JPWO2015008398A1 - Water purification material, method for producing the same, and method for purification of water quality in fish farm - Google Patents

Abstract

Provided is a water purification material capable of purifying the quality of breeding water without causing any harm to fish and shellfish due to the elution of harmful substances in a fish farm. It consists of porous granules containing calcium silicate hydrate as a main component, the aluminum content is 10% by mass or less in terms of oxide, and the titanium content is 1.0% by mass or less in terms of oxide. Water purification material. The water purification material preferably has a proportion of particles of 0.01 mm or more and less than 0.1 mm in the range of 5 to 30% by mass, a proportion of granules in the particle size of 0.1 mm or more and less than 1.0 mm of 10 to 10%. 50 mass%, the proportion of particles having a particle size of 1.0 mm or more and less than 2.5 mm is 10 to 50 mass%, the proportion of particles having a particle size of 2.5 mm or more and 4.0 mm or less is 5 to 30 mass% %, And a particle size distribution of 0 to 30% by mass of particles having a particle size of less than 0.01 mm or exceeding 4.0 mm.

Description

  The present invention relates to a water purification material, a method for producing the same, and a water purification method for fishery products using the water purification material.

In the breeding water of fishery, shrimp, crab and other seafood farms, water-soluble phosphorus components, ammonium ions, etc., derived from food residues and seafood excrement, reduce the quality of the breeding water, Adversely affects the growth of
For this reason, various methods for removing water-soluble phosphorus components and ammonium ions from breeding water have been proposed.
For example, Patent Document 1 describes a water tank purification method characterized by immersing a porous purification agent mainly composed of calcium silicate having a porosity of 50 to 90% in a water tank.
Also, in this document, a porous purification material is obtained by adding a foaming agent such as aluminum powder to a slurry mainly composed of a siliceous raw material and a calcareous raw material, and hydrothermal reaction treatment under high temperature and high pressure. Or a crushed product obtained by crushing the molded product.
Furthermore, in this document, when producing a porous purification material containing tobermorite as a main constituent, 5 parts by weight of silica powder, 2 parts by weight of quicklime powder, 3 parts by weight of ordinary Portland cement, 0 parts of metal aluminum powder It is described that 0.008 parts by weight and 7 parts by weight of water were used.
On the other hand, Non-Patent Document 1 reports that monomeric aluminum ions contained in the wastewater of Kawayu Onsen are toxic to salmon fry.

JP-A-63-42788

“Environmental Destruction by Hot Spring Wastewater -I”, Susumu Hashimoto, Sake / Masufu Kenho (Hokkaido Sake / Matsu Hatoba Research Report), 43, 29-38, 1989

As above-mentioned, in the Example of patent document 1, mineral origin raw materials, such as normal Portland cement, are used as a raw material of a tobermorite purification material. These mineral-derived materials usually contain metal elements such as aluminum and titanium. In addition, it is thought that the metal aluminum powder which is one of the raw materials of a tobermorite purification material has a very small addition amount, and therefore hardly affects the aluminum content contained in the tobermorite purification material.
On the other hand, as described above, Non-Patent Document 1 describes that monomeric aluminum ions are toxic to salmon fry.
According to the descriptions in these documents, when water purification material is used for purification of breeding water of fishery products, harmful substances such as aluminum are contained in the water purification material at a high content rate. It is necessary to consider whether or not there is.
The present invention relates to a water purification material capable of purifying the quality of breeding water without causing harm to the fish and shellfish due to the elution of harmful substances, etc. in a fishery farm, and a fish and seafood using the water purification material. It aims at providing the purification method of the water quality of aquaculture farm.

  As a result of intensive studies to solve the above problems, the present inventor is composed of porous granules containing calcium silicate hydrate as a main component, and the aluminum content is 10% by mass or less in terms of oxides and According to the water purification material having a titanium content of 1.0% by mass or less in terms of oxide, water in the breeding water can be used in fish farms without causing harm to the fish and shellfish by elution of harmful substances. The present inventors have found that the concentrations of sex phosphorus components and ammonium ions can be greatly reduced in a short period of time, and the quality of the breeding water can be sufficiently purified.

