JPS5976540A - Production of water treatment material - Google Patents

Abstract

PURPOSE:To produce easily a water treatment material having excellent treating power for oil component by melt-extruding a mixture consisting essentially of an org. polymer and an inorg. compd., and pelletizing the porous foam strand obtd. by solidifying the melt-extruded mixture at a low degree of stretching. CONSTITUTION:A mixture which consists essentially of 30-80pts.wt. an org. polymer and 20-70pts. an ionrg. compd. and is added with required amts. of auxiliary components such as a foaming agent, a cationic component or the like is melt-extruded to a strand. The degree of stretching until such strand solidifies is maintained at <=1.5 times, more preferably the strand is made into a strandlike porous foam without stretching, whereafter, the strand is pelletized with a strand cutter. A water treatment material having a narrow grain size distribution and has excellent treating power for oil component such as oil-contg. waste water is obtd. with a simple production stage. The strands melt-extruded from a nozzle having plural holes by using the above-mentioned mixture are bundled or the strands are cooled while the strands are bundled, whereby the breakage of the strands is prevented and the strands having a small diameter are produced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention mainly relates to a method for producing a water treatment material that is effective for purifying oil-containing water such as industrial wastewater and urban sewage.

One of the methods for treating oil-containing water is an adsorption treatment method that uses water treatment materials, but in general, water treatment materials have a large specific surface area (due to the large amount of oil in the water) in order to exhibit sufficient oil treatment ability. It is necessary to have high contact efficiency, for example, a material with a foam structure is effective.Furthermore, a packed column treatment method is usually used to treat dispersed oil and emulsified oil that exist as fine oil droplets in water. Therefore, as a water treatment material for treating dispersed oils and emulsified oils, it is desirable to use granular materials, and it is also desirable that these granular materials have a narrow particle size distribution and settle in water.

With regard to foams for water treatment, various foams made of organic polymers or polypolymers and inorganic fillers have been proposed. Methods for producing foams from organic polymers and inorganic fillers are described, for example, in JP-A-48-92288, JP-A-49-2786, JP-A-52-31992, etc. Usually, a method is adopted in which a foaming agent is used to form a large foamed material into a plate-like or block-like shape, and then the foamed material is cut into appropriate sizes or granulated by pulverization. Therefore, in order to obtain a granular foam, a crushing step and a subsequent sieving step are necessary, making the process complicated. or,
This method has the disadvantage that it is difficult to efficiently obtain the required particle size because the particle size distribution of the granular foam is wide.

In JP-A-50-137887, in order to efficiently obtain pellets of desired particle size, a melt extruder was used with Jl, U
A method is adopted in which the foamed strands are made into foamed strands and then pelletized. However, this is a foamed pellet based solely on the ff machine polymer, and the manufacturing process is exactly the same as the manufacturing process for normal organic polymer pellets, and the nozzle hole diameter of the die that can be manufactured is 2n or more. .

In this way, foamed strands with large strand diameters and made solely from organic polymers can be easily manufactured using ordinary melt extrusion technology, but the smaller the strand diameter (i.e. nozzle hole diameter), the more The higher the proportion of inorganic compounds, the more likely strand breakage occurs before cooling and solidification, which requires more sophisticated manufacturing technology. To date, foamed strands made of organic polymers and inorganic compounds have not been produced.

In other words, a method is known in which foam particles are obtained by extruding a mixture of an organic polymer and an inorganic compound in an extrusion manner, but this method does not necessarily yield foam strands;
Currently, only particles with extremely irregular particle sizes can be obtained, and in particular, foamed strands with a diameter of less than 2 mm cannot be obtained.

The inventors of the present invention conducted extensive studies in light of the above circumstances, and as a result succeeded in developing a method for producing a water treatment material that has a simple production process, a narrow particle size distribution, and excellent oil treatment performance.

The object of the present invention is to combine 30 to 80 parts by weight of an organic polymer and 20 to 70 parts by weight of an inorganic compound! In the method of melt extruding a mixture containing 1 part and 1 part to form a strand-shaped foam and then pelletizing it, the stretching ratio of the strand after melt extrusion and before solidification is 1.5 times or less. An object of the present invention is to provide a method for producing a water treatment material characterized by the following.

The raw materials and method used in the present invention will be explained below.

