JPH068422B2 - Super heavy oil emulsion fuel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ultra heavy oil emulsion fuel.

[Problems to be Solved by Prior Art and Invention]

As fossil fuel resources not included in oil, coal and LNG,
Oil sands and bitumens (Orinocotal, Athabasca bitumen) and the like have received a great deal of attention due to their large reserves. Further, even in petroleum-based products, a large amount of asphalt or its heat-treatment residues except for distillate distillate such as naphtha is contained. These ultra-heavy oils are oily substances that contain about 60-70% or more of heavy fractions of 420-450 ° C or higher, which are usually vacuum distillation residues, and do not flow as they are or have high viscosity of tens of thousands of centipoise or more. have. Therefore, in order to use it as a fuel, there is a problem in handling and atomization unless it is heated to a high temperature of 280 to 300 ° C., and troubles such as clogging of pipes are likely to occur.

[Means for Solving the Problems]

We have found that with the use of suitable surfactants, super heavy oil (O)
Oil-in-water type (O / W) of ultra-heavy oil in which water is emulsified in water (W)
It has been found that (type) emulsion fuel can be produced. This emulsion fuel has a viscosity relatively close to that of water,
It is a very easy-to-handle fuel because it can atomize sufficiently at a temperature of 90 ° C. In O / W type emulsion fuel, W
The lower the content of (water), that is, the higher the content of O (oil), the more preferable as a fuel and the less the fuel loss. In order for emulsion fuels to be handled like ordinary liquid fuel oils, they must be stable enough to withstand transport and storage for some period of time. Conventionally, it has been reported that many oils with good fluidity such as kerosene, heavy oil A, heavy oil B, and heavy oil C are used by emulsification, but the heavy fraction is very high and does not flow or tens of thousands of centipoise or more. It has hardly been reported to emulsify the super heavy oil having high viscosity as described above and use it as a fuel.

The present inventors 100 parts of super heavy oil (weight basis, the same applies hereinafter),
30-80 parts of water, 0.05-10 parts of an anionic surfactant selected from the group represented by the following (i) to (vii), preferably 0.1-
The present inventors have completed the present invention by discovering that an O / W type super heavy oil emulsion fuel having a low viscosity can be produced by stirring 4 parts of a mixture with a mechanical force such as a line mixer.

(I) A formalin condensate of a sulfonic acid or a sulfonate of an aromatic ring compound such as naphthalene, alkylnaphthalene, alkylphenol and alkylbenzene. However, the average degree of condensation of formalin is 1.2 to 100, preferably 2 to 20.
Salts are lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, magnesium and calcium.

(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. As the salt in any of the above cases, ammonium, lower amines such as monoethanolamine, diethanolamine, triethanolamine and triethylamine, sodium, potassium, calcium,
It is an alkali metal such as magnesium or an alkaline earth metal. The average degree of condensation of formalin is 1.2 to 50, preferably 2 to 20. Among the lignins, a modified lignin, for example, having a small amount of a carboxyl group introduced exhibits excellent performance especially at high temperatures.

(Iii) Polystyrene sulfonic acid or a salt thereof, a copolymer of styrene sulfonic acid and another copolymerizable monomer, and a salt thereof. However, the molecular weight is 500 to 500,000, preferably 2000 to 10
Ten thousand. The salts are lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, calcium and magnesium. Typical examples of the copolymerizable monomer include acrylic acid, methacrylic acid, vinyl acetate, acrylic acid ester, olefin, allyl alcohol and ethylene oxide adduct thereof, AMPS and the like.

(Iv) Dicyclopentadienesulfonic acid polymer or a salt thereof. The molecular weight of the polymer is 500 to 500,000, preferably 2000 to 1
0,000. The salts are lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, calcium and magnesium.

(V) A copolymer of maleic anhydride or / and itaconic anhydride with another copolymerizable monomer, and an acid or salt thereof. However,
The molecular weight is 500 to 500,000, preferably 1,500 to 100,000.
Salts are ammonium and alkali metals such as sodium and potassium. As the copolymerizable monomer, olefins (ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene), styrene, vinyl acetate, acrylic ester, methacryl Acid, acrylic acid, etc.

(Vi) Maleates of liquid polybutadiene and salts thereof.
However, the molecular weight of the liquid polybutadiene is 500 to 200,000, preferably 1000 to 50,000, and the maleation degree is 40 to 70%, although it is only necessary to dissolve it in water. Examples of the salt include ammonium and alkali metals such as sodium and potassium.

(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. However, 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. Sodium dodecyl sulfate,
A typical example thereof is sodium octyl sulfate.

