WO2015008397A1 - Water quality purification material and method for purifying water quality of fish and shellfish farm - Google Patents

Water quality purification material and method for purifying water quality of fish and shellfish farm Download PDF

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Publication number
WO2015008397A1
WO2015008397A1 PCT/JP2013/074337 JP2013074337W WO2015008397A1 WO 2015008397 A1 WO2015008397 A1 WO 2015008397A1 JP 2013074337 W JP2013074337 W JP 2013074337W WO 2015008397 A1 WO2015008397 A1 WO 2015008397A1
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Prior art keywords
water
granule
mass
purification material
particle size
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PCT/JP2013/074337
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French (fr)
Japanese (ja)
Inventor
晶子 西城
神谷　隆
阿部　信彦
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太平洋セメント株式会社
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Priority to JP2015527136A priority Critical patent/JP6198826B2/en
Publication of WO2015008397A1 publication Critical patent/WO2015008397A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K63/00—Receptacles for live fish, e.g. aquaria; Terraria
    • A01K63/04—Arrangements for treating water specially adapted to receptacles for live fish
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C02F3/107—Inorganic materials, e.g. sand, silicates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/302—Nitrification and denitrification treatment
    • C02F3/303—Nitrification and denitrification treatment characterised by the nitrification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a water purification material and a water purification method for a seafood farm using the water purification material.
  • Patent Document 1 discloses 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.
  • the present invention also provides a water-soluble phosphorus component derived from food residue, seafood excrement and the like, ammonium ions, etc. even in fish farms in subtropics where the temperature of the breeding water exceeds 20 ° C., for example. It is an object of the present invention to provide a water purification material capable of significantly reducing the concentration of harmful components in breeding water in a short period of time, and a method for purification of water quality in seafood farms using the water purification material. To do.
  • the particle size is 0.01 mm or more and less than 1.0 mm and that the calcium silicate hydrate is a main component, and the particle size is 1. If porous granules containing 0 to 4.0 mm and containing calcium silicate hydrate as a main component are used in a specific blending ratio, water-soluble phosphorus components and ammonium ions in the breeding water of the farm As a result, the inventors have found that any of these concentrations can be significantly reduced in a short period of time, and have completed the present invention.
  • the present invention provides the following [1] to [8].
  • [1] Granule A having a particle size of 0.01 mm or more and less than 1.0 mm and containing calcium silicate hydrate as a main component, and a particle size of 1.0 mm or more and 4.0 mm or less, and silicic acid A porous granule B containing calcium hydrate as a main component is contained, and the ratio of the granule B in the total amount of the granule A and the granule B is 10 to 95% by mass.
  • Water purification material [2] The water purification material according to [1], wherein the water purification material is used by being sprayed on breeding water of a seafood farm.
  • breeding water means the water stored in the water storage means which can culture fishery products, such as an aquaculture pond, and any of fresh water and seawater may be sufficient as it.
  • the water purification material of the present invention has a particle size of 0.01 mm or more and less than 1.0 mm, and a granule A containing calcium silicate hydrate as a main component, and a particle size of 1.0 mm or more and 4.0 mm or less. And a porous granule B containing calcium silicate hydrate as a main component, and the ratio of the granule B in the total amount of the granule A and the granule B is 10 to 95% by mass Is.
  • the concentration of the water-soluble phosphorus component in the breeding water can be greatly reduced in a short period of time compared to the case of using only the granule B.
  • the growth of algae and the like due to the high concentration of the water-soluble phosphorus component is suppressed, and it is possible to prevent fish and shellfish diseases and mass death of fish and shellfish due to lack of oxygen in water.
  • concentration of ammonium ion can be reduced significantly in a short period of time. As a result, it is possible to prevent seafood diseases caused by high ammonium ion concentration.
  • Calcium silicate hydrate is composed of calcareous raw materials (for example, quicklime powder), siliceous raw materials (for example, silica powder), water, and other raw materials blended as necessary (for example, cement or aluminum as a foaming agent). It can be obtained by mixing a powder or the like and causing a hydrothermal reaction.
  • Examples of the calcium silicate hydrate constituting the main components of the granule A and the granule B include tobermorite, zonotlite, CSH gel, foshygite, gyrolite, and hillbrandite.
  • 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).
  • 3CaO ⁇ 2SiO 2 ⁇ Calcium silicate hydrate having a chemical composition of 3H 2 O.
  • Granule A and granule B each contain calcium silicate hydrate in a ratio of preferably 50% by volume or more, more preferably 60% by volume or more, in 100% by volume of the solid phase excluding voids.
  • the granule B is a porous granule.
  • the porosity of the granule B is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more.
  • 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 B.
  • the granule A may be either a porous granule or a non-porous granule.
  • the granule A is preferably porous. It is a granule.
  • the granule A is a non-porous granule
  • examples of the granule A include pulverized products of waste materials such as slate plates and outer wall materials.
  • the granules A and granules B are porous granules, the granules A and granules B are made of the same material (for example, the light weight described later) from the viewpoint of ease of preparation of these two types of granules. It is preferable that it is composed of aerated concrete waste material).
  • the ground material of the lightweight foam concrete (ALC) waste material is mentioned from a viewpoint of the reuse of the waste material of a building material.
  • the particles A and particles B can be obtained by sieving the obtained particles.
  • 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.
  • 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.
  • 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).
  • 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.
  • the lightweight cellular concrete can be obtained, for example, by autoclaving a raw material (for example, a hardened body made of a mixture thereof) containing quartzite powder, cement, quicklime powder, foaming agent (for example, aluminum powder), water and the like.
