JP2008238131A - Water cleaning agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water cleaning agent capable of safely and effectively removing ammonia and nitrous acid in water by means of a simple operation without employing a special, large-scale device for preventing the deterioration of water quality in using water such as running water, industrial water, sewage, etc., or water from a water area such as a sea, river, pond, swamp, etc., or a closed water area such as an ornamental fish tank, fish preserve, plastic bag for carrying a live fish/ornamental fish, etc. <P>SOLUTION: The water cleaning agent is made up of compounds comprising elements belonging to the group IIA of the periodic table and provided as a powder as well as a granule or a molding bonded by a binder, etc. The ammonia and nitrous acid in the water can be removed conveniently by simply immersing the agent into the water. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to water purification, particularly removal of ammonia and nitrous acid dissolved in water, water areas such as seas, rivers, ponds, swamps, ornamental fish tanks, fish tanks, live fish and ornamental fish The present invention relates to prevention of water quality deterioration in the use of closed water areas such as bags and tap water, industrial water, sewage and other water.
More specifically, it is to provide a water purification agent capable of easily removing ammonia and nitrous acid in water by immersing a compound comprising an element belonging to Group 2A of the periodic table in water.

In general, ammonia and nitrous acid dissolved in water may adversely affect aquatic organisms and other living organisms. Water such as seas, rivers, ponds, swamps, ornamental fish tanks, fish tanks, live fish and ornamentals Ammonia and nitrous acid dissolved in closed water areas such as plastic bags for transporting fish and tap water, industrial water, sewage and other water are treated in various ways.

For example, methods for removing ammonia in water include biological treatment, treatment by addition of chlorine, treatment by ion exchange, and other methods disclosed in Patent Documents 1 to 4.

The biological treatment method is a treatment method that utilizes oxidation by microorganisms by contacting treated water with a carrier on which microorganisms that decompose ammonia and nitrous acid are attached and propagated. There is a problem that it takes time for the microorganisms to settle.

The treatment method by ion exchange is a method of removing ammonium ions by exchanging ions of a substance having ion exchange ability (ion exchanger) and ions in water, but the installation space and the ion exchanger are regenerated. There is a problem that wastewater containing ammonium ions with a high concentration is discharged.

In the chlorine treatment method, chlorine gas is injected into treated water, and ammonia and chlorine in the water are reacted to produce chloramine (bound chlorine). As the amount of chlorine injected increases, the amount of chloramine increases and eventually reaches a maximum point, and then chloramine is further decomposed by excess chlorine added to form nitrogen, chloramine is decomposed and eliminated, and ammonia is removed. The However, in order to completely remove ammonia, a slight excess of chlorine is added in the actual treatment, leaving free residual chlorine in the water, which may adversely affect aquatic organisms and other living organisms. There is a problem that must be removed.

Patent Document 1 discloses a method of injecting an oxidizing agent into water in which ammoniacal nitrogen is dissolved to decompose ammonia in the water and removing the generated gas with a deaeration device. There is a problem that the installation space of the apparatus for removing ammonia becomes large.

Patent Document 2 discloses a titanium oxide molded body for removing ammonia in water. At this time, it is necessary to irradiate the titanium oxide molded body with ultraviolet rays, and unless an ultraviolet lamp is specially installed. There are problems such as not becoming.

Patent Document 3 discloses a water treatment method in which an air diffuser is arranged at the bottom, and it is described that ammonia components in treated water are nitrified by nitrifying bacteria held in a treatment tank. There is a problem that the installation space of the apparatus for removing the odor increases, and it takes time until the nitrifying bacteria are fixed.

Patent Document 4 discloses a method of decomposing ammonia nitrogen in water by adding halogen to water containing ammonia nitrogen and further treating with ozone. Although a large-scale apparatus such as a biological filtration tank is not necessary, there is a problem that a process of adding a chemical and controlling pH is necessary and the operation is complicated.

