JPH0539498A - Cleanser exhibiting oil-water separation - Google Patents

Abstract

PURPOSE:To provide the subject cleanser comprising an amphoteric surfactant, a nonionic surfactant, an anionic surfactant, etc., an anionic fluoro surfactant and water, having an excellent cleansing property, givung cleansed waste water by exhibiting rapid oil-water separation, and useful for cleansing decks, etc. CONSTITUTION:The objective oil-water separation cleanser exhibiting a good cleansing property on a cleansing work and exhibiting the extremely rapid oil-water separation in cleansing waste water after the cleansing work comprises 10-70wt.% of one kind or more of surfactants such as an amphoteric surfactant (e.g. alkylbetaine), a nonionic surfactant (e.g. polyoxyethylene nonyl phenyl ether), an anionic surfactant (e.g. polyoxyethylene nonyl phenyl ether sulfuric acid sodium salt), etc., 0.0005-5wt.% of an anionic fluoro surfactant (e.g. perfluoroalkyl sulfonic acid ammonium salt) and water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-water separable cleaning agent which exhibits good detergency during cleaning and exhibits a rapid oil-water separation after cleaning.

[0002]

2. Description of the Related Art Conventionally, a large amount of mineral oil or the like is liable to adhere to the engine room, deck, settling tank, etc. of a ship, and it is necessary to change the cargo capacity of a cargo tank or a deep tank, or the oil capacity of a land tank. For cleaning such as when
Mineral oil and the like are removed using oil-soluble and water-soluble detergents. The above-mentioned cleaning agent waste liquid is I. M. O. (Under the Marine Pollution Control Law) Unless the oil concentration of 15 ppm or less is cleared, it cannot be dumped into the ocean. Therefore, the cleaning waste liquid from a ship under voyage is collected in a bilge tank and then treated with a separator such as a bilge separator. It was then necessary to separate it into oil and water.

[0003]

However, the above-mentioned oil-soluble and water-soluble detergents have a high emulsifying / dispersing action, and the oil in the washing waste liquid is about 0.05 to several hundreds of microns. Since it is stabilized as fine particles, the separation of oil and water from the cleaning waste liquid takes a very long time. Moreover, since the elements of the bilge separator are clogged by the fine particles of oil, the life of the element is short and it is necessary to replace the element frequently, so that the oil-water separation treatment cannot be effectively shortened.

In view of the above-mentioned circumstances, cleaning agents having improved oil-water separability have been investigated, but these are merely those in which the oil-water separability is slightly improved at the expense of detergency. It did not reach its intended purpose as a cleaning agent. In particular, oil-soluble detergents have such a tendency, and some of them are 100% petroleum-based solvents. Further, in the case of a water-soluble detergent, there is a drawback that the washed oil to be washed is partially solubilized in the detergent and is detected as an oil component. In addition, even if the current cleaning agent separates oil and water by letting the cleaning waste liquid stand still, it will re-emulsify and disperse the oil when remixed, which is a factor that makes oil-water separation more difficult. Was there.

Therefore, the present invention is excellent in detergency, prevents solubilization of the oil to be washed, rapidly separates oil and water after washing, and after separation, does not re-emulsify and disperse even if re-mixed. It is an object of the present invention to provide an oil / water separation detergent which can be rapidly separated into oil and water.

[0006]

SUMMARY OF THE INVENTION The present invention has been proposed in view of the above, and comprises at least one selected from the group consisting of amphoteric surfactants, nonionic surfactants, and anionic surfactants.
˜70% by weight, and an anionic fluorosurfactant of 0.
The present invention relates to an oil-water separable detergent comprising 0005 to 5% by weight and water.