  • a raw material for example, a hardened body made of a mixture thereof
  • quartzite powder, cement, quicklime powder, foaming agent for example, aluminum powder
  • foaming agent for example, aluminum powder
  • the preferable particle size distribution of the granules A and B is as follows when the total amount of the granules A and B is 100% by mass. First, the granule A will be described.
  • the proportion of particles having a particle size of 0.01 mm or more and less than 0.1 mm is preferably 0 to 40% by mass, more preferably 0 to 35% by mass, and particularly preferably 0 to 30% by mass.
  • the ratio is 40% by mass or less, the overall particle size distribution of the granules A and B is not sharp (high mountain shape having a steep slope) but broad (low mountain shape having a gentle slope).
  • the proportion of particles having a particle size of 0.1 mm or more and less than 0.5 mm is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and particularly preferably 0 to 30% by mass. When the proportion is 50% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
  • the proportion of particles having a particle size of 0.5 mm or more and less than 1.0 mm is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and particularly preferably 0 to 30% by mass.
  • the proportion is 50% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
  • the proportion of particles having a particle size of 1.0 mm or more and less than 2.5 mm is preferably 0 to 70% by mass, more preferably 3 to 60% by mass, further preferably 5 to 55% by mass, and further preferably 5 to 50%. % By mass, particularly preferably 10 to 50% by mass.
  • the proportion is 70% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
  • the proportion of particles having a particle size of 2.5 mm or more and 4.0 mm or less is preferably 0 to 70% by mass, more preferably 3 to 60% by mass, still more preferably 5 to 50% by mass, and particularly preferably 5 to 45%. % By mass.
  • the proportion is 70% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
  • the water purification material of the present invention can include one or both of granules having a particle size of less than 0.01 mm and granules having a particle size of more than 4.0 mm.
  • the amount of granules having a particle size of less than 0.01 mm is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, per 100 parts by mass of the total amount of granules A and granules B. It is.
  • the amount of the granules having a particle size exceeding 4.0 mm is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less, per 100 parts by mass of the total amount of the granules A and B. It is.
  • the proportion of the granule A tends to decrease, and the portion (inside) other than the surface portion of the granule having a particle size exceeding 4.0 mm reduces the concentration of ammonium ions. Therefore, the effects of reducing the concentration of each of the water-soluble phosphorus compound and ammonium ion may be reduced.
  • the proportion of the granule B in the total amount of the granule A and the granule B is 10 to 95% by mass, preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and still more preferably 20%. It is ⁇ 70 mass%, more preferably 25 to 60 mass%, particularly preferably 25 to 55 mass%.
  • the proportion is less than 10% by mass, it is difficult to obtain a sufficient effect of reducing the concentration of ammonium ions.
  • the ratio exceeds 95% by mass, it becomes difficult to sufficiently obtain the effect of reducing the concentration of the water-soluble phosphorus compound.
  • 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 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, preferably 0.5 to 2 parts by mass per 100 parts by mass of the breeding water in the fishery farm. Part.
  • the amount is less than 0.1 parts by mass, it is difficult to sufficiently obtain the effect of reducing the concentrations of the water-soluble phosphorus compound and ammonium ion.
  • the amount exceeds 5 parts by mass the amount of the water purification material is large, so that the cost of water purification increases.
  • 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.
  • the fish and shellfish in the breeding water of the farm are captured and put in another breeding water. Return to the breeding water.
  • 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.
  • Example 1 (1) Preparation of water purification material Light-weight cellular concrete (tobermorite content: 70% by volume in the solid phase, porosity: 80% by volume) was pulverized, and the pulverized product was sieved using a sieve. Thereafter, the particle size distribution was adjusted to obtain a purification material 1 having the particle size distribution shown in Table 1.
  • the cleaning materials 1 to 13 described in Table 1 do not include any particles having a particle size of less than 0.01 mm and particles having a particle size of more than 4.0 mm.
  • a reagent water-soluble phosphorus compound: sodium dihydrogen phosphate, ammonium salt: ammonium chloride
  • phosphate ion (PO 4 3 ⁇ ) content is A test breeding water having a concentration of 1633 mg / liter and an ammonium ion (NH 4 + ) concentration of 350 mg / liter was prepared.
  • the content of phosphate ions was measured using an ion analyzer (product model: IA-300) manufactured by Toa DKK Corporation.
  • the concentration of ammonium ions was measured using an indophenol blue colorimetric method.
  • Examples 2 to 10, Comparative Examples 1 to 3 An experiment was conducted in the same manner as in Example 1 except that the purification materials 2 to 13 having the particle size distribution shown in Table 1 were used in place of the purification material 1. The above measurement results are shown in Table 1.
  • Examples 1 to 10 using the purifying materials 1 to 10 obtained by mixing the granule A and the granule B at a mass ratio of 10:90 to 90:10. Then, the content of phosphate ions was greatly reduced from 1,633 mg / liter to less than 300 mg / liter, and the concentration of ammonium ions was greatly reduced from 350 mg / liter to less than 120 mg / liter.
  • cleaning material 12 which consists only of the granule B the content rate of the phosphate ion exceeded 300 mg / liter greatly even after the process.

