JPH06100873A - Regeneration of deteriorated o/w superheavy oil emulsion fuel - Google Patents

Abstract

PURPOSE:To reproduce a fuel good in flowability and low in non-combustible matter content from a deteriorated superheavy oil emulsion fuel. CONSTITUTION:Using a nonionic surfactant selected from the following groups (i) and (ii), a fuel is reproduced from an O/W superheavy oil emulsion fuel deteriorated so slightly as to be transportable via a pump and handleable as a flowable liquid. Using the nonionic surfactant and an anionic surfactant, a fuel is also reproduced from an O/W superheavy oil emulsion fuel deteriorated so gravely as to be hardly transportable via a pump and unhandleable as a flowable liquid. Group (i): tail oil fatty acids, tail oil rosin acids, gum rosin, wood rosin, adducts of a mixture thereof with an alkylene oxide, and mono- and/or di-esterification products of such a mixture with an alkylene oxide polymer. Group (ii): adducts of an arom. compd. having at least one carboxyl group per molecule and prepd. from petroleum or coal as the raw material with an alkylene oxide, and mono and/or di-esterification products of such an arom. compd. with an alkylene oxide polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating deteriorated O / W type (oil-in-water type) super heavy oil emulsion fuel.

[0002]

2. Description of the Related Art Petroleum,
As fossil fuel resources not included in coal and LNG, oil sands, bitumens (orinocotal, Athabasca bitumen, etc.), etc. have a lot of reserves, so they are receiving much attention. In addition, even petroleum-based distillation of naphtha,
A large amount of asphalt or its heat-treated residues excluding distillate oil is in a state of being filled. These ultra-heavy oils usually contain about 600-450 ° C or higher heavy distillate, which is the vacuum distillation residue.
It is an oily substance containing 60 to 70% or more and does not flow as it is or has a high viscosity of tens of thousands of centipoise or more. Therefore, to use as fuel, 280-300 ℃
If you do not make it to a high temperature such as, there is a problem in handling and atomization, and it is easy to cause problems such as clogging of piping,
It is a very difficult fuel to use. Recently, attempts have been made to emulsify this extremely heavy oil, which is difficult to handle, into water to make its viscosity close to that of water. In that case, it is known that the surfactant plays an important role in keeping the emulsion fuel of the super heavy oil emulsified in water in a stable state for a long time.

Emulsions are thermodynamically unstable systems that break down over time. The above-mentioned ultra-heavy emulsion fuel is also partially undesired in terms of combustion, such as when the emulsion is partially broken during long-term storage or ship transportation, that is, it has deteriorated, and there is a large amount of unburned content when burned as it is. . Further, as the deterioration proceeds, the fluidity decreases, the viscosity becomes so high that it cannot be handled as a fluid liquid, and pumping becomes difficult. Therefore, it is important to regenerate the super heavy oil emulsion fuel that has deteriorated before combustion into a fuel having good fluidity and a low unburned content, that is, to regenerate the fuel.

[0004]

Means for Solving the Problems As a result of various studies, the present inventors have found that a deteriorated O / W type super heavy oil emulsion fuel can be regenerated by using a specific nonionic surfactant as a surfactant. Found.

That is, the present invention provides (i) mono- and / or diesterification products of tall oil fatty acids, tall rosin acids, gum rosins, wood rosins and mixtures thereof with alkylene oxide adducts or alkylene oxide polymers and (ii) petroleum or coal. Using a nonionic surfactant selected from an alkylene oxide adduct of an aromatic ring compound having one or more carboxyl groups in the molecule as a raw material, or a mono- and / or di-esterified product with an alkylene oxide polymer. , A method for regenerating deteriorated O / W type super heavy oil emulsion fuel. still,
If the degree of deterioration is so high that pumping is difficult, and the fluid cannot be handled as a fluid liquid, an anionic surfactant is used in combination.

The present invention has the following two types depending on the degree of deterioration.
There are two methods to regenerate the deteriorated O / W type super heavy oil emulsion fuel.

(1) A method of regenerating an O / W type super heavy oil emulsion fuel which is pumpable and is mildly deteriorated so that it can be handled as a fluid liquid.