That is, the present invention provides the following [1] to [10].
[1] It is composed of porous granules containing calcium silicate hydrate as a main component, the aluminum content is 10% by mass or less in terms of oxide, and the titanium content is 1.0% by mass in terms of oxide. A water purification material characterized by:
[2] The water purification material according to [1], wherein the porous particles are particles having a porosity of 50% or more.
[3] In the total amount of the porous particles, the proportion of particles having a particle size of 0.01 mm or more and less than 0.1 mm is 5 to 30% by mass, and the particle size is 0.1 mm or more and less than 1.0 mm. The ratio of the particles is 10 to 50% by mass, the ratio of the particles having a particle size of 1.0 mm or more and less than 2.5 mm is 10 to 50% by mass, and the particle size is 2.5 mm or more. [1] or [2] above, wherein the proportion of granules having a particle size of 0 mm or less is 5 to 30% by mass, and the proportion of granules having a particle size of less than 0.01 mm or more than 4.0 mm is 0 to 30% by mass. Water purification material as described in 1.
[4] The water purification material according to any one of [1] to [3], wherein the porous particles are made of a lightweight cellular concrete waste material.
[5] The water purification material according to any one of the above [1] to [4], wherein the water purification material is used by being sprayed on the breeding water of a seafood farm.

[6] A method for producing the water purification material according to any one of [1] to [5] above, wherein a hydrothermal reaction raw material containing a calcareous raw material, a siliceous raw material and water is pressurized and A hydrothermal reaction by heating to obtain a porous cured body, and a pulverizing step to pulverize the porous cured body to obtain the water purification material, and the hydrothermal reaction. When the total amount of raw materials excluding water is 100% by mass, the aluminum content is 10% by mass or less in terms of oxide and the titanium content is 1.0% by mass or less in terms of oxide. A method for producing a water purification material, characterized by using a material.
[7] The method for producing a water purification material according to the above [6], wherein the pulverizing means in the pulverizing step uses a material not containing aluminum and titanium.
[8] A method for producing the water purification material according to any one of [1] to [5] above, wherein two or more kinds of porous granules containing calcium silicate hydrate as a main component A step of preparing, a step of measuring each content of aluminum and titanium for each of the two or more kinds of porous particles, a content of aluminum of 10% by mass or less in terms of oxide, and a content of titanium A method for producing a water purification material comprising a step of selecting and recovering porous particles having a rate of 1.0% by mass or less in terms of oxide as a water purification material.
[9] A method for purifying the water quality of a seafood farm, comprising spraying the water purification material according to any one of [1] to [5] above to the breeding water of the seafood farm.
[10] The amount of the water purification material sprayed is 0.01 to 5 parts by mass per 100 parts by mass of the rearing water of the seafood farm. Purification method.

When the concentration of water-soluble phosphorus compounds (for example, phosphates), ammonium ions, etc. derived from food residues, seafood excrement, etc. is increased in the breeding water of seafood farms, If water purification material is used, the concentration of water-soluble phosphorus compounds and ammonium ions will be greatly reduced in a short period of time without causing the aluminum and titanium to elute from the water purification material and harming fish and shellfish. Water quality can be sufficiently purified.
In addition, in this specification, breeding water means the water stored in the water storage means in which fishery products can grow, such as a culture pond, and any of fresh water and seawater may be sufficient as it. The seafood includes fish, shrimps, crabs, shellfish, amphibians (edible frogs) and the like.