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  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Marine Sciences & Fisheries (AREA)
  • Animal Husbandry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Farming Of Fish And Shellfish (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

　Provided is a water quality purification material capable of quickly and significantly reducing the concentration of harmful substances in breeding water, such as water-soluble phosphorus components and ammonium ions derived from feed residues, fish and shellfish excrement, and the like, even in a fish and shellfish farm in subtropical regions or the like where the temperature of the breeding water exceeds, e.g., 20°C. A water quality purification material containing granules (A) which have a granularity of 0.01 mm or greater and less than 1.0 mm and contain calcium silicate hydrate as a main component, and porous granules (B) which have a granularity of 1.0-4.0 mm and contain calcium silicate hydrate as a main component, the proportion of the granules (B) in relation to the total amount of the granules (A) and (B) being 10-95 mass%. The granules (B) preferably comprise granules having a void ratio of 50% or greater.

Description

水質浄化材および魚介類の養殖場の水質の浄化方法Water purification material and water quality purification method for seafood farm
　本発明は、水質浄化材、および該水質浄化材を用いた魚介類の養殖場の水質の浄化方法に関する。 The present invention relates to a water purification material and a water purification method for a seafood farm using the water purification material.
　魚、エビ、カニ等の魚介類の養殖場の飼育水中において、餌の残渣や魚介類の排泄物等に由来する水溶性リン成分、アンモニウムイオン等は、飼育水の水質を低下させ、魚介類の生育に悪影響を及ぼす。
　そのため、飼育水から水溶性リン成分やアンモニウムイオンを除去するための種々の方法が、従来、提案されている。
　例えば、特許文献１に、５０～９０％の空隙率を有する珪酸カルシウムを主たる構成物とする多孔質浄化剤を水槽中に浸漬することを特徴とする水槽の浄化方法が、記載されている。この文献には、多孔質浄化材の製造例として、ＣＳＨゲル浄化材、トバモライト浄化材、およびゾノトライト浄化材の各製造例が記載されている。これら製造例の浄化材は、いずれも、５～１０ｍｍの粒径を有するものである。また、この文献には、上記浄化方法によれば、養魚用水槽において、有機物、アンモニア、リンなど、魚類の生息に不都合な物質が除去され、清澄な状態が長時間に亘って維持されることが記載されている。 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 discloses 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. In this document, as examples of the production of the porous purification material, respective production examples of the CSH gel purification material, the tobermorite purification material, and the zonotlite purification material are described. All of the purification materials in these production examples have a particle size of 5 to 10 mm. Further, according to this document, according to the purification method described above, in the fish tank, organic substances, ammonia, phosphorus, and other substances unfavorable for fish habitat are removed, and a clear state is maintained for a long time. Is described.
特開昭６３－４２７８８号公報JP 63-42788 A
　夏季の日本国内や、東南アジア等の亜熱帯または熱帯の地域にて、養殖池等で魚介類を養殖する場合、飼育水の水質の適切な管理を行わないと、餌の残渣や魚介類の排泄物等に由来する水溶性リン成分、アンモニウムイオン等の濃度が高くなって、飼育水中に微生物、藻等が大量に増殖し、魚介類が病気にかかったり死んだりすることがある。
　本発明は、飼育水の水温が例えば２０℃を超えるような亜熱帯の地域等における魚介類の養殖場においても、餌の残渣や魚介類の排泄物等に由来する水溶性リン成分、アンモニウムイオン等の、飼育水中の有害成分の濃度を、短期間で大幅に低減させることのできる水質浄化材、および該水質浄化材を用いた魚介類の養殖場の水質の浄化方法を提供することを目的とする。 When seafood is cultivated in aquaculture ponds, etc., in Japan in the summer or in subtropical or tropical areas such as Southeast Asia, food residues and seafood excrement must be prepared unless the water quality of the breeding water is properly managed. Concentrations of water-soluble phosphorus components, ammonium ions, etc. derived from the sea urchins, etc. may cause a large amount of microorganisms, algae, etc. to grow in the breeding water, and fish and shellfish may get sick or die.
The present invention also provides a water-soluble phosphorus component derived from food residue, seafood excrement and the like, ammonium ions, etc. even in fish farms in subtropics where the temperature of the breeding water exceeds 20 ° C., for example. It is an object of the present invention to provide a water purification material capable of significantly reducing the concentration of harmful components in breeding water in a short period of time, and a method for purification of water quality in seafood farms using the water purification material. To do.
　本発明者は、上記課題を解決するために鋭意検討した結果、粒度が０．０１ｍｍ以上、１．０ｍｍ未満であり、かつ珪酸カルシウム水和物を主成分として含む粒体と、粒度が１．０ｍｍ以上、４．０ｍｍ以下であり、かつ珪酸カルシウム水和物を主成分として含む多孔質の粒体を、特定の配合割合で併用すれば、養殖場の飼育水中の水溶性リン成分とアンモニウムイオンのいずれの濃度についても、短期間で大幅に低減させることができることを見出し、本発明を完成した。 As a result of intensive studies in order to solve the above problems, the present inventor has found that the particle size is 0.01 mm or more and less than 1.0 mm and that the calcium silicate hydrate is a main component, and the particle size is 1. If porous granules containing 0 to 4.0 mm and containing calcium silicate hydrate as a main component are used in a specific blending ratio, water-soluble phosphorus components and ammonium ions in the breeding water of the farm As a result, the inventors have found that any of these concentrations can be significantly reduced in a short period of time, and have completed the present invention.
