JP3056429B2 - Emulsified oil wastewater treatment material and treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsified oil wastewater treatment material and a treatment method, and more particularly, to an emulsified oil wastewater treatment material and a treatment method for removing oil dispersed and emulsified in water.

[0002]

2. Description of the Related Art Many methods have been proposed for treating organic substances in water, especially for treating emulsified oil wastewater. For example, mechanical separation methods such as natural levitation, forced levitation, filtration, gravitational separation by centrifugal force, separation methods using electromagnetics such as ultrasonic waves and electrophoresis, and physical separation methods such as adsorption, absorption, ion exchange, and aggregation. Alternatively, a chemical method, a method using a microorganism, and the like are known. Among these,
Various adsorbents have been proposed for adsorption methods that are relatively simple and stable in operation management. For example, Japanese Patent Publication No. 60-671
No. 5 discloses that, after treating an emulsified oil wastewater with a treatment material in which an amine compound having a hydrocarbon group having 6 to 60 carbon atoms is adhered to a base material such as a synthetic fiber with a binder such as styrene, a polypropylene or the like is used. A method of treating with an oil adsorbent is disclosed, and JP-A-58-128147 discloses a treatment material in which a cationic crosslinked polymer is adhered to polyester fiber or the like.

[0003]

However, even if any of the above-mentioned treatment materials is used, the durability may be lowered due to poor adhesion between the base material and the holding component, and even if the durability is good, the processing time may be reduced.
There is a problem that processing capacity is insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have developed an emulsified oil wastewater treatment material and a treatment method for easily removing organic substances which are easy to produce, have excellent durability, and are efficiently dispersed and emulsified in water. As a result of repeated studies, the present invention has been reached.
That is, the present invention provides an emulsified oil wastewater treatment material characterized in that a (co) polymer (A) having a vinyl carboxylic acid ester (a1) having a nitrogen-containing heterocycle as a constitutional unit is supported on a support. It is.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of a nitrogen-containing hetero ring include a nitrogen-containing alicyclic ring [aziridine ring (aziridine, 2-methylaziridine, etc.), pyrrolidine ring (pyrrolidine, 2-methylpyrrolidine, 3-pyrrolidine). , 2-pyrrolidinone, succinimide, etc.), piperidine ring (piperidine, 2-methylpiperidine, etc.), piperazine ring (piperazine, 1-methylpiperazine, etc.), morpholine ring (morpholine, 2-methylmorpholine, etc.) and 2-oxazolidone, ε -Caprolactam and the like]; and nitrogen-containing unsaturated rings (3-pyrroline, pyrrole, pyrazole, imidazoline, triazole, tetrazole, 2-aminopyrazine, indole, indazole, carbazole and the like) and the like. Of these, a nitrogen-containing alicyclic ring is preferable, a more preferable one is a piperidine ring and a morpholine ring, and the most preferable one is a morpholine ring.

Examples of the vinyl carboxylic acid include (meth) acrylic acid, (iso) crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylbenzoic acid and 2-carboxy-4-isopropenyl-3-pyrrolidineacetic acid. No. Of these, (meth) acrylic acid, maleic acid, and vinylbenzoic acid are preferred, and (meth) acrylic acid is particularly preferred.

Specific examples of (a1) include morpholinoethyl (meth) acrylate, morpholinopropyl (meth)
Acrylate, morpholinobutyl (meth) acrylate, morpholinoethoxyethyl (meth) acrylate, piperidinoethyl (meth) acrylate, piperidinobutyl (meth) acrylate, pyrrolidinoethyl (meth) acrylate, di (morpholinoethyl) maleate, di (piperidinoethyl) fumarate, etc. Is mentioned.

As the vinyl carboxylate (a1) having a nitrogen-containing hetero ring used in the present invention, those exemplified above may be used alone or in combination of two or more. Particularly preferred are vinyl carboxylic acid ester monomers having a morpholine ring.

In the present invention, the (co) polymer (A) comprises:
Further, an alkyl (meth) acrylate (a2) or (a2) having an alkyl group having 8 to 40 carbon atoms and another vinyl monomer (a3) can be used as a structural unit.

The alkyl (meth) acrylate having an alkyl group having 8 to 40 carbon atoms (a2) includes
And alkyl (meth) acrylates having up to 40 linear or branched saturated or unsaturated alkyl groups. Specific examples include lauryl (meth) acrylate, tridodecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate,
Isostearyl (meth) acrylate, oleyl (meth) acrylate, eicosyl (meth) acrylate and the like can be mentioned. Of these, preferred are those having 1 carbon atom.
2-18 alkyl (meth) acrylates. (A
2) may use the above-mentioned examples alone,
Two or more kinds may be used in combination.

