JP2709027B2 - Ultra heavy oil emulsion fuel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a super heavy oil emulsion fuel.

[0002]

BACKGROUND OF THE INVENTION Oil,
As fossil fuel resources not included in coal and LNG, oil sands, bitumens (orinoco tar, Athabasca bitumen), etc. have attracted much attention due to their large reserves. In addition, even in petroleum systems, asphalt or its heat-treated residues other than distillate distillate such as naphtha are contained in a large amount. These ultra-heavy oils are oils containing about 60-70% or more of heavy fractions of 420-450 ° C or higher, which are residues of vacuum distillation, 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 the temperature is raised to a high temperature of 280 to 300 ° C. In addition, it is easy to cause blockage of pipes and the like, and the fuel is very difficult to use.

[0003]

Means for Solving the Problems The inventors of the present invention used an appropriate surfactant to emulsify an ultra-heavy oil (O) in water (W) to form an oil-in-water type (O / (W-type) emulsion fuel. This emulsion fuel shows a viscosity relatively close to water, and high temperature, for example, 80-90 ° C
It is a fuel that can be atomized sufficiently at this temperature and is very easy to handle. In an O / W emulsion fuel, W
The lower the (water) content, that is, the higher the O (oil) content, the more preferable the fuel and the lower the fuel loss. In order for emulsion fuels to be handled like ordinary liquid fuel oils, they must have long-term stability to withstand transportation and storage. Conventionally, there have been many reports of emulsifying and using oils having good fluidity, such as kerosene, fuel oil A, fuel oil B, and fuel oil C,
It has not been reported that a heavy fraction is very high and emulsifies an ultra-heavy oil which does not flow or has a high viscosity of tens of thousands of centipoise or more and is used as a fuel.

[0004] The present inventors have determined that 100 parts of super heavy oil (weight basis,
The same applies hereinafter), 30 to 80 parts of water, preferably 33 to 50 parts,
0.01 to 4 parts by weight of an anionic surfactant selected from the group represented by (i) to (ii) and HLB (hydrophilic lipophilic balance) selected from the group represented by the following (I) to (IV) 14
When the nonionic surfactants of No. to 19 are used in an anionic surfactant / nonionic surfactant (weight ratio) of 10/90 to 40/60 and stirred by a mechanical force such as a line mixer, a low viscosity O The present inventors have found that a W-type super heavy oil emulsion fuel can be produced, and have completed the present invention.

<Anionic surfactant> (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, triethylamine, and alkali or alkaline earth metals such as sodium, potassium, magnesium, and calcium. (ii) Lignin sulfonic acid, lignin sulfonic acid salt, derivatives thereof, formalin condensate or co-condensate of lignin sulfonic acid and sulfonic acid of an aromatic compound such as naphthalene or alkylnaphthalene, and salts thereof. As the salt, in any of the above, ammonium, monoethanolamine,
They are lower amines such as diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, calcium and magnesium. Average degree of condensation of formalin is 1.2 to 5
It is 0, preferably 2 to 20. Among the lignins, a modified lignin, for example, a little introduction of a carboxyl group shows excellent performance especially at high temperatures.

<Nonionic surfactant of HLB 14-19> (I) Block or random addition polymer of ethylene oxide and propylene oxide or / and butylene oxide and styrene oxide. (II) glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin,
Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol, or those polyhydric alcohols and 8 to 18 carbon atoms
Alkylene oxide adduct of an ester with a fatty acid. Alkylene oxide is ethylene oxide or / and propylene oxide, butylene oxide, styrene oxide. (III) An alkylene oxide adduct of a polyvalent amine having a plurality of active hydrogens such as ethylenediamine, tetraethylenediamine, and polyethyleneimine (molecular weight: 600 to 10,000). Alkylene oxide is ethylene oxide or / and propylene oxide, butylene oxide, styrene oxide. (IV) 1 mol of triglyceride type fat and oil, glycerin,
One or more polyhydric alcohols selected from the group consisting of trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylene glycol, polyethylene glycol having a molecular weight of 1000 or less, propylene glycol, and polypropylene glycol having a molecular weight of 1000 or less and / or A product obtained by adding an alkylene oxide to a mixture of water and 0.1 to 5 mol of water. Alkylene oxide is ethylene oxide or / and propylene oxide, butylene oxide, styrene oxide.