The water purification material of the present invention is composed of porous particles containing calcium silicate hydrate as a main component, the aluminum content is 10% by mass or less in terms of oxide, and the titanium content is in terms of oxide. 1.0 mass% or less.
In the present invention, the main component of the porous particles is calcium silicate hydrate, so that calcium ions of the calcium silicate hydrate and water-soluble phosphorus components (for example, phosphate ions) in the breeding water are contained. In response, an insoluble calcium-containing substance is generated, and the concentration of the water-soluble phosphorus component in the breeding water can be reduced.
Examples of calcium silicate hydrates include tobermorite, zonotlite, CSH gel, foshygite, gyrolite, and Hilleblandite.

Among them, tobermorite is a crystalline calcium silicate hydrate, and is Ca ₅ · (Si ₆ O ₁₈ H ₂ ) · 4H ₂ O (plate-like form), Ca ₅ · (Si ₆ O ₁₈ H ₂ ). It has a chemical composition such as (plate-like form), Ca ₅ · (Si ₆ O ₁₈ H ₂ ) · 8H ₂ O (fibrous form).
Zonotolite is a crystalline calcium silicate hydrate and has a chemical composition such as Ca ₆ · (Si ₆ O ₁₇ ) · (OH) ₂ (fibrous form).
CSH _{gel, αCaO · βSiO 2 · γH 2} O ( provided that, α / β = 0.7~2.3, a γ / β = 1.2~2.7.), For example, 3CaO · 2SiO ₂ · Calcium silicate hydrate having a chemical composition of 3H ₂ O.

The porous particles constituting the water purification material of the present invention are calcium silicate hydrate in a proportion of 100% by volume of the solid phase excluding voids, preferably 50% by volume or more, more preferably 60% by volume or more. including. When the proportion is 50% by volume or more, the effect of water quality purification can be further enhanced.
Since the porous granule constituting the water purification material of the present invention is porous, microorganisms are easily carried in the voids on the surface of the granule, and nitrification of ammonium ions by the microorganisms can be promoted.
The porosity of the porous particles is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more from the viewpoint of increasing the amount of microorganisms supported. The upper limit of the porosity is not particularly limited, but is preferably 90% from the viewpoint of ensuring the mechanical strength (for example, compressive strength) of the granules.

As a preferable example of the porous particles, a lightweight aerated concrete (ALC) waste material is pulverized from the viewpoint of reuse of building material waste. After pulverizing the lightweight cellular concrete waste material, if necessary, it is classified using a classification means such as a sieve, and by combining the particles of various particle sizes after classification, porous particles having a desired particle size distribution You can get a body.
In the present specification, the term “waste material” broadly includes product waste material, scrap material generated in the manufacturing process of the product, trial product in the factory, and the like. Moreover, the pulverized material of the waste material means both particles having a particle size of less than 1.0 mm and particles having a particle size of 1.0 mm or more.
The lightweight cellular concrete is made of tobermorite represented by a chemical formula of Ca ₅ · (Si ₆ O ₁₈ H ₂ ) · 4H ₂ O and unreacted silica, and has a porosity of about 80% by volume.
In the present specification, the porosity means the ratio of the sum of the volume of all the voids in the entire volume of the particles (for example, particles made of lightweight cellular concrete). Here, the void refers to both a continuous void communicating with the space outside the particle and a non-continuous void formed only inside the particle without communicating with the space outside the particle. means.
The proportion of tobermorite in the lightweight cellular concrete is about 65 to 80% by volume, with the whole solid phase excluding voids inside the concrete being 100% by volume.

In the present invention, the preferred particle size distribution of the porous particles is as follows.
The proportion of particles having a particle size of 0.01 mm or more and less than 0.1 mm is preferably 5 to 30% by mass, more preferably 5 to 25% by mass. When the ratio is 5% by mass or more, the effect of reducing the concentration of the water-soluble phosphorus compound can be further enhanced. When the ratio is 30% by mass or less, the particle size distribution of the entire porous granule is not sharp (high mountain shape having a steep slope) but broad (low mountain shape having a gentle slope). Since there is a tendency, the balance between the effect of reducing the concentration of the water-soluble phosphorus compound and the effect of reducing the concentration of ammonium ions becomes better.
The proportion of particles having a particle size of 0.1 mm or more and less than 1.0 mm is preferably 10 to 50% by mass, more preferably 15 to 45% by mass. When the ratio is in the range of 10 to 50% by mass, the particle size distribution becomes broad, and the balance between the effect of reducing the concentration of the water-soluble phosphorus compound and the effect of reducing the concentration of ammonium ions becomes better.