In either case, the equipment is large, the treatment process is long, and it is suitable for the treatment of high-concentration ammonia, but it is not cost-effective in the treatment of low-concentration ammonia with a small amount of water. In addition, there are problems such as installation space and complicated ammonia processing operations.

For example, breeding water used in aquariums for ornamental fish that cannot be treated with ammonia and nitrous acid by the large-scale method as described above, cistern tanks, plastic bags for transporting live fish and ornamental fish, etc. The water quality deteriorates due to ammonia excreted from the organism, and the concentration of carbon dioxide in the water increases significantly due to the respiration of aquatic organisms such as fish. And there is a problem that the vitality of aquatic organisms such as fish is reduced and death occurs.

When aquatic organisms such as fish are kept in a small amount of breeding water, excrement, residual food, and withered aquatic plants cause ammonia nitrogen, and nitrite is decomposed by nitrite bacteria in the excrement. Nitrogen, which is harmful to aquatic organisms such as fish.

Nitrous acid (NO ₃ ) is oxidatively decomposed ammonia, and is toxic to aquatic organisms and other living organisms. It is particularly likely to occur in the early and overcrowded breeding water of aquariums, etc. .

In order to quickly decompose toxic nitrite nitrogen, microorganisms can be propagated well, and the water quality can be purified by changing to relatively stable and less harmful nitrate nitrogen. There is a problem that it takes several weeks for the to settle and to exert the effect.

In a water system having a large amount of water, such a rapid deterioration of water quality is unlikely to occur. On the other hand, in the water transport using the plastic bag for transporting the live fish and ornamental fish, the amount of water is extremely small, and harmful nitrite nitrogen is rapidly generated due to changes in the water temperature, pH, etc. High concentrations can cause fish to die. Even if it does not lead to death, the fish suffers damage such as being stressed and prone to illness.

Plastic bag transport is a method of transporting water and fish and other aquatic organisms in a plastic bag, sealing it with a headspace, and then transporting it in a cardboard box. Used. Plastic bag transportation is a low-cost and simple method, and is widely used for transportation of cultured fish, natural fish, or ornamental fish.

However, in plastic bag transportation, since the water temperature, dissolved oxygen concentration, and water quality during transportation cannot be controlled, there is a problem in that the vitality of fish during transportation and mortality are likely to occur even during short transportation.
Therefore, in plastic bag transport, various measures such as lowering the temperature of the water to be sealed, enclosing oxygen gas in the headspace, and stopping food to prevent the loss of vitality and death of aquatic organisms such as fish during transport. Ingenuity is given.

However, these methods alone are not sufficient to prevent the decline of vitality and death of aquatic organisms such as fish. Especially in the summer when the temperature rises, the vitality of the aquatic organisms declines or disappears, and products of aquatic organisms such as fish. The value is significantly reduced.

An aquarium fish is a particularly serious problem, and an aquarium fish that has died during transportation loses its value at all, and even if it is not vigorous or one animal in the transport bag dies, the merchandise value is significantly reduced.

Many ornamental tropical fish are transported by air from other countries. Domestic goldfish and Nishikigoi are also trucked from the production area to each region. The major difference in water transportation of these ornamental fish from other water systems is that they must be transported using a small amount of water in a short time.

In the case of ornamental fish, etc. with a small amount of water to be transported, implementation of large-scale equipment for purifying water quality, such as other water systems, or complicated operations with chemicals added will lead to increased transportation costs from an economic perspective. Can not.

The smaller the amount of water, the faster the water quality becomes worse due to the excrement of aquatic organisms such as fish, the water quality is very difficult to control, and the number of fish that can be transported is limited.

In order to treat ammonia and nitrous acid by a biological method, it is necessary to fix microorganisms. However, this method cannot be applied because microorganisms are not sufficiently fixed by setting fresh water and transporting in a short time.

If the installation space of the water treatment facility is sufficient, ammonia and nitrous acid can be removed and the water quality can be purified.However, if a large-scale device cannot be introduced due to physical reasons such as the installation space is not available, Ammonia and nitrous acid cannot be removed.
For this reason, there is a demand for a simple method for preventing the vitality of aquatic organisms such as fish from being lowered or dead due to changes in water temperature and pH during transportation and excreted ammonia.