Stirring the nonionic surfactant selected from the groups (i) and (ii) described above with 0.01 to 2 parts by weight per 100 parts by weight of the emulsion fuel by a high shear stirrer such as a line mixer. Depending on the high temperature, for example 80 ~
O / W type super heavy oil emulsion fuel that can be sufficiently atomized and has little unburned content is regenerated at a temperature of 90 ° C. Preferably,
The nonionic surfactant HL should be O / W type at manufacturing, storage and transportation temperature and W / O type at atomizing temperature.
Combustibility is improved by selecting the B value and the addition amount.

Next, the nonionic surfactants (i) and (ii) used in the present invention will be described in more detail.

(I) tall oil fatty acid, tall rosin acid,
Mono- and / or di-esterified products of gum rosin, wood rosin and mixtures thereof with alkylene oxide adducts or alkylene oxide polymers.

Tall oil fatty acid and tall rosin which are made from raw materials such as raw wood are produced, for example, by the following processes. Chips made from raw wood with a chipper, NaOH,
Digest in a digester containing Na ₂ S and remove pulp with a filter. The pulp-free filtrate is stored, the black liquor separated is removed, and sulfuric acid is added. After removing the produced Glauber's salt solution, washing with warm water and dehydration with a centrifuge give crude tall oil. After removing the pitch from the crude tall oil, the crude tall oil fatty acid is obtained by topping, and the tall oil rosin is obtained from the distillation residue. The nonionic surfactant of the present invention is produced from the above crude tall oil fatty acid, purified tall oil fatty acid, rosin alone or a mixture thereof by adding alkylene oxide or by esterification reaction with alkylene oxide polymer. To be done. Polymers of diesters and alkylene oxides are also included in the reaction product. HLB (hydrophilic / lipophilic balance) of the nonionic surfactant of the present invention
Is 8 to 16, preferably 10 to 14.

In addition to tall rosin, rosin is cut directly from pine trees to collect raw pine resin, and rosin is chipped from gum rosin and pine root obtained by distilling turpentine oil from the raw pine resin, and the rosin component is extracted with a solvent. There is rod rosin obtained by distilling the solvent from this solution. Table 1 shows typical compositions of these three types.

[0013]

[Table 1]

The alkylene oxides mentioned above are ethylene oxide and / or propylene oxide, butylene oxide, styrene oxide.

(Ii) A mono- and / or di-esterified product of an alkylene oxide adduct or an alkylene oxide polymer of an aromatic ring compound having one or more carboxyl groups in the molecule derived from petroleum or coal.

The aromatic ring compound having one or more carboxyl groups in the molecule derived from petroleum or coal refers to all compounds containing a carboxyl group produced by distillation or decomposition of petroleum or coal. . Examples thereof include those having one or more carboxyl groups on each ring such as a benzene ring, naphthalene ring, and anthracene ring, and those containing an alkyl group, an aromatic ring, or a functional group on these rings. The nonionic surfactant of the present invention uses, as a raw material, an aromatic ring compound having the above-mentioned carboxyl group in the molecule,
It is formed by addition of alkylene oxide or esterification reaction of alkylene oxide with a polymer. The HLB (hydrophilic / lipophilic balance) of the nonionic surfactant of the present invention is 8 to 16, preferably 10 to 14. Alkylene oxides are ethylene oxide and / or propylene oxide, butylene oxide, styrene oxide.

(2) The viscosity is so high that pumping is difficult,
As a fluid liquid, it is a method of regenerating an O / W type super heavy oil emulsion fuel that has deteriorated to such a degree that it cannot be handled.

Anionic surfactants selected from the groups represented by the following (I) to (VII) and HLB8 to 16 nonionics selected from the groups represented by (i) and (ii) of the above (1). Anionic surfactant / nonionic surfactant weight ratio 100/10 to 100/1000, preferably 100/100 to 100/400, both of the surfactants, anionic surfactant and nonionic surfactant. Emulsion fuel
0.01 to 3 parts by weight, preferably 0.3 to 100 parts by weight
By adding 1.5 parts by weight and stirring, it is possible to regenerate an emulsion fuel having good fluidity and capable of being sufficiently atomized at a high temperature, for example, a temperature of 80 to 90 ° C. The anionic surfactant has a large effect of decreasing the viscosity of the emulsion fuel, and the nonionic surfactant has a large effect of preventing the emulsion particles from aggregating, coalescing and dispersing. It is preferable to select the HLB value and the addition amount of the emulsifier so that the emulsion fuel is O / W type at the temperature during production, storage and transportation, and is the W / O type at the atomization temperature during combustion.