　すなわち、本発明は、以下の［１］～［８］を提供するものである。
［１］　粒度が０．０１ｍｍ以上、１．０ｍｍ未満であり、かつ珪酸カルシウム水和物を主成分として含む粒体Ａ、および、粒度が１．０ｍｍ以上、４．０ｍｍ以下であり、かつ珪酸カルシウム水和物を主成分として含む多孔質の粒体Ｂを含み、かつ、粒体Ａと粒体Ｂの合計量中の粒体Ｂの割合が１０～９５質量％であることを特徴とする水質浄化材。
［２］　上記水質浄化材は、魚介類の養殖場の飼育水に散布して用いるためのものである、上記［１］に記載の水質浄化材。
［３］　粒体Ｂが、５０％以上の空隙率を有する粒体からなる、上記［１］又は［２］に記載の水質浄化材。
［４］　粒体Ａと粒体Ｂの合計量中、粒度が０．０１ｍｍ以上、０．１ｍｍ未満の粒体の割合が、０～４０質量％であり、粒度が０．１ｍｍ以上、０．５ｍｍ未満の粒体の割合が、０～５０質量％であり、粒度が０．５ｍｍ以上、１．０ｍｍ未満の粒体の割合が、０～５０質量％であり、粒度が１．０ｍｍ以上、２．５ｍｍ未満の粒体の割合が、０～７０質量％であり、粒度が２．５ｍｍ以上、４．０ｍｍ以下の粒体の割合が、０～７０質量％である、上記［１］～［３］のいずれかに記載の水質浄化材。
［５］　粒体Ａおよび粒体Ｂが、軽量気泡コンクリートの廃材からなる上記［１］～［４］のいずれかに記載の水質浄化材。
［６］　上記［１］～［５］のいずれかに記載の水質浄化材を、魚介類の養殖場の飼育水に散布することを特徴とする魚介類の養殖場の水質の浄化方法。
［７］　上記水質浄化材の散布量が、上記飼育水１００質量部当たり、０．１～５質量部である、上記［６］に記載の魚介類の養殖場の水質の浄化方法。
［８］　上記飼育水への上記水質浄化材の散布が、上記飼育水に魚介類が存在しない状態で行われる、上記［６］又は［７］に記載の魚介類の養殖場の水質の浄化方法。 That is, the present invention provides the following [1] to [8].
[1] Granule A having a particle size of 0.01 mm or more and less than 1.0 mm and containing calcium silicate hydrate as a main component, and a particle size of 1.0 mm or more and 4.0 mm or less, and silicic acid A porous granule B containing calcium hydrate as a main component is contained, and the ratio of the granule B in the total amount of the granule A and the granule B is 10 to 95% by mass. Water purification material.
[2] The water purification material according to [1], wherein the water purification material is used by being sprayed on breeding water of a seafood farm.
[3] The water purification material according to [1] or [2], wherein the granule B is composed of a granule having a porosity of 50% or more.
[4] In the total amount of the granule A and the granule B, the proportion of the granule having a particle size of 0.01 mm or more and less than 0.1 mm is 0 to 40% by mass, the particle size is 0.1 mm or more, and 0.0. The proportion of particles less than 5 mm is 0 to 50% by mass, the particle size is 0.5 mm or more, the proportion of particles less than 1.0 mm is 0 to 50% by mass, and the particle size is 1.0 mm or more. [1] to [1], wherein the proportion of granules having a particle size of less than 2.5 mm is 0 to 70 mass%, and the proportion of granules having a particle size of 2.5 mm to 4.0 mm is 0 to 70 mass%. [3] The water purification material according to any one of [3].
[5] The water purification material according to any one of the above [1] to [4], wherein the granule A and the granule B are made of lightweight cellular concrete waste.
[6] 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.
[7] The method for purifying water quality of a fishery product farm according to [6], wherein the amount of sprayed water purification material is 0.1 to 5 parts by mass per 100 parts by mass of the breeding water.
[8] Purification of the water quality of the seafood farm according to [6] or [7], wherein the water purification material is sprayed on the breeding water in a state where no seafood is present in the breeding water. Method.
　本発明によれば、飼育水の水温が例えば２０℃を超えるような亜熱帯の地域等における魚介類の養殖場においても、餌の残渣や魚介類の排泄物等に由来する水溶性リン成分（例えば、リン酸塩）、アンモニウムイオン等の、飼育水中の有害成分の濃度を、短期間で大幅に低減させることができる。
　そのため、養殖場の飼育水中に微生物、藻等が大量に増殖して、養殖中の魚、エビ、カニ等の魚介類が病気にかかったり死んだりする事態を、水温が低い飼育水においてのみならず、水温が高い飼育水（例えば、２０℃を超える水温の水）においても、効果的に防止することができる。
　なお、本明細書中、飼育水とは、養殖池等の、魚介類を養殖可能な水貯留手段の中に貯留された水を意味し、淡水と海水のいずれであってもよい。 According to the present invention, even in a seafood farm in a subtropical region where the temperature of breeding water exceeds 20 ° C., for example, water-soluble phosphorus components derived from food residues, seafood excrement, etc. (for example, , Phosphate), ammonium ions, and other harmful components in the breeding water can be greatly reduced in a short period of time.
Therefore, the situation where fish, shrimp, crab and other fish and shellfish under cultivation grow ill and die in large quantities in the aquaculture farm's breeding water can only be observed in breeding water with low water temperature. In addition, even in breeding water having a high water temperature (for example, water having a water temperature exceeding 20 ° C.), it can be effectively prevented.
In addition, in this specification, breeding water means the water stored in the water storage means which can culture fishery products, such as an aquaculture pond, and any of fresh water and seawater may be sufficient as it.
