JPS58183979A - Treatment of water - Google Patents

Abstract

PURPOSE:To inhibit the propagation of noxious microbes, by treating industrial water or the like in the system where anion-exchange resin containing amine and/or quaternary ammonium groups in addition to iodine is made existent together with active carbon. CONSTITUTION:Iodine resin and active carbon are sufficiently mixed and dipersed together. The mixture is charged in a treating tank, e.g. a column or a water purifier, in the process of water treatment, and water is treated by letting it flow therethrough. Said iodine resin is easily obtained by bringing the aqueous solution of an iodine compound such as potassium, sodium or ammonium iodide into contact with anion-exchange resin. Any optional form such as a spheroidal, fine-grained or crushed one may be used according to a purpose. Said active carbon may be any kind, as far as it can be used as the water-treating agent to adsorb colors, smell, taste, organic substance, halogen, etc., and one formed into an optional shape such as a powdery or crushed shape may be used.

Description

Detailed Description of the Invention The present invention provides treatment for water treated by a method for preventing or killing bacteria, yeast, algae, and other harmful microorganisms that grow in activated carbon used in water treatment processes. It is about obtaining cleanliness.

Halogens and/or their compounds have been used in drinking water and domestic water for a long time to kill harmful microorganisms, and generally chlorine or chlorine compounds that have a bactericidal effect in water and quaternary ammonium are used in drinking water and domestic water. Salt, etc. are used, and chlorine is the most representative because of its high sterilizing effect and established technology. In recent years, due to the deterioration of the environment, rivers, lakes, and other areas that are sources of drinking water and domestic water have become increasingly polluted, and the deterioration of water quality continues to increase. To deal with this, water treatment plants are barely able to meet the water quality standards by injecting large amounts of chemicals such as chlorine gas and flocculants. Particularly in the summer, the amount of chlorine injected is increased to enhance the sterilization effect, so in addition to the smell of chlorine, the taste is also significantly worse due to the presence of lomethane, which is produced when chlorine reacts with organic matter such as algae that is present in small amounts. .

Chlorine dissolved in trace amounts in the water as a disinfectant and other mixed substances such as lomethane are easily adsorbed by passing through the activated carbon layer, and can be removed from the water. Activated carbon water purifiers and the like that apply this principle to remove chlorine and the like from tap water are widely used. Activated carbon with □ adsorbs chlorine in water in a short period of time, but on the other hand, chlorine adsorbed on activated carbon □ has the property of significantly reducing its bactericidal power. Therefore, the water becomes an environment where bacteria, yeast, algae, and other harmful microorganisms can easily breed.
In particular, when the water supply is stopped, these harmful microorganisms, etc. breed rapidly, and in activated carbon water purifiers, harmful microorganisms, etc. breed in the activated carbon layer after about six months of use, and sometimes even slime forms. .

In such a state, it becomes impossible to obtain water suitable for drinking or for industries that use chlorinated water, even if the activated carbon layer is washed by running water for a long time before use. However, it is impossible to wash away these harmful microorganisms and slime. Furthermore, even new activated carbon, etc., becomes a breeding ground for microorganisms during storage and retains harmful microorganisms.

In this way, water used for drinking and other industries is treated with chlorine and other chemicals to remove harmful effects caused by bacteria, yeast, algae, and other harmful microorganisms that are contained in the water. Treatment is performed using chemicals such as quaternary ammonium salts3. Although this method achieves the objective, the chemicals used remain in the water after treatment, causing odor and local irritation. .

Activated carbon is used as a method to treat water.
As a result, by adsorbing and removing the agent that prevents and/or kills the proliferation of these harmful microorganisms from the water, the proliferation of these harmful microorganisms that remained unkilled in the water becomes more likely to occur again. .