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

(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. In any of the above cases, the salt is a lower amine such as ammonium, monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali metal or alkaline earth metal such as sodium, potassium, calcium or magnesium. The average degree of condensation of formalin is 1.
It is 2 to 50, preferably 2 to 20.

(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 100,000. 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.

(IV) A dicyclopentadienesulfonic acid polymer or a salt thereof. The molecular weight of the polymer is 500 to 500,000, preferably 2000 to 100,000. 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 1500 to 100
In many cases. Salts are ammonium and alkali metals such as sodium and potassium. As the copolymerizable monomer, olefin (ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene), styrene, vinyl acetate, acrylic ester, methacrylic acid , Acrylic acid, etc.

(VI) Maleates of liquid polybutadiene and salts thereof. However, the molecular weight of liquid polybutadiene is 500
.About.200,000, preferably 1,000 to 50,000, and the degree of maleation is only required to be dissolved in water, but is preferably 40 to 70%. 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 alcohol having 4 to 18 carbon atoms. However, as salts, lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine, and triethylamine, sodium,
These are alkali metals or alkaline earth metals such as potassium, magnesium and calcium.

(B) Alkanes, alkenes and / or alkylaryl sulfonic acids having 4 to 18 carbon atoms or salts 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. Salts include ammonium, sodium, potassium, magnesium and calcium.

(D) A sulfosuccinate which is an ester of a saturated or unsaturated fatty acid having 4 to 22 carbon atoms. However, salts include ammonium, sodium and potassium.

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

(F) Rosin acid or a salt thereof. The salts are ammonium, sodium and 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 salts are ammonium, potassium and sodium.

(H) An α-sulfofatty acid ester salt represented by the following general formula.

[0034]

[Chemical 2]

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

Among the above-mentioned anionic surfactants, the types (I) and (II) are preferable. In terms of performance, type (I) is somewhat superior. In the type (I), if the condensation degree is 2 or more, there is not much difference. (II)
In the above type, the modified lignin in which a carboxylic acid group was introduced instead of the sulfonic acid group showed somewhat superior performance.
The HLB value of the nonionic surfactant is 8-16 as in (1),
It is preferably 10 to 14.

In any of the cases (1) and (2), any effective stirring means may be used, or a combination of two or more methods may be used. 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 called super heavy oils in the present invention include the following oils that do not flow unless heated to a high temperature. (1) A mixture of petroleum-based asphalt and its oil. (2) Various processed products of petroleum-based asphalt, intermediate products, residues, and oil mixtures thereof. (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).

The super heavy oil is limited to those having a volatile content of 12% or less at 340 ° C. Therefore, the molecular weight is higher than that of common oil components, for example, asphaltene (MW 1500-250).
Examples thereof include resin components (aromatics), oil components, and the like, and include, for example, polycyclic aromatic rings and alkyl chains added as shown below.

[0040]

[Chemical 3]

Therefore, the surfactants having a polycyclic aromatic ring or those having an alkyl chain have a structure similar to that of oil, and thus have a good affinity and an excellent performance as an emulsifier.

[0042]

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

Example 1 300 g of slightly deteriorated O / W type super heavy oil emulsion fuel was sampled in an 800 ml SUS container, immersed in a heating bath and heated to 60 ° C. After adding a predetermined amount of nonionic surfactant and reaching a constant temperature (60 ° C.), the mixture is stirred with a paddle type stirring blade at 300 rpm for 5 minutes. Further, the mixture was re-emulsified by high-shear stirring at 6000 rpm for 2 minutes with a TK homomixer, and put in a constant temperature bath at 60 ° C to measure the viscosity. A part of the re-emulsified emulsion fuel was kept warm at 50 ° C, taken out, and the passing amount through a 100-mesh sieve was measured. Viscosity was measured with Shibaura System Co., Ltd. Vismetron VS-AI type, No.2, 60 rpm rotor, and the amount of sieve passed was about 10 g on a φ70 mm 100 mesh stainless steel sieve in an atmosphere of 50 ° C. for 10 minutes. The remaining sieve amount was measured and calculated. The results are shown in Tables 2 and 3. The above-mentioned mildly deteriorated emulsion fuel is used in the Middle Eastern petroleum-based Alfalto (penetration of 60 to 80) or Athabasca bitumen (softening temperature 1
2.5 ℃, Canada) 0.1 parts of lignin sulfonic acid in 100 parts by weight
2 parts by weight and 0.48 parts by weight of polyoxyethylene nonyl phenyl ether (HLB15.2) were added, and the mixture was stirred at a temperature of 75 ° C by TK Homo mixer (with low viscosity stirring blade) manufactured by Tokushu Kika Co., Ltd. to produce emulsion fuel. It was stored at 50 ℃ for 1 month. The evaluation is good in the order of ◯>Δ> ×.

