JPH06306375A - Additive for emulsified heavy oil fuel and fuel - Google Patents

Abstract

PURPOSE:To obtain the title additive which can promote the combustion of heavy oil, can improve its complete combustion to markedly reduce the amount of smoke dust contained in the combustion exhaust gas and arising from the residual carbon abundantly contained in heavy oil. CONSTITUTION:The additive is prepared by using a rare earth metal salt of an aromatic sulfonic acid/formaldehyde condensate as the essential component, and the title fuel is prepared by adding this additive to heavy oil.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel additive added as a combustion accelerator for heavy oil emulsion fuels, and a fuel composition containing the fuel additive.

[0002]

2. Description of the Related Art In recent years,
Oil, which has been used most as a primary energy source, has been soaring in price due to the limit of its reserves. Against this background, the use of oil sands, bitumen, and the like, and the use of petroleum distillation residues and heavy oil such as asphalt as fuel are being studied.

However, these heavy oils are poor in burn-out due to the large amount of residual carbon content, and also inferior in ignitability due to the small amount of low-boiling point, making it difficult to obtain a stable combustion state. For this reason, unburned carbon, that is, soot and dust is often generated, and it can be said that it is extremely difficult to comply with the environmental standard of exhaust gas.

In order to solve these problems, addition of a combustion accelerator has been tried. Examples of the combustion accelerator include, for example, JP-A-61-152794, JP-A-62-106992, JP-A-53-12907, JP-A-61-225282, and JP-A-3-17187. There are many studies such as JP-B No. 63-17315 and JP-B No. 63-17315, but all of them are solid powder in the form of combustion accelerator or oil-soluble substance with high viscosity, so they are mixed with fuel. It is not good and the effect of promoting combustion is not satisfactory. In particular, a water-soluble substance is desirable in a water-based fuel such as a heavy oil emulsion fuel, and it cannot be said to be satisfactory from this point as well.

Heavy oil such as oil sand, bitumen, distillation residue of petroleum, and asphalt does not flow at room temperature or has a high viscosity of tens of thousands of centipoise or more, and must be heated to a high temperature of about 300 ° C. There is a problem with handling and atomization. Therefore, a method of emulsifying heavy oil and using it as a fuel has been studied, but it cannot be said to be a clean fuel because a large amount of soot and dust is generated due to its poor burn-out property as described above. Therefore, there is a strong demand for the development of a combustion accelerator that suppresses the generation of soot and dust.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the rare earth metal salt of an aromatic sulfonic acid formaldehyde condensate has an excellent combustion promoting effect, and is particularly useful for heavy oil emulsion fuel and coal / water slurry. When added to such a water-based fuel, it is confirmed that not only good compatibility with the water-based fuel but also an excellent combustion promoting effect is exhibited, and burnout is improved to significantly reduce the amount of dust in exhaust gas, The present invention has been completed.

That is, the present invention relates to a heavy oil emulsion fuel additive containing a rare earth metal salt of an aromatic sulfonic acid formaldehyde condensate as an essential component, and a heavy oil emulsion fuel containing the additive.

The additive for heavy oil emulsion fuel of the present invention is a rare earth metal salt of an aromatic sulfonic acid formaldehyde condensate, and it is desirable to use naphthalenesulfonic acid as the aromatic sulfonic acid. Alkylnaphthalenesulfonic acid It is possible to use ligninsulfonic acid, styrenesulfonic acid, or the like. The formaldehyde condensate is a homo- and / or co-condensate of the above-mentioned sulfonic acid, and its weight average molecular weight is preferably 1,000 to 30,000 as measured by gel permeation chromatography.

Examples of the rare earth metal salts include salts of cerium, neodymium, lanthanum, braseodymium, samarium, brometium, europium, gadolinium, terbinium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
Of these, cerium, neodymium and lanthanum are particularly preferable. This rare earth metal salt is generally obtained as a mixture of two or more kinds, but each may be used alone, or two or more kinds may be artificially combined and used.

As one of the methods for obtaining the rare earth salt of the aromatic sulfonic acid formaldehyde condensate of the present invention, an aromatic sulfonic acid formaldehyde condensate is obtained by a conventional method,
It is synthesized by salt exchange with a rare earth metal salt. The rare earth metal salt in this case is not particularly limited, but carbonate is preferable.

The additive for heavy oil emulsion fuel of the present invention contains a rare earth metal salt of an aromatic sulfonic acid formaldehyde condensate as an essential component, but it is dispersed or dissolved with water from the viewpoint of easy handling. It may be in a state. Further, a known combustion accelerator may be contained.