Other vinyl monomers (a3) include, for example, hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, N-
Examples include (4-hydroxyphenyl) maleimide, (meth) acrylic acid, maleic anhydride, styrene, vinyl acetate, vinyl chloride, 1-butene, cyclohexene, butadiene, isoprene, cyclohexadiene, and the like, and mixtures thereof. As the other vinyl monomers (a3) used in the present invention, those exemplified above may be used alone or in combination of two or more.

The (co) polymer (A) may further comprise a crosslinking agent as a constituent unit. 2 as a crosslinking agent
Monomers having at least two functional groups are exemplified. For example,
(1) Bis (meth) acrylamide; N, N-alkylene (C1-6) bis (meth) acrylamide (for example, N, N-methylenebisacrylamide). (2) Polyesters of polyols or polyepoxides with unsaturated mono- or polycarboxylic acids, such as ethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol or cyclohexene diepoxide with (meth) acrylic acid or maleic acid Di- or tri- (meth) acrylates derived from

(3) Carbamyl esters: polyisocyanates [tolylene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate and NCO group-containing prepolymer (obtained by reacting the above polyisocyanate with an active hydrogen atom-containing compound) ) And hydroxyethyl (meth) acrylate.

(4) Polyvinyl compounds: divinylbenzene, divinyltoluene, divinylxylene, divinylether, divinylketone, trivinylbenzene and the like. (5) Di- or poly- (meth) allyl ether of polyol: poly (meth) allyl ether of polyols [alkylene glycol, glycerin, polyalkylene glycol, polyalkylene polyol, carbohydrate, etc.] (for example, polyethylene glycol diallyl ether, allyl) Starch and allylated cellulose).

(6) Polyallyl esters of polycarboxylic acids: diallyl phthalate, diallyl adipate and the like. (7) Ester of unsaturated mono- or polycarboxylic acid and mono (meth) allyl etherified polyol: (meth) acrylate of polyethylene glycol monoallyl ether and the like. (8) Hydroxyl group-containing ethylenically unsaturated compound [N
-Methylol (meth) acrylamide and the like] (9) Epoxy group-containing ethylenically unsaturated compound [glycidyl (meth) acrylate and the like] (10) Tertiary amino group-containing ethylenically unsaturated compound [dimethylaminoethyl (meth) acrylate; (Meta)
Diethylaminoethyl acrylate, etc.].

The content of (a1) in the (co) polymer (A) is usually 20 to 1 based on the weight of the (co) polymer (A).
00%, preferably 30 to 100%, more preferably 40 to 100%, and the content of (a2) is usually 0 to 80%.
%, Preferably 0 to 70%, more preferably 0 to 60%
%, And the content of (a3) is usually 0 to 80%, preferably 0 to 70%, and more preferably 0 to 60%.

As the support used in the present invention, a water-insoluble inorganic or organic substance can be used. As inorganic substances, for example, silica, alumina, molecular sieve, zeolite, activated carbon, diatomaceous earth, sand, activated clay,
Asbestos, glass fiber, peat fiber and the like can be used.
As the organic substance, a natural or synthetic high molecular polymer is used.

As the natural or synthetic high-molecular polymer, any type may be used as long as it is insoluble in water. Examples of the natural product include cellulose, wool, silk and the like. In addition, natural products such as cellulose derivatives such as acetylcellulose, methylcellulose, ethylcellulose and carboxymethylcellulose may be used. Examples of the synthetic polymer include styrene derivatives such as styrene and α-methylstyrene divinylbenzene: acrylic acid derivatives such as ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl acrylate, butyl acrylate, acrylamide and methacrylamide. : Ethylene-based unsaturated monomers such as ethylene, propylene, butylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile: and butadiene, isoprene,
Examples include a homopolymer using a monomer such as a diene monomer such as chloroprene, and a copolymer using two or more of the above monomers. Other examples of the condensation or addition polymer include polyurethane, polyurea, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, nylon, aromatic polyamide, polycarbonate, polyphenylene oxide, polysulfone, and polyether sulfone . Furthermore, it is also possible to use a blend of two or more of the above-mentioned high molecular polymers.