[0044]

[Table 2]

[0045]

[Table 3]

Example 2 300 g of severely deteriorated O / W type super heavy oil emulsion fuel was sampled in an 800 ml SUS container, immersed in a heating bath and heated to 60 ° C. Add a prescribed amount of a mixture of anionic and nonionic surfactants and add 6000rp with TK homomixer.
High shear stirring was performed at m 2 for 2 minutes, and the mixture was placed in a constant temperature bath at 60 ° C. and the viscosity was measured. A part of the emulsion fuel was kept warm at 50 ° C, taken out, and the amount passed through a 100-mesh sieve was measured. Viscosity is Vismetron VS-AI manufactured by Shibaura System Co., Ltd.
Type, No.2, rotor 60 rpm, and the amount of passing through the sieve is about 10 on a 100 mesh stainless sieve of φ70 mm in an atmosphere of 50 ° C.
A sample of g was placed, and the remaining amount of the sieve after 10 minutes was measured and calculated. The results are shown in Tables 4 and 5. Severe degraded O / W above
Type super heavy oil emulsion fuel is Middle East Petroleum based asphalt (penetration 60 to 80) or Athabasca bitumen (softening temperature 12.5 ° C, produced in Canada) 100 parts by weight and polyoxyethylene nonylphenyl ether (HLB15.5) 1.0 parts by weight. Was added and stirred with a TK homomixer (with low viscosity stirring blade) manufactured by Tokushu Kika Co., Ltd. at a temperature of 75 ° C. to produce an emulsion fuel, which was stored at 50 ° C. for 1 month. The viscosity of emulsion fuel is 500c.P. immediately after production and 7,000c.P. After one month. The evaluation is good in the order of ◯>Δ> ×.

[0047]

[Table 4]

[0048]

[Table 5]

Front Page Continuation (72) Inventor Akio Kai 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Sanryo Heavy Industries Ltd. Nagasaki Research Institute

Claims (2)

[Claims] 1. A group shown in the following (i) and (ii) for 100 parts by weight of an O / W type super heavy oil emulsion fuel that has been slightly deteriorated to the extent that it can be pumped and handled as a fluid liquid. 0.01 to select nonionic surfactant
A method for regenerating a deteriorated O / W type super heavy oil emulsion fuel, which comprises adding 2 parts by weight and performing high shear stirring. (I) tall oil fatty acid, tall rosin acid, gum rosin,
Mono- or / and alkylene oxide adducts of wood rosins and their mixtures with alkylene oxide polymers
And diesters. (Ii) Mono- and / or di-esterification products of alkylene oxide adducts or alkylene oxide polymers of aromatic ring compounds having one or more carboxyl groups in the molecule derived from petroleum or coal. 2. The following (I) to (VII) are applied to the severely deteriorated O / W type super heavy oil emulsion fuel, which is so viscous that pumping is difficult and deteriorated so that it cannot be handled as a fluid liquid. The anionic surfactant selected from the group represented by and the nonionic surfactant according to claim 1 are used in a weight ratio of anionic surfactant / nonionic surfactant of 100/10 to 100/1000, both. A method for regenerating a deteriorated O / W type super heavy oil emulsion fuel, which comprises adding 0.01 to 3 parts by weight to 100 parts by weight of emulsion fuel and stirring. (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, and 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. is there. (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 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. (IV) A dicyclopentadienesulfonic acid polymer or a salt thereof. The polymer has a molecular weight of 500,000 to 500,000, and the salt is a lower amine such as ammonium, monoethanolamine, diethanolamine, triethanolamine and triethylamine, and an alkali metal or alkaline earth metal 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 500,000 to 500,000, and the salts are ammonium and alkali metals such as sodium and potassium. (VI) Maleates of liquid polybutadiene and salts thereof.
However, the liquid polybutadiene has a molecular weight of 500 to 200,000, and salts thereof 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. (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, and the salt is ammonium, sodium, potassium, magnesium or calcium. (f) Rosin acid or a salt thereof. The salt is ammonium, 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. (h) An α-sulfo fatty acid ester salt represented by the following general formula. [Chemical 1] However, 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, and n is 1 or Represents 2.