In the method for producing a water treatment material of the present invention, an organic polymer and an inorganic compound are used as the main raw materials, and a blowing agent is used as the auxiliary raw material. Further, cationic components, auxiliary components, etc. can be used as necessary.

Organic polymers are expected to act as oil adsorption moieties. Inorganic compounds are expected to primarily increase the true density of water treatment materials and improve their sedimentation properties in water, and although they do not necessarily have to act as adsorbents, they must have adsorption performance. is preferred. Furthermore, in consideration of strand breakage during extrusion, it is desirable that the proportion of the inorganic compound be small. The ratio of organic polymer to inorganic compound is usually 80 to 30% of the stone statue polymer, considering the adsorption characteristics of the water treatment material, the underwater sedimentation property, and the extrusion characteristics of the strand.
It is necessary that the amount of the inorganic compound be about 20 to 70 parts based on the nail punching part.

Examples of ag combinations include ethylene and propylene.

Polymers or copolymers of styrene, butadiene, isoprene, vinyl chloride, vinyl acetate, and acrylonitrile are used.

As an inorganic compound, C is Ca, Mg, Ba, hl,
Fen st.

Ni, Zn, Pb, Mn, C, O, H, and S
A compound known as an ordinary inorganic filler composed of the following elements is used. Examples include calcium carbonate, calcium silicate, magnesium oxide, magnesium sulfate, barium sulfate, iron oxide, alumina, silica, zinc oxide, manganese dioxide, and clay minerals such as kaolin clay, talc, and attapulgite. Examples of materials having adsorption properties include magnesium oxide, iron oxide, alumina, chestnut, manganese dioxide, and the like. These inorganic compounds can be used alone or in combination.

Foaming agents include azodicarbonamide, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide,
A decomposition-type bound blowing agent such as Dinitronpe/Tamethylene Tetrami 7, or a decomposition-type inorganic blowing agent such as carbonaceous IJum can be used.

The cationic component is used to improve the oil treatment ability of the water treatment material, and is preferably retained in the water treatment material as a crosslinked I ((). Ami7'JA,
) Amino alcohols such as reethanolamine, dialkylaminoethyl methacrylate, dicyandiamide.

Vinylpyridine and other substances known as ionic polymer flocculants or their starting materials can be used.

The auxiliary components include ordinary foaming auxiliaries such as fatty acids, fatty acid salts, and zinc oxide, as well as epoxies, acrylates, epoxy acrylates, incyanates, polybutadiene/polymers containing terminal hydroxyl groups, etc. as crosslinking agents for cationic components. A peroxide such as dicumyl oxide can be used as a crosslinking agent for a hydrous acid group compound such as an ether polyol and an organic compound as a main raw material.

Next, the manufacturing method of the present invention will be explained.

The raw materials are mixed using a conventional mixer such as a type blender or drum tumbler 1/0/shell mixer, and then fed to a melt extrusion device. Melt? As the Nll extrusion device, a non-vent type melt extruder is usually used.

The diameter of the nozzle hole of the die is arbitrary, but it is usually 0.5 to 4. O
A diameter of about tnmφ is used. Generally, the smaller the strand diameter, that is, the nozzle hole diameter, or the higher the proportion of inorganic compounds in the raw material, the more likely the strand before cooling and solidification tends to break, and it is necessary to reduce this strand breakage. One way to reduce strand breakage is to suppress the stretching of the strand before cooling and assimilation, and the stretching ratio should preferably be as small as possible, and should be kept to about 1.5 times or less. is preferable, and it is more preferable to keep it in a substantially unstretched state. By adopting such a method, in the present invention, the diameter is 2 mm.
Even with strands of less than

