JP2001220574A - Self-stirring type spilled oil-treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a self-string type spilled oil-treating agent which requires no mechanical stirring, is easily produced on a large scale, shows low toxicity, is easy handled and efficiently disperses spilled oil a short time with a small amount of use. SOLUTION: The self-stilling type oil-treating agent comprises a nonionic surfactant having an HLB of 9 to 13, a hydrocarbon solvent and a water-soluble glycol ether solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-stirring type oil spill treatment agent, and more particularly, it can be easily mass-produced without requiring any particular mechanical stirring, has low toxicity and is convenient for handling. The present invention relates to a self-stirring spilled oil treating agent which can efficiently disperse oil spilled in a short time with a small amount of use and is particularly suitable for dispersion treatment of oil spilled into the ocean.

[0002]

2. Description of the Related Art Oil spills such as crude oil and fuel oil spilled into the ocean due to a tanker accident or the like cause serious environmental problems such as polluting the ocean and destroying ecosystems. The recovery of such spilled oil is generally performed using an oil recovery device, an oil adsorbent, or the like, while preventing its diffusion by an oil fence or the like. The spilled oil that cannot be collected is dispersed using an spilled oil treating agent. However, depending on the weather and geographical environment, it may not be possible to use an oil recovery device or the like. In such a case, the spilled oil is dispersed using only the spilled oil treating agent.

Conventionally, various spilled oil treating agents are known, but spilled oil treating agents containing anionic surfactant as a main component are widely used. However, since this oil spill remediation agent is highly toxic, it may cause environmental problems such as ecosystem destruction. Therefore, recently, an oil spill treating agent containing a low-toxic nonionic surfactant as a main component has been proposed.

However, these proposed oil spill treating agents require mechanical stirring when dispersing the oil spill, and it is difficult to disperse the oil spill in a short time with a small amount of use. There is a problem that is.

As means for solving this problem, there is an invention described in Japanese Patent Application Laid-Open No. 9-256162. The invention described in this publication includes a polyoxyethylene sorbite fatty acid ester (A) having an HLB of 10 to 13,
A nonionic surfactant (B) having an HLB of 2 to 6,
A high viscosity oil treating agent composition containing a hydrocarbon solvent (C).

[0006] However, the oil spill treating agent of the present invention requires forcible mechanical agitation when the surface of the oil spill is calm, and depending on the weather and geographical environment of bad weather, At present, the work cannot be performed because it involves danger.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems. The present invention provides a self-stirring spilled oil treating agent that does not particularly require forced mechanical stirring and can efficiently disperse the spilled oil in a short time while using a small amount of oil. Aim. Another object of the present invention is to provide a self-stirring type oil spill agent which is particularly suitable for dispersion treatment of oil spilled into the ocean.

[0008]

According to the present invention, there is provided a nonionic surfactant (A) having an HLB of 9 to 13, a hydrocarbon solvent (B), and a water-soluble glyco- A self-stirring spilled oil treating agent characterized by comprising a luter-based solvent (C). In a preferred self-stirring spilled oil treating agent of the present invention, the nonionic surfactant (A) is a polyoxyethylene sorbit fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyglycerin fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyethylene glycol
At least one selected from the group consisting of fatty acid esters, polyoxyethylene castor oil, and polyoxyethylene hydrogenated castor oil. In a preferred self-stirring spilled oil treatment agent of the present invention, the hydrocarbon solvent ( B)
Is at least one selected from the group consisting of paraffinic solvents, naphthenic solvents, spindle oils, n-decane, kerosene and light oils. In the preferred self-stirring type spilled oil treating agent of the present invention, the hydrocarbon The weight ratio ((B) :( C)) between the solvent (B) and the water-soluble glycol ether solvent (C) is 90:10 to 10:90. Preferred self-stirring spilled oil treating agents include the hydrocarbon solvent (B) and water-soluble glyco-
It contains a total of 30 to 80% by weight of the ether-based solvent (C) and 20 to 70% by weight of the nonionic surfactant (A).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (Self-stirring type oil spill agent) The self-stirring type oil spill agent of the present invention comprises a nonionic surfactant (A), a hydrocarbon solvent (B) and a water-soluble glycoside. -It contains a luether-based solvent (C).