The proportion of particles having a particle size of 1.0 mm or more and less than 2.5 mm is preferably 10 to 50% by mass, more preferably 15 to 45% by mass. When the ratio is in the range of 10 to 50% by mass, the particle size distribution becomes broad, and the balance between the effect of reducing the concentration of the water-soluble phosphorus compound and the effect of reducing the concentration of ammonium ions becomes better.
The proportion of particles having a particle size of 2.5 mm or more and 4.0 mm or less is 5 to 30% by mass, more preferably 5 to 25% by mass. When the proportion is 5% by mass or more, the effect of reducing the concentration of ammonium ions can be further enhanced. When the ratio is 30% by mass or less, the particle size distribution becomes broad, and the balance between the effect of reducing the concentration of the water-soluble phosphorus compound and the effect of reducing the concentration of ammonium ions becomes better.
The proportion of the particles having a particle size of less than 0.01 mm or more than 4.0 mm is preferably 0 to 30% by mass, more preferably 0 to 25% by mass. When the ratio is 30% by mass or less, turbidity of breeding water during purification of water quality due to a large amount of granules having a particle size of less than 0.01 mm, and the amount of granules having a particle size of more than 4.0 mm are present. The disadvantage of reducing the concentration of water-soluble phosphorus compound and ammonium ion per unit mass of the water purification material due to the large amount can be reduced.

Respective contents of aluminum (Al) and titanium (Ti) contained in the porous particles constituting the water purification material of the present invention are as follows.
The content of aluminum (Al) is 10% by mass or less, more preferably 9.5% by mass or less, and particularly preferably 9.0% by mass or less in terms of oxide. If the content exceeds 10% by mass, the seafood may be abnormal in swimming behavior or die.
The content of titanium (Ti) is 1.0% by mass or less, more preferably 0.9% by mass or less, in terms of oxide. If the content exceeds 1.0% by mass, the seafood may cause abnormal swimming behavior or die.

  One example of the method for producing a water purification material of the present invention is (A) a hydrothermal reaction raw material containing a calcareous raw material, a siliceous raw material, and water, causing a hydrothermal reaction to cause a porous curing. A reaction step for obtaining a body, and (B) a pulverization step for pulverizing the porous cured body obtained in step (A) to obtain a water purification material. Hereinafter, each step will be described in detail.

[(A) Reaction step]
Examples of the calcareous raw material include quick lime powder and slaked lime powder.
Examples of the siliceous raw material include quartzite powder and quartz sand.
Other solid raw materials that are optionally blended include cement (various Portland cements, etc.), aluminum powder, surfactant, gypsum and the like. Among these, aluminum powder and surfactant are foaming agents.
The proportion of the calcareous raw material in the total amount of the solid raw material is not particularly limited, but is preferably 5 to 30% by mass from the viewpoint of avoiding a large amount of unreacted raw material remaining after the reaction.
The ratio of the siliceous raw material in the total amount of the solid raw material is not particularly limited, but is preferably 30 to 65% by mass from the viewpoint of avoiding a large amount of unreacted raw material remaining after the reaction.
Although the ratio of the other solid raw material in the total amount of the solid raw material is not particularly limited, it is usually 5 to 40% by mass. When cement is used as the solid raw material, the proportion of the cement in the total amount of the solid raw material is preferably 5 to 40% by mass from the viewpoint of increasing the compression strength of the porous cured body. When a foaming agent such as aluminum powder is used as the solid raw material, the proportion of the foaming agent in the total amount of the solid raw material is preferably 0.005 to 0.1 mass from the viewpoint of giving an appropriate porosity to the porous cured body. %.
The amount of water is preferably 50 to 100 parts by mass per 100 parts by mass of the total amount of raw materials other than water (solid raw material) from the viewpoint of efficiently performing a hydrothermal reaction.