A thermosetting resin can also be used as the support,
For example, a phenol resin, an epoxy resin, a phenol epoxy resin, an amino resin, a petroleum resin, and the like can be used. The shape of the support used in the treatment material of the present invention is arbitrary, but it is integrated with the (co) polymer supported thereon,
It is desirable that the shape be such that a larger surface area is obtained. Examples of such a shape include a granular shape, a strip shape, a flake shape, a sponge shape, a ribbon shape or a fibril shape, a filament shape, a woolen shape, a web shape, a mat shape, a woven fabric shape, and a non-woven fabric shape. Is used. In this case, a fibrous support having a coarsening effect when fine oil particles pass through is particularly preferably used.

The fibrous material may be a natural fiber or a high molecular weight copolymer, for example, an arbitrary denier fiber produced by a melt spinning method, a dry spinning method or a wet spinning method, or a mixed fiber composed of fibers. Alternatively, after a polymer polymer is formed into a film, a fibrous material obtained by shredding by an arbitrary method, or a polymer containing a foaming substance (eg, nitrogen gas) is extruded through a slit die, and is unidirectionally extruded. A fibrous material obtained by stretching the fiber, a composite fiber comprising two or more layers of a polymer, or a fibrous material formed by an arbitrary method can be used. In the case of a fibrous material, the diameter is 1000
Denier or less is used, preferably 100 denier or less, particularly preferably 0.1 to 50 denier. Therefore, among the above fibrous materials, a reticulated fibrous material produced by using an expandable substance is particularly preferably used because of its small diameter (average). Among these supports, one or more fibrous materials selected from the group consisting of polyamide, polyester, polyolefin and polyvinyl are preferred.

The emulsified oil wastewater treatment material of the present invention can be obtained, for example, by the following method. The method for supporting the (co) polymer (A) constituting the treatment material of the present invention on a support is not limited. For example, (a1), (a2) or (a2) and (a3) are mixed if necessary. The solution is added dropwise to an organic solvent such as toluene, for example, and if necessary, heated using a crosslinking agent or a radical polymerization catalyst, or irradiated with radiation, electron beam, ultraviolet ray, or the like, to give the (co) polymer (A) an organic solvent. Make a solution.

After the prepared solution is brought into contact with the support, the solvent is evaporated to dryness, whereby (A) is supported on the support. The means for bringing the solution into contact with the support is generally a solvent immersion method in which the support is immersed in the solution.However, a method in which the solution is sprayed onto the support by spraying, the solution is poured from the upper part A method in which the support is continuously moved below to support the support and the solution is exemplified.

Further, (a1), if necessary (a2) or (a2) and (a3), if necessary, a crosslinking agent and a radical polymerization catalyst were added, and the mixed solution was brought into contact with the support. Thereafter, a method of heating or irradiating radiation, electron beam, ultraviolet ray or the like to react on the support, and the like are also exemplified. When the support and the (co) polymer are supported, an adhesive may be used or other additives may be added to increase the adhesion.

Examples of the radical polymerization catalyst include azo compounds [azobisisobutyronitrile, azobiscyanovaleric acid, 2,2'-azobis (2-aminodipropane) dihydrochloride, etc.], inorganic peroxides [hydrogen peroxide] ,
Ammonium persulfate, potassium persulfate, sodium persulfate, etc.], organic peroxides [benzoyl peroxide, di-t-
Butyl peroxide, cumene peroxide,
A redox catalyst [a reducing agent such as an alkali metal sulfite or bisulfite, ammonium sulfite, ammonium bisulfite, ascorbic acid and an alkali metal peroxide], a succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc. Consisting of a combination of oxidizing agents such as sulfate, ammonium persulfate and peroxide]; and a combination of two or more of these. The amount of the catalyst to be used is generally 0.1 based on the total weight of the monomers used.
0005 to 5%, preferably 0.001 to 2%.
The number average molecular weight of the (co) polymer is usually 1,000 to 30.
000, preferably from 5,000 to 100,0
00.

According to the method for treating emulsified oil wastewater of the present invention, first, the emulsified oil wastewater is treated with the treatment material (A) of the present invention to coarsen or break emulsion particles to generate oil droplets. Is used to adsorb and separate oil.
Usually, the particle size of the emulsified oil before treatment is about 1 to 10 μm, but after passing through the emulsified oil wastewater treatment material, the particle size of the emulsion is coarsened to several times to several hundred times, and in some cases, the emulsion In some cases, micelles forming particles are destroyed and the free oil inside is separated.

Examples of the oil adsorbent include inorganic compounds (for example, clay, calcium carbonate, silica), natural compounds (for example, cotton and pulp), and synthetic fibers (for example, polypropylene, polystyrene, and polyurethane resin). Of these, preferred are synthetic fibers, and particularly preferred are polypropylene and / or polystyrene fibers.