-Nonionic surfactant (A)-The nonionic surfactant (A) in the present invention has an HLB of 9 to 13, particularly preferably 9.5 to 12.5. When the HLB is within the above range, the dispersibility with respect to spilled oil and the self-emulsifying agitation property in the sea are good. When the HLB is less than 9, the permeability with respect to the oil is improved, but the self-emulsifying agitation property in the sea is deteriorated. If it exceeds 13, the self-emulsifying and agitating properties in the ocean will be improved, but the permeation and dispersibility in oil will be poor. Here, the self-emulsifying agitating property is determined by the following formula: Y ≧ 3.875X + 31.2, where the emulsification ratio Y measured by the measurement of the emulsification ratio described in the examples described below and the addition ratio X of the treating agent to the amount of the oil to be treated.
It means that the relational expression of 5 is satisfied.

Examples of the nonionic surfactant (A) include polyoxyethylene sorbite fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Oxyethylene castor oil, polyoxyethylene hydrogenated castor oil, and the like. In the present invention, these nonionic surfactants may be used alone or in a combination of two or more.

Examples of the polyoxyethylene sorbite fatty acid ester include polyoxyethylene sorbite monolaurate, polyoxyethylene sorbite tetraoleate, polyoxyethylene sorbit hexastearate, and polyoxyethylene sorbite tetraester. Stearate, polyoxyethylene sorbite isostearate and the like. In the present invention, the polyoxyethylene sorbite fatty acid ester may be used alone or in a combination of two or more. In the polyoxyethylene sorbite fatty acid ester, the addition mole number of ethylene oxide is preferably 10 to 50 moles.

Examples of the polyoxyethylene sorbitan fatty acid ester include polyoxyethylene sorbitan monooleate, polyoxysorbitan trioleate, and polyoxyethylene sorbitan monostearate.
, Polyoxyethylene sorbitan isostearate,
Examples thereof include polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan coconut oil fatty acid, and polyoxyethylene sorbitan monopalmitate.
In the present invention, the polyoxyethylene sorbitan fatty acid ester can be used alone or in combination of two or more. In polyoxyethylene sorbitan fatty acid ester,
It is preferable that the number of moles of added ethylene oxide is 6 to 25 mol.

Examples of the polyglycerin fatty acid ester include hexaglyceryl monostearate, decaglyceryl isostearate, decaglyceryl diisostearate, diglyceryl triisostearate, decaglyceryl monostearate, hexaglyceryl monooleate, and monooleate. Decaglyceryl, hexaglyceryl monomyristate, and the like. In the present invention, the polyglycerin fatty acid ester may be used alone or in combination of two or more.

Examples of the polyoxyethylene glycerin fatty acid ester include polyoxyethylene glyceryl monooleate, polyoxyethylene glyceryl trioleate, polyoxyethylene glyceryl monostearate, and polyoxyethylene glyceryl vegetable oil ( For example, soybean oil) fatty acid ester and the like. In the present invention, the polyoxyethylene glycerin fatty acid ester may be used alone or in combination of two or more. In the polyoxyethylene glycerin fatty acid ester, the addition mole number of ethylene oxide is preferably 5 to 10 moles.

Examples of the polyethylene glycol fatty acid ester include polyethylene monostearate, polyethylene glycol monooleate, and the like.
Examples include polyethylene glycol dioleate, polyethylene glycol monolaurate, and polyethylene glycol in tall oil. In the present invention, the polyethylene glycol fatty acid ester may be used alone or in combination of two or more.

It is preferable that the polyoxyethylene castor oil and the polyoxyethylene hydrogenated castor oil have an addition mole number of ethylene oxide of about 20 to 40 moles each.