Of the raw materials for hydrothermal reaction, when the total amount of raw materials excluding water (for example, the total amount of quicklime powder, silica powder, cement and aluminum powder) is 100% by mass, the raw materials for hydrothermal reaction are aluminum and titanium. It is preferable to use a material having each content within the following range.
The content of aluminum (Al) is 10% by mass or less, more preferably 9.5% by mass or less, and particularly preferably 9.0% by mass or less in terms of oxide.
The content of titanium (Ti) is 1.0% by mass or less, more preferably 0.9% by mass or less, in terms of oxide.
If each content rate of aluminum and titanium is within the above numerical range, each content rate of aluminum and titanium contained in the porous particles obtained by the hydrothermal reaction may be adjusted within the above numerical range. It becomes easy.

Prior to the hydrothermal reaction, the raw material for hydrothermal reaction (a mixture of the solid raw material and water) may be granulated to an appropriate particle size. In this case, the particle size of the hydrothermal reaction raw material is preferably 5 to 100 mm.
The pressure of the hydrothermal reaction is preferably 3,000 to 30,000 hPa, more preferably 4,000 to 25,000 hPa, from the viewpoint of efficiently performing the hydrothermal reaction.
The temperature of the hydrothermal reaction is preferably 100 to 250 ° C, more preferably 120 to 230 ° C, and particularly preferably 150 to 210 ° C from the viewpoint of efficiently performing the hydrothermal reaction.
Although the time of a hydrothermal reaction is not specifically limited, Usually, it is 5 to 15 hours.
Examples of means for performing the hydrothermal reaction include an autoclave.

[(B) Grinding step]
As the pulverizing means for pulverizing the porous cured body obtained in the step (A), a pulverizing medium not containing aluminum and titanium and an accommodating means are preferable.
Examples of preferable crushing means include a crusher having a material that does not contain aluminum and titanium as a material for obtaining particles having a large particle size (for example, particles having a particle size of 1 mm or more). (For example, those having a particle size of less than 1 mm) include an iron ball mill containing an iron ball as a grinding medium.
In the pulverization step, after the porous cured body is pulverized, the obtained pulverized product is classified by sieving or the like, and then the obtained two or more types of particle sizes are combined and mixed at an appropriate ratio. And an operation for obtaining a porous cured body having the above-mentioned preferred particle size distribution.

When the water purification material of the present invention is a pulverized product of lightweight cellular concrete, an example of a method for producing the water purification material is as follows.
First, 30 to 65% by mass of silica powder, 5 to 30% by mass of quicklime powder, 5 to 40% by mass of ordinary Portland cement, 0.005 to 0.1% by mass of aluminum powder (foaming agent) (the total amount above: 100%) %) To obtain a mixture.
Next, 100 parts by mass of the mixture and 60-80 parts by mass of water are mixed to obtain a slurry.
This slurry is accommodated in a box-shaped formwork having an internal dimension of 1,000 to 2,000 mm (length) x 600 to 1,000 mm (width) x 500 to 1,000 mm (height). And curing at room temperature (eg, 10 to 40 ° C.) for 3 to 10 hours.
Thereafter, the cured product in the mold is removed from the mold, and this cured product is subjected to an autoclave at a temperature of 150 to 250 ° C., a pressure of 5,000 to 15,000 hPa, and a reaction time of 5 to 15 hours. And hydrothermal reaction to obtain a porous cured body.
Part of the porous cured body is crushed using an iron crusher, and the remainder of the porous cured body is pulverized using an iron ball mill having an iron ball as a pulverization medium. Accordingly, after classification using a sieve, the obtained two or more kinds of particles having a particle size are combined at an appropriate blending ratio to obtain a water purification material comprising porous particles having a desired particle size distribution.