The additive amount of the heavy oil emulsion fuel additive of the present invention is preferably in the range of 10 to 10,000 ppm with respect to the emulsion. If the addition amount is less than 10 ppm, the combustion promoting effect is not sufficiently expressed, and reduction of the amount of dust cannot be expected. Again 10,000
If it exceeds ppm, the combustion promoting effect does not appear for the added amount, which is economically unfavorable.

The method for adding the additive for heavy oil emulsion fuel of the present invention may be added and dissolved during the production of the heavy oil emulsion fuel, and it should be used by mixing with the fuel immediately before combustion. Is also possible.

The heavy oil emulsion fuel to which the additive for heavy oil emulsion fuel of the present invention is blended is an oil-in-water type, and its composition contains heavy oil, water and a surfactant as essential components. Other than these components, if necessary, polymer stabilizers, water-soluble polymers, polyhydric alcohols, fats and oils, fatty acids, fatty acid esters, oligosaccharides or oligosaccharide derivatives, and if necessary, known combustion aids and fuel oils Blending of additives is also possible.

The blending composition of the heavy oil emulsion fuel in the present invention is not particularly limited, but it is preferably 40 to 85% by weight of heavy oil, 10 to 50% by weight of water, and 0.1 to 10% of a surfactant. 10% by weight, 0.001 to 1% by weight of the rare earth metal salt of the formaldehyde condensate of aromatic sulfonic acid.

The surfactant which is an essential component of the heavy oil emulsion fuel in the present invention is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. One kind or two or more kinds are used. Examples of the surfactant that can be used include the following.

<Nonionic Surfactant> (i) An alkylene oxide adduct of a compound having a phenolic hydroxyl group such as phenol, cresol, butylphenol, nonylphenol, dinonylphenol, dodecylphenol, paracumylphenol and bisphenol A. (Ii) An alkylene oxide adduct of a formalin condensate of a compound having a phenolic hydroxyl group such as alkylphenol, phenol, metacresol, styrenated phenol, and benzylated phenol. The average degree of condensation is 1.2-
100, preferably 2-20. (Iii) An alkylene oxide adduct of a monohydric aliphatic alcohol having 2 to 50 carbon atoms. (Iv) An alkylene oxide adduct of a monovalent aliphatic amine having 2 to 50 carbon atoms. (V) A block or random addition polymer of alkylene oxide. (Vi) Alkylene oxide adduct of polyhydric alcohol. (Vii) An alkylene oxide adduct of an ester of a polyhydric alcohol and a fatty acid having 8 to 18 carbon atoms. (viii) An alkylene oxide adduct of a polyvalent amine having a plurality of active hydrogens such as ethylenediamine, tetraethylenediamine, polyethyleneimine (molecular weight 600 to 10,000). (Iv) A product obtained by adding an alkylene oxide to a mixture of 1 mol of a triglyceride type oil and fat and 0.1 to 5 mol of a polyhydric alcohol and / or water.

The polyhydric alcohols (vi) and (vii) include glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol and the like. It is illustrated.

<Anionic Surfactant> (I) A formalin condensate of sulfonic acid or sulfonate of an aromatic ring compound such as naphthalene, alkylnaphthalene, alkylphenol and alkylbenzene. Preferably, the average degree of condensation of formalin is 1.2 to 100.

(II) Lignin sulfonic acid, lignin sulfonate, derivatives thereof, formalin condensates of lignin sulfonic acid and sulfonic acids of aromatic compounds such as naphthalene and alkylnaphthalene, and salts thereof. Preferably, the average degree of condensation of formalin is 1.2 to 50.

(III) Polystyrene sulfonic acid or a salt thereof, a copolymer of styrene sulfonic acid and another copolymerizable monomer, and a salt thereof. Preferably the molecular weight is between 500 and 500,000.

(IV) A dicyclopentadienesulfonic acid polymer or a salt thereof. Preferably, the molecular weight of the polymer is from 500 to
It is 500,000.

(V) A copolymer of maleic anhydride or / and itaconic anhydride with another copolymerizable monomer, and an acid or salt thereof. Preferably the molecular weight is between 500 and 500,000.

(VI) Maleates of liquid polybutadiene and salts thereof. Preferably, the liquid polybutadiene has a molecular weight of 500,000 to 200,000.