Another possible method for suppressing strand breakage is to place a plurality of nozzles on a die relatively close to each other to collect and take off the strands. Usually, unfoamed strands made of an organic polymer alone or an organic polymer and an inorganic compound are taken out one by one through a die with a single or multiple hole nozzle, cooled and solidified, and then pelletized. . Although this method can be adopted in the present invention, it is also possible to adopt a method in which several or several dozen strands are bundled, cooled and assimilated (-1), and then pelletized.Generally, when the strand diameter is large, When the proportion of inorganic compounds in the raw material is small, both the method of pulling the strands one by one and the method of pulling the strands together can be adopted, but when the diameter of the strands is small or the proportion of amorphous compounds is high, the yarn It is desirable to adopt a method of collecting and pulling the strands in terms of breakage and handling of the strands.This method of collecting and pulling the strands in this manner is applicable only to foamed strands with a severely uneven surface. It is suitable for unfoamed strands with no unevenness or foamed strands with few surface unevenness.The reason is '
Foamed strands with a highly uneven surface may be converged before being cooled and assimilated, or even if they are condensed and cooled and solidified, adjacent strands will fuse to each other only on a small portion of the surface. This is because the impact force when cutting the bundle causes the fusion point 11a to be distorted, making it possible to form an independent pellet.

In the present invention, the diameter of the strand, that is, the diameter of the nozzle hole of the die, is arbitrary, but when dispersing oil or emulsified oil is to be treated in a packed column method, the diameter of the strand is approximately 0.5 to 2.0 mm. These are particularly effective.

The manufacturing method of the present invention has been explained above, and the granular foam obtained in this way has an extremely narrow particle size distribution.
Furthermore, it has extremely good sedimentation properties in water and is suitable for use in a packed column system.

In addition, since it has a foamed structure with a large specific surface area, the probability of contact with oil droplets existing in water is high, and the oil treatment ability is excellent.

The water treatment material of the present invention can be applied to a wide range of oil-containing water treatments as an adsorbent for oil droplets and as a coarsening material, and can be applied to a wide range of oil-containing water treatments, such as cutting oil wastewater,
Rolling oil wastewater, oil tank cleaning wastewater 2 machine cleaning wastewater,
Vehicle washing wastewater, painter' J, 5 wastewater 1 food factory wastewater, compressor drain, oil tanker ballast water,
Effective for treating bilge water, crude oil mining wastewater, etc. It is also effective in removing oil from various types of circulating water for water gate use.

Examples will be explained below.

Example 1 50 parts of low density polyethylene powder, 50 parts of barium sulfate,
and 1 part of azodicarbonamide were mixed in a Henschel mixer. Next, a strand diameter product was extruded using a non-vent type melt extruder with a screw diameter of 30 inches and equipped with eight 1.5 mm diameter nozzles at the tip, and the maximum temperature of the barrel was set at 170°C. The eight strands were bundled together and introduced into a cooling water tank where they were cooled and solidified. After extrusion, stretching was carried out without any shading until solidification. The solidified strand bundle is cut with a pelletizer to a diameter of about 1.5 mm and a length of about 1.5 mm.
A 5 mm granular foam was obtained. More than 99% of the granules showed a good particle size distribution in the range of 9 to 2 mes++ -1!9.

Next, the core granular foam 120F was packed into a column with an inner diameter of 20 mm to a height of 800 mrn, and model raw water was passed through the column at 1.251/Hr (4 m/Hr) for 200 hours. As model raw water, Tokuturbi/Oil (manufactured by Maruzen Oil)
4/ and Wednesday 11! Mix with a mixer for 8 minutes, then add 401! with water! A dispersion oil diluted to The turbidity of the model raw water and treated water was measured using a turbidity meter and is shown in Table 1. The amount of oil processed after 200 hours is approximately 0.20! // material, and the pressure drop of the column at that time is 0.01 ky, /c
m,' or less, and it can be seen that it has practical performance.

The two mixtures were extruded, cooled, and assimilated under the same moxibustion conditions except that the stretching ratios until solidification after extrusion were set to 1, 1, 163, 1, 5, 1, 8, and 2.0, respectively. Stretching ratio is 1.5
When the ratio was less than 1.8 times, a good strand bundle with no strand breakage was obtained, but when the ratio was 1.8 times or more, there were many strand breaks and a stable strand bundle could not be obtained.

Example 50 parts of low-density polyethylene powder, 45 parts of barium sulfate L, 5 parts of silica, 3 parts of polyethyleneimine, 1.5 parts of trimethylolpropane polyglycidyl 7, and 1 part of azodicarbonamide were placed in a Henschel mixer. They were added one after another and mixed.

