JPS5982991A - Removing or recovering method of oil - Google Patents

Abstract

PURPOSE:To remove and recover efficiently the oil floating on a water surface by adding a slurry prepd. by dispersing a pulverized norbornene polymer into water contg. a water soluble monobasic aliphat. carboxylic acid and its ester to said oil. CONSTITUTION:A monobasic aliphat. carboxylic acid and its ester are dissolved in water and a pulverized norbornene polymer is added to such aq. soln. under stirring, whereby the slurry of the norbornene polymer powder is prepd. The slurry prepd. in such a way is sprayed on the surface of water or sea water on which oil floats, by a suitable means to bring the same into contact with the oil. The thin film of the norbornene polymer absorbing therein the oil is recovered. There are formic acid, acetic acid, methyl acetate, methyl acrylate, etc. as the above-described monobasic aliphat. carboxylic acid and its ester, which are adequately added to the water at >=5wt% based on the weight of the norbornene polymer used.

Description

[Detailed Description of the Invention] The present invention relates to a method for treating waste oil, waste oil, etc.
More specifically, a powdered norbornene-based polymer is dispersed in water containing a water-soluble monovalent aliphatic carboxylic acid and its esters to form a slurry, which is then added to water or oil floating on the surface of seawater. It relates to a method for removing or recovering oil.

When norbornene polymer powder comes into contact with various oils, it easily absorbs oil and forms an agar-like (gel-like) thin film. Furthermore, since this thin film has sufficient strength, it has the characteristic that various recovery methods can be used.

Conventionally, utilizing the above-mentioned properties of norbornene-based polymer powder, norbornene-based polymer powder has been used to directly absorb and remove waste oil and waste oil from the surface of water, seawater, etc. A method of spraying on the surface has been proposed (Japanese Patent Application No. 50-128263). However, although the polymer is lighter than water or seawater and floats on the water surface, it does not disperse in water or seawater, so it absorbs oil on the surface of water or seawater, but it absorbs oil dispersed in water or seawater. As a result, the oil absorption efficiency is poor (and not completely satisfactory).

The present inventors have arrived at the present invention as a result of repeated studies to improve the above-mentioned drawbacks. An object of the present invention is to provide a method for removing or recovering oil that is easy to handle and has improved oil absorption efficiency. This is achieved by dispersing and slurrying the esters thereof in water and adding the slurry to water or oil floating on the surface of seawater. The method of the present invention can absorb not only oil above the water surface but also below the water surface (dispersed in water), so it is an oil removal or recovery method with excellent oil absorption efficiency.

The norbornene-based polymer used in the present invention does not contain large amounts of solvents (1-toluene, benzene, forylene, etc.) and various oils (A-C heavy oil, spindle oil, machine oil, light oil, kerosene, gasoline, etc.) even at room temperature. Easily absorbed and becomes l-agar-like (
Ring-opening polymers or copolymers of bicyclo(&S1)-\Pran-2 or 1-2 derivatives have the property of gelling), and can be polymerized, for example, by the method described in Publication No. 1147-35800. The polymer obtained by
-) 7-1 ,, [The monomers used are bicyclo(2,2,1)hebun-2, methyl-5-bicyclo(2GZ])-\butene-2, ethyl-5-bicyclo (z:z〕)-\butene-z? , H and (7) furkyl-
5-bicyclo(221)hebutene-2 monomer, methoxy-5-bicyclo(211)hebutene-2, ethoxy-
5-bicyclo0(421) to alkoxy-5-bicyclo(z Z ], ) such as butene-2] to butene-2 monomer cyano-5-bicyclo(Z Z ], )] butene-2bicyclo(2 , 2,1,) hebutene-2-5 carboxylic acid ester monomer, bicyclo(λ21)hebutene-2-5,6 dicarbo/acid diester monomer, and mixtures thereof. .

Bicyclo (Z 2 ], ) for representative polymers]
Polynorbornene, which is a ring-opening polymer of butene, can be mentioned. Things! suitable for holding. The particle size of the powder is particularly preferably about 0.01 to Imjn.