　本発明の水質浄化材は、粒度が０．０１ｍｍ以上、１．０ｍｍ未満であり、かつ珪酸カルシウム水和物を主成分として含む粒体Ａ、および、粒度が１．０ｍｍ以上、４．０ｍｍ以下であり、かつ珪酸カルシウム水和物を主成分として含む多孔質の粒体Ｂを含み、かつ、粒体Ａと粒体Ｂの合計量中の粒体Ｂの割合が１０～９５質量％であるものである。
　本発明では、粒体Ａを用いることによって、粒体Ｂのみを用いる場合に比べて、飼育水中の水溶性リン成分の濃度を短期間で大幅に低減させることができる。その結果、水溶性リン成分の濃度が高いことによる藻等の増殖が抑制され、魚介類の病気や、水中の酸素不足に起因する魚介類の大量死などを未然に防止することができる。
　また、本発明では、粒体Ｂを用いることによって、粒体Ａのみを用いる場合に比べて、アンモニウムイオンの濃度を短期間で大幅に低減させることができる。その結果、アンモニウムイオンの濃度が高いことによる魚介類の病気などを未然に防止することができる。
　珪酸カルシウム水和物は、石灰質原料（例えば、生石灰粉末）、珪酸質原料（例えば、珪石粉末）、水、および必要に応じて配合される他の原料（例えば、セメントや、発泡剤としてのアルミニウム粉末等）を混合し、水熱反応を生じさせることによって得ることができる。 The water purification material of the present invention has a particle size of 0.01 mm or more and less than 1.0 mm, and a granule A containing calcium silicate hydrate as a main component, and a particle size of 1.0 mm or more and 4.0 mm or less. And a porous granule B containing calcium silicate hydrate as a main component, and the ratio of the granule B in the total amount of the granule A and the granule B is 10 to 95% by mass Is.
In the present invention, by using the granule A, the concentration of the water-soluble phosphorus component in the breeding water can be greatly reduced in a short period of time compared to the case of using only the granule B. As a result, the growth of algae and the like due to the high concentration of the water-soluble phosphorus component is suppressed, and it is possible to prevent fish and shellfish diseases and mass death of fish and shellfish due to lack of oxygen in water.
Moreover, in this invention, compared with the case where only the granule A is used by using the granule B, the density | concentration of ammonium ion can be reduced significantly in a short period of time. As a result, it is possible to prevent seafood diseases caused by high ammonium ion concentration.
Calcium silicate hydrate is composed of calcareous raw materials (for example, quicklime powder), siliceous raw materials (for example, silica powder), water, and other raw materials blended as necessary (for example, cement or aluminum as a foaming agent). It can be obtained by mixing a powder or the like and causing a hydrothermal reaction.
　粒体Ａおよび粒体Ｂの主成分を構成する珪酸カルシウム水和物の例としては、トバモライト、ゾノトライト、ＣＳＨゲル、フォシャジャイト、ジャイロライト、ヒレブランダイト等が挙げられる。
　このうち、トバモライトは、結晶性の珪酸カルシウム水和物であり、Ｃａ5・（Ｓｉ6Ｏ18Ｈ2）・４Ｈ2Ｏ（板状の形態）、Ｃａ5・（Ｓｉ6Ｏ18Ｈ2）（板状の形態）、Ｃａ5・（Ｓｉ6Ｏ18Ｈ2）・８Ｈ2Ｏ（繊維状の形態）等の化学組成を有するものである。
　ゾノトライトは、結晶性の珪酸カルシウム水和物であり、Ｃａ6・（Ｓｉ6Ｏ17）・（ＯＨ）2（繊維状の形態）等の化学組成を有するものである。
　ＣＳＨゲルは、αＣａＯ・βＳｉＯ2・γＨ2Ｏ（ただし、α／β＝０．７～２．３、γ／β＝１．２～２．７である。）、例えば、３ＣａＯ・２ＳｉＯ2・３Ｈ2Ｏの化学組成を有する珪酸カルシウム水和物である。
　粒体Ａおよび粒体Ｂは、各々、空隙部分を除く固相１００体積％中、好ましくは５０体積％以上、より好ましくは６０体積％以上の割合で、珪酸カルシウム水和物を含む。 Examples of the calcium silicate hydrate constituting the main components of the granule A and the granule B include tobermorite, zonotlite, CSH gel, foshygite, gyrolite, and hillbrandite.
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.
Granule A and granule B each contain calcium silicate hydrate in a ratio of preferably 50% by volume or more, more preferably 60% by volume or more, in 100% by volume of the solid phase excluding voids.
　粒体Ｂは、多孔質の粒体である。粒体Ｂが多孔質であることによって、粒体Ｂの表面の空隙に微生物が担持され易くなり、微生物によるアンモニウムイオンの硝化が促進される。
　粒体Ｂの空隙率は、好ましくは５０％以上、より好ましくは６０％以上、特に好ましくは７０％以上である。該空隙率の上限値は、特に限定されないが、粒体Ｂの機械的強度（例えば、圧縮強度）を確保する観点から、好ましくは９０％である。
　粒体Ａは、多孔質の粒体と非多孔質の粒体のいずれでもよいが、水溶性リン成分とカルシウムイオンの反応による不溶性カルシウム含有物質の生成を促進する観点から、好ましくは、多孔質の粒体である。
　粒体Ａが非多孔質の粒体である場合、粒体Ａの例としては、スレート板、外壁材等の廃材の粉砕物が挙げられる。
　粒体Ａおよび粒体Ｂが共に多孔質の粒体である場合、粒体Ａおよび粒体Ｂは、これら２種の粒体の調製の容易性の観点から、同じ材料（例えば、後述の軽量気泡コンクリートの廃材）によって構成することが好ましい。 The granule B is a porous granule. When the granule B is porous, microorganisms are easily carried in the voids on the surface of the granule B, and nitrification of ammonium ions by the microorganisms is promoted.
