JPS62167391A - Fuel additive - Google Patents

Abstract

PURPOSE:An additive having an inorganic substance such as a metallic compound, etc., in high concentration and improved compatibility with fuel oil, comprising a composition as an active ingredient obtained by dispersing a bivalent - tetravalent metallic oxide(hydroxide) subjected to adsorption treatment with a specific compound into water by the use of a water-soluble surface active agent. CONSTITUTION:The aimed fuel additive comprising a composition as an active ingredient obtained by dispersing fine particles of one or more oxides(hydroxides) of bivalent - tetravalent metals selected from Mg, Ca, Al, Ba, Mn, Cu, Zn, Fe, Cr, Ti, Sn, Mo and Co having 100-600Angstrom particle diameters subjected to adsorption treatment with one or more of naphthenic acid, tall oil fatty acid, alkylphosphoric acid ester, oleic acid and lauric acid into water by the use of a water-soluble surface active agent.

Description

Detailed Description of the Invention (Field of Industrial Application) This invention is directed to crude oil, heavy oil, etc., which contain a high concentration of metal compounds and are 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 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 sulfur oxides and nitrogen oxides, to suppress the generation of sludge dispersants, emulsion breakers, corrosion inhibitors, and to prevent the accumulation of fuel ash. agent,
It is known as a combustion accelerator, soot inhibitor, ignition accelerator, cetane number improver, freezing point depressant, etc., but these fuel additives are in the form of inorganic metals, metal oxides, metal hydroxides,
It is made into a slurry by mixing fine powder such as carbonate 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 aluminium contained in the composition may precipitate or separate during storage, or when added to fuel oil, it may leak into piping. It may precipitate and block the burner or 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 the contact effect with harmful substances present in combustion flames, exhaust gas, etc. is insufficient. Therefore, sufficient effects as an additive cannot be expected.

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 the content of the metal component, which is the active ingredient of the methane, is low and the price is high.

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 above problems, in this invention, one or two types of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphoric acid ester, oleic acid, and lauric acid are used. Ca, which is made up of fine particles with a particle size of 100 to 600, was subjected to the adsorption treatment as described above.

AI%Ba, Mn, Cu, Zn%Fe,
2~ represented by Cr, Ti%Sn, Mo%Go
One or more types of oxides or hydroxides of tetravalent metals,
The present invention proposes a fuel additive whose active ingredient is a composition obtained by dispersing a water-soluble surfactant in water.

That is, in this invention, one or more of the above-mentioned oxides or hydroxides of di- to tetravalent metals, which are made of fine particles having a particle size of 100 to 600 and have been adsorbed with naphthenic acid or the like, are added to a water-soluble interface. A composition prepared by dispersing an activator in water is used as a fuel additive, and this fuel additive is prepared, for example, as follows.

The above di- to tetravalent metal water-soluble salts, such as chlorides, nitrates,
0HSN11 to NaOH1 to aqueous solution of sulfate, acetate, etc.
．． Add an alkaline agent such as 01+, Ca(OH), etc.
After raising the pH of the liquid to 9 to 11, an oil-soluble oil produced by adding one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate, oleic acid, and lauric acid. The aggregates are filtered, further washed with water for the purpose of desalting, and dehydrated to obtain a powder consisting of fine particles.

The obtained powder composition is added to a water-soluble surfactant and water, and a stable fuel additive using water as a solvent is prepared using a motor, a disperser, a homogenizer, etc.

In this case, the obtained powder is dehydrated and dried to form a water-containing cake (30 to 4 oz of moisture), and a water-soluble surfactant is added to this and stirred to create a stable fuel additive that uses water as a solvent. You can also.

To explain in more detail the method for producing the above powder using 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 Mg(Oll) particles are aggregated and exist as coarse particles.

In this invention, before the fine particles of Mg(01+)2 aggregate and become coarse, the surface is coated with naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate, oleic acid, lauric acid, etc. to coarsen the particles. At the same time, it changes the particles to be lipophilic (oil-soluble).

That is, fine particles of Mg(Otl)z suspended in water are positively charged, and in addition to this, water-insoluble negatively charged substances such as naphthenic acid, petroleum sulfonic acid, tall oil fatty acid, oleic acid, lauric acid, etc. When an organic substance is added, an adsorption reaction due to positive and negative charges generates oil-soluble aggregates as described above.

