JPH0770574A - Heavy-oil-based emulsion fuel composition and its production - Google Patents

Abstract

PURPOSE:To substitute a heavy oil such as bitumen or asphalt formerly not utilized effectively as an energy source for a fuel oil and obtain an epoch- making emulsion fuel with enhanced storage stability and versatility. CONSTITUTION:The heavy-oil-based emulsion fuel compsn. comprises a heavy oil(A) obtd. by adjusting the viscosity of a high-viscosity heavy oil with a viscosity-adjusting agent, water (B), and a surfactant (C) in wt. ratios of A:B and C/(A+B) of (90:10)-(60:40) and 0.1-5%, respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to heavy oil emulsion fuel compositions and processes for their manufacture. More specifically, a heavy oil having a high viscosity heavy oil whose viscosity is adjusted by a viscosity adjusting material,
The present invention relates to a heavy oil emulsion fuel composition comprising water and a surfactant, which provides a fuel having excellent storage stability and good flammability, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years,
Oil, which has been used most as an energy source,
Due to the limit of reserves and the rise in prices associated with them, the development of alternative energy sources for petroleum is required. Against this background, as a new fossil resource, oil sands, bitumen, petroleum distillation residues, and heavy oil such as asphalt are being considered as fuels.

However, these heavy oils usually contain vacuum distillation residue of about 420 to 450 ° C. and a heavy fraction of about 60 to 70.
% Oily substance, which does not flow as it is or has a high viscosity of tens of thousands of centipoise or more.
Therefore, when used as fuel, there are problems with handling and atomization unless it is heated to a high temperature such as 280 to 300 ℃, and it is easy to cause problems such as clogging of the piping of the combustion boiler, making it extremely difficult to use. .

In order to solve this drawback, JP-A-63-501578
JP-A No. 3-97788 and JP-A-3-97788 are known, but in these emulsion fuels, it is indispensable to use a large amount of expensive surfactant, and there is a problem in the cost performance as a fuel, which is poor in practicability. There are also problems with storage stability and flammability, and it cannot be said that the emulsion is satisfactory.

In general, there are various kinds of heavy oils. For example, even in the case of vacuum residual oil obtained in the production process of petroleum refining, its properties are greatly different depending on the kind of crude oil and the degree of distillation. Attempting to obtain a heavy oil emulsion fuel with constant properties using these as raw materials is difficult under constant emulsification conditions, and it is currently impossible to obtain a constant heavy oil emulsion fuel with excellent storage stability. is there.

[0006]

As a result of intensive research, the present inventors have paid attention to the viscosity of heavy oil, and by controlling the viscosity of the heavy oil itself, a heavy oil emulsion fuel with excellent stability is obtained. Was developed.

That is, the present invention comprises a heavy oil / water emulsion fuel composition, characterized in that it contains a heavy oil (hereinafter referred to as a compounded oil) whose viscosity is adjusted by a viscosity adjusting agent. And a method for producing the same, more specifically, (a) a blended oil, (b) water and (c) an emulsion fuel containing a surfactant as essential components, wherein (a): (b) = 60
~ 90:10 to 40 (weight ratio), and (c) is (a) + (b)
A heavy oil emulsion fuel composition having a composition of 0.1 to 5% by weight with respect to the above and a high viscosity heavy oil and a viscosity adjusting agent are mixed in advance to a predetermined viscosity, and then mixed with a surfactant and water. The present invention relates to a method for producing a heavy oil emulsion fuel composition obtained by the above method.

Although the heavy oil emulsion fuel composition of the present invention has an extremely high concentration of heavy oil, it has a viscosity relatively close to that of water and is excellent in fluidity. It provides a fuel composition that is capable of sufficient atomization and is excellent in handling properties, and that is extremely stable without emulsion separation or decomposition even when stored for a long period of time.

In the present invention, the features that the heavy oil emulsion fuel excellent in long-term stability can be easily obtained are as follows.

