JPS58124540A - Water treating material and preparation thereof - Google Patents

Abstract

PURPOSE:To enable the effectuation of treatment of waste water contg. oil by mixing and kneading a base material component consisting of a water treating material, an organic cationic component, a crosslinking component and an org. polymer or a combination of an org. polymer with an inorg. filler. CONSTITUTION:An org. polymer such as polyethylene, polypropyrene, polystyrene or polyvinyl acetate and an inorg. filler containing an element such as Si, Al, Ca or Mg (e.g., calcium carbonate, silica or alumina) are mixed to obtain a base material component. In this base material component, an org. cationic component such as ethylenediamine or diethylenetriamine and a crosslinking component such as polyethylene glycol glycidyl ether are mixed. In the next step, the obtained mixture is heated, decomposed and foamed by a melt-extruder to obtain a columnar or a sheet like foamed body.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water treatment material that has excellent ability to remove organic or inorganic substances dispersed, emulsified, or dissolved in water, and a method for producing the same.

Many treatment methods have been proposed for the treatment of organic substances in water, particularly for treatment of oil-containing wastewater. For example, mechanical separation methods such as natural flotation 1 forced flotation, filtration, and gravity separation using centrifugal force.

Separation methods using electromagnetism such as ultrasound and electrophoresis, physical or chemical methods using means such as adsorption, absorption, ion exchange, and aggregation, and methods using microorganisms are known.

Among these, various adsorbents have been proposed for adsorption methods that are relatively easy to manage and stable, but an effective adsorbent for treating finely dispersed oils and emulsified oils has not yet been found. For example, in the proposed adsorbents, hydrophobic synthetic fibers and synthetic resin microstructures are mainly used for floating oil and coarsely dispersed oil. Granular activated carbon is effective to some extent for finely dispersed oils, but its adsorption capacity is extremely small and is not practical (it is hardly effective for emulsified oils).

Anion exchange resin has a large amount of cationic groups on its surface, but has a high swelling degree against water pressure, and is effective against low molecular weight substances such as ions, but it is effective against 9 μ-order oil droplets. However, it is not effective because the cation effect is not sufficient. Moreover, since the true density also depends on the original resin, the trap cannot withstand the backwashing pressure normally applied. Furthermore, in JP-A No. 53-42450, a flexible polyurethane foam containing cationic groups has been proposed, but this material is prone to compaction due to oil adsorption and suspended solids (and is also difficult to backwash). It is impossible. Furthermore, JP-A-49-18784 and JP-A-49-11
No. 5087 1% 1987-101369, 1977 Japanese Patent Application No. 101369
-136591, JP-A-53-61575, etc., fibers and resin microstructures.

Treated materials have been proposed in which surfactants, silicone oils, amines, etc. are retained on the surface of base materials such as wood leather powder or silica alumina granules, and these are neutralized by forming fine oil droplets and emulsification in the initial stage of use. Some products show good treatment performance for oil, but the adhesion between the base material and the retained components is insufficient and the retained components fall off during use, making backwashing virtually impossible and long-term use. The disadvantage is that it cannot withstand use.

Furthermore, regarding the method of molding foams made of a single polymer or a polymer and an inorganic filler, Japanese Patent Application Laid-Open No. 48-92288 discloses
No. 4I Publication No. 49-2786, Japanese Patent Publication No. 49-9483
However, these foams are only effective for treating oils floating on the water surface and dispersing oil with relatively large particle sizes. .

Further, in JP-A-52-19190, there is a description of a foam that retains oil in advance in order to improve the oil treatment effect, but in this case as well, the target oil is floating oil.

As described above, at present, no effective processing material has been found for processing fine oil droplets, emulsified oil, and the like.

Normally, colloids, fine oil droplets, or organic polymers (hereinafter referred to as oil droplets) that are stably dispersed in water have negative charges distributed on the surface layer of the oil droplets, and the stability of the oil droplets is mainly determined by the oil droplet diameter. The treatment material used to remove these oil droplets must have the ability to neutralize the electric charge existing on the surface of the oil droplets and destabilize the oil droplets, as well as the ability to destabilize the oil droplets and to The material must be electrically charged and have an attractive force for oil droplets, it must contain an organic high molecular weight substance that has the property of adsorbing or holding oil, it must be preferably porous and have a large surface area, and it must be made of a material that is porous and has a large surface area. The increase in water pressure is small due to blockage caused by
, and preferably scales that can be unblocked by a cleaning operation such as backwashing in the event of blockage, and/or have high mechanical hardness and low swelling ability in water so that they sink in water.