In the present invention, as the nonionic surfactant, an appropriately synthesized one may be used, or a commercially available nonionic surfactant may be used.

-Hydrocarbon Solvent (B)-The hydrocarbon solvent in the present invention is not particularly limited, and examples thereof include a paraffin solvent, a naphthene solvent, a spindle oil, n-decane, kerosene, and a light oil. No. In the present invention, among these, paraffinic solvents are preferred. The use of these hydrocarbon solvents is effective in improving familiarity, permeation, and solubility of the spilled oil. In the present invention, these hydrocarbon solvents may be used alone or in a combination of two or more. In the present invention, a commercially available product can be suitably used as the hydrocarbon solvent.

-Water-soluble glycol ether solvent (C)-The water-soluble glycol ether solvent in the present invention is not particularly limited, but ethylene glycol ether solvent is not particularly limited.
And propylene-based glycol ethers and their acetates. Water-soluble glycole
One of the tellurium solvents can be used alone, or two of them can be used in combination.

The water-soluble glycol ether-based solvent, combined with the non-ionic surfactant and the hydrocarbon-based solvent, can be used for oil spilled into the ocean without mechanical stirring. The self-stirring spilled oil treatment agent permeates and diffuses and disperses the oil in seawater, which promotes a so-called self-stirring action.

The ethylene glycol ether includes ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, and diethylene glycol monoisopropyl ether. Ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monoallyl ether, ethylene glycol dimethyl ether -Ter, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether
Ter and 3-methoxy-3-methyl-1-butanol. The propylene-based glycol eluate
Examples of the ter include propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, tripropylene glycol monomethyl ether, and methyl propylene glycol acetate. Examples of the acetic acid ester of the ethylene glycol ether or the propylene glycol ether include 3-methoxy-3-methylbutyl acetate, ethylene glycol ethyl ether tereate, and propylene glycol methyl ether. Teracetate, propylene glycol diacetate
And the like.

In the present invention, these water-soluble glycol ether solvents can be used alone or in combination of two or more. In the present invention, a commercially available product can be suitably used as the water-soluble glycol ether-based solvent.

-Composition of the self-stirring type oil spill-treating agent- The self-stirring type oil spilling agent of the present invention comprises a mixture of a hydrocarbon solvent (B) and a water-soluble glycol ether solvent (C). The weight ratio ((B) :( C)) is 90:10
The ratio is preferably 10:90, particularly 80:20 to 2
It is preferably 0:80. When the weight of the hydrocarbon solvent (B) with respect to the glycol ether solvent (C) exceeds 90, the self-emulsifying effect on the spilled oil is inferior, and mechanical stirring is required. In such a case, the permeation and solubility of the spilled oil become poor, and the dispersing effect is poor. When the weight ratio is within the above range, the oil spill can be efficiently dispersed in a short time without requiring mechanical stirring.

In the self-stirring type oil spill treating agent of the present invention, the total of the nonionic surfactant (A), the hydrocarbon solvent (B) and the water-soluble glycol ether solvent (C) is used. The total amount of the hydrocarbon solvent (B) and the water-soluble glycol ether solvent (C) is preferably 30 to the amount.
To 80% by weight, particularly preferably 40 to 70% by weight.
And a nonionic surfactant (A) based on the total amount of the nonionic surfactant (A), the hydrocarbon solvent (B) and the water-soluble glycol ether solvent (C). Is preferably 70 to 20% by weight, particularly preferably 6 to 20% by weight.
0 to 30% by weight. In particular, the self-stirring type oil spill treating agent having the above composition emulsifies the oil spill to provide particularly stable O / W
Mold emulsions can be formed over extended periods of time.

(Manufacture of Self-Stirring Type Oil Spill Treatment Agent) The self-stirring type oil spill treating agent of the present invention may be, for example, a nonionic surfactant (A) or a hydrocarbon solvent (B) appropriately synthesized or selected. ) And a water-soluble glycol ether-based solvent (C) are separated and mixed, and the like.

