JPH0560516B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) This invention is applicable to crude oil, heavy oil, petroleum coke, petroleum pit, and lamps that contain a high concentration of metal compounds and are used in combustion engines such as diesel engines, boilers, heating furnaces, and gas turbines. This invention relates to a fuel additive that has good miscibility with fuel oils such as light oil 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 sludge dispersants, emulsion breakers, corrosion inhibitors, fuel ash deposition inhibitors, Combustion accelerator, soot prevention agent,
Known as ignition accelerators, cetane number improvers, freezing point depressants, etc., these fuel additives are made by surface-activating fine powders of inorganic metals, metal oxides, metal hydroxides, carbonates, etc. It is made into a slurry by mixing it with water together with a dispersant whose main component is a dispersing agent. (Problems to be Solved by the Invention) However, inorganic substances contained in the composition of fuel additives of this type may precipitate or separate during storage, or when added to fuel oil, may cause damage to piping parts or It may precipitate and become clogged in 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 the combustion flame, exhaust gas, etc. is insufficient. A sufficient effect 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 mix and dissolve uniformly with fuel oil, and therefore have good stability and good contact efficiency with harmful components present in exhaust gas and other substances during combustion, but oil-soluble metal compounds The disadvantage is that the content of the metal component, which is an active ingredient, 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, the particle size of naphthenic acid, petroleum sulfonic acid, and alkyl phosphoric acid ester is Mg, Ca, consisting of fine particles of 100 to 600 Å,
Al, Ba, Mn, Cu, Zn, Fe, Cr, Ti, Sn,
1 of hydroxides of di- to tetravalent metals represented by Mo and Co
The present invention proposes a fuel additive whose active ingredient is a composition obtained by acidifying a species or two or more species in water using a water-soluble surfactant. That is, in this invention, the above-mentioned materials 2 to 4 are made of fine particles with a particle size of 100 to 600 Å that have been adsorbed with naphthenic acid or the like.
A composition prepared by dispersing one or more hydroxides of valuable metals in water using a water-soluble surfactant is used as a fuel additive. Created by For aqueous solutions of the above di- to tetravalent metal aqueous salts, such as chlorides, nitrates, sulfates, acetates, etc.
After adding an alkaline agent such as NaOH, KOH, _NH4OH , Ca(OH) ₂ , etc. to raise the pH of the liquid to 9-11, naphthenic acid, tall oil fatty acid, petroleum sulfonic acid,
Oil-soluble aggregates produced by adding one or more of alkyl phosphate esters, oleic acid, and lauric acid are filtered, further washed with water for desalting purposes, and dehydrated to form a powder consisting of fine particles. get. The obtained powder composition is added to a water-soluble surfactant and water, and a stable fuel additive having a solubility in water is prepared using a motor, a disper, a homogenizer, etc. In this case, the obtained powder is made into a water-containing cake (30 to 40% moisture) without dehydration and drying, and a water-soluble surfactant is added to this and stirred to form a stable fuel additive using water as a solvent. You can also create one. 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. generated
Mg(OH) ₂ exists as coarse particles that are aggregated together. In this invention, before the fine particles of Mg(OH) ₂ aggregate and become coarse, the surface is coated with naphthenic acid, petroleum sulfonic acid, alkyl phosphate ester, etc. to prevent the particles from becoming coarse and to make the particles lipophilic (oil-resistant). soluble). That is, fine particles of Mg(OH) ₂ suspended in water are positively charged, which causes naphthenic acid, petroleum sulfonic acid, tall oil fatty acid, oleic acid,
When a water-insoluble organic substance having a negative charge such as lauric acid is added, an oil-soluble aggregate as described above is generated due to an adsorption reaction due to the positive and negative charges. Specifically, as described above, an alkali agent is added to an aqueous solution of a magnesium compound to raise the pH to 9 to 11 to generate fine particles of Mg(OH) ₂ , and then the liquid temperature is raised to 80 to 85 °C. Then, the naphthenic acid is added and sufficiently heated and stirred to be adsorbed onto the surface of the Mg(OH) ₂ fine particles. As a result, the surface of the fine particles becomes lipophilic (insoluble in water) and aggregates. In this case, naphthenic acid, petroleum sulfonic acid, alkyl phosphoric acid ester, etc. may be added as is, or the above organic substances may be added as Na salt, K salt, etc.
It may be added as a salt such as NH ₄ salt, and it may also be added as a solution of the above organic substance in kerosene, normal paraffin, isoparaffin, liquid paraffin, animal or vegetable oil, etc. In this case, especially a water-soluble surfactant. A uniform colloidal solution of an O/W type emulsion is formed which has very good dispersibility in water containing water, and its stability is also good. In this case, the dissolution ratio of the organic substance and solvent is 1:
A range of 0.5 to 1.3 is appropriate. 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 divalent to tetravalent metal oxide or hydroxide are stably dispersed using water as a medium. is created. The water-soluble surfactants used in this invention include alkyl sulfonates, fatty acid soaps,
Dialkyl sulfone succinate, higher alkyl phosphate, sulfate ester salt of higher fatty acid ester,