[0007] The action of the anionic surfactant is to adsorb at the interface of the particles of the superheavy oil and help the particles to become smaller while at the same time charging the particles and preventing reaggregation of the particles. Nonionic surfactants are strongly affected by temperature, but the addition of anionic surfactants reduces the effect of temperature and improves the storage stability of the emulsion.

The action of the above nonionic surfactant is to adsorb at the interface of the particles of the super heavy oil and help the particles to become smaller, and at the same time, to prevent the particles from reaggregating due to the protective action.

The storage stability of the anionic surfactant alone is insufficient, and the nonionic surfactant alone is strongly affected by the temperature, so that a similarly stable emulsion fuel cannot be obtained. By adding an anionic surfactant to a nonionic surfactant and weakening its temperature dependence, a long-term stable emulsion fuel can be produced.

The weight ratio of anionic surfactant / nonionic surfactant in the emulsion fuel of the present invention is from 10/90 to 40 /.
60. The addition amount of the anionic surfactant in the emulsion fuel of the present invention is 0.005 to 2.2% by weight, preferably 0.06 to 2.2% by weight.
~ 0.61% by weight. As the anionic surfactant and the nonionic surfactant, a mixture of two or more kinds may be used. Further, the anionic surfactant and the nonionic surfactant may be added separately, or may be added as a mixture in advance. In the production of an emulsion fuel, it is preferable that foaming be as small as possible.On the other hand, if the chain length of the lipophilic group is not less than a certain level, even if it is adsorbed on the particle surface of the super heavy oil, its surface energy cannot be sufficiently reduced. Cannot make particles. Therefore, it is easier to produce a stable emulsion fuel if the chain length of the lipophilic group of the anionic surfactant and / or nonionic surfactant is 4 or more, preferably 8 or more. Since the viscosity of ultra-heavy oil is very high, emulsion fuel is generally manufactured by emulsification at a high temperature of 60 ° C. or higher. Higher temperatures require higher temperatures. The surfactant may be added to either water or oil, but it is easier to handle when added to water. The HLB of the nonionic surfactant varies depending on the emulsification temperature.
19, preferably 15-17.

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

The super heavy oil emulsion fuel 100 produced using the anionic surfactant and the nonionic surfactant described above.
The following HLB 1.5-14, preferably 4.3-14, more preferably 12-14 second nonionic surfactant is added to
Addition of 0.5 part, preferably 0.1 to 0.35 part, and stirring with a suitable stirrer can produce a stable emulsion fuel for a longer time. However, when atomizing at an atomization temperature of, for example, 90 ° C., it is preferable that the emulsion system inverts from the O / W type to the W / O type below this temperature, and the necessary amount is preferably added. . The temperature of re-emulsification is below 70 ° C, preferably 60
It is preferable to emulsify at a temperature of about ° C. HLB mentioned above
The nonionic surfactants having a molecular weight of 1.5 to 14 have exactly the same structure as the nonionic surfactants having a molecular weight of 14 to 19 and have a small HLB, that is, a small number of added alkylene oxides.

The oil referred to as a super heavy oil in the present invention includes the following oils which do not flow unless heated to a high temperature. (1) Petroleum asphalts and mixtures of such oils. (2) Various petroleum asphalt products, intermediate products,
Residues and their oil mixtures. (3) High pour point oil or crude oil that does not flow at high temperatures. (4) Petroleum-based tar pitch and its oil mixture. (5) Bitumens (Orinoco tar, Athabasca bitumen).

It is generally said that naphthenic asphalt is easy to emulsify, and that asphalt derived from paraffinic base oil or mixed base oil is difficult to emulsify. In addition, the naphthene system also sufficiently distills volatile components, making it difficult to emulsify asphalt with a high heavy fraction. In recent years, asphalt in which volatile components have been sufficiently distilled has increased in many cases, but the asphalt of the present invention mainly targets asphalt in which it is difficult to produce a long-term stable emulsion by a conventional method.