The monovalent aliphatic carboxylic acids and their esters used in the present invention may be of any type as long as they are partially or completely soluble in water and the norbornene polymer powder is dispersed in water to form a slurry. Without restrictions, formic acid, acetic acid, propionic acid, butyric acid, helical-1-acid, enanthic acid, acrylic acid, crotonic acid, inocloto/acid, tsukurirulic acid, methynopeacetate, ethyl acetate, methyl acrylate, ethyl acrylate. etc. are included.

These carboxylic acids and esters can be used alone or in combination.

There is no restriction on the amount of monovalent aliphatic carboxylic acid and its esters added to water as long as the powdered norbornene polymer is dispersed in a slurry form. Normally, it is 1 weight of the norbornene polymer used. The weight is above 5, preferably 5 weight or higher, more preferably 10 weight or higher. There is no limit to the concentration of the polymer, and it can be determined as appropriate in consideration of the amount of oil, oil absorption efficiency, and ease of handling. Furthermore, the -valent aliphatic carboxylic acids and their esters can be used in combination with surfactants and alcohols.

The method for preparing the slurry of the norbornene polymer powder of the present invention is not limited at all, and for example, monovalent aliphatic carboxylic acids and their esters are dissolved in water, and the powdered norbornene polymer is added to this aqueous solution and stirred. A method in which -valent aliphatic carboxylic acids and their esters are sprayed onto the polymer powder and then dispersed in water to form a slurry; Examples include a method of impregnating polymer powder and dispersing it in water to form a slurry.

In the method of the present invention, the norbornene-based polymer in the form of a slurry may be sprayed on the surface of water or seawater in which oil is floating by an appropriate means and brought into contact with the oil, and the method of spraying itself is not limited in any way.
Commonly used spraying methods, such as spraying from a nozzle under pressure, can be used.

The thin film of norbornene-based polymer that absorbs oil, swells, and becomes an agar-like gel has sufficient strength and does not break into pieces due to wave action, making it suitable for conventional methods such as net collection and suction pump collection. It is collected using the following collection method. The method of the present invention uses an oil absorbent in the form of a slurry, so it is easy to handle, absorbs oil above and below the water surface, turns it into a gel, and reduces the harmfulness of the oil ((oil absorbent from water, seawater, etc.). It can be said that this is an excellent method of absorbing oil that makes it easier to remove oil.

J,′,7,The present invention will be specifically explained with reference to the following examples.

Example 1 Add 0.19 g of aliphatic carboxylic acid and its esters listed in Table 1 (Wako Tsumugi and Tokyo Kasei Kogyo Co., Ltd. - grade reagents) to 100 g of water and stir thoroughly for 1-7 hours. After that, norbornene polymer powder (N0R8ORE, a product of France's Cdl) was added.
X, particle size 0.01~], mm) was added and thoroughly stirred to prepare a slurry of the polymer.

500 cc beaker], 00 cc water aromatic oil (Japan Zan Oil Co., Ltd. product 5undex 790
, Viscous LWS US / 38°C, 3500) 30.
Then, the entire amount of the above slurry or 10 g of norbornene polymer powder was added and stirred for 2 minutes.

The state of oil absorption after being left at room temperature for 24 hours was visually determined.The results shown in Table 1 were obtained.

The results in Table 1 show that the method of the present invention absorbs almost all of the oil above and below the water surface, whereas the conventional method of adding norbornene polymer powder absorbs only the oil above the water surface.

The same experiment as above was conducted using B heavy oil as the oil, but the first
Exactly the same results as listed in the table were obtained.

Table 1 Patent applicant: Zeon Corporation

Claims (1)

[Claims] An oil obtained by adding a slurry of a powdered norbornene polymer dispersed in water containing a water-soluble monovalent aliphatic carboxylic acid and its esters to oil floating on the surface of water or seawater. How to remove or recover.