(Use and Usage of Self-Stirring Oil Spill) The self-stirring oil spill of the present invention can be used for oil dispersion treatment. The oil is not particularly limited, but includes, for example, crude oil floating in oceans, rivers, lakes, and the like, heavy fuel oil A, heavy fuel oil B, heavy fuel oil C (fuel oil), and the like. However, the self-stirring type spilled oil dispersant according to the present invention can be used in any of the above oils in the range of 5 to 3000 cst /
It is suitable for treating oils having a viscosity of 20 ° C., preferably 5 to 1000 cst / 20 ° C., particularly preferably 5 to 300 cst / 20 ° C. The state of the oil is not particularly limited, but may be, for example, a film on a water surface, a mousse, a lump, or the like.

According to the self-stirring type oil spill agent of the present invention, mechanical stirring is not particularly required, and for example, an oil film floating on the surface of ocean water can be efficiently emulsified by the action of waves and dispersed. Further, the emulsification / dispersion treatment of the spilled oil can be performed reliably even with a small amount of use.

[0029]

EXAMPLES Examples of the self-stirring spilled oil treating agent of the present invention will be described below. The present invention is not limited to the following embodiments.

(Examples 1 to 4, Comparative Examples 1 to 5) Self-stirring spilled oil treating agents having the compositions shown in Tables 1 and 2 were used.

[0031]

[Table 1]

<Evaluation> (Measurement of emulsification rate) Fuel oil C (2,500 cst / 25 ° C.)
A test oil was prepared by mixing 10 g with 1 g and 0.2 g (10% and 2% based on C heavy oil) of a self-stirring spilled oil treating agent having the above composition.

The capacity shown in FIG. 1 is 1,110 ml and the outer diameter is 65.
550 ml of seawater was placed in a glass-made improved cylindrical separatory funnel having a length of ± 1 mm and a length of 405 mm (in a state where the axis was horizontal), and 1 g of the test oil prepared above was suspended therein. In FIG. 1, reference numeral 1 denotes an improved cylindrical liquid separating funnel, 2 denotes a liquid storage cylinder, 3 denotes a drip pipe connected to one end of the liquid storage cylinder in the longitudinal direction, and 4 denotes a drip pipe. A stopcock, 5 is a central liquid inlet provided in the body of the liquid storage cylinder, 6 is a plug head fitted into the central liquid inlet,
Reference numeral 7 denotes an end liquid inlet provided at one end of the liquid storage cylinder, and reference numeral 8 denotes a plug head fitted to the end liquid inlet.

The improved cylindrical type separation funnel was set to an amplitude of 40 m.
The mixture was shaken under the conditions of m and 35 reciprocations / minute for 20 minutes. This shaking was used to simulate ocean waves. After the shaking, the improved cylindrical separatory funnel was slowly set up vertically and allowed to stand for 10 minutes, and 100 ml of a sample solution was collected from the lower part of the improved cylindrical separatory funnel. With respect to this sample solution, the oil content was extracted with chloroform, the oil content was obtained from a calibration curve prepared in advance from the test oil, and the emulsification rate was obtained from the following equation. Table 2 shows the measurement results.

Emulsification ratio (Y) = [oil content in test liquid (g) /
The total amount of test oil loaded in the improved cylindrical separatory funnel (g) x (1
0/11 or 10 / 10.2)] × 550

[0036]

[Table 2]

As is clear from the results in Table 2, the self-stirring type spilled oil dispersant according to the present invention is particularly effective for spilled oil without the need for mechanical stirring, as compared with the conventional dispersant. In addition, a high emulsifying and dispersing effect is exhibited even when a small amount is used for spilled oil.