For bitumens such as orinoco tar, oil is extracted by a steam injection method or the like. In this step, the anionic surfactant and / or the nonionic surfactant of HLB 14 to 19 may be used. it can. After extraction, sand or other solid particles may be removed or desalted, and then the above-mentioned anionic surfactant and / or nonionic surfactant of HLB 14-19 may be added to produce an emulsion fuel. Furthermore, emulsification using the above-mentioned nonionic surfactant of HLB 1.5 to 14 gives O /
A W-type emulsion fuel can be manufactured.

[0016]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. Example 1 Middle East petroleum asphalt (penetration of 60 to 80) or Athabasca bitumen (softening temperature 12.5 ° C, made in Canada), water,
A predetermined amount of each of the surfactants shown in Tables 1 and 2 is weighed to a total amount of 300 g, placed in an 800 ml centrifuge tube, and heated to 75 ° C. After reaching a certain temperature, it is stirred with a TK homomixer (with a low viscosity stirring blade) manufactured by Tokushu Kika Co., Ltd. to prepare an emulsion fuel, put in a thermostat at 60 ° C, and after reaching a certain temperature, measure the viscosity. did. When a nonionic surfactant having an HLB of 1.5 to 14 is further added, after adding a predetermined amount of this surfactant, the temperature of the system is heated to 50 ° C., and further stirred with the TK homomixer described above. Put in a 60 ° C thermostat,
The viscosity was measured. A part of the emulsion fuel was kept at 50 ° C., and the state was observed after one day, three days, and seven days. A part of the emulsion fuel was taken out, and the amount passed through a 100-mesh sieve was measured. Viscosity is Vismetron VS-AI type manufactured by Shibaura System Co., Ltd., N
o.2, Measured with a rotor at 60 rpm, the sieve passing amount was calculated by placing about 10 g of a sample on a 100-mesh stainless steel sieve of φ70 mm in an atmosphere of 50 ° C., and measuring the remaining amount of the sieve after 10 minutes. The results are shown in Tables 1 and 2.

The overall evaluation was made by comprehensively observing the viscosity of the emulsion, the amount passed through the sieve, and the visual observation of the dispersed state of the emulsion after standing. ＞>○>△> x are good in this order, and △ and above are systems in which the effect is recognized. However, the dispersion state after standing was evaluated by observing the three layers of the surface layer 1, the intermediate layer 2 and the settling layer 3 as shown in FIG. did. In the surface layer 1, the size of the oil droplets on the surface and the size of the oil film in which the size was large were observed. The dispersion state is as follows: no oil droplets> small oil droplets> small oil film> large oil film. In the mid layer 2, the quality of the emulsified state was observed. The emulsified state is good in the order of good emulsification> slightly creamy>creamy> separated state> large separation> complete separation. In the sedimentary layer 3, no sediment is present> soft sediment> hard sediment. A soft sediment is a soft sediment that is easily redispersed, and a hard sediment is a hard sediment that is difficult to redisperse.

[0018]

[Table 1]

[0019]

[Table 2]

(Note) * 1: Naphthalenesulfonic acid Na / ligninsulfonic acid N
The molar ratio of a is 2/1. * 2: Naphthalenesulfonic acid Na / ligninsulfonic acid N
The molar ratio of a is 1/1.

[Brief description of the drawings]

FIG. 1 is a schematic view of a centrifuge tube used for evaluation of a dispersion state after standing.