Other examples of the method for producing a water purification material of the present invention include: (a) a step of preparing two or more types of porous granules containing calcium silicate hydrate as a main component; and (b) two or more types of these. A step of measuring the content of each of aluminum and titanium for each of the porous particles, and (c) the content of aluminum is 10% by mass or less in terms of oxide and the content of titanium in terms of oxide Including a step of selecting and recovering 1.0% by mass or less of porous particles as a water purification material.
The types of porous particles prepared in step (a) are 2 or more, preferably 3 or more, more preferably 5 or more, and particularly preferably 8 or more.
The porous particles not recovered in the step (c) are porous particles having an aluminum content of 10% by mass or less in terms of oxide and a titanium content of 1.0% by mass or less in terms of oxide. If the aluminum content is 10% by mass or less in terms of oxide and the content of titanium is 1.0% by mass or less in terms of oxide as a whole mixture after mixing with granules, the present invention It can be used as a part of water purification material.

The method for purifying the water quality of a fishery farm according to the present invention is to spray the water purification material described above on the breeding water of a fishery farm.
The application amount of the water purification material is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, preferably 0.1 to 2 parts by mass per 100 parts by mass of the breeding water of the seafood farm. Part. When the amount is less than 0.01 parts by mass, it is difficult to sufficiently reduce the concentrations of the water-soluble phosphorus compound and ammonium ion, and the purification of water quality is insufficient. When the amount exceeds 5 parts by mass, the amount of the water purification material is large, so that the cost of water purification increases.
In the present invention, the application of the water purification material to the breeding water of the farm is preferably performed in a state where there is no seafood in the breeding water. As an example of this embodiment, before the water purification, the fish and shellfish in the breeding water of the farm are captured and put in another breeding water. Return to the breeding water. As another example, after catching and shipping fish and shellfish in the breeding water of the farm, water purification is carried out, and after completion of the water purification, fresh fish and other fish are put into the breeding water. Is mentioned.

Hereinafter, the present invention will be described by way of examples. The present invention is not limited to those described in the examples, and various embodiments can be adopted as long as they are included in the scope of the claims.
In the following examples and comparative examples, the Al (aluminum) content and the Ti (titanium) content are both oxide equivalent values.
[Example 1]
(1) Preparation of water purification material Silica stone powder (Al content: 4.6% by mass, Ti content: 0.1% by mass) 50% by mass, quick lime powder (Al content: 1.2% by mass) , Ti content: 0.0% by mass) 20% by mass, ordinary Portland cement (Al content: 5.0% by mass, Ti content: 0.1% by mass), 30% by mass, aluminum powder (foaming) Agent) 0.01% by mass (total amount: 100% by mass) was mixed to obtain a mixture.
Next, 100 parts by mass of the mixture and 70 parts by mass of water were mixed to obtain a slurry.
This slurry was accommodated in a box-shaped mold having an internal dimension of 400 mm (length) × 100 mm (width) × 100 mm (height) and cured at room temperature (20 ° C.) for 5 hours.
Thereafter, the cured body in the mold was removed from the mold, and this cured body was hydrothermally reacted in an autoclave at a temperature of 180 ° C., a pressure of 10,000 hPa, and a reaction time of 10 hours.

Part of the porous cured body after the hydrothermal reaction is pulverized using an iron crusher, and the remainder is pulverized using an iron ball mill having an iron ball as a pulverization medium, and then these pulverized products. Each of the products is classified using a sieve, and the obtained particles of a plurality of types of particle sizes are combined at an appropriate blending ratio to obtain porous particles having the following particle size distribution (tobermorite content: solid A water purification material A comprising 70% by volume and porosity of 80% by volume in the phase was obtained. In the porous particles, the aluminum content was 8.8% by mass and the titanium content was 0.1% by mass. The porosity of this porous particle was 80%. This porous granule has a chemical composition and porosity corresponding to the pulverized material of lightweight cellular concrete waste.
(Particle size distribution)
Ratio of particles having a particle size of 0.01 mm or more and less than 0.1 mm: 10% by mass
Ratio of particles having a particle size of 0.1 mm or more and less than 1.0 mm: 35% by mass
Ratio of particles having a particle size of 1.0 mm or more and less than 2.5 mm: 35% by mass
Ratio of particles having a particle size of 2.5 mm to 4.0 mm: 15% by mass
Ratio of particles having a particle size of less than 0.01 mm or more than 4.0 mm: 5% by mass