This phenomenon occurs particularly when water reaches a stagnant state. In this way, activated carbon can be used to remove chlorine and quaternary
As a method for preventing problems caused by adsorption treatment of grade ammonium salts, etc., the present invention proposes a composition in which an anion exchange resin contains iodine (
Hereinafter, this will be referred to as iodine resin. ) can be easily prevented from propagating and/or killed, and clean water can be obtained. Water treated by this method has almost no odor or irritation to local areas, and can be used safely as it is in better condition than water treated with chemicals such as chlorine or quaternary ammonium salts. Everything included in these technical ideas is treated as the present invention.

Traditionally, halogens such as iodine, bromine, and their compounds have been recognized to have bactericidal properties similar to chlorine, and among them, iodine and its compounds have been in the spotlight. This is due to the characteristics of iodine, such as its high bactericidal effect, low irritation to local parts of the human body, and the fact that it is tasteless and odorless in dilute solutions that are actually used, making it ideal for sterilizing pool water and emergency drinking water. It is used as a drug. Water-soluble iodine compounds are used as these disinfectants, and due to their nature, iodine and its compounds remain in the water even after treatment.

It goes without saying that when considering the amount of ml used, it is desirable that the amount remaining in the water be small. From this perspective, Motoyama 1
Special Publication No. 51-6730 and Special Publication No. 55-1 by the applicant
According to No. 2882 and U, S, P, 3,817,860, anion exchange resins, which are crosslinked addition polymers having amine groups and/or quaternary ammonium groups as functional groups, are capable of tightly bonding with iodine compounds. However, it has been recognized that it forms a composition that is extremely stable in water, and that this iodine stalk oil has extremely high bactericidal activity.

This polymer has a crosslinked structure and is insoluble in water, various organic solvents, and the like. In the crosslinked structure, monomers include aromatic monomers such as styrene, methylstyrene, vinyltoluene, vinylxylene, etc. Monomers for crosslinking these monomers include polyvinyl monomer, 1+1. Examples of +e include novinylbenzene, divinyltoluene, novinylethylbenzene, novinylxylene, novinylnaphthalene, trivinylbenzene, novinylpyridine, and ethylene glycol dimethacrylate. These monomers can be polymerized using known polymerization methods such as suspension polymerization and emulsion polymerization.

It may be copolymerized by a solution polymerization method or the like, and may have any physical structure such as a glue type, a porous type, or a macroreticular (MR) type. These crosslinked polymers are then treated with a chloromethylating agent and then aminated. And these are amine groups such as -NH2, NHR, NR2
The object of the present invention can be achieved even if the functional group has a functional group of a primary, secondary, or tertiary amine group such as, or an ammonium group, for example, a quaternary ammonium group such as N''Rs, simultaneously or separately. Of course, an anion exchange resin obtained by carrying out amination by the above-mentioned known method using a copolymer in which a monomer such as vinylbenzylnolide is crosslinked with the above-mentioned polyvinyl monomer may also be used. Can be used.

An anion exchange resin containing iodine can be easily prepared by, for example, bringing an anion exchange resin into contact with an aqueous solution of an iodine compound containing iodine (■2), such as potassium iodide, sodium iodide, ammonium iodide, etc. Made. The iodine resin of the present invention can be easily produced as described above, but iodine resins that have been subjected to waste treatment can also be used in the present invention. In other words, iodine is recovered from natural brine in a device using an anion exchange resin, and the anion exchange resin used in this recovery process and the anion exchange resin that is disposed of are hard to retain iodine in the resin. It is suitable for this reason.

These iodine resins that can be used in the present invention can be in any form such as spherical, fine granular, crushed, etc., and embodiments of the present invention will be described below.