[Explanation of symbols]

 1 surface layer 2 intermediate layer 3 sedimentation layer

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akio Kai, 1-1, Akunouramachi, Nagasaki City, Nagasaki Prefecture Mitsubishi Heavy Industries, Ltd. Nagasaki Research Laboratory (56) References JP-A-63-54498 (JP, A) Sho 61-247757 (JP, A) British patent 2182345 (GB, A) US patent 4249554 (US, A) US patent 4666457 (US, A)

Claims (10)

(57) [Claims] 1. 100 parts by weight of super heavy oil, 30 to 80 parts by weight of water,
0.01 to 4 parts by weight of an anionic surfactant selected from the group represented by the following (i) to (ii) and HLB (hydrophilicity / lipophilicity selected from the group represented by the following (I) to (IV)) Balance) An ultra-heavy oil emulsion fuel obtained by emulsifying 14 to 19 nonionic surfactants with an anionic surfactant / nonionic surfactant (weight ratio) of 10/90 to 40/60. <Anionic surfactant> (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 the salts are ammonium, monoethanolamine, diethanolamine, triethanolamine, lower amines such as triethylamine, alkali metals such as sodium, potassium, magnesium, and calcium or alkaline earth metals. is there. (ii) Lignin sulfonic acid, lignin sulfonic acid salt, derivatives thereof, formalin condensate or co-condensate of lignin sulfonic acid and sulfonic acid of an aromatic compound such as naphthalene or alkylnaphthalene, and salts thereof. As the salt, in any of the above, ammonium, monoethanolamine,
They are lower amines such as diethanolamine, triethanolamine and triethylamine, and alkali metals or alkaline earth metals such as sodium, potassium, calcium and magnesium. The average degree of condensation of formalin is 1.2 to 50
It is. <Nonionic surfactant of HLB 14-19> (I) Block or random addition polymer of ethylene oxide and propylene oxide or / and butylene oxide and styrene oxide. (II) glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin,
Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol, or those polyhydric alcohols and 8 to 18 carbon atoms
Alkylene oxide adduct of an ester with a fatty acid. Alkylene oxide is ethylene oxide or / and propylene oxide, butylene oxide, styrene oxide. (III) An alkylene oxide adduct of a polyvalent amine having a plurality of active hydrogens such as ethylenediamine, tetraethylenediamine, and polyethyleneimine (molecular weight: 600 to 10,000). Alkylene oxide is ethylene oxide or / and propylene oxide, butylene oxide, styrene oxide. (IV) 1 mol of triglyceride type fat and oil, glycerin,
One or more polyhydric alcohols selected from the group consisting of trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylene glycol, polyethylene glycol having a molecular weight of 1000 or less, propylene glycol, and polypropylene glycol having a molecular weight of 1000 or less and / or A product obtained by adding an alkylene oxide to a mixture of water and 0.1 to 5 mol of water. Alkylene oxide is ethylene oxide or / and propylene oxide, butylene oxide, styrene oxide. 2. 100 parts by weight of the ultra-heavy oil emulsion fuel according to claim 1, further comprising HLB 1.5 to 14 having the same chemical structure as the nonionic surfactants (I) to (IV) according to claim 1.
An ultra-heavy oil emulsion fuel obtained by adding 0.01 to 0.5 parts by weight of a nonionic surfactant. 3. The super heavy oil emulsion fuel according to claim 1, wherein the HLB of the nonionic surfactant is 15 to 17. 4. The HLB of the second nonionic surfactant is
The super heavy oil emulsion fuel according to claim 2, which is 4.3 to 14. 5. The super heavy oil emulsion fuel according to claim 4, wherein the addition amount of the second nonionic surfactant is 0.1 to 0.35% by weight based on the emulsion fuel. 6. The nonionic surfactant according to claim 1, wherein the nonionic surfactant is a nonionic surfactant.
(IV) or / and / or the equivalent of claim 2.
Or the super heavy oil emulsion fuel according to 2. 7. The method according to claim 1, wherein the anionic surfactant is used.
(i) or / and (ii), wherein the nonionic surfactant is equivalent to (IV) according to claim 1 or / and / or the nonionic surfactant according to claim 2. High quality oil emulsion fuel. 8. The super heavy oil emulsion fuel according to claim 1, wherein the anionic surfactant and the nonionic surfactant are each a mixture of two or more kinds. 9. The super heavy oil emulsion fuel according to claim 1, wherein the amount of water added is 33 to 50 parts by weight based on 100 parts by weight of the super heavy oil. 10. The HLB of the second nonionic surfactant is
The super heavy oil emulsion fuel according to claim 2, which is 12 to 14.