An object of the present invention is to provide a water treatment material with excellent ability to remove organic or inorganic substances dispersed, emulsified, or dissolved in water, and a method for producing the same. An object of the present invention is to provide a water treatment material suitable for treating oil-containing wastewater and a method for producing the same.

The present invention relates to a water treatment material which is a foam in which a cationic crosslinked polymer is retained on at least a part of the surface of a base component, and an organic cationic component.

A method for producing a foam obtained by mixing, kneading, and foaming a crosslinking agent component, a base material component consisting of an organic polymer or an organic polymer and an inorganic filler, or a raw material component consisting of a crosslinking agent.

The raw material components and manufacturing method of this invention 1111 will be sequentially explained below.

The base material component in the present invention is an organic polymer or a mixture or composite of an organic polymer and an inorganic filler.

Organic polymers include ethylene/propylene.

Polymers or copolymers of styrene, vinyl acetate, vinyl chloride, acrylonitrile, (meth)acrylamide, (meth)acrylic acid, (meth)acrylic methyl, divinylbenze/, phthadiene, imprene, chloroprene, etc.
Alternatively, polyurethane, polyurea, polyethylene terephthalate, nylon, aromatic polyamide, polycarbonate, borisulfo/polyethersulfone, etc. can be used. Sit Al1 as an inorganic filler
．． Known materials containing elements such as Cm, Mg, Fs, Ba, and Cm2O are used, such as calcium carbonate, silica, alumina, all pig iron barium sulfate, and carbon black.

Organic cationic components (A) include ethylenediamine, diethylenetriamine, triethylenetetramine/,
Amines such as hexamethylene diamine, vinylamine, ethyleneimine, aniline, N,N-diethylethanolamine, aminoethylethanolamine, N-methyl-N,N-jetanolamine, N,N-diisopropylethanolamine, N, Amino alcohols such as N-dipylethanolamine, N-methylethanolamine, and triethanolamine, dialkylaminoethyl methacrylate, vinylpyridine, dicyandiamide, vinylimidacillin, or the above compounds are combined with benzyl chloride, dimethyl sulfate, methyl chloride, etc. Quaternary ammoniums cationized with a reagent or 2-hydroxy-3-metapolyester polyamine/, polyamide polyamine, or cationic vinyl lactam-acrylamide copolymer, cyclized heavy metal compound of diallylammonium decagenide,
A semi-amide obtained by reacting a diamine with a copolymer of inbutylene and maleic anhydride, a polycondensate of ammonia and epichlorohydrin, and a copolymer of styrene and maleic anhydride with a diamine and methyl chloride. The resulting quaternary ammonium salts, polycondensates of alkylene dichloride and alkyl dichloride polyamines, polycondensates of aspartic acid and hexamethylene diamine, polycondensates of aniso/formaldehyde, and cationic polymers such as chitosan. Polymers known as flocculants are used.

Furthermore, sulfonium compounds such as alkyldimethylsulfonium, phosphonium compounds such as tetraalkylphosphonium salts, etc. can also be used.

As the crosslinking agent component (B), (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, (di)glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, Epoxies such as sohydrin, (poly)ethylene glycol di(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,4-butanediol diacrylate), 1,6-hexanediol diacrylate, neopentyl glycol diacrylate (meth)acrylates such as acrylate, trimethylolgulon triacrylate, and pentaerythritol triacrylate;
di) Epoxy acrylates such as ethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate, glycerol polyglycidyl ether polyacrylate, phthalic acid diglycidyl ester diacrylate, diphenylmethane diisocyanate, tolylene diisocyanate.