As described above, the oil-water separable detergent of the present invention comprises one or more selected from amphoteric surfactants, nonionic surfactants and anionic surfactants, and anionic fluorine-based surfactants. It is composed of three components, water. Each of these components will be described. First, amphoteric, nonionic,
Examples of anionic surfactants include amino acid type amphoteric surfactants, betaine type amphoteric surfactants, sulfate ester type surfactants, sulfonic acid type amphoteric surfactants, phosphate ester type amphoteric surfactants, and polyoxyethylene alkyl. Ether, polyoxyethylene alkylphenol ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl fatty acid ester, tetronic type polyoxyethylene fatty acid amide, polyoxyethylene alkyl Amine, alkylallyl sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkyl phosphate,
There are polyoxyethylene alkyl phosphate ester salts and the like, which can be used in appropriate combination. Of the above-mentioned amphoteric, nonionic and anionic surfactants, nonionic surfactants are most preferable, and HLB is 18 or less,
Particularly, those having about 7 to 15 are preferable, and for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester and the like are particularly preferable. The amount of at least one compound selected from the above-mentioned amphoteric, nonionic and anionic surfactants in the oil-water separable detergent of the present invention is 10 to 70% by weight, particularly 10
It is preferably up to 50% by weight.

Next, as an anionic fluorosurfactant constituting the oil-water separating detergent of the present invention, one or more selected from the above-mentioned amphoteric, nonionic and anionic surfactants is a perfluoroalkyl. Examples thereof include sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates and the like. The amount of the above-mentioned anionic fluorine-based surfactant compounded in the oil-water separable detergent of the present invention is 0.0005 to 5% by weight, and 0.00
If it is less than 05% by weight, the oil / water separation rate after washing is slow, the effect of preventing solubilization of the oil to be washed is poor, and if the washing waste liquid is remixed after the oil / water separation, the oil is re-emulsified and dispersed. On the other hand, even if 5% by weight or more is added, the effect of preventing solubilization of the oil to be washed and the oil-water separation rate do not improve any further, and it becomes economically worse. The cause of contributing to the oil-water separability of the anionic fluorosurfactant and the effect of preventing solubilization of the oil to be washed is unknown, but the molecule of the anionic fluorosurfactant is the amphoteric or nonionic system described above. It is presumed that the anionic surfactant adsorbs the oil emulsified / dispersed to the oil and causes the oil to agglomerate to exert an oil collecting action. Other nonionic, cationic or amphoteric fluorosurfactants do not have the above effects.

Water has the advantage that it becomes a solvent for the above-mentioned components and at the same time does not become a dangerous substance.

An engine room of a ship to which mineral oil or the like is attached by using the oil-water separating detergent of the present invention having the above-mentioned structure,
When the deck, settling tank, etc. are washed, mineral oil, etc. becomes fine particles of 0.05 to several hundreds of micron in the washing liquid and emulsifies and disperses. Aggregates and quickly forms an oil layer. In this way, the cleaning waste liquid is separated into an oil layer, an emulsified layer and an aqueous layer,
The oil concentration of the water layer is I. M. O. Since it is 15 ppm or less, which clears the regulation of No. 1, the water layer can be dumped into the ocean without treating the bilge separator.
Further, when the bilge separator is used, it is not necessary to frequently replace the element unlike the conventional cleaning agent, and the life of the element can be extended. On the other hand, the oil layer can be recovered and used as a fuel, and the emulsified layer becomes extremely small compared to the case where a detergent is used conventionally, and it can be recovered together with the oil layer and used as a fuel. In this way, the engine room of the ship, the deck,
Most of the mineral oil and the like attached to the settling tank is contained in the oil layer and the emulsified layer. The oil-water separation detergent of the present invention is extremely effectively used as described above.

When the oil-water separation cleaning agent of the present invention is used, after the cleaning waste liquid is allowed to stand and the oil layer and the water layer are separated,
Even when re-mixed, it does not re-emulsify and disperse as in the case of using a conventional detergent, and exhibits stable oil-water separation property.
In this case, the oil layer merely becomes oil droplets of coarse particles of about 0.1 to 1.0 mm and is dispersed in water, and rapidly separates into an oil layer and a water layer. Therefore, by using the oil-water separable cleaning agent of the present invention, the cleaning waste liquid collected after cleaning can be stored in the bilge tank, and the time to stand still can be significantly shortened, and the oil-water separation and the subsequent treatment can be extremely performed. It can be performed easily and in a short time, and also has an economical effect. In addition, the oil-water separating detergent of the present invention exerts a sufficient effect on the washing treatment of not only mineral oils but also animal and vegetable oils and various waste oils. Therefore, it is used for the engine room of ships, decks and set ring tanks. It is not limited to and can be used for various oil contaminants.