The porosity of the granule B is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more. 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 B.
The granule A may be either a porous granule or a non-porous granule. From the viewpoint of promoting the production of an insoluble calcium-containing substance by the reaction between a water-soluble phosphorus component and calcium ions, the granule A is preferably porous. It is a granule.
When the granule A is a non-porous granule, examples of the granule A include pulverized products of waste materials such as slate plates and outer wall materials.
When both the granules A and the granules B are porous granules, the granules A and granules B are made of the same material (for example, the light weight described later) from the viewpoint of ease of preparation of these two types of granules. It is preferable that it is composed of aerated concrete waste material).
　粒体Ａおよび粒体Ｂの好ましい例としては、建築資材の廃材の再利用の観点から、軽量気泡コンクリート（ＡＬＣ）の廃材の粉砕物が挙げられる。軽量気泡コンクリートの廃材を粉砕した後、得られた粒体を篩分けすることによって、粒体Ａおよび粒体Ｂを得ることができる。なお、本明細書中、廃材とは、製品の廃材、製品の製造過程で生じる端材、工場内の試製品等を広く含むものである。また、廃材の粉砕物とは、１．０ｍｍ未満の粒度を有する粒体と、１．０ｍｍ以上の粒度を有する粒体の両方を意味する。
　軽量気泡コンクリートは、Ｃａ5・（Ｓｉ6Ｏ18Ｈ2）・４Ｈ2Ｏの化学式で表されるトバモライト、および、未反応の珪石からなるものであり、８０体積％程度の空隙率を有する。
　本明細書中、空隙率とは、粒体（例えば、軽量気泡コンクリートからなる粒体）の体積全体中に占めるすべての空隙の体積の総和の割合をいう。ここで、空隙とは、粒体の外部の空間と連通する連続的な空隙と、粒体の外部の空間と連通せずに粒体の内部にのみ形成される非連続的な空隙の両方を意味する。
　軽量気泡コンクリート中のトバモライトの割合は、コンクリートの内部の空隙部分を除く固相の全体を１００体積％として、６５～８０体積％程度である。
　軽量気泡コンクリートは、例えば、珪石粉末、セメント、生石灰粉末、発泡剤（例えば、アルミニウム粉末）、水等を含む原料（例えば、これらの混合物からなる硬化体）をオートクレーブ養生することによって得ることができる。なお、軽量気泡コンクリートの製造例は、上述の特許文献１にも記載されている。 As a preferable example of the granular material A and the granular material B, the ground material of the lightweight foam concrete (ALC) waste material is mentioned from a viewpoint of the reuse of the waste material of a building material. After pulverizing the lightweight cellular concrete waste, the particles A and particles B can be obtained by sieving the obtained particles. 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.
The lightweight cellular concrete can be obtained, for example, by autoclaving a raw material (for example, a hardened body made of a mixture thereof) containing quartzite powder, cement, quicklime powder, foaming agent (for example, aluminum powder), water and the like. . In addition, the manufacture example of lightweight cellular concrete is also described in the above-mentioned patent document 1.
　本発明において、粒体Ａおよび粒体Ｂの好ましい粒度分布は、粒体Ａと粒体Ｂの合計量を１００質量％とした場合、次のとおりである。
　まず、粒体Ａについて説明する。
　粒度が０．０１ｍｍ以上、０．１ｍｍ未満の粒体の割合は、好ましくは０～４０質量％、より好ましくは０～３５質量％、特に好ましくは０～３０質量％である。該割合が４０質量％以下であると、粒体Ａと粒体Ｂの全体の粒度分布がシャープ（急な傾斜を有する高い山の形）でなく、ブロード（緩やかな傾斜を有する低い山の形）になる傾向があるので、水溶性リン化合物の濃度の低減効果とアンモニウムイオンの濃度の低減効果のバランスがより良好になる。
　粒度が０．１ｍｍ以上、０．５ｍｍ未満の粒体の割合は、好ましくは０～５０質量％、より好ましくは０～４０質量％、特に好ましくは０～３０質量％である。該割合が５０質量％以下であると、全体の粒度分布がブロードになる傾向があるので、水溶性リン化合物とアンモニウムイオンの各濃度の低減効果のバランスがより良好になる。
　粒度が０．５ｍｍ以上、１．０ｍｍ未満の粒体の割合は、好ましくは０～５０質量％、より好ましくは０～４０質量％、特に好ましくは０～３０質量％である。該割合が５０質量％以下であると、全体の粒度分布がブロードになる傾向があるので、水溶性リン化合物とアンモニウムイオンの各濃度の低減効果のバランスがより良好になる。 In the present invention, the preferable particle size distribution of the granules A and B is as follows when the total amount of the granules A and B is 100% by mass.
First, the granule A will be described.