(2) Breeding experiment using medaka 100 medaka were put in a water tank storing 100 liters of water. Next, 100 g of “water purification material A” was sprayed on the water in the water tank. When March passed from the time of spraying, the killing rate and abnormal response rate of medaka were examined.
The killing rate of medaka refers to the ratio (%) obtained by dividing the number of medaka dead at the time of March by the number of medaka (100) at the time of spraying the water purification material.
Abnormal response rate of medaka is the number of medakas observed abnormal in balance, swimming behavior, breathing, body color, etc. in March, divided by the number of medakas (100) when spraying water purification material. Percentage (%).
The results are shown in Table 1.

(3) Experiment to confirm the effect of water purification Reagent (water-soluble phosphorus compound: sodium dihydrogen phosphate, ammonium salt: ammonium chloride) is added to the water collected from the pond, and phosphate ions (PO ₄ ³⁻ ) A test water having a content of 1633 mg / liter and an ammonium ion (NH ₄ ⁺ ) content of 350 mg / liter was prepared. In addition, the content rate of the phosphate ion was measured using the Toa DK company ion analyzer (product model number: IA-300). Moreover, the content rate of ammonium ion was measured using the indophenol blue colorimetric method.
Next, 10 g of “water purification material A” was sprayed from above into 1000 ml of breeding water (water temperature: 25 ° C.) in a room temperature of 25 ° C. and stirred for 1 minute.
After 60 minutes from the time of spraying, breeding water was collected and the content of phosphate ions was measured. Moreover, the breeding water was extract | collected 7 days after the time of spraying, and the content rate of ammonium ion was measured.
As a result, the phosphate ion content was reduced from 1633 mg / liter to 216 mg / liter. Further, the ammonium ion content was reduced from 350 mg / liter to 96 mg / liter.

[Example 2]
Instead of silica powder (Al content: 4.6 mass%, Ti content: 0.1 mass%), silica powder (Al content: 1.6 mass%, Ti content: 1. The experiment was performed in the same manner as in Example 1 except that 5% by mass) was used.
In the obtained water purification material B, the aluminum content was 4.2 mass% and the titanium content was 0.9 mass%. The particle size distribution and porosity of this porous granule were the same as in Example 1. Table 1 shows the results of the killing rate and response abnormality rate of medaka.
Further, when an experiment similar to “(3) Experiment for confirming the effect of water purification” in Example 1 was performed, the content of phosphate ions was reduced from 1633 mg / liter to 211 mg / liter. Further, the ammonium ion content was reduced from 350 mg / liter to 95 mg / liter.

[Comparative Example 1]
Instead of silica powder (Al content: 4.6% by mass, Ti content: 0.1% by mass), silica powder (Al content: 6.9% by mass, Ti content: 0.00%). The experiment was performed in the same manner as in Example 1 except that 9% by mass) was used.
In the obtained water purification material C, the aluminum content was 11.0% by mass and the titanium content was 0.6% by mass. The particle size distribution and porosity of this porous granule were the same as in Example 1. Table 1 shows the results of the killing rate and response abnormality rate of medaka.
[Comparative Example 2]
Instead of silica powder (Al content: 4.6 mass%, Ti content: 0.1 mass%), silica powder (Al content: 4.5 mass%, Ti content: 2. The experiment was performed in the same manner as in Example 1 except that 1% by mass) was used.
In the obtained water purification material D, the aluminum content was 8.5 mass% and the titanium content was 1.2 mass%. The particle size distribution and porosity of this porous granule were the same as in Example 1. Table 1 shows the results of the killing rate and response abnormality rate of medaka.
[Reference Example 1]
An experiment was performed in the same manner as in “(2) Breeding experiment using medaka” in Example 1 except that the water purification material was not used. Table 1 shows the results of the killing rate and response abnormality rate of medaka.