The method of the present invention can be basically carried out by efficiently combining an emulsified oil wastewater treatment material and an oil adsorbent and bringing them into contact with the emulsified oil wastewater. Therefore, any combination method may be used as long as the wastewater can efficiently contact the treated material and the oil adsorbent, but generally, emulsified oil wastewater is used to form the treated material and the oil adsorbent. A method of passing through the material is used. For example, specifically, there is a method in which an emulsified oil treatment material and an oil adsorbent are packed in the same or separate columns, and the emulsified oil wastewater is passed through a pump or the like. Further, there is a method in which the emulsified oil-treated material is crushed by emulsifying the emulsified oil by immersing the emulsified oil-treated material in wastewater and blowing air, and then adsorbing and separating oil droplets coarsened by the oil adsorbent.

[0028]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in the examples are parts by weight.

Example 1 200 parts of toluene was charged into a 1 L four-necked flask equipped with a temperature controller, a vacuum stirring blade, a nitrogen inlet and an outlet. In a separate container, 300 parts of morpholinoethyl methacrylate, 2,2'-azobisisobutyronitrile 3
Parts and 100 parts of toluene. After raising the temperature of the toluene in the flask to 110 ° C. while stirring, the mixed solution was stirred for 3 hours.
It was dropped over time. After dropping, aging for 3 hours,
A copolymer (A) was synthesized. The copolymer (A) is impregnated into a polyester non-woven fabric support (“Axter D5100” manufactured by Toray Industries, Inc.) so that the resin weight per unit area is 100 g / m _2, and the support is dried to obtain an emulsified oil wastewater treatment material. B1 was obtained. (The number average molecular weight of the polymer is 20,000)

A column having a diameter of 100 mm was packed with 40 g of the obtained treated material, and the column was filled with heavy oil A ("GENERAL CLEAN A 03F" manufactured by General Petroleum Co., Ltd.).
UEL ") Emulsified oil wastewater obtained by emulsifying 3000 PPM with an emulsifier (" Seicle N-800 "manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was passed at a flow rate of 100 ml / min to obtain a heavy oil layer and an aqueous layer flowing out of the column. The oil concentration of the aqueous layer was measured for each treatment amount. Table 1 shows the results. The concentration of the treated water oil was measured by an n-hexane extraction method based on "JIS K-0102".

Example 2 300 parts of morpholinoethyl methacrylate of Example 1
Instead of a mixed solution of 3,2'-azobisisobutyronitrile 3 parts and toluene 100 parts, morpholinoethyl methacrylate 200 parts, C14-15 alkyl methacrylate 100 parts, 2,2'-azobisisobutyronitrile 3 And a mixed solution of 100 parts of toluene were obtained in the same manner as in Example 1 to obtain an emulsified oil wastewater treatment material B2 (the number average molecular weight of the polymer was 10,000). Was measured. Table 1 shows the results.

Example 3 300 parts of morpholinoethyl methacrylate of Example 1
Instead of a mixed solution of 3,2'-azobisisobutyronitrile 3 parts and toluene 100 parts, morpholinoethyl methacrylate 210 parts, C14-15 alkyl methacrylate 70 parts, styrene 20 parts, 2,2'-azobisiso Except that a mixed solution of 3 parts of butyronitrile and 100 parts of toluene was used, the same procedure as in Example 1 was carried out to obtain an emulsified oil wastewater treatment material B3 (the number average molecular weight of the polymer was 15,000). And the oil concentration was measured. Table 1 shows the results.

Example 4 180 parts of morpholinoethyl methacrylate, C14-1
In a solution obtained by mixing 90 parts of 5-alkyl methacrylate, 30 parts of styrene, 1 part of dipentaerythritol pentaacrylate, 100 parts of toluene, and 3 parts of a radical polymerization catalyst, a polyester nonwoven fabric support (“Axter D5100” manufactured by Toray Industries, Inc.) With a resin weight of 100 g / m ²
Then, the mixture was polymerized and dried in an oven at 110 ° C. to obtain an emulsified oil wastewater treatment material B4. The obtained emulsified oil wastewater treatment material was subjected to the same operation as in Example 1 to measure the oil concentration of the treated water. Table 1 shows the results.