Japanese Patent Laid-Open No. 06-226274 Japanese Patent Laid-Open No. 10-128319 JP 2000-033371 A JP 2001-239279 A

An object of the present invention is to provide a water purification agent capable of removing ammonia and nitrous acid in water safely and effectively by a simple operation without using a special and large-scale apparatus or equipment.

As a result of various studies to solve the above-mentioned problems, the present inventors have found that water areas such as the sea, rivers, ponds and swamps, aquariums for aquarium fish, aquariums for fish, and plastic bags for transporting live fish and aquarium fish In order to prevent water quality degradation in the use of closed water areas such as tap water, industrial water, sewage and other water, etc., by immersing a water purification agent comprising a compound of an element belonging to Group 2A of the periodic table in water, The present inventors have found that ammonia and nitrous acid dissolved in water can be efficiently removed, and have found an optimal water purification agent that is effective in preventing deterioration of water quality without using special and large-scale equipment and equipment, and have reached the present invention. Is.

That is, this invention relates to the water purification agent which consists of a compound of the element which belongs to periodic table 2A group, and removes ammonia and nitrous acid. Here, the compound is preferably a hydroxide or an oxide. Further, the oxide is preferably magnesium oxide or calcium oxide, and the hydroxide is preferably magnesium hydroxide or calcium hydroxide. Most preferred is magnesium hydroxide.

The compound can be provided in the form of a powder or a granulated body or a molded body formed by binding powder with a binder.

Moreover, it is preferable that the said granulated body or molded object mixes 3-30 mass% binder with respect to the said powder, More preferably, 5-20 mass% binder is mixed and manufactured.

The binder is water-insoluble, such as ethyl cellulose or other cellulose derivative, methacrylic copolymer, colloidal silica, or water-soluble and slow dissolving rate, such as sodium starch glycolate, starch sodium phosphate ester, carboxy 1 selected from the group consisting of methylcellulose calcium, sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylcellulose, sodium alginate, propylene glycol alginate, sodium polyacrylate, polyvinyl alcohol, sodium silicate It can be produced with two or more species.

The granulated body or molded body preferably has a diameter of 0.1 to 10 mm.
In addition, 0.1 to 20 g of the water purification agent of the present invention can be immersed in 1 liter of treated water to remove ammonia, nitrous acid, and carbon dioxide in the water.

By using the water purification agent of the present invention, it is possible to suppress the deterioration of water quality due to the biological activity of aquatic organisms such as fish, inexpensively with a small amount of addition, without using expensive and large-scale water purification facilities and equipment. it can.
In particular, it is possible to prevent deterioration of water quality due to ammonia and nitrous acid during transportation and rearing of live fish, ornamental fish, etc., reduce stress of aquatic organisms due to environmental changes, and increase survival rate. In addition, since the transportation time can be extended, it is possible to transport plastic bags of live fish, ornamental fish, etc. to distant areas, which was impossible until now. Furthermore, since the amount of seafood that can be enclosed in the transport bag can be increased, the cost of transport can be reduced.

The present invention provides a water purification agent that can easily treat ammonia and nitrous acid in water without using complicated and expensive operations such as expensive and large-scale water purification equipment, equipment, chemicals, etc. that have been generally used. provide.

By immersing the water purification agent of the present invention in water, it is possible to efficiently remove ammonia, nitrous acid and carbon dioxide generated in plastic bags for transportation due to excretion and respiration of aquatic organisms such as fish, It can prevent a decrease in vitality and death of aquatic organisms such as fish.

The water purification agent is composed of a compound of an element belonging to Group 2A of the periodic table, preferably a compound composed of a hydroxide or an oxide thereof. More preferably, magnesium oxide, calcium oxide, magnesium hydroxide, or calcium hydroxide is used as a raw material.