From Table 1, in Comparative Example 1 using the water purification material C in which the aluminum content exceeds 10% by mass and in Comparative Example 2 using the water purification material D in which the titanium content exceeds 1.0% by mass It can be seen that the killing rate and abnormal reaction rate of medaka are both high and are not suitable as water purification materials for fish and shellfish breeding water. On the other hand, in Examples 1 and 2 using the water purification materials A and B in which the aluminum content is 10% by mass or less and the titanium content is 1.0% by mass or less, the lethality and reaction abnormality rate of medaka Both are zero, indicating that it is suitable as a water purification material for seafood breeding water.
Further, from the results of “(3) Experiment for confirming the effect of water purification” in Examples 1 and 2, according to the water purification material of the present invention, the water-soluble phosphorus component and ammonium in the breeding water of the seafood farm It can be seen that the concentration of ions can be greatly reduced in a short period of time and the quality of the breeding water can be sufficiently purified.

Claims (10)

  It consists of porous granules containing calcium silicate hydrate as a main component, the aluminum content is 10% by mass or less in terms of oxide, and the titanium content is 1.0% by mass or less in terms of oxide. A water purification material characterized by that.   The water purification material according to claim 1, wherein the porous particles are particles having a porosity of 50% or more.   In the total amount of the porous particles, the proportion of particles having a particle size of 0.01 mm or more and less than 0.1 mm is 5 to 30% by mass, and the particle size is 0.1 mm or more and less than 1.0 mm. The proportion of particles having a particle size of 1.0 mm or more and less than 2.5 mm is 10 to 50% by mass, and the particle size is 2.5 mm or more and 4.0 mm or less. The water purification material according to claim 1 or 2, wherein the proportion of granules is 5 to 30 mass%, and the proportion of granules is less than 0.01 mm or more than 4.0 mm is 0 to 30 mass%.   The water purification material according to any one of claims 1 to 3, wherein the porous granules are made of a lightweight cellular concrete waste material.   The water purification material according to any one of claims 1 to 4, wherein the water purification material is used by being sprayed on breeding water of a fishery farm. A method for producing the water purification material according to any one of claims 1 to 5,
A reaction process of obtaining a porous cured body by causing a hydrothermal reaction by pressurizing and heating a raw material for hydrothermal reaction including a calcareous raw material, a siliceous raw material and water;
And crushing the porous cured body to obtain the water purification material, and as the hydrothermal reaction raw material, the total amount of raw materials excluding water is 100% by mass. What is claimed is: 1. A method for producing a water purification material comprising using a material having a rate of 10% by mass or less in terms of oxide and a content of titanium of 1.0% by mass or less in terms of oxide.   The method for producing a water purification material according to claim 6, wherein the pulverizing means in the pulverizing step uses a material that does not contain aluminum and titanium. A method for producing the water purification material according to any one of claims 1 to 5,
A step of preparing two or more kinds of porous granules containing calcium silicate hydrate as a main component;
For each of these two or more types of porous particles, a step of measuring each content of aluminum and titanium,
A step of selecting and recovering porous particles having an aluminum content of 10% by mass or less in terms of oxide and a titanium content of 1.0% by mass or less in terms of oxide as a water purification material; A method for producing a water purification material.   A method for purifying the water quality of a seafood farm, comprising spraying the water purification material according to any one of claims 1 to 5 on the breeding water of the seafood farm.   The method for purifying water quality of a seafood farm according to claim 9, wherein the amount of the water purification material sprayed is 0.01 to 5 parts by mass per 100 parts by mass of breeding water in the seafood farm.