(VII) The following anionic surfactant having one or two hydrophilic groups in the molecule. (a) Sulfate ester salt of an alcohol having 4 to 18 carbon atoms. (b) Alkane, alkene or / and alkylaryl sulfonic acid having 4 to 18 carbon atoms or a salt thereof. (c) Sulfates or phosphates of alkylene oxide adducts of compounds having one or more active hydrogens in the molecule, and salts thereof. (d) A sulfosuccinate which is an ester of a saturated or unsaturated fatty acid having 4 to 22 carbon atoms. (e) Alkyl diphenyl ether disulfonic acid or a salt thereof. The alkyl group is an alkyl group having 8 to 18 carbon atoms. (f) Rosin acid or a salt thereof. Tall oil mixed acid which is a mixed acid of rosin acid and higher fatty acid and its salt. (g) Alkane or alkene fatty acid having 4 to 18 carbon atoms and salts thereof. (h) An α-sulfo fatty acid ester salt represented by the following general formula.

[0026]

[Chemical 1]

However, R ₁ is an alkyl group or an alkenyl group having 6 to 22 carbon atoms, R ₂ is an alkyl group having 1 to 22 carbon atoms, and M is 1
A divalent or divalent metal atom, NH ₄ , an organic amine, and n represents 1 or 2.

Regarding the compounds (I) to (VII), as salts, lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine and triethylamine, alkali metals such as sodium, potassium, magnesium and calcium, or alkalis. It is an earth metal.

<Cationic Surfactant and Amphoteric Surfactant> (I) An alkyl or / and alkenylamine salt obtained by neutralizing an alkyl or / and alkenylamine having 4 to 18 carbon atoms with an inorganic acid or an organic acid.

(II) A quaternary ammonium salt represented by the following formulas (1) to (3).

[0031]

[Chemical 2]

[0032]

[Chemical 3]

[0033]

[Chemical 4]

(III) An alkyl betaine represented by the following formula.

[0035]

[Chemical 5]

(IV) An alkylamine oxide represented by the following formula.

[0037]

[Chemical 6]

(V) An alkylalanine represented by the following formula.

[0039]

[Chemical 7]

(VI) A polyamate represented by the following formula (4) or (5).

[0041]

[Chemical 8]

(VII) A polyamine salt represented by the following formula (6) or (7).

RNHC ₃ H ₆ NHX ′ (6) RNH (C ₃ H ₆ NH) ₂ X ′ (7) (wherein R has the same meaning as described above, and X ′ is an inorganic acid or an organic acid. (VIII) An imidazoline type amphoteric surfactant represented by the following formula.

[0044]

[Chemical 9]

(IX) A sulfobetaine-type amphoteric surfactant represented by the following formula.

[0046]

[Chemical 10]

The amount of surfactant used depends on the emulsion.
It is in the range of 0.1 to 10% by weight. If the amount used is less than this, the emulsification and emulsion stability of the heavy oil are insufficient, and if the amount used is more than this, not only is it uneconomical, but foaming during emulsification and particle size control are difficult, which is not preferable.

The heavy oil used in the present invention is an oil that has poor fluidity at room temperature and does not flow unless heated to a high temperature, and includes the following oils. (1) Mixtures of petroleum-based asphalts and their oils (2) Various treated petroleum-based asphalts, their intermediate products, residues, and mixtures thereof (3) High pour point oils that do not flow at room temperature (4) Petroleum-based tar pitch And oil mixture thereof (5) Bitumens, natural asphalt, orinocotal If further limited, those containing 90% by weight or more of a component having a boiling point of 340 ° C or higher at normal pressure are preferable.

The present invention relates to a combustion accelerator for a heavy oil emulsion fuel used as a fuel for a boiler or a fuel for a heating furnace, and its combustion method is the same as that for light oil or heavy oil which is a liquid fuel. Atomizer is spray combustion.

[0050]

As described above, the additive for heavy oil emulsion fuel according to the present invention uniformly diffuses in the fuel, efficiently exhibits the function as an oxidation catalyst, and promotes combustion.
As a result, it is an epoch-making additive for heavy oil emulsion fuels that can significantly reduce the amount of soot and dust in exhaust gas by improving the burn-out property. In addition, the heavy oil emulsion fuel containing the additive for heavy oil emulsion fuel according to the present invention has a drawback that the amount of dust in exhaust gas is large due to residual carbon contained in a large amount of heavy oil. It provides a clean fuel that is improved by promoting combustion and has an extremely small amount of soot dust.