Next, in the same manner as in Example 1, a granular foam with a diameter of about 1.5 mm and a diameter of about 1.5 mm was obtained, and the granular foam 115/
After filling a column with an inner diameter of 20 mm to a height of 800 mm, the model raw water was packed at 1.251/Dr (4 m7'Ilr).
) for 200 hours. As the model raw water, an emulsified oil was used in which 4/1 of turbine oil (Marukubi Sekiyu M), 0.2 P of polyoxyethylene nonylphenyl ether, and 11 parts of water were stirred in a mixer for 8 minutes, and then diluted to 401 with water. . The turbidity of the model raw water and treated water was measured using a turbidimeter and shown in Table 1. The amount of oil processed after 200 hours is approximately 0.
20 J' // material, and the pressure loss of the sword ram at that time is 0
．． (+ 1 ky/cyrrt' or less, and it can be seen that it has practical IL performance.

Example 3 A foam was obtained by adding 70 parts of low-density polyethylene powder to barium sulfate, and after filling the foam into a chamber, model raw water was poured into the foam. The model raw water and turbidity were measured using a turbidity meter, and the results are shown in Table 1. The amount of oil processed after 200 hours is approximately 0.20 //F month, and the pressure drop in the column at that time is 0.01 ky/c.
It can be seen that the value is rrt2 or less, and has practical performance.

Table 1 Te ``Itomiri Yu9j 1E　i Station ■、・Displaying 11 items ! t ~ order closing number 57-186949 2. Name of the invention Method for manufacturing water treatment materials 3. Person who makes corrections Relationship with matter 1 Patent applicant 2-3-19 Kyobashi, Chuo-ku, Tokyo (60’3) Mitsubishi Rayon Co., Ltd. President and Director: Akio Kawasaki 5. Request for amendment order 1. 7. Contents of correction 2) The following section 1■J of the specification is supplemented as follows.

3) Specification ff page 13 line 15 [lines 1 to 16 [1 r5
The nozzle hole diameter of a die that can be manufactured is said to be 2 mm or more. "The strands are drawn at a high stretching ratio of about 1.5 to 6.0 times,
<jf: The foamed strands taken off generally have a smooth surface and the internal foamed structure is insufficiently developed. In addition, the diameter of pellets that can be produced by this method is 2 mm or more.
1-, and the strand diameter before stretching is 2.5 mm.
It is presumed that the following is 1-, and it can be seen that it is difficult to manufacture strands with small particle diameters. 4) Insert the following sentence after Table 1 on page 15 of the specification.

Comparative Example 1 20 parts of low-harm polyethylene powder, 80 parts of pallid sulfate, and 1 part of azodicarbonamide were melt extruded under the same conditions as in Example 1. The resulting strand had severe strand breakage and strand curling. It was difficult to obtain.

Comparative Example 2 A porous foam with a diameter of about 1.5 mm and a length of about 1.5 mm was obtained in the same manner as in Example 1 using 90 parts of low W 1 degree polyethylene powder, 10 parts of barium sulfate, and 1 part of azodicarbonate 1ζ. . After putting 10 g of the water treatment material and water IJI in a beaker and stirring with IW at 15 Qrpm for 5 minutes using a motor equipped with a stirring blade, the ratio of what floated to what settled was examined, and the rate of what settled was 15. %, and the sedimentation properties were insufficient. In addition, in the case of the water treatment materials obtained in Examples 1 to 3, the values were 98%, 99%, and 90%, respectively, indicating good sedimentation properties. ” Amended claims [1, 30 to 80 parts by weight of organic polymer, 20 parts by weight of inorganic compound
- In a method in which a mixture containing 70 parts by weight as a main component is melt-extruded to form a strand-shaped porous foam and then pelletized, the stretching ratio of the strand after melt-extrusion and before solidification is 1.5 times or less A method for producing a water treatment material, characterized in that:

Claims (1)

[Claims] 1. 30 to 80'N parts of specific polymer, 2 inorganic compound
゛0 to 70M [In the method of melt extruding a mixture whose main component is a foam, making it into a strand-shaped foam, and then pelletizing it, the stretching ratio of the strand after melt extrusion and before solidification is 1.5 times. t) below! r￥
Signs of water usage■ Production method in January. 2. The method for producing a water treatment material according to claim 1, characterized in that the strands are melt-extruded through a nozzle with multiple holes, and the strands are bundled or cooled and solidified while being bundled.