(b) Alkane, alkene or / and alkylaryl sulfonic acid having 4 to 18 carbon atoms or a salt thereof. However, 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. Sodium dodecylbenzene sulfonate,
Representative examples are sodium butylnaphthalene sulfonate and sodium dodecane sulfonate.

(c) Sulfates or phosphates of alkylene oxide adducts of compounds having one or more active hydrogens in the molecule, and salts thereof. The salt is ammonium, sodium, potassium, magnesium or calcium.
Polyoxyethylene (3 mol) Nonylphenyl ether sulfate sodium salt, polyoxyethylene (3
A typical example is the sodium salt of phosphoric acid ester of (mol) dodecyl ether.

(d) A sulfosuccinate which is an ester of a saturated or unsaturated fatty acid having 4 to 22 carbon atoms. However, the salt is ammonium, sodium or potassium. Typical examples thereof are dioctylsulfosuccinic acid sodium salt, ammonium salt, dibutylsulfosuccinic acid sodium salt and the like.

(e) Alkyl diphenyl ether disulfonic acid or a salt thereof. The alkyl group is an alkyl group having 8 to 18 carbon atoms,
The salt is ammonium, sodium, potassium, magnesium or calcium.

(f) Rosin acid or a salt thereof. Ammonium as salt,
It is sodium or potassium. Tall oil mixed acid, which is a mixed acid of rosin acid and higher fatty acid, and its salt are also included in this.

(g) Alkane or alkene fatty acid having 4 to 18 carbon atoms and salts thereof. The salt is ammonium, potassium or sodium.

When an anionic surfactant selected from the group represented by (i) to (vii) above is used, the greatest feature is that the viscosity of the emulsion fuel can be remarkably reduced. But,
The effect of maintaining the stability of the system is weaker than that of the nonionic surfactant, and it is particularly suitable when the emulsion fuel is produced and then burned for a relatively short time. Further, since the viscosity of the system can be remarkably reduced, the ratio of oil in the emulsion can be increased. That is, the value as fuel can be increased.

Among the anionic surfactants used in the present invention selected from the group represented by (i) to (vii) above, particularly, lignin sulfonate or a formalin condensate of lignin sulfonic acid and naphthalene sulfonic acid or their The salt and naphthalene sulfonate fomalurin condensate showed overall excellent performance. The action of the anionic surfactant is to adsorb at the interface of the particles of the superheavy oil, help the particles get smaller, and at the same time load the particles and prevent them from reaggregating.

The amount of anionic surfactant added is 100 parts of super heavy oil,
It is 0.05 to 10 parts, preferably 0.1 to 4 parts. As the anionic surfactant, a mixture of two or more kinds may be used.
In the production of ultra-heavy oil emulsion fuel, it is preferable that foaming be as small as possible, but on the other hand, if the chain length of the lipophilic group exceeds a certain level, the surface energy of the ultra-heavy oil will be sufficiently reduced even if it is adsorbed on the particle surface Because it cannot, it cannot make small particles. Therefore, it is easier to form a stable emulsion when the chain length of the lipophilic group of the anionic surfactant is 4 or more, preferably 8 or more. Although sodium lignin sulfonate and naphthalene sulfone Na formalin condensate have a very strong effect of lowering the viscosity of the emulsion system, they do not have a strong ability to keep the system stable. Since the viscosity of super heavy oil is very high, it is generally emulsified at a high temperature of 80 ° C or higher,
Manufactures emulsion fuel. The higher the viscosity, the higher the temperature required. The surfactant may be added to either water or oil, but it is easier to handle when added to water.

The mechanical means for producing the emulsion fuel of the present invention may be any method as long as it is an efficient stirring means, or a combination of two or more methods.
A high shear type stirring device is particularly preferable. For example, a line mixer, an arrow blade turbine blade, a propeller blade, a bull margin blade, a paddle blade, and the like.

Oils referred to as extra heavy oils in the present invention include the following oils that do not flow unless heated to high temperatures.

(1) A mixture of petroleum-based asphalt and its oil.

(2) Various processed products of petroleum-based asphalt, intermediate products,
Residues and their oil mixtures.

(3) High pour point oil or crude oil that does not flow at high temperatures.

(4) Petroleum tar pitch and its oil mixture.

(5) Bitumens (Orinoco tar, Athabasca bitumen).

It is generally said that naphthene-based asphalt is easy to emulsify, and asphalt derived from paraffinic base oil or mixed base oil is difficult to emulsify. In addition, naphthenic compounds sufficiently distill off volatile components, making it difficult to emulsify asphalt having a high heavy fraction. Although many of the recent asphalts are those in which the volatile components have been sufficiently distilled off, the asphalt of the present invention mainly targets asphalts for which it is difficult to produce an emulsion that is stable over a long period of time by conventional methods.

