain a powder with a moisture content of 5%. The dried powder is dispersed in kerosene using a disper to obtain a 50% (wt%) dispersion.

Production Example 5 Solution A...15% CaCl, aqueous solution 650 parts Solution B...
・-NH,OH aqueous solution 200 parts Add B solution to A solution and p
After fine particles of CG (OH) are generated to raise H to 9.5 to 10, the liquid temperature is raised to 80°C and liquid C is added to 80°C.
When sufficiently heated and stirred at ~85°C, the calcium-containing oil-soluble powder aggregates and the liquid becomes transparent.

Next, the powder was rinsed with water to remove the inorganic salts contained therein. The powder after the rinse, which contained 60 grams of water, was made into spherical pellets of φ10 mm and placed on a 200-mesh steel plate. Spread and dry with hot air at 90° C. for 1 hour at a wind speed of 1 m/see to obtain a powder with a moisture content of 2%.

The dried powder is mixed with alkylbenzene and stirred with a disper to obtain a 4CI dispersion.

Usage Example: The canned liquid from 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 plancher pump, and then injected into the boiler's flame together with the fuel, which is then used to heat the boiler's air heater. Nitrogen oxide generated at the outlet,
Measure the amount of S02 dust and send it to S03 at the Eco-Tsumasizer outlet.
, and also put a test piece (JIS G) on the air heater.
! +101, material 88-41) The amount of corrosion was measured and compared with that without additives. The results are shown in the table below.

The foiler used is a Mitsubishi CB natural circulation type with a maximum continuous steam volume of 550T/H1 and a maximum working pressure of 125 Kv/c.
d Maximum operating temperature is 540℃ Fuel consumption is 21.5KII
It is A.

However, the measured values are NOX, So, SO, soot and dust are all p, and the amount of corrosion on the test piece is mdd.

] Mi cormorant Procedural amendment (own ship) June 12, 1986

Claims (1)

[Claims] Mg, Ca, Al, Ba, Mn, Cu, Zn, Cr, T
i, consisting of one or more oxides or hydroxides of di- to tetravalent metals represented by Sn, and whose particle size is 200 to 4
The active ingredient is a composition obtained by adsorbing one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphoric acid ester, oleic acid, and lauric acid into fine particles of 00 Å size. fuel additive.