JP2793190B2 - Heavy oil, water mixed fuel composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to heavy oil and water-mixed fuel oil, and more particularly to heavy oil and water-mixed fuel oil that can be used in motors, diesels, boilers, and the like.

[Conventional technology]

As fossil fuel resources that are not included in crude oil, coal and LNG, heavy oils such as oil sands and natural asphalt are attracting attention due to their reserves. Also, in petroleum-based systems, a large amount of asphalt or heat-treated residues thereof, excluding distillation and distillate components such as naphtha, remains.

[Problems to be solved by the invention]

These heavy oils are usually 420 ° C. to 450 ° C.
It is an oily substance containing about 60% to 70% or more of a heavy fraction above ℃ and does not flow as it is or exhibits high viscosity of tens of thousands of centipoise or more. Therefore, when used as fuel, it is necessary to raise the temperature to a very high level due to handling or atomization by spraying, and it is easy to cause troubles such as blockage of pipes and the like, and it is very difficult to use as fuel.

For this reason, if these heavy oils are mixed with water to form oil-in-water (O / W), the viscosity can be reduced close to that of water in the medium, but if the content of heavy oil decreases, it becomes a fuel. For this reason, a dispersant, a stabilizer and the like are indispensable for adjusting the heavy oil content to an O / W type fuel by increasing the concentration.

Thus, by adding an additive including water and a dispersing agent to a heavy fuel oil that is highly viscous or solidified at normal temperature to form an O / W emulsion fuel, it can be used at room temperature or up to tens of degrees Celsius. It was necessary to improve it so that it could be handled by heating.

The present invention has been made in view of the above technical level, and aims to provide a heavy oil / water mixed fuel oil having a high heavy oil concentration and a stable oil-in-water emulsion by specifying the type of additive. is there.

[Means for solving the problem]

The present invention provides (1) an anionic surfactant comprising (a) a heavy hydrocarbon which does not flow unless heated to a high temperature, (b) water, (c) a polymerizable hydrocarbon monomer or a polymer or condensate thereof. (D) a nonionic surfactant having a phase inversion temperature of 50 ° C. or higher, which is a polyether compound or a derivative thereof obtained by adding ethylene oxide or an alkylene oxide mixture containing ethylene oxide to a compound having at least one active hydrogen at one molecular weight. And (e) the above (d) wherein the HLB value is 8 to 14
A heavy oil / water mixed fuel composition comprising an oil-in-water emulsion composed of the same type of nonionic surfactant.

Oil-in-water emulsion with the above configuration (O / W)
Thus, a highly concentrated heavy oil / water mixed fuel oil having a heavy oil concentration of 65 to 78% can be obtained.

 Hereinafter, the components of the present invention will be described.

(A): Heavy hydrocarbons that do not flow unless heated to a high temperature The following heavy oils are used as oil components, and those that solidify at room temperature and those that flow by heating are more desirable.

(A-1) Petroleum-based asphalts and oil mixtures thereof (a-2) Various processed products of petroleum-based asphalts, intermediate products, residues and oil mixtures thereof (a-3) High pour point oil or crude oil which does not flow at room temperature (A-4) Coal-based tar pitch and its oil mixture (a-5) Bitumen (orinoco tar, Athabasca bitumen) (b): Water (c): From polymerizable hydrocarbon monomer or its polymer or condensate Anionic surfactants obtained The following anionic surfactants are preferred, and the polymerization average molecular weight range is preferably up to 20,000.

(C-1) an aliphatic aldehyde adduct of a sulfone compound of naphthalene, alkylnaphthalene, or alkylbenzene or a salt thereof (c-2) a ligninsulfonic acid salt or a derivative thereof (c-3) a polystyrenesulfonic acid polymer or a salt thereof (c -4) dicyclopentadiene sulfonic acid polymer or salt thereof (c-5) sulfonated product of tar oil such as naphthalene oil,
Salt or aliphatic aldehyde addition polymer The salts (c-1) to (c-5) are alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts.

(D) a non-ionic polyether compound or a derivative thereof obtained by adding ethylene oxide or an alkylene oxide mixture containing ethylene oxide to a compound having one or more active hydrogen atoms at a molecular weight, and having a phase inversion temperature of 50 ° C., preferably 70 ° C. or more Surfactant Specific examples of the compound having active hydrogen in the molecule include the following.

(D-1): phenol, cresol, tertiary butyl phenol, octyl phenol, nonyl phenol, dinonyl phenol, dodecyl phenol, xylenol, naphthol, methyl naphthol, butyl naphthol, paracumyl phenol, (D-2): monohydric alcohols such as benzyl alcohol (d-3): catechol, resorcin, pyrogallol, etc.
Polyhydric alcohols such as pisphenol A and phenol formalin condensate The nonionic surfactant is indispensable as a stabilizer together with the anionic surfactant (c).
Since heavy oil has a high pour point and high viscosity, it needs to be heated in order to be emulsified.
° C, so that the phase inversion temperature was 50 ° C or higher.