The proportion of particles having a particle size of 0.01 mm or more and less than 0.1 mm is preferably 0 to 40% by mass, more preferably 0 to 35% by mass, and particularly preferably 0 to 30% by mass. When the ratio is 40% by mass or less, the overall particle size distribution of the granules A and B is not sharp (high mountain shape having a steep slope) but broad (low mountain shape having a gentle slope). ), 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 0.5 mm is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and particularly preferably 0 to 30% by mass. When the proportion is 50% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
The proportion of particles having a particle size of 0.5 mm or more and less than 1.0 mm is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and particularly preferably 0 to 30% by mass. When the proportion is 50% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
　次に、粒体Ｂについて説明する。
　粒度が１．０ｍｍ以上、２．５ｍｍ未満の粒体の割合は、好ましくは０～７０質量％、より好ましくは３～６０質量％、さらに好ましくは５～５５質量％、さらに好ましくは５～５０質量％、特に好ましくは１０～５０質量％である。該割合が７０質量％以下であると、全体の粒度分布がブロードになる傾向があるので、水溶性リン化合物とアンモニウムイオンの各濃度の低減効果のバランスがより良好になる。
　粒度が２．５ｍｍ以上、４．０ｍｍ以下の粒体の割合は、好ましくは０～７０質量％、より好ましくは３～６０質量％、さらに好ましくは５～５０質量％、特に好ましくは５～４５質量％である。該割合が７０質量％以下であると、全体の粒度分布がブロードになる傾向があるので、水溶性リン化合物とアンモニウムイオンの各濃度の低減効果のバランスがより良好になる。 Next, the granule B will be described.
The proportion of particles having a particle size of 1.0 mm or more and less than 2.5 mm is preferably 0 to 70% by mass, more preferably 3 to 60% by mass, further preferably 5 to 55% by mass, and further preferably 5 to 50%. % By mass, particularly preferably 10 to 50% by mass. When the proportion is 70% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
The proportion of particles having a particle size of 2.5 mm or more and 4.0 mm or less is preferably 0 to 70% by mass, more preferably 3 to 60% by mass, still more preferably 5 to 50% by mass, and particularly preferably 5 to 45%. % By mass. When the proportion is 70% by mass or less, the overall particle size distribution tends to be broad, and the balance of the reduction effect of each concentration of the water-soluble phosphorus compound and ammonium ion becomes better.
　本発明の水質浄化材は、粒度が０．０１ｍｍ未満の粒体と、粒度が４．０ｍｍを超える粒体のいずれか一方または両方を含むことができる。
　粒度が０．０１ｍｍ未満の粒体の量は、粒体Ａと粒体Ｂの合計量１００質量部当たり、好ましくは２０質量部以下、より好ましくは１０質量部以下、特に好ましくは５質量部以下である。該量が２０質量部を超えると、粒体Ａよりも粒度が小さい粒子の量が多いため、本発明の水質浄化材を飼育水に散布したときに、水が濁っている期間が長くなり、その間、魚介類を飼育水に入れることができないなどの問題が生じうる。
　粒度が４．０ｍｍを超える粒体の量は、粒体Ａと粒体Ｂの合計量１００質量部当たり、好ましくは３０質量部以下、より好ましくは２０質量部以下、特に好ましくは１０質量部以下である。該量が３０質量部を超えると、粒体Ａの割合が小さくなる傾向があり、また、粒度が４．０ｍｍを超える粒体の表面部分以外の部分（内部）が、アンモニウムイオンの濃度の低減に貢献しないので、水溶性リン化合物およびアンモニウムイオンの各濃度の低減効果が共に低下する可能性がある。 The water purification material of the present invention can include one or both of granules having a particle size of less than 0.01 mm and granules having a particle size of more than 4.0 mm.
The amount of granules having a particle size of less than 0.01 mm is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, per 100 parts by mass of the total amount of granules A and granules B. It is. When the amount exceeds 20 parts by mass, since the amount of particles having a smaller particle size than the granule A is large, when the water purification material of the present invention is sprayed on the breeding water, the period during which the water is cloudy becomes longer, Meanwhile, problems such as being unable to put seafood into the breeding water can occur.
The amount of the granules having a particle size exceeding 4.0 mm is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less, per 100 parts by mass of the total amount of the granules A and B. It is. When the amount exceeds 30 parts by mass, the proportion of the granule A tends to decrease, and the portion (inside) other than the surface portion of the granule having a particle size exceeding 4.0 mm reduces the concentration of ammonium ions. Therefore, the effects of reducing the concentration of each of the water-soluble phosphorus compound and ammonium ion may be reduced.
　本発明において、粒体Ａと粒体Ｂの合計量中の粒体Ｂの割合は、１０～９５質量％、好ましくは１０～９０質量％、より好ましくは１５～８０質量％、さらに好ましくは２０～７０質量％、さらに好ましくは２５～６０質量％、特に好ましくは２５～５５質量％である。該割合が１０質量％未満では、アンモニウムイオンの濃度の低減効果を十分に得ることが困難になる。該割合が９５質量％を超えると、水溶性リン化合物の濃度の低減効果を十分に得ることが困難になる。 In the present invention, the proportion of the granule B in the total amount of the granule A and the granule B is 10 to 95% by mass, preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and still more preferably 20%. It is ˜70 mass%, more preferably 25 to 60 mass%, particularly preferably 25 to 55 mass%. When the proportion is less than 10% by mass, it is difficult to obtain a sufficient effect of reducing the concentration of ammonium ions. When the ratio exceeds 95% by mass, it becomes difficult to sufficiently obtain the effect of reducing the concentration of the water-soluble phosphorus compound.