[0034]

[Table 1]

Example 5 A first tank was prepared by packing 140 parts of the emulsified oil wastewater treatment material B obtained in Example 1 in a column having a diameter of 100 mm, and the oil adsorbent “Wosep” made of a nonwoven polypropylene fabric ( Toray Industries, Inc.)
Same diameter § Inn Chemical Co., Ltd.) 160 parts of a 10
What was packed in another column of 0 mm was used as a second tank, which was connected in the order of the first tank and the second tank. In this column, A heavy oil ("GENERAL CLEA" manufactured by General Sekiyu KK)
Emulsified oil wastewater obtained by emulsifying NA03FUEL ”3000 PPM with an emulsifier (“ SEICLE N-800 ”manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was passed at 100 ml / min, and the oil concentration of the treated water was measured. Table 2 shows the results.

Example 6 The lower part of a column having a diameter of 100 mm was filled with 160 parts of a polypropylene nonwoven oil adsorbent "Wosep" (manufactured by Toray Fine Chemicals Co., Ltd.). 40 parts of the obtained emulsified oil wastewater treatment material B2 was filled.
In this column, A heavy oil (“GEN
ERAL CLEAN A 03 FUEL "3000
PPM as an emulsifier (“SEICLE N” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
-800 ") emulsified oil wastewater emulsified in 100 ml / m
The solution was passed in, and the oil concentration of the treated water was measured. Table 2 shows the results.

Example 7 Forty parts of the emulsified oil wastewater treatment material B3 obtained in Example 3 and an oil adsorbent “Wosep” made of a nonwoven polypropylene fabric ( Toray Industries, Inc.)
After mixing in advance 160 parts (manufactured by Fine Chemical Co., Ltd.), the mixture was packed in a column having a diameter of 100 mm. This column is filled with heavy oil A ("GENERAL C"
LEAN A 03 FUEL ”3000 PPM as an emulsifier (“ SEICLE N-800 ”manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
The emulsified oil wastewater emulsified in the above was passed at 100 ml / min, and the oil concentration of the treated water was measured. Table 2 shows the results.

Example 8 Emulsion oil wastewater was treated in the same manner as in Example 5 except that B4 was used instead of the emulsified oil wastewater treatment material B1 of Example 5. Table 2 shows the results.

[0039]

[Table 2]

As shown in Tables 1 and 2, according to the emulsified oil wastewater treatment material and the treatment method of the present invention, the separation effect of the emulsified oil when the emulsified oil wastewater was treated was determined by the oil concentration by the n-hexane extraction method. It is possible to separate oil and water to such an extent that it cannot be detected by measurement.

[0041]

The emulsified oil wastewater treatment material and treatment method of the present invention exhibit the above-mentioned effects. Therefore, a very simple method of merely filling the column with the treatment material and subjecting the wastewater to liquid filtration is provided. This is an epoch-making method that can reduce the oil concentration below the emission standard, and it can be said that it is an industrially valuable pollution prevention method from the viewpoint of low equipment costs. In addition, cutting oil wastewater, rolling oil wastewater, oil tank washing wastewater, machine washing wastewater, paint factory wastewater, food factory wastewater, emulsified oil wastewater such as compressor drains, and ballast water for oil tankers, which were conventionally considered difficult to treat. , Bilge water,
It is extremely effective in treating wastewater in a wide range of fields such as emulsified oil or dispersed oil such as crude oil drilling wastewater.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Iori Nakabayashi 1-1-1 Oe, Otsu City, Shiga Prefecture Toray Industries, Inc. Seta Plant (72) Inventor Kazuya Otani 11-1, Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto-shi Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Tetsushi Kawamoto 1 Sanyo Kasei Kogyo Co., Ltd., 11-11 Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto (58) Field surveyed (Int. Cl. ⁷ , DB name) B01D 17 / 05 501 B01D 17/04 504

Claims (4)

(57) [Claims] 1. An emulsified oil wastewater treatment material characterized in that a (co) polymer (A) having a vinyl carboxylic acid ester (a1) having a nitrogen-containing heterocycle as a constitutional unit is supported on a support. . 2. The composition according to claim 1, wherein (A) further comprises an alkyl (meth) acrylate (a2) or (a2) having an alkyl group having 8 to 40 carbon atoms and another vinyl monomer (a3). The emulsified oil wastewater treatment material according to the above. 3. The support according to claim 1, wherein the support is polyamide, polyester,
The emulsified oil wastewater treatment material according to claim 1, wherein the material is one or more fibrous materials selected from the group consisting of polyolefin and polyvinyl. 4. After being treated with the emulsified oil wastewater treating material according to any one of claims 1 to 3 to coarsen or destroy emulsion particles in wastewater, the emulsion particles are made of polypropylene and / or polystyrene fibers. A method for treating emulsified oil wastewater, wherein oil / water separation is performed by treating with an oil adsorbent.