Bitumens such as orinocotar extract oil by a steam injection method or the like, and the anionic surfactant described above can be used in this step. Further, after the extraction, sand and other contaminants may be removed, or after desalting, the anionic surfactant may be added to produce an emulsion fuel of super heavy oil. Especially when used immediately before combustion, the viscosity of the emulsion system is lowered, a uniform emulsion can be formed, and atomization can be sufficiently performed, so that a fuel suitable for combustion with almost no incomplete combustion can be produced.

〔Example〕

Examples of the present invention will be shown below, but the present invention is not limited to these examples.

Example 1 Middle Eastern petroleum-based asphalt (penetration of 60 to 80) or Athabasca bitumen (softening temperature 12.5 ° C, produced in Canada), water,
A predetermined amount of each surfactant is weighed so that the total amount becomes 300 g, put into an 800 ml centrifuge tube, and heated to 75 ° C. After reaching a certain temperature, stir with TK Homo Mixer (with low viscosity stirring blade) manufactured by Tokushu Kika Co., Ltd. to prepare emulsion fuel, and
The mixture was placed in a constant temperature bath at ℃, and after reaching a certain temperature, the viscosity was measured. Viscosity is Vismetron VS-AI manufactured by Shibaura System Co., Ltd.
Mold, No. 2, rotor 60 rpm. The evaluation was based on the results of both the viscosity of the emulsion and the amount passed through the screen. ◎
It is good in the order of>○>Δ> ×.

The results are shown in Tables 1 and 2.

Claims (4)

[Claims] 1. An emulsified mixture of 100 parts by weight of super heavy oil, 30 to 80 parts by weight of water, and 0.05 to 10 parts by weight of an anionic surfactant selected from the group represented by the following (i) to (vii): Ultra heavy oil emulsion fuel. (I) A formalin condensate of a sulfonic acid or a sulfonate of an aromatic ring compound such as naphthalene, alkylnaphthalene, alkylphenol and alkylbenzene. However, the average degree of condensation of formalin is 1.2 to 100, the salt is ammonium,
Lower amines such as monoethanolamine, diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, magnesium and calcium. (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. As the salt in any of the above cases, ammonium, lower amines such as monoethanolamine, diethanolamine, triethanolamine and triethylamine, sodium, potassium, calcium,
It is an alkali metal such as magnesium or an alkaline earth metal. The average degree of condensation of formalin 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. However, the molecular weight is 500-500,000, the salt is ammonium,
Lower amines such as monoethanolamine, diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, calcium and magnesium. (Iv) Dicyclopentadienesulfonic acid polymer or a salt thereof. The molecular weight of the polymer is 500 to 500,000, and the salts are lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, calcium and magnesium. . (V) A copolymer of maleic anhydride or / and itaconic anhydride with another copolymerizable monomer, and an acid or salt thereof. However,
The molecular weight is 500 to 500,000, and the salt is ammonium or an alkali metal such as sodium or potassium. (Vi) Maleates of liquid polybutadiene and salts thereof.
However, the molecular weight of the liquid polybutadiene is 500 to 200,000, and the salt is ammonium or an alkali metal such as sodium or potassium. (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. However, 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. (b) Alkane, alkene or / and alkylaryl sulfonic acid having 4 to 18 carbon atoms or a salt thereof. However, 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. (c) Sulfates or phosphates of alkylene oxide adducts of compounds having one or more active hydrogens in the molecule, and salts thereof. The salt is ammonium, sodium, potassium, magnesium or calcium. (d) A sulfosuccinate which is an ester of a saturated or unsaturated fatty acid having 4 to 22 carbon atoms. However, the salt is ammonium, sodium or potassium. (e) Alkyl diphenyl ether disulfonic acid or a salt thereof. The alkyl group is an alkyl group having 8 to 18 carbon atoms,
The salt is ammonium, sodium, potassium, magnesium or calcium. (f) Rosin acid or a salt thereof. Ammonium as salt,
It is sodium or potassium. Tall oil mixed acid, which is a mixed acid of rosin acid and higher fatty acid, and its salt are also included in this. (g) Alkane or alkene fatty acid having 4 to 18 carbon atoms and salts thereof. The salt is ammonium, potassium or sodium. 2. The anionic surfactant according to claim 1, which is (i).
The super heavy oil emulsion fuel according to claim 1, which is 3. The anionic surfactant according to claim 1 (ii).
The super heavy oil emulsion fuel according to claim 1, which is 4. The amount of the anionic surfactant added is 10% for super heavy oil.
The super heavy oil emulsion fuel according to claim 1, which is 0.1 to 4 parts by weight with respect to 0 parts by weight.