[0010] Generally speaking, there are various kinds of heavy oils, and for example, the vacuum residual oil obtained in the oil refining manufacturing process defined as heavy oil is used as an example, when the type of crude oil used and the light fraction are collected. Due to the difference in the distillation temperature (cut temperature) of
The viscosities vary greatly. When an emulsion fuel is to be produced using heavy oils having greatly different viscosities, it is necessary to set the emulsification energy to match the raw material viscosity and to select the emulsifier. However, when industrially producing a large amount of emulsion fuel, changing the emulsification conditions and formulation depending on the viscosity of the raw oil not only complicates the production process, but also the product obtained is not constant. However, it is difficult to obtain an emulsion having truly excellent stability.

Therefore, the inventors of the present invention pay attention to the viscosity of the heavy oil, and add a viscosity adjusting material to the high-viscosity heavy oil to make the viscosity of the heavy oil constant in advance. It was presumed that by emulsifying the oil with a constant oil viscosity, it was possible to easily obtain an emulsion fuel with excellent stability and a stable property even with a small amount of the surfactant added.

The viscosity adjusting agent for high-viscosity heavy oil in the present invention is a low-viscosity oil such as distillate oil obtained from a process such as petroleum refining. By adding this to a high-viscosity heavy oil, a high viscosity is obtained. It suffices that the viscosity of the heavy oil can be adjusted to a predetermined viscosity, and that the properties do not change after mixing and separation does not occur, and examples thereof include the following oils.

(1) Distillate oil obtained in the distillation step in petroleum refining. (2) Distillate oil obtained in cracking processes such as catalytic cracking, hydrocracking and thermal cracking in petroleum refining. (3) Distillate oil obtained from solvent extraction processes such as oil refining of lubricating oil and solvent refining. (4) Industrial waste oil such as waste oil discharged at the time of tank open inspection at refineries and waste oil discharged from gas stations. (5) Distillate oil obtained when steam-decomposing naphtha, butane, etc.

The compounding ratio of the viscosity adjusting material added to the high-viscosity heavy oil may be within a range capable of adjusting the viscosity of the high-viscosity heavy oil to a predetermined viscosity. The weight ratio of 1 to 99: 1 to 99 is possible, and preferably the weight ratio of high viscosity heavy oil: viscosity modifier is 40 to 99: 1 to 60,
The viscosity of high-viscosity heavy oil, which is the base oil, the viscosity of the viscosity modifier,
And automatically determined by the value of the target adjusted viscosity.

The viscosity of the high-viscosity heavy oil in the present invention is not particularly limited as long as it is a heavy oil, but the effect of the present invention is remarkably obtained at 20,000 cSt (50 ° C.) or higher. Among them, 50,000 to 5,000,000 cSt (50 ° C) is preferable. 5 million cSt (50 ° C)
Above this, it is necessary to heat considerably for emulsification, which is practically difficult.

The viscosity range of the high-viscosity heavy oil of the present invention adjusted by a viscosity adjusting material is preferably 500 to 300,000 cSt (50 ° C.), more preferably 1000 to 200,000 cSt (50 ° C.). 500cSt
When the temperature is lower than (50 ° C), the viscosity is similar to that of heavy oil, and it becomes unnecessary to use the emulsion fuel in the present invention. Also,
When it exceeds 300,000 cSt (50 ° C.), a large amount of surfactant needs to be added, which is not preferable.

The method for blending the viscosity adjusting material in the present invention is to preliminarily mix the high viscosity heavy oil and the viscosity adjusting material before producing the emulsion to adjust the high viscosity heavy oil to a predetermined viscosity. There are a method of blending in a container such as a tank and a method of blending the high-viscosity heavy oil and the viscosity adjusting material using a line mixer or the like using a piping line immediately before the production of the emulsion.

It is considered that premixing the high viscosity heavy oil and the viscosity adjusting agent can reduce the mixing energy in the uniform mixing with water and the surfactant.