The oxides of elements belonging to Group 2A of the periodic table become more reactive with water in the order of MgO, CaO, SrO, BaO. In contrast, hydroxides have a slow reaction with water, but have a higher molecular weight than that of the oxides. In view of these points, it has been found that magnesium oxide, calcium oxide, magnesium hydroxide, and calcium hydroxide are suitable as water purification agents that efficiently remove ammonia and nitrous acid in water. Furthermore, magnesium hydroxide is most preferable as a material to be used by immersing in water in consideration of safety.

Magnesium hydroxide or the like used as a raw material for the water purification agent of the present invention is good in that there is no fear of eluting ions harmful to aquatic organisms such as fish, and the purity is preferably 90% by mass or more. More preferably, it is 95 mass% or more.

The magnesium hydroxide is produced by mixing a magnesium ion-containing solution such as a magnesium chloride solution and an alkali precipitant while stirring and reacting for a predetermined time to produce primary particles, which are filtered, washed and dried. be able to.
Magnesium hydroxide used as a raw material may be synthesized by a known method as described above, or commercially available magnesium hydroxide may be used.

In addition, the water purification agent of the present invention may be powdered or bound with a binder to immerse the granulated body or molded body in water, or fill them into a container or nonwoven fabric for ease of handling. Can also be used.

As the granulation and molding method, any known method such as extrusion molding, Malmerizer method, bread granulation, rolling granulation, extrusion granulation, stirring granulation, uniaxial press molding, CIP molding, etc. can be adopted. .

As the binder to be used, water-insoluble and water-insoluble ones can be used, and typical examples include ethyl cellulose and other cellulose derivatives, methacrylic copolymers, colloidal silica, and the like.

A water-soluble binder with a low dissolution rate can also be used, such as sodium starch glycolate, sodium starch phosphate ester, carboxymethylcellulose calcium, carboxymethylcellulose sodium, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropyl. Typical examples include, but are not limited to, cellulose, sodium alginate, propylene glycol alginate, sodium polyacrylate, polyvinyl alcohol, and sodium silicate. These binders can be used alone or in combination of two or more.

The water purification agent of the present invention can be produced using at least one binder selected from the above. The granulated body or molded body preferably has a size of 0.1 to 10 mm, and is preferably used by immersing 0.1 to 20 g in 1 liter of treated water.

The water purification agent of the present invention can be immersed in water to efficiently remove ammonia and nitrous acid in water. Further, it acts as a carbon dioxide removal and pH adjuster. Usually, the water quality becomes low pH due to the life activity of aquatic organisms such as fish, but when the water purification agent of the present invention is immersed, the pH reduction can be suppressed by the neutralization reaction.

In addition to using the water purification agent of the present invention alone, it can be mixed with a known carbon dioxide adsorbent or pH adjuster to change the composition ratio, thereby providing ammonia, nitrous acid, carbon dioxide and pH adjusting functions. It can be arbitrarily increased or decreased, and it is possible to create an optimum blended state from various environmental conditions such as the safety against aquatic organisms such as fish according to the amount and quality of water.

The water purification agent of the present invention can adsorb ammonia and nitrous acid in water on its surface.

The water purification agent of the present invention is not limited to use in the form of powder, granulated body, and molded body soaked in water, and can be used by filling various containers. The effect can also be exerted by bringing it into contact with circulating water, such as by installing it in the water.

EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

[Example 1]
Magnesium hydroxide powder, purity 99% by mass (trade name: Magstar, manufactured by Tateho Chemical Co., Ltd.), a solution prepared by dissolving 10% by mass of ethyl cellulose in 1600 ml of ethyl alcohol was added to 3000 g, and kneader (trade name: universal mixing stirrer). , Manufactured by Dalton Co., Ltd.) and dried in a dryer at 80 ° C. for 24 hours. Subsequently, the mixture was pulverized by a pulverizer and passed through a box type sieve to obtain 3.6 to 1.0 mm granules.

[Ammonia concentration measurement method]
Measurement of the ammonia concentration was carried out by using a mercuric potassium iodide solution (Nessler's reagent, Kanto Kagaku) to produce a brown complex salt and quantifying it by a colorimetric method.