Incyanates such as hexamethylene diisocyanate, polyester polyols, polyether polyols,
Hydrous acid group compounds such as acrylic polyols, castor oil derivatives, tall oil derivatives, terminal hydroxyl group-containing polyptadiene, and prepolymers thereof are used.

Furthermore, instead of component (B), a cationic crosslinked polymer itself such as fine powder of anion exchange resin can be used.

Also, a must! According to
- Usual polymerization initiators such as organometallic compounds such as butyltin dilaurate, foaming aids, crosslinking aids, etc. are used.

The amount of cationic crosslinked polymer retained in the water treatment material of the present invention obtained as described above is arbitrary;
Preferably it is 0.1 to 30 weight ratio.

If the cationic crosslinked polymer is less than 0.1% by weight, the removal effect of organic and inorganic substances present in water will not be sufficient (
In addition, even if the weight exceeds 30%, no further improvement in the treatment effect is observed because the cationic groups are formed inside the water treatment material.Also, if the cationic crosslinked polymer is a nitrogen-containing compound. If the nitrogen content in the water treatment material is preferably o, oo
s to 10% by weight, more preferably 0, 1 to 5% by weight.

In the present invention, any method such as a gas mixing method, a blowing agent decomposition method, a solvent diffusion method, a chemical reaction method, an elution method, or a sintering method can be adopted as a method for forming the foam. The manufacturing method of the present invention will be explained using a blowing agent decomposition method using a decomposable blowing agent as an example, but it is understood from the spirit of the present invention that the method of molding the foam of the present invention is not limited to this method. is also clear.

As the blowing agent decomposition method, a normal pressure foaming method, a pressure foaming method, an extrusion foaming method, an injection foaming method, or the like is used.

For example, raw material components are mixed using a mixer such as a Henschel mixer, and then thermally decomposed and foamed using a melt extruder to obtain a cylindrical or sheet-like foam. The obtained foam is granulated using a pelletizer or a pulverizer, if necessary.

Alternatively, the raw material components are melt-kneaded using a Banbury mixer, mixed wire roll, etc. at a temperature above the melting point of the base material component and below the decomposition temperature of the blowing agent, and then filled into a closed mold and heated under pressure. A foam can also be obtained by depressurizing K. As the mold, any shape such as a plate, nine discs, two cylinders, or a hollow cylinder can be used. The obtained foam can be used as it is, or it can be pulverized into granules.

In the production of the water treatment material of the present invention, the cationic component (4
) and its crosslinking agent component (B) differs depending on the type and amount added, and in some cases, the reaction may occur immediately after the two are mixed, or during crosslinking or heating in the mold C or melt extruder. Sometimes they react.

The form of the water treatment material in the present invention depends on the form at the time of foam molding, and may be pellet-like, flat plate-like, or bi-disc-like.

It can be cylindrical or hollow, but in either case it is a must!
It can be granulated and used according to the requirements.

As blowing agents, organic decomposition type blowing agents such as azodicarbonamide, dinitrosobentamethylene/tetramine, valatoluenesulfonyl hydrazide, benzenesulfonyl hydrazide, etc. or inorganic blowing agents such as ammonium carbonate, sodium bicarbonate, ammonium nitrite, and calcium azide are used. A decomposable blowing agent is used. Further, as a crosslinking agent, dicumyl peroxide, dimethyl ditert-butyl peroxyhexane, and tert-butyl peroxyin x lobilbenzene are used.

Conventional organic retreatants such as bister-butylperoxytrimethylcyclohexane are used.

The water treatment material of the present invention can be effectively used in the purification of wastewater containing various oils, animal and vegetable oils, singly or in a mixed state. It is possible to remove oil even if it is present. Furthermore, even if the wastewater contains solids and other contaminants other than oil, the treatment capacity will not be affected.

The water treatment material of the present invention is also effective in removing not only oil but also negatively charged colloids such as silica colloids.

Furthermore, this water treatment material has extremely excellent adhesion between the base material component and the cationic crosslinked polymer, and has the ability to withstand long-term use.

The water treatment material of the present invention can be used not only as an adsorbent but also as a coarsening material. When used as an adsorbent,
Although it is possible to employ a slurry adsorption system, it is usually preferable to employ a packed column adsorption system. Also, when used as a coarsening material, a packed column method can be adopted.