Specifically, as described above, an alkali agent is added to an aqueous solution of a magnesium compound to increase Pl+ to 9 to 11, and M
After generating fine particles of g(OH) 2, the liquid temperature is lowered to 80~
Raise the temperature to 85°C, add the above naphthenic acid, heat for 7 minutes, stir W1 to make it adsorbed on the surface of Mg(011)2 fine particles,
As a result, the surface of the fine particles becomes lipophilic (water-insoluble) and aggregates.

In this case, naphthenic acid, tall oil fatty acid, sulfonic acid, alkyl phosphoric acid ester, oleic acid, etc. may be added as they are.

There are also 4 of the above! ! The substance may be added as a salt such as Na salt, Ni salt, N114 salt, etc. Furthermore, the above organic substance may be added dissolved in kerosene, normal paraffin, isoparaffin, liquid paraffin, animal or vegetable oil, etc. In this case, In particular, a uniform colloidal solution of an O/W type emulsion with very good dispersibility in water containing a water-soluble surfactant is obtained, and its stability is also good.

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 aggregates generated as described above are filtered, washed with water for the purpose of desalting, and further dehydrated to obtain an oil-soluble magnesium-containing powder.

When this powder is added to water containing a water-soluble surfactant and mixed and stirred with a disper etc., the fine particles of the above-mentioned di- to tetravalent metal oxide or hydroxide are stably dispersed using water as a medium. is created. In addition, the water-soluble surfactants used in this invention include alkyl sulfonates, right end fatty acids, dialkyl sulfone succinates, higher alkyl phosphates, sulfate ester salts of higher fatty acid esters, sulfated oils, and polyoxyethylene alkyls. Phosphate ester salt, polyoxyethylene alkyl ether tarboxate,
Anionic surfactants such as polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl allyl ether, polyoxyethylene alcohol ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene alkyl amide, polyoxy Ethylene alkylamine, polyoxyethylene sorbitol fatty acid ester,
IILB such as Pluronic type and Tetronic type
There are II to 15 nonionic surfactants, and these surfactants may be used alone or in combinations of 28 or more.

The amount of these water-soluble surfactants added must be at least 1%, and if it is less than 1%, the stability of the fuel additive will be affected.

The fuel additive according to the present invention can be used as it is, or a solution obtained by dispersing it in a suitable solvent can be added to fuel oil.

(Effects of the Invention) The fuel additive according to the present invention has naphthenic acid, tall oil fatty acid, petroleum sulfuric acid, etc. , a structure in which one or more of alkyl phosphate esters, oleic acid, and lauric acid are adsorbed, and a lipophilic group of a water-soluble surfactant is adsorbed on the surface and dispersed in an aqueous medium, Therefore, it is extremely stable and does not aggregate or settle even when stored for a long period of time.

In addition, since fuel additives use water as a medium, they have the advantage of being cheaper and easier to handle than additives that use conventional petroleum-based solvents. Uniformly dispersed in the fuel oil by the action of the activator,
This has the advantage that it does not precipitate and does not clog or wear out fuel oil piping or burners.

Further, the fuel additive according to the present invention has the above-mentioned di- to tetravalent gold 1.
i! Contains high concentrations of oxides or hydroxides. For example, regarding magnesium, it has a higher magnesium content than general organic magnesium compounds such as magnesium petroleum sulfonate, magnesium naphthenate, magnesium oleate, and magnesium octylate.
5oz exists as gO. Moreover, since the above metal oxides or hydroxides are composed of fine particles with a particle size of 100 to 600, they have a large surface area, are highly physically and chemically active, and have good contact effects with harmful components. It is.

Therefore, it can be expected that the fuel additive according to the present invention will have sufficient effects even if added in small amounts to fuel oil. For example, it not only suppresses the generation of soot containing a large amount of SOx and NOx, which are sources of air pollution, but also prevents high-temperature corrosion of super heaters due to V, Na, and S, and corrosion of low-temperature parts of boilers due to the generation of SO2 and SOi. Can be suppressed.

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

Production Example 1 Solution A... 15% MgCl 2 aqueous solution 620 parts Solution B --- 20$ NaOH aqueous solution 375 parts Solution C... Added 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 9.5-10. After the fine particles of Mg(OH)* are generated, the liquid temperature is 8.
When the temperature is raised to 0°C, liquid C is added, and the temperature is sufficiently heated and stirred at 80 to 85°C, the magnesium-containing oil-soluble powder aggregates and the liquid becomes transparent.