(Examples 5 to 7, Comparative Example 6) Vertical 5 m, horizontal 5
and water to a depth of 1 m in a water tank with a depth of 1.5 m and a viscosity of 5,000 to a thickness of 1 μm on the water surface.
cst / 20 ° C. oil (heavy oil) was added.

On the other hand, a self-stirring spilled oil treating agent having the composition shown in Table 3 was prepared. The self-stirring spilled oil treatment agent was sprayed into the above-mentioned water tank at a spray amount shown in Table 3.
5m after spraying, 50m from liquid level in water tank
The liquid at the position of m was sucked, and the oil concentration and the particle diameter of the oil droplets in the sucked liquid were measured. The particle size of the oil droplets was measured with a coater counter of Shimadzu Corporation.

[0040]

[Table 3]

(* 1): The oil remained floating on the water surface. (* 2): This is a state before spraying the self-stirring type oil spill, and no oil particles were present in the sucked liquid.

When the average particle size of the oil present in the sucked liquid is 30 μm or less, the oil on the liquid surface is emulsified to such an extent that the rainbow gloss of the liquid surface is not observed. The above Examples 5 to 7 and Comparative Example 6 also simulate the ocean surface. Since the calm ocean surface has calm waves, even the oil on the stationary water surface such as the above-mentioned water tank is emulsified, and therefore, the self-stirring type oil spill treating agent according to the present invention flows into the wave surface. It has been found that the oil can be emulsified without stirring.

[0043]

According to the present invention, the above-mentioned conventional problems can be solved. According to the present invention, it is possible to provide a self-stirring spilled oil treating agent which can be easily mass-produced and is easy to handle. According to the present invention, it is possible to provide a self-stirring spilled oil treating agent which does not particularly require mechanical stirring and can efficiently disperse and emulsify the spilled oil in a short time even with a small amount of use. According to the present invention, it is possible to provide a self-stirring spilled oil treating agent that can be reliably dispersed even if the spilled oil is moistened. According to the present invention, it is possible to provide a self-stirring spilled oil treating agent particularly suitable for dispersion treatment of oil spilled into the ocean.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an improved cylindrical liquid separating funnel.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Improved cylindrical liquid separation funnel, 2 ... Liquid storage cylinder, 3 ... Dripping pipe, 4 ... Cock, 5 ... Central liquid inlet, 6 ... Plug head, 7 ... End liquid inlet, 8 ... Stopper Head.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hide Ogura 1-1-4 Kamariya Nishi, Kanazawa-ku, Yokohama-shi, Kanagawa Prefecture 801 F-term (reference) 4D077 AA07 AB09 AB20 AC01 BA04 BA07 BA15 DD08Y DD32Y DD36Y DE02Y DE07Y DE08Y DE09Y DE13Y

Claims (5)

[Claims] 1. A nonionic surfactant (A) having an HLB of 9 to 13, a hydrocarbon solvent (B) and a water-soluble glyco-
A self-stirring spilled oil treating agent comprising a luter-based solvent (C). 2. The nonionic surfactant (A) comprises a polyoxyethylene sorbite fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyglycerin fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyethylene glycol fatty acid ester, 2. The self-stirring oil spill according to claim 1, which is at least one selected from the group consisting of polyoxyethylene castor oil and polyoxyethylene hardened castor oil. 3. The method according to claim 1, wherein the hydrocarbon solvent (B) is a paraffin solvent, a naphthene solvent, a spindle oil, n-decane,
3. The self-stirring oil spill according to claim 1, which is at least one selected from the group consisting of kerosene and light oil. 4. A weight ratio of the hydrocarbon solvent (B) to the water-soluble glycol ether solvent (C) ((B):
The self-stirring spilled oil treating agent according to any one of claims 1 to 3, wherein (C)) is 90:10 to 10:90. 5. A total of 30 to 80% by weight of the hydrocarbon solvent (B) and the water-soluble glycol ether solvent (C).
The self-stirring oil spill according to any one of claims 1 to 4, comprising 20 to 70% by weight of the nonionic surfactant (A).