Sulfated oils, anionic surfactants such as polyoxyethylene alkyl phosphate salts, polyoxyethylene alkyl ether tarboxates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl allyl ethers, polyoxyethylene alcohol ethers, HLB11-15 such as polyoxyethylene fatty acid ester, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene alkylamide, polyoxyethylene alkylamine, polyoxyethylene sorbitol fatty acid ester, Pluronic type, Tetronic type, etc. There are nonionic surfactants, and these surfactants may be used alone or in combination of two or more types. The amount of these water-soluble surfactants added must be at least 1%, and if it is less than 1%, there will be problems with the stability of the fuel additive. In addition, the fuel additive according to this invention can be used as is.
Alternatively, a solution obtained by dispersing this in a suitable solvent can be added to fuel oil for use. (Effects of the Invention) The fuel additive according to the present invention has the above divalent to tetravalent metal hydroxide having a particle size of 100 to 600 Å on the particle surface of one or two of naphthenic acid, petroleum sulfonic acid, and alkyl phosphate ester. It has a structure in which it is dispersed in an aqueous medium with the lipophilic group of a water-soluble surfactant adsorbed on its surface, and is therefore extremely stable and does not aggregate even after long-term storage. , no sedimentation. In addition, since fuel additives also use water as a medium,
Compared to additives using conventional petroleum solvents, it has the advantage of being cheaper and easier to handle, and is evenly dispersed in fuel oil by the action of the water-soluble surfactant contained in the fuel additive. Therefore, it does not precipitate and has the advantage of not clogging or abrasion of fuel oil piping or burners. Moreover, the fuel additive according to this invention is
Contains high concentrations of valent metal hydroxides. For example, regarding magnesium, the content of magnesium is higher than that of general organic magnesium compounds such as magnesium petroleum sulfonate, magnesium naphthenate, magnesium oleate, and magnesium octylate, and 50% is present as MgO. Moreover, since the metal hydroxide is composed of fine particles with a particle size of 100 to 600 Å, it has a large surface area, high physical and chemical activity, and has a good contact effect with harmful components. Therefore, even if the fuel additive according to the present invention is added in small amounts to fuel oil, sufficient effects can be expected. 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 caused by the generation of SO ₂ and SO ₃ . Corrosion can be suppressed. (Example) Examples of the present invention will be shown below. Formulation example 1 Solution A... 620 parts of 15% MgCl ₂ aqueous solution Solution B... 375 parts of 20% NaOH solution Solution C... Mixed solution of 10 parts of naphthenic acid and 13 parts of isoparaffin Add solution B to solution A. Raise the pH to 9.5-10,
After fine particles of Mg(OH) ₂ are generated, the liquid temperature is raised to 80℃, liquid C is added, and the oil-soluble powder containing magnesium is aggregated and the liquid is stirred at 80-85℃. It becomes transparent. Next, the inorganic salts contained are removed by filtering and washing with water. The powder obtained after filtration and washing with water has a moisture content of 50%.
This is made into spherical pellets with a diameter of 10 mm, spread on a 200-mesh wire mesh, and dried with hot air at a wind speed of about 3 m/sec at 95°C for 40 minutes to reduce the moisture content to 2.1%. 50 parts of dried powder, 7 parts of sodium dodecylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenol ether (HLB 13.0), tap water
38 parts were stirred with a mixing device bar for 30 minutes to obtain a uniform dispersion. Furthermore, the MgO content in the produced powdered acid solution was 26%.
It was hot. Production example 2 Solution A...350 parts of 15% _CaCl2 solution Solution B...200 parts of NH ₄ OH solution Solution C...A mixed solution of 8 parts of petroleum sulfonic acid and 8 parts of kerosene Adding solution B to solution A. Raise the pH to 9.5-10
After fine particles of Ca(OH) ₂ are generated, increase the liquid temperature to 80℃, add liquid C, and heat and stir thoroughly at 80 to 85℃. The calcium-containing oil-soluble powder will coagulate and the liquid will form. It becomes transparent. Next, the inorganic salts contained are removed by filtering and washing with water. The powder obtained after filtering and washing with water has a moisture content of 60%.
This was made into spherical pellets with a diameter of 10 mm, spread on a 200-mesh wire mesh, and dried with hot air at a wind speed of about 1 m/sec at 90° C. for 1 hour to obtain a powder with a moisture content of 2%. 45 parts of dried powder, 2 parts of sodium oleate
1 part, polyoxyethylene dodecyl sodium sulfate 3 parts, polyoxyethylene sorbitan fatty acid ester (HLB 10.5) 3 parts, and tap water 47 parts were stirred with a mixing device bar to obtain a uniform dispersion. The CaO content in the produced dispersion was 22%. Example of action: Using a plunger pump, the liquids obtained in Production Examples 1 and 2 are forcibly mixed into the fuel pipe of the boiler at a rate of 1/1000 of the fuel, and are injected together with the fuel into the flame of the boiler. , measure the amount of nitrogen oxide, SO ₂ and dust generated at the outlet of the air heater of the boiler, measure SO ₃ at the outlet of the economizer, and measure the amount of nitrogen oxide, SO 2 and dust generated at the outlet of the air heater of the boiler, and measure the amount of SO 3 at the outlet of the economizer.
A test piece (JIS G3101 material SS-41) was hung from an air heater, and the amount of corrosion was measured and compared with that without additives. The results are shown in the table below. The boiler used is a Mitsubishi CE natural circulation type with a maximum continuous evaporation rate of 350T/H and a maximum working pressure of 125
Kg/ ^cm2 Maximum operating temperature is 540℃, fuel usage fee is
It is 21.3KI/H.

[Table] Yes.

Claims (1)

[Claims] 1 Mg consisting of fine particles with a flow diameter of 100 to 600 Å that has been adsorbed with one or more of naphthenic acid, petroleum sulfonic acid, and alkyl phosphate ester,
Ca, Al, Ba, Mn, Cu, Zn, Fe, Cr, Ti, Sn,
1 of hydroxides of di- to tetravalent metals represented by Mo and Co
A fuel additive characterized in that its active ingredient is a composition obtained by dispersing one or more species in water using a water-soluble surfactant.