The emulsion fuel composition of the present invention
The weight ratio of (a) compounded oil to (b) water is 60:40 to 90:10, preferably 70:30 to 85:15. This is because if the proportion of oil is too low, the calorific value decreases, and in some cases direct combustion becomes difficult, and on the contrary, if the proportion of oil is too high, the viscosity of the emulsion increases and the fluidity decreases, Coalescence and agglomeration of particles occur during storage, which reduces storage stability.

As the surfactant in the present invention, one or more selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants 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 formaldehyde 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
It is 1.2 to 100, preferably 2 to 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). (Ix) 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.

Examples of 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) Formaldehyde condensate of sulfonic acid or sulfonate of aromatic ring compound such as naphthalene, alkylnaphthalene, alkylphenol and alkylbenzene. Preferably, the average degree of condensation of formaldehyde is 1.2-100
Is.

(II) Formaldehyde condensate of ligninsulfonic acid, ligninsulfonic acid salt, its derivative, ligninsulfonic acid and sulfonic acid of aromatic compounds such as naphthalene and alkylnaphthalene, and salts thereof. Preferably, the average degree of condensation of formaldehyde is 1.2-50.

(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) 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.

[0030]

[Chemical 1]

(Wherein R ₁ is an alkyl group or alkenyl group having 6 to 22 carbon atoms, R ₂ is an alkyl group having 1 to 22 carbon atoms, M is a monovalent or divalent metal atom, NH ₄ , an organic amine, n represents 1 or 2.) For the compounds (I) to (VII),
Examples of the salt include lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, magnesium and calcium.

<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).

[0034]

[Chemical 2]

[0035]

[Chemical 3]

[0036]

[Chemical 4]

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

[0038]

[Chemical 5]

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

[0040]

[Chemical 6]

(V) An alkylalanine represented by the following formula.

[0042]

[Chemical 7]

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

[0044]

[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.

[0047]

[Chemical 9]

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

[0049]

[Chemical 10]

The amount of the surfactant used is in the range of 0.1 to 5% by weight based on the mixture of oil and water, preferably
It is 0.1 to 1% by weight. If the amount used is less than this range, the emulsification of the oil component and the expression of emulsion stability are insufficient, and if the amount used is more than this range not only is uneconomical, but foaming during emulsification and particle size control are difficult, which is not preferable.

The amount of water in the heavy oil emulsion fuel composition of the present invention is important, and it is preferable to increase or decrease it depending on the ratio of the high-viscosity heavy oil in the oil. In other words, if the proportion of high-viscosity heavy oil in the oil content is high, it may be adjusted to be slightly high, and if it is low, it may be adjusted to low.

In the present invention, if necessary, a polyhydric alcohol and / or a polymer stabilizer may be added for the purpose of further improving the stability. Any polyhydric alcohol may be used as long as it has two or more hydroxyl groups in the molecule and is soluble in water. For example, glycerin, polyglycerin, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, oligosaccharides, sorbitol, glucose. And monosaccharides and polysaccharides. The amount of polyhydric alcohol is based on the mixture of oil and water
0.1 to 50% by weight. As the polymer stabilizer, various water-soluble polymers having a molecular weight of 10,000 or more shown in Table 1 can be blended, and the blending amount is 0.005 to 3% by weight with respect to the mixture of oil and water.

[0053]

[Table 1]

The high-viscosity 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 Tar Pitch and Oil Mixtures Thereof (5) Bitumens, Natural Asphalt, Orinocotar 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 feature of the heavy oil emulsion fuel in the present invention is that the heavy oil feedstock viscosity is constant as described above, so that any heavy oil feedstock can be processed in an emulsification process under constant conditions. In addition, there is no variation in the product emulsion properties, and as a result, a heavy oil emulsion fuel with excellent storage stability can be obtained. In addition, by adding a light viscosity modifier to the heavy oil, it has the effect of improving the combustibility as compared with the conventional heavy emulsion fuel.

[0057]

As described above, the emulsion according to the present invention allows heavy oils such as bitumen and asphalt, which have not been effectively used as energy sources, to be used as heavy oil substitute fuels, and also has improved storage stability. This is an epoch-making emulsion fuel that is even more versatile.