Next, filter and wash with water to remove the contained inorganic salts! The powder obtained after washing with water contains about 50 dollars of water, but it is made into spherical pellets of φ10s and spread on a wire mesh of 200 mesh at a wind speed of about 3 m1sec.
Dry with hot air at 95° C. for 40 minutes to reduce the moisture content to 2.1%.

50 parts of the dried powder, 7 parts of sodium dodecylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenol ether (IILB l:1.0), and 38 parts of tap water were stirred with a mixing disper for 30 minutes to form a uniform dispersion. I got it.

Note that the MgO content in the produced dispersion was 26%.

Production Example 2 Solution A...15zFeC13 aqueous solution 300 parts Solution B
--20! KOH aqueous solution 150 parts Solution C: Mixed solution of 4 parts tall oil fatty acid and 8 parts kerosene Solution B was added to Solution A, and the pH was raised to 9.5-10 to form fine particles of Fe(Oll)z. After generating, reduce the liquid temperature to 80
When the temperature is raised to 80 DEG C., liquid C is added thereto, and the temperature is sufficiently heated and stirred at 80 to 85 DEG C., the barium-containing oil-soluble powder eventually becomes transparent.

Next, perform filtration and washing with water, &! The powder collected after perhydration contains 40% water, and 80 parts of this water-containing powder (containing 40 parts water), 5 parts of dioctyl sulfone sodium succinate, and polyoxyethylene polyoxypropylene block polymer. (Pluronic) 5 parts and 10 parts of tap water were mixed and stirred for 30 minutes using a dispersion device to obtain a stable dispersion.

Note that the content of Fe, 03 in the produced dispersion was 23%.

Production example 3 A liquid...15zCaC1□ aqueous solution 350 parts B liquid...
... NIl, OH aqueous solution 200 parts Solution C... Mixed solution of 8 parts of petroleum sulfonic acid and 8 parts of kerosene Add Solution B to Solution A to raise the pH to 9.5-IO to make Ca(O) l) After the fine particles are generated, the liquid temperature is increased to 80°.
When the temperature is raised to E, C is raised to E, liquid C is added, and the temperature is sufficiently heated and stirred at 80 to 85°C, the calcium-containing oil-soluble powder aggregates and the liquid becomes transparent.

Next, filtering and washing with water are performed to remove the a-free salts contained therein. The powder obtained after washing the cancer with water contains about 60 dollars of water, but it is made into a spherical pellet of φ10s- 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.

45 parts of dried powder, 2 parts of sodium oleate, 3 parts of polyoxyethylene dodecyl sulfate sodium salt, polyoxyethylene sorbitan fatty acid ester (HLB 10
．． 5) 3 parts and 47 parts of tap water were stirred with a mixing disper to obtain a uniform dispersion. The CaO content in the produced dispersion was 22%.

Usage Example Using a plunger pump, the 6 liquid obtained in Production Example 1.2.3 is mixed into 1/1000th of the fuel and forced into the boiler's fuel piping, causing the boiler's flame to flow together with the fuel. Chipping occurs at the boiler air heater outlet.
Measure the amount of X oxide, S02, and dust, and use the economizer.
803 was measured at the exit, and the super heater (JIS
G:1462 material 5TBA-24) and test piece with air heater (JIS G:1101 material 5S-41)
) was suspended, the amount of corrosion was measured, and each was compared with that without additives. The results are shown in the table below.

The boiler used was a Mitsubishi CE natural circulation type with a maximum continuous evaporation rate of 1507/11 and a maximum working pressure of 125 g/
cI12 maximum operating temperature is 540℃, fuel usage fee is 211
Kg/II.

Procedural amendment (voluntary) September 26, 1986

Claims (1)

[Claims] Adsorption treatment with one or more of naphthenic acid, tall oil fatty acid, petroleum sulfonic acid, alkyl phosphate ester, oleic acid, and lauric acid has a particle size of 100 to 600 Å.
Mg, Ca, Al, Ba, Mn, C consisting of fine particles of
One or more oxides or hydroxides of di- to tetravalent metals represented by u, Zn, Fe, Cr, Ti, Sn, Mo, and Co are added to water using a water-soluble surfactant. A fuel additive characterized by containing a dispersed composition as an active ingredient.