[0012]

EXAMPLES Examples of the present invention will be shown below. Example 1 Softanol 120 (manufactured by Nippon Shokubai Kagaku Co., Ltd.) 20.0 wt% [polyoxyethylene alkyl ether, EO = 12 mol: nonionic] Fluorard FC-98 (manufactured by Sumitomo 3M Ltd.) 1.0 wt% [Perfluoro Alkylsulfonic acid potassium salt: anion, fluorine-based] Water 79.0 wt% Example 2 Neugen EA120 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 15.0 wt% [polyoxyethylene nonylphenyl ether, EO = 9 mol: nonionic ] Megafac F-191 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.5 wt% [perfluoroalkyl phosphate ester: anion, fluorine-based] water 84.5 wt% Example 3 Nikkor SBL-4T (Nikko Chemicals Co., Ltd.) Made) 60.0 wt% [polyoxyethylene Lauryl ether Triethanolamine sulfate, EO = 4 mol: anionic] Amogen K (Daiichi Kogyo Seiyaku Co., Ltd.) 10.0 wt% [alkylbetaine type, amphoteric system] Fluorard FC-126 (Sumitomo 3M Ltd.) 5 0.0 wt% [Ammonium salt of perfluoroalkylsulfonic acid: anion, fluorine-based] Water 25.0 wt% Example 4 Neomalite S (manufactured by Japan Neoma Giken Co., Ltd.) 10.0 wt% [higher alkylsilicic acid ethylate: anionic] 4. Florard FC-95 (manufactured by Sumitomo 3M Limited) 0.0005 wt% [potassium salt of perfluoroalkylsulfonic acid: anion, fluorine-based] water 89.99995 wt% Example 5 Softanol 30 (manufactured by Nippon Shokubai Kagaku Co., Ltd.) 5. 0 wt% [Polyoxyethylene Alkyl ether, EO = 3 mol: nonionic type] Softanol 150 (manufactured by Nippon Shokubai Kagaku Co., Ltd.) 30.0 wt% [Polyoxyethylene alkyl ether, EO = 15 mol: nonionic type] Fluorard FC-93 (Sumitomo 3M Limited) ) 1.0 wt% [Ammonium salt of perfluoroalkylsulfonic acid: anion, fluorine-based] Water 64.0 wt% Example 6 Softanol 160 (manufactured by Nippon Shokubai Kagaku Co., Ltd.) 30.0 wt% [Polyoxyethylene alkyl ether, EO] = 16 mol: nonionic] Nikkor SNP-4N (manufactured by Nikko Chemicals Co., Ltd.) 15.0 wt% [sodium polyoxyethylene nonylphenyl ether sulfate, EO = 4 mol: anionic] Surflon S-112 (manufactured by Asahi Glass Co., Ltd.) 2.0 wt [Perfluoroalkyl phosphate: anion, fluorine-based] Water 53.0 wt% Example 7 Amogen K 10.0 wt% Neugen EA120 10.0 wt% Florard FC-98 0.3 wt% Megafac F-191 0.01 wt% Water 79.69 wt%

Comparative Example 1 Softanol 90 30.0 wt% [Polyoxyethylene alkyl ether, EO = 9 mol: Nonionic] Nikkor SNP-4N 15.0 wt% Water 55.0 wt% Comparative Example 2 Softanol 120 20.0 wt% Florard FC-170C (manufactured by Sumitomo 3M Ltd.) 0.5 wt% [perfluoroalkylpolyoxyethylene ethanol: nonion, fluorine-based] water 79.5 wt% Comparative Example 3 Sofanol 30 5.0 wt% Softanol 150 30.0 wt% Megafac F-150 (manufactured by Dainippon Ink and Chemicals, Inc.) 1.0 wt% [Perfluoroalkyltrimethylammonium salt: cation, fluorine-based] Water 64.0 wt% Comparative Example 4 Neomalite S 10.0 wt% Surflon S-131 (Asahi Child Ltd.) 5.0 wt% [C ° perfluoroalkyl F Bu Tyne: amphoteric, fluorine-based] water 85.0Wt%