[0058]

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

Example 1 The heavy oils B to E shown in Table 2 were adjusted in viscosity with the viscosity adjusting agents shown in Table 3 at the adjustment ratios shown in Table 4.

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

The following were used as raw materials for the production of emulsion fuel. -Viscosity adjusted compounded oil: Compounded oils G to R (210
g) -Water: Ion-exchanged water (90g) -Surfactant: Formulations A to C shown in Table 5 (1.8g)

[0064]

[Table 5]

Note) * 1 Kao Corporation, Emulgen 931 * 2 Kao Corporation, Emulgen 913 * 3 Kao Corporation, OS Soap * 4 Kao Corporation, Emulgen 430 * 5 Kao Corporation ), NeoPerex No.25 * 6 PVA220 manufactured by Kuraray Co., Ltd.

After weighing the above raw materials and heating to 80 ° C., using a TK homomixer (with a low-viscosity stirring blade) manufactured by Tokushu Kika Kogyo Co., Ltd., the rotation speed of the stirring blade was 10,000 rpm, and the stirring time was The emulsion fuel was produced in 3 minutes. After production, after leaving at 20 ℃ for 24 hours, the average particle size and viscosity of emulsion fuel,
Storage stability was measured.

The measuring method is as follows. Average particle size; Laser diffraction / scattering particle size distribution analyzer
(LA700, manufactured by Horiba, Ltd.) was used to determine the average particle size. Viscosity (cSt); 100 ℃ and 140 ℃ according to JIS K 2283-1983
Was measured and calculated by the calculation method. Viscosity (cps); Tokyo Keiki Seisakusho B type viscometer (type B
M) was used and rotor No. 3 was used at 60 rpm to measure the value one minute after the start of rotation. Stability: Using a sedimentation test tube (100cc), after 3 months of standing and 6
After a month, the state was observed, and the presence or absence of water separation on the surface and the presence or absence of sedimentation of the lower layer were evaluated. ⊚: No water separation, no sedimentation ○: Water separation was slightly present, no sedimentation Δ: Water separation was present, some sedimentation was present ×: Water separation was present, sedimentation was present.

The results are shown in Experiment Nos. 4 to 15 of Table 6. Experiment Nos. 1 to 3 of the reference example are examples using heavy oil that does not require viscosity adjustment, and Experiments Nos. 16 to 21 of comparative examples are examples using high-viscosity heavy oil without viscosity adjustment. is there.

[0069]

[Table 6]

In the present invention, compared with the comparative example, the particle size of the oil droplets is extremely fine and the stability for 6 months is satisfactory, even though the amount of the surfactant added is as small as 1/2. It can be said that it is an extremely excellent emulsion fuel that exhibits performance. Also,
Compared to the reference example, due to the effect of adjusting the viscosity with the viscosity adjuster, it shows almost the same excellent performance in the particle size, viscosity, and stability as the reference example, even though the amount of surfactant added is small. It was

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takao Taniguchi 531-4 Sonobe, Wakayama City (72) Inventor Kazuo Isobe 674-68 Hironishi, Wakayama City Inventor Sayuri Tamaki 1-3-3-9 Minami Sunayama, Wakayama City

Claims (3)

[Claims] 1. A heavy oil / water emulsion fuel composition comprising a high-viscosity heavy oil, the viscosity of which is adjusted by a viscosity modifier. 2. An emulsion fuel comprising (a) a high-viscosity heavy oil, the viscosity of which is adjusted by a viscosity modifier, (b) water and (C) a surfactant as essential components, wherein: ): (B) = 60
~ 90:10 to 40 (weight ratio), and (c) is (a) + (b)
A heavy oil emulsion fuel composition having a composition of 0.1 to 5% by weight with respect to. 3. A method for producing a heavy oil emulsion fuel composition obtained by previously mixing a high-viscosity heavy oil and a viscosity modifier, adjusting the viscosity to a predetermined value, and then mixing it with a surfactant and water.