(E): Nonionic surfactant similar to the above (d) having an HLB value of 8 to 14 It is similar to the nonionic surfactant of the above group (d), and is added to a compound having active hydrogen. As the alkylene oxide, ethylene oxide is used alone or together with another alkylene oxide. The proportion of ethylene oxide in the total alkyl oxide is suitably from 80% to 100% (% by weight). As alkylene oxides other than ethylene oxide, propylene oxide, butylene oxide and the like are used. The polyether compound has a weight average molecular weight of preferably 400 to 4,000, and more preferably 500 to 4,000.
3,000.

The nonionic surfactants of group (e) are added to promote the stabilization of the emulsion, and as a result of experiments, their HLB values (here, HLB calculated by WCGriffin)
Indicates a value. ) Has been confirmed to be effective if it is in the range of 8 to 14.

Emulsion of heavy oil and water is in a predetermined ratio of each,
Generally, heavy oil is blended to 65-78% by weight,
A predetermined amount of the additive (anionic surfactant, nonionic surfactant) of the present invention is added, and the heavy oil is adjusted to fine droplets by stirring. As the stirring method, a very common paddle type or helical lipon type stirring may be used, but it is preferable to perform high-speed stirring known as a line mixer or the like. In addition, it is possible to obtain a result in which both of these stirring methods may be used in combination.

Heavy oil of the present invention, when obtaining a water-mixed fuel composition,
The composition of (a) heavy oil, (b) water, (c) anionic surfactant, (d) nonionic surfactant and optionally used (e) nonionic surfactant is generally Specifically, it is in the following range.

(1); (a) heavy oil: (b) water: (c) anionic surfactant: (d) a composition comprising a nonionic surfactant; (a); 65 to 78%; (B); 22-35%, (c) +
(D); 0.2 to 2.5%, (c) / (d); 45/55 to 5/95 (2) (a) heavy oil: (b) water: (c) anionic surfactant: ( d) a nonionic surfactant; (e) a composition comprising a nonionic surfactant; (a): 65 to 78
%, (B): 22 to 35%, (c) + (d) + (e): 0.2 to
2.5%, (c) / (d) + (e): 5/95 to 45/55, (e)
/ (D): 5 / 95-40 / 60 Usually, solid or very high-viscosity heavy oil is used as the heavy oil-water mixed fuel composition of the present invention, and is handled at room temperature or slightly heated. And atomization during combustion can be easily performed. Next, one embodiment will be described.

(Example) Heavy oil and water are mixed with a predetermined additive to make a total amount of 500 g.
After mixing with a double helical ribbon blade stirrer at 200 rpm for 5 minutes, 6000 rp with a high-speed shear stirrer
The emulsion was prepared by mixing at m for 3 minutes.

The fluidity and standing stability of this emulsion were evaluated by the following methods.

(1) Fluidity The viscosity of the adjusted emulsion was measured with a Brookfield viscometer (No. 2 rotor, 12 rotations, measured after 1 minute), and a certain amount of the emulsion was passed through a 100 mesh sieve for 10 minutes. The atomization rate was determined from the residual rate on the sieve of the emulsion obtained by measuring the amount on the remaining sieve later and evaluated as follows.

：: Very good ○: Good △: Insufficient ×: Poor (2) Stability at rest The above emulsion was placed in a sealed plastic bottle, stored at room temperature for one month, and then evaluated for the fluidity of the above (1). Natsuta

 Table 1 shows composition examples of the present invention.

Table 2 shows the measurement results of the properties of the heavy oil emulsion using the present invention.

[Effect of the Invention] Usually, a solid or very high-viscosity heavy oil is used in the O / W of the present invention.
By using a heavy oil-water mixed fuel composition of the emulsion type, a fuel that can be easily handled and atomized during combustion at room temperature or slightly heated can be obtained.

Continuation of the front page (72) Inventor Tatsuro Miyazaki 1-1, Akunoura-cho, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Nagasaki Research Laboratory (56) References JP-A-52-37907 (JP, A) JP-A-56- 7640 (JP, A) JP-A-56-112992 (JP, A) JP-A-61-233085 (JP, A) JP-A-61-233086 (JP, A) JP-A-60-104190 (JP, A) JP-A-1-203498 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C10L 1/32

Claims (1)

(57) [Claims] 1. An anionic surfactant comprising (a) a heavy hydrocarbon which does not flow unless heated to a high temperature, (b) water, (c) a polymerizable hydrocarbon monomer or a polymer or condensate thereof, d) a nonionic surfactant having a phase inversion temperature of 50 ° C. or higher, which is a polyether compound or a derivative thereof obtained by adding ethylene oxide or an alkylene oxide mixture containing ethylene oxide to a compound having one or more active hydrogens at one molecular weight; e) A heavy oil / water mixed fuel composition comprising an oil-in-water emulsion comprising a nonionic surfactant similar to the above (d) having an HLB value of 8 to 14.