(Test Method) Detergency Test Examples 1 to 7 and Comparative Examples 1 to 1 described above for a 1 l separating funnel.
1 l of a 1.0 wt% aqueous solution of the cleaning agent of 4 was added to C heavy oil 1
After adding 0 g and shaking vigorously for 5 minutes, it left still for 5 minutes.
Then, 900 ml of the cleaning liquid is withdrawn from the lower part and n-
It was extracted with hexane and the oil concentration in the liquid was measured. The results are shown in Table 1.

Oil-Water Separation Test Examples 1 to 7 and Comparative Examples 1 to 1 described above for a 1 l separating funnel.
1 l of a 1.0 wt% aqueous solution of the cleaning agent of 4 was added to C heavy oil 1
After adding 0 g and shaking vigorously for 5 minutes, it left still for 8 hours.
Then, 900 ml of the cleaning liquid is withdrawn from the lower part and n-
It was extracted with hexane and the oil concentration in the liquid was measured. The results are shown in Table 1.

Oil-Water Separation Test after Remixing Examples 1 to 7 and Comparative Examples 1 to 1 described above for a 1 l separating funnel.
1 l of a 1.0 wt% aqueous solution of the cleaning agent of 4 was added to C heavy oil 1
After adding 0 g and shaking vigorously for 5 minutes, it left still for 8 hours.
Then, the separatory funnel was vigorously shaken for 1 minute and allowed to stand for 1 hour, 900 ml of the washing liquid was withdrawn from the lower portion, and extracted with n-hexane to measure the oil concentration in the liquid. Result is,
The results are shown in Table 1.

[0017]

[Table 1]

Each of the above-mentioned tests 1 to 3 was carried out at room temperature, and the C heavy oil used in each test had the following physical properties. Density (g / cm ³ , 15 ° C): 0.960 Viscosity (50 ° C, cst): 169 Residual carbon content (%): 8.28 Flash point (° C): 99 Ash content (%): 0.02

[0019]

As described above, the oil-water separable detergent of the present invention imparts oil-water separability without deteriorating the cleaning ability of conventional detergents, and emulsifies various oils during washing. -It is possible to disperse the oil to be washed, prevent solubilization of the oil to be washed, and collect the washing waste liquid and leave it for a short time to easily separate oil and water. In addition, even if the washing waste liquid is separated from the oil and water and then remixed, the oil is not re-emulsified and dispersed, and extremely stable oil-water separation can be maintained. Has an extremely low residual concentration of oil. Therefore, when the oil-water separating cleaning material of the present invention is applied to the cleaning of the engine room, deck, settling tank, etc. of ships to which mineral oil or the like is attached, the cleaning waste liquid is collected in the bilge tank and left standing for a short time. You can quickly separate oil and water,
The separated aqueous layer had an extremely low oil content and had an I.V. M. O.
It can be discharged into the ocean without being treated by the bilge separator without violating the regulations of.

Further, even if the bilge separator is used, it is possible to use a long-life element without having to frequently replace the element as in the conventional case.

Further, the oil layer and the emulsified layer remaining after discharging the water layer can be recovered and used as fuel, and the mineral oil and the oil-water separating detergent of the present invention can be effectively reused. Further, since the oil-water separable detergent of the present invention is water-based, it has an advantage that there is no risk of ignition.

Claims (1)

[Claims] 1. At least one selected from the group consisting of amphoteric surfactants, nonionic surfactants, and anionic surfactants.
˜70% by weight, and an anionic fluorosurfactant of 0.
An oil-water separable detergent comprising 0005 to 5% by weight and water.