The water treatment material of the present invention used as an adsorbent or coarsening material in a packed column system can also be reused by backwashing or surface washing. Water or air can be used for cleaning.

The water treatment material of the present invention can be used to treat tank cleaning wastewater, machine cleaning wastewater, and paint factory wastewater, which are more difficult to treat than conventional ones.

Emulsified oil from food factory wastewater, compressor drain, etc.
It is extremely effective in the treatment of wastewater in a wide range of fields, such as water, ballast water from oil tankers, bilge water, emulsified oil or dispersed oil such as wastewater from crude oil drilling, and is also effective in treatment for the purpose of reuse.

The present invention will be explained below with reference to Examples.

Examples 1 to 3 When the base material components shown in Table 1, the cationic component (A), and its crosslinking agent component (B) are mixed for 10 minutes in a Henschel mixer, the components (A) and (B) are mixed. reaction started and the temperature of the mixture rose to 60-75°C.

After the reaction was completed and the temperature of the mixture was cooled to 50° C., a blowing agent and a crosslinking agent for the base component were added and mixed for an additional 5 minutes. Next, it was extruded at a barrel temperature of 160 to 180°C using a vented melt extruder equipped with a 3 mφ nozzle at the tip, and cut with a V-tizer to obtain a product with a diameter of 3 mm and a length of 3 mm.
A foam of a certain size was obtained. Furthermore, a pulverizer was used to form granules of 7 to 48 meshes, from which granules of 9 to 28 meshes were taken out.

Nucleus particles were packed into columns under the conditions of 20 φ x 800 m, and model raw water was packed into these columns at a flow rate of 4 m/Hr for 50 m/hr.
Time passed. The model raw waters are Tokuturbi/Oil (manufactured by Maruzen Sekiyu) 4P and polyoxyethylene nonylphenyl ether α2I.

and water 11 and stirred for 5 minutes in a mixer, then diluted with water 20
Emulsified oil diluted to 0.013 was used.

The turbidity of the model raw water and treated water was measured using a turbidity meter, and the results are shown in Table 1.

Comparative Example 1 The raw materials shown in Table 1, consisting only of base material components and blowing agents, were mixed in a Henschel mixer for 10 minutes, melt-extruded under the same conditions as in Example 3, and then mixed with a pelletizer and a pulverizer for 90 minutes.
~28 mesh granules were obtained. Next, a column experiment was conducted under the same conditions as in Example 3, and the turbidity of the treated water showed a considerably high value.

Procedural amendment document May 2fJ, 1982 1, Indication patent @ 57-7335 No. 2, Name of the invention Water @ il# and its manufacturing method 3, Person making the amendment Relationship with the case Patent applicant Tokyo Chuo 2-3-19 Kyobashi, Chuo-ku, Tokyo (603) Miho Reiyoshi Co., Ltd. President Osamu Kanazawa 34, Agent 7, 2-3-19 Kyobashi, Chuo-ku, Tokyo Contents of the amendment Page 16, line 4 from the bottom Correct "pent type" to "non-vent type".

Claims (6)

[Claims] (1) A water treatment material with a small base material consisting of an organic polymer or an organic polymer and an inorganic filler (both of which are foams partially holding a cationic crosslinked polymer). (2) The amount of cationic crosslinked polymer retained is 0.1~
30. The water treatment material according to claim 1, which has a weight ratio of 30%. (3) The water treatment material according to claim 1 or 2, wherein the cationic crosslinked polymer is a nitrogen-containing compound and the amount of nitrogen retained is 0.005 to 10% by weight. (4) It is characterized by mixing and kneading an organic cationic component, its crosslinking agent component, and an organic polymer or a base component consisting of an organic polymer and an inorganic filler, or further a crosslinking agent, and foaming. Manufacturing method O of a foamed water treatment material in which a cationic crosslinked polymer is retained in at least a part of the base material component
\ (5) The method for producing a water treatment material according to claim 4, characterized in that a foaming agent is used for foaming. (6) A method for producing a water treatment material according to claim 4 or 5, in which foaming is performed using melt extrusion.