When the iodine resin of the present invention is made to coexist in a water treatment process using activated carbon, the object of the present invention can be achieved if the iodine resin is used simultaneously with the activated carbon or before or after the activated carbon layer. More specifically, the present invention can be achieved by sufficiently mixing and dispersing the iodine resin and activated carbon, charging the mixture into a treatment tank such as a column, water purifier, etc. during a water treatment process, and passing the liquid through the treatment tank. This objective can be achieved, and even if this mixed composition is put into a batch-type treatment tank, water treatment is possible in the same way. In addition, this mixed composition is enclosed in a paper pack or cloth pack with good water permeability, and this is added to the treatment tank.
Column processing and batch processing are also possible. In such a case, the iodine resin can be contained in an amount of 90 to 0.5%, preferably 20 to 0.5%, based on the mixed composition.

As another practical method, an activated carbon layer and an iodine resin layer may be formed in the same water treatment tank, and the treatment may be performed by stacking such activated carbon layers and iodine resin layers in multiple layers. The object of the present invention can also be achieved by connecting an iodine resin tank next to the activated carbon treatment tank during the water treatment process, which is a preferred means.

When using the water treated according to the method of the present invention, if it is circulated through the treatment process of the present invention again, it is possible to prevent and kill fungi that have grown again. ,
Specifically, it can be safely used in medical fields that require sterile water.

In this way, iodine resin has high bactericidal power, and at the same time, the iodine contained in the resin has the property that only a very small amount of iodine is liberated from ordinary water such as tap water. Therefore, the effect can be maintained for a long period of time.

Furthermore, the activated carbon used in the present invention has different color, depth, and taste.

This is possible as long as it adsorbs organic matter, logs, etc. and is used for water treatment, and these can be broadly classified into those obtained by carbonizing vegetable matter, coal, or petroleum-based minerals as raw materials. Any commonly used one can be used. These can be used in the form of powder, single grain (crushed), or processed into any desired shape.

The present invention will be explained with reference to the following examples, but the present invention is not limited to these specific examples.

Example 1 1) A quaternary anhinium type of Amberlite IRA-900 with a macroreticular structure and a particle size of 3 to 0.81III11 was used as an anion exchange resin (Amberlite is a product of Rohm and Haas and is registered trademark). Iodizing power containing 4.5% (by weight) of iodine1. ) liquid 50
0- and wet resin 100- were placed in an Erlenmeyer flask and gently stirred for 12 hours to allow the ion exchange resin to sufficiently retain iodine.

Next, put an iodine resin into the column and use deionized water at SV: 150, and the effluent is converted into a cadmium iodide indicator (Ca
dmium 1odine-1inear 5tarc
h reagent ) until the blue color no longer developed. The amount of iodine resin at this time was 18 ml, and the weight was 959 in the wet state. Further, the total iodine contained in the iodine resin was 55 units by dry weight.

2) When Amberley IRA-400 was treated in the same manner, the total iodine weight was 67 inches, and Amberley) IRA-93 had a dry weight of 52 inches.

Example 2 Granular activated carbon (manufactured by Pittsburgh Activated Carbon Co., Ltd.) and the iodine resin shown in Example 1 (Amberlite IRA-900) were mixed in a weight ratio of 80:20°, 90:10,
95:5, 97:3, 99:1.

99.5: 0.5, 100: O, these 302 amounts were put into a 100-mm Erlenmeyer flask, and tap water was poured into the activated carbon so that it was about 5 mm above the top surface of the activated carbon. ) suspension (5,0x1o7/mg) at 1rnI! Added to each flask and stirred thoroughly. These flasks were left standing in a thermostat adjusted to 36°C, and after 2, 6, 24, and 48 hours, sample liquids were taken from each flask, diluted with sterilized water, and the number of E. coli bacteria was investigated using the agar plate method. The results are shown in Table 1.

Iodine and iodine compounds were not detected in any of the water treated by coexisting the granular charcoal and iodine resin of the present invention.

Example 3 Granular activated carbon (manufactured by Pittsburgh Actei Peito Carbon Co.) and the iodine resin shown in Example 1 (Amberlite IRA-900) were mixed in a weight ratio of 80:20° to 90:10°.
95:5, 97:3.99:1.