[Nitrite concentration measurement method]
The concentration of nitrous acid was quantified by a colorimetric method using a commercially available tetratest nitrite reagent (Tetra Japan Co., Ltd.).

[Test water adjustment]
Pour water into a 50 liter tank, raise 12 medium-sized goldfish (about 150 g / animal), prepare breeding water with increased ammonia concentration, and dilute this breeding water 3 times with water. Test water having an ammonia concentration of 5 ppm was used.

5 g of the granule of Example 1 was immersed in 1 liter of preliminarily prepared test water having an ammonia concentration of 5 ppm and left at room temperature for 3 days to measure the ammonia concentration.
A measurement result is as showing in Table 1, and it turns out that the ammonia concentration in water is reducing.

[Comparative Example 1]
As a comparative example, the ammonia concentration was measured by leaving the water purifier of the present invention for 1 day at room temperature without immersing it in 1 liter of test water having an ammonia concentration of 5 ppm. The measurement results are as shown in Table 1. It can be seen that the ammonia concentration in the water did not change before and after the test.

[Example 2]
In a 300 ml beaker, 250 ml of water and 15 tails of shrimp were placed, and 3 g of the granules produced in Example 1 were immersed therein and allowed to stand at room temperature for several days to measure ammonia concentration, nitrous acid concentration and carbon dioxide concentration. Table 2 shows the measurement results of the ammonia concentration, and Table 3 shows the measurement results of the nitrous acid concentration.

[Comparative Example 2]
In a 300 ml beaker, 250 ml of water and 15 tails of shrimp were put and left at room temperature for several days without immersing the water purification agent of the present invention, and the ammonia concentration, nitrous acid concentration and carbon dioxide concentration were measured. Table 2 shows the measurement results of the ammonia concentration, and Table 3 shows the measurement results of the nitrous acid concentration.

From the results of Tables 2 and 3, in Example 2 using the water purification agent of the present invention, the ammonia concentration and the nitrous acid concentration were kept low. As a result, viability of white shrimp was high. In Example 2 using the treatment agent of the present invention, the carbon dioxide gas concentration was also kept low.

As is clear from the above results, the water purification agent of the present invention can remove ammonia and nitrous acid dissolved in water that are harmful to aquatic organisms such as fish. Moreover, the removal method of ammonia and nitrous acid in water using the water purification agent of the present invention is simple, can be performed at low cost without requiring large-scale equipment and complicated processing steps.

Claims (9)

A water purification agent comprising a compound of an element belonging to Group 2A of the periodic table and removing ammonia and nitrous acid in water. The water purification agent according to claim 1, wherein the compound comprises a hydroxide or an oxide. The water purification agent according to claim 2, wherein the oxide is magnesium oxide or calcium oxide, or the hydroxide is one or more of magnesium hydroxide or calcium hydroxide. The water purification agent according to any one of claims 1 to 3, wherein the compound is in a powder form, a granulated body, or a molded body. The water purification agent according to any one of claims 1 to 3, wherein 3 to 30% by mass of a binder is mixed with the compound powder and granulated or molded. 6. The water purification agent according to claim 5, wherein the binder is one or more selected from the group consisting of water-insoluble or water-soluble and slow dissolving speed. The water-insoluble binder is ethyl cellulose or other cellulose derivatives, methacrylic copolymers, colloidal silica, or the water-soluble binder having a low dissolution rate is sodium starch glycolate, sodium starch phosphate, carboxymethyl cellulose. One selected from the group consisting of calcium, sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylcellulose, sodium alginate, propylene glycol alginate, sodium polyacrylate, polyvinyl alcohol, sodium silicate Or the water purification agent of Claim 6 which is 2 or more types. The water purification agent of any one of Claims 5-7 whose diameter of the said granulated body or a molded object is 0.1-10 mm. A method for removing ammonia and nitrous acid in water by immersing 0.1 to 20 g of the water purification agent according to any one of claims 1 to 8 with respect to 1 liter of treated water.