[0051]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 [Synthesis of Additive for Heavy Oil Emulsion Fuel] 410 g of naphthalene was weighed and put into a 3-liter four-necked flask at 90 ° C.
After heating and dissolving at 98%, 98% sulfuric acid was added dropwise over 1 hour.
After the completion of the dropping, the temperature was raised to 160 ° C. over 2 hours and then aged for 3 hours to obtain a sulfonated naphthalene. Then water 1
After adding 35 g and cooling to 95 ° C., 250 g of 37% formalin was added dropwise over 4 hours. 105 ℃ over 1 hour after the dropping
After the temperature was raised to, the mixture was aged for 6 hours to obtain a naphthalenesulfonic acid formaldehyde condensate. Next, after adding 450 g of water and cooling to 70 ° C., cerium carbonate, neodymium carbonate,
By adding and neutralizing each slurry of lanthanum carbonate,
A rare earth metal salt of the naphthalenesulfonic acid formaldehyde condensate of the present invention was obtained.

[Production of Heavy Oil Emulsion Fuel] The following materials were used as raw materials for producing the heavy oil emulsion fuel.・ Asphalt: Asphalt extracted from Arabian light crude oil (specific gravity 1.015, viscosity 595 cP / 100 ℃, softening point 2
9 ℃, Penetration 370/25 ℃) ・ Water; Ion-exchanged water ・ Nonionic surfactant; Polyoxyethylene nonylphenyl ether, Kao Co., Ltd. Emulgen 921 Weigh the above raw materials as follows and weigh about 3000 kg. A quality oil emulsion fuel was produced. Asphalt = 2100 kg, water = 900 kg, nonionic surfactant = 30 kg, emulsion is manufactured in a 5 m ³ reaction tank (tank diameter 1.9 m) with asphalt, water and surfactant at 80 ° C.
After heating, the mixture was charged and stirred for 60 minutes while maintaining the temperature at 80 ° C. The stirring blade type is a Fadler blade, the blade diameter is 1.1 m, and the rotation speed is 64 rpm. After completion of preliminary stirring, Tokushu Kika Kogyo Co., Ltd.
It emulsified by the batch circulation system using a PL-SL type line mixer manufactured by. The rotation speed of the mixer was 3600 rpm, and the emulsification time was 4 hours. After completion of the emulsification, the emulsion was cooled to 20 ° C. over 10 hours to prepare an emulsion for combustion test. The general properties are shown in Table 1.

[0054]

[Table 1]

[Combustion Test] A combustion test was carried out using the heavy oil emulsion fuel produced above. Prior to the combustion test, 0.1% by weight of the heavy oil emulsion fuel additive was added to the emulsion in the fuel tank and mixed with stirring. The differential heat balance (Shimadzu ECC-
30) was used and the temperature was raised at 20 ° C./min while flowing 20 ml / min of air into the combustion section. The amount of soot and dust in the exhaust gas was measured by burning a heavy oil emulsion fuel using a horizontal cylindrical double-wall water-cooled experimental reactor (1.2 mφ x 3.4 ml, manufactured by Nippon Furnace Industries Co., Ltd.) -8808. The combustion conditions are as follows. Burner; Internal mixing type (manufactured by Nippon Furnace Industries Co., Ltd.) Atomized steam; Temperature = 170 ° C, flow rate = 60 liters / hr, pressure = 4.3 kg / cm ² emulsion fuel; Temperature = 50 ° C, flow rate = 150 liters /
hr, pressure = 3.8 kg / cm ² air amount; 1230 m ³ / hr The measurement results are shown in Table 2.

[0056]

[Table 2]

From the measurement results in Table 2, Experiment N which is a comparative example
In o.1 and No.2, the burnout temperature was about 750 ° C and the amount of dust was as high as about 0.13 g / m ³ . On the other hand, in Experiment No. 3 to No. 6 in which the rare earth metal salt of the aromatic sulfonic acid formaldehyde condensate of the present invention was added, the burnout temperature was reduced by 60 to 70 ° C. and the combustion promoting effect was remarkable as compared with the comparative example. As a result, the amount of soot and dust could be reduced by about 25%.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Sayuri Tamaki, 1-3-9 Sunami, Minami, Wakayama City (72) Inventor, Taichi Yamashita, 8th place, Chidori-cho, Naka-ku, Yokohama City, Japan Central Research Institute of Petroleum Corporation (72) Inventor Shinichi Satake 1-3-12 Nishishimbashi, Minato-ku, Tokyo Japan Oil Co., Ltd.

Claims (2)

[Claims] 1. An additive for heavy oil emulsion fuel containing a rare earth metal salt of a formaldehyde condensate of aromatic sulfonic acid as an essential component. 2. A heavy oil emulsion fuel containing the additive for heavy oil emulsion fuel according to claim 1.