Mix 99.5: 0.5, 100: O, put 32 amounts of these into a test tube, and add 30 - of tap water and Escherichia coli suspension (:L4 x 1'05/+++l) 0.5 rM
After injection, shaking culture was performed at 36°C. After starting the test,
2, 6. After 24 and 48 hours, the supernatant liquid was taken from each test tube and the number of E. coli bacteria was investigated using the agar plate method. The results are shown in Table 2.

Iodine and iodine compounds were not detected in any of the water treated by coexisting the granular charcoal and iodine resin of the present invention.

Furthermore, by the same operation, Amber Ray) IRA-400
When treated, the growth of E. coli could be prevented, similar to the above results.

Example 4 A glass column (φ30 tan) was coated with iodine resin (Amberly IRA-400) and granular activated carbon (manufactured by Pittsburgh McTervey Tesod Carbon Co., Ltd.) as horizontal layers as shown below, and three types of treatment layers were formed. formed. ■1.52 iodine resin +12.75 sequentially from the upper layer? granular charcoal + 1.52 iodine resin + 12.759 granular charcoal + 1.
52 iodine resin, (I3) 1.52 iodine resin + 27. Of granular carbon + 1.52 iodine resin and C) upper layer 28.5 F granular carbon + lower layer 1.52 iodine resin, and for comparison, a column with activated carbon 302 was used.

Next, E. coli (
E, coli) suspension was added to the solution (2,4X 1
o'/I7 was prepared, water was passed through the column at SV: 120, and water was passed for 15 minutes, 30 minutes,
Samples were taken after 1 hour. Next, the mixture was immediately diluted with sterilized water, and the number of E. coli bacteria was determined using an agar plate method containing 5% of the yam extract in a thermostat adjusted to 36°C. The results are shown in Table 3.

Table 3 Iodine and iodine compounds were not detected in any of the water treated by coexisting the granular carbon and iodine resin of the present invention.

Example 5 After completing the column water flow test in Example 3, the cock was closed and the column was allowed to stand at room temperature for 24 hours, after which a test was conducted in the same manner as in Example 4. The results are shown in Table 4.

Table 4 (Stock solution E, coli near, 0x106/m/) Iodine and iodine compounds were not detected in any of the water treated by coexisting the granular carbon of the present invention and the iodine resin.

Example 6 Iodine resin shown in Example 1 (Amberlite IRA-9
00) in a small column and tap water at SV:1
The durability of the bactericidal effect was investigated using samples after water was passed through the tube at a temperature of 1,000 yen for a continuous month.

A horizontal layer of the above iodine resin (Amberlite IRA-900) and granular activated carbon (manufactured by Bishippa Gumakteibei Tenodo Carden Co., Ltd.) was placed on a glass column (φ20fi). That is, from the upper layer, 2.22 iodine resin + 10.59 granular carbon + 2.32 iodine resin, and for comparison, activated carbon 15F.
A column with .

Next, E. coli (
E, coli) suspension added (36Kari05/rn
1. ) was prepared, water was passed through the column at SV: 120, and Sannol was collected at the start of water flow, 30 minutes, and 1 hour later for a bactericidal effect test. Next, immediately dilute with sterile water and hold at 36°C.
The number of Escherichia coli bacteria was determined using the agar plate method containing 5 g of potato extract in a thermostatic chamber adjusted to . The results are shown in Table 5.

Table 5 Iodine and iodine compounds were not detected in any of the water treated with the coexistence of the granular charcoal and iodine resin of the present invention.

Agent: Patent attorney Masahiro Shiozaki

Claims (1)

[Claims] It is a crosslinked polymer that holds amine groups and/or quaternary ammonium groups as functional groups in the process of treating water for drinking and other industrial purposes with sterilizing substances such as chlorine using activated carbon. A water treatment method characterized in that a composition comprising an anion exchange resin containing iodine is allowed to coexist in an activated carbon treatment step.