　本発明の魚介類の養殖場の水質の浄化方法は、上述の水質浄化材を、魚介類の養殖場の飼育水に散布するものである。
　水質浄化材の散布量は、魚介類の養殖場の飼育水１００質量部当たり、好ましくは０．１～５質量部、より好ましくは０．３～３質量部、好ましくは０．５～２質量部である。該量が０．１質量部未満では、水溶性リン化合物およびアンモニウムイオンの各濃度の低減効果を十分に得ることが困難となる。該量が５質量部を超えると、水質浄化材の量が大きいために、水質浄化のコストが増大する。
　本発明において、養殖場の飼育水への水質浄化材の散布は、好ましくは、飼育水に魚介類が存在しない状態で行われる。この実施形態の一例としては、水質浄化の前に、養殖場の飼育水の中の魚介類を捕獲して、別の飼育水の中に入れ、水質浄化が終了した後に、魚介類を元の飼育水の中に戻すことが挙げられる。他の例としては、養殖場の飼育水の中の魚介類を捕獲して出荷した後に、水質浄化を行い、水質浄化の終了後に、魚介類の稚魚等を新たに飼育水の中に入れることが挙げられる。 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 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, preferably 0.5 to 2 parts by mass per 100 parts by mass of the breeding water in the fishery farm. Part. When the amount is less than 0.1 parts by mass, it is difficult to sufficiently obtain the effect of reducing the concentrations of the water-soluble phosphorus compound and ammonium ion. 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.
　以下、実施例によって本発明を説明する。本発明は、実施例に記載のものに限定されず、特許請求の範囲に包含される限りにおいて、種々の実施形態を採ることができる。
［実施例１］
（１）水質浄化材の調製
　軽量気泡コンクリート（トバモライトの含有率：固相中の割合で７０体積％、空隙率：８０体積％）を粉砕した後、篩を用いて粉砕物を篩分けした。その後、粒度分布を調整して、表１に示す粒度分布を有する浄化材１を得た。なお、表１に記載した浄化材１～１３は、いずれも、０．０１ｍｍ未満の粒度を有する粒体、および、４．０ｍｍを超える粒度を有する粒体を含まない。
（２）飼育水の調製
　池から採取した水に試薬（水溶性リン化合物：リン酸二水素ナトリウム、アンモニウム塩：塩化アンモニウム）を添加して、リン酸イオン（ＰＯ4 3－）の含有率が１６３３ｍｇ／リットルでかつアンモニウムイオン（ＮＨ4 ＋）の濃度が３５０ｍｇ／リットルである試験用の飼育水を調製した。なお、リン酸イオンの含有率は、東亜ディーケーケー社のイオン分析計（製品の型番：ＩＡ－３００）を用いて測定した。また、アンモニウムイオンの濃度は、インドフェノール青比色法を用いて測定した。
（３）飼育水への水質浄化材の散布
　室温２５℃の室内で、１リットルの飼育水（水温：２５℃）に、上方から「水質浄化材１」１０ｇを散布した後、１分間撹拌した。
　散布した時から６０分後に、飼育水を採取して、リン酸イオンの含有率を測定した。また、散布した時から７日後に、飼育水を採取して、アンモニウムイオンの濃度を測定した。これらの測定値を、以下、処理後の値と称する。 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.
[Example 1]
(1) Preparation of water purification material Light-weight cellular concrete (tobermorite content: 70% by volume in the solid phase, porosity: 80% by volume) was pulverized, and the pulverized product was sieved using a sieve. Thereafter, the particle size distribution was adjusted to obtain a purification material 1 having the particle size distribution shown in Table 1. The cleaning materials 1 to 13 described in Table 1 do not include any particles having a particle size of less than 0.01 mm and particles having a particle size of more than 4.0 mm.
(2) Preparation of breeding water A reagent (water-soluble phosphorus compound: sodium dihydrogen phosphate, ammonium salt: ammonium chloride) is added to the water collected from the pond so that the phosphate ion (PO 4 3− ) content is A test breeding water having a concentration of 1633 mg / liter and an ammonium ion (NH 4 + ) concentration of 350 mg / liter was prepared. The content of phosphate ions was measured using an ion analyzer (product model: IA-300) manufactured by Toa DKK Corporation. The concentration of ammonium ions was measured using an indophenol blue colorimetric method.
(3) Application of water purification material to breeding water After spraying 10 g of “water purification material 1” from above into 1 liter of breeding water (water temperature: 25 ° C.) in a room temperature of 25 ° C., the mixture was 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 spraying, and the density | concentration of ammonium ion was measured. These measured values are hereinafter referred to as processed values.
［実施例２～１０、比較例１～３］
　浄化材１に代えて、表１に示す粒度分布を有する浄化材２～１３を用いた以外は実施例１と同様にして、実験した。
　以上の測定結果を表１に示す。 [Examples 2 to 10, Comparative Examples 1 to 3]
An experiment was conducted in the same manner as in Example 1 except that the purification materials 2 to 13 having the particle size distribution shown in Table 1 were used in place of the purification material 1.
The above measurement results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すとおり、粒体Ａと粒体Ｂを１０：９０～９０：１０の質量比で混合してなる浄化材１～１０（本発明の水質浄化材）を用いた実施例１～１０では、リン酸イオンの含有率が、１６３３ｍｇ／リットルから、３００ｍｇ／リットル未満に大きく減少し、かつ、アンモニウムイオンの濃度が、３５０ｍｇ／リットルから、１２０ｍｇ／リットル未満に大きく減少した。
　一方、粒体Ａのみからなる浄化材１１を用いた比較例１、および、粒体Ａと粒体Ｂを９５：５の質量比で混合してなる浄化材１３を用いた比較例３では、アンモニウムイオンの濃度が、処理後であっても、１２０ｍｇ／リットルを大きく超えていた。
　また、粒体Ｂのみからなる浄化材１２を用いた比較例２では、リン酸イオンの含有率が、処理後であっても、３００ｍｇ／リットルを大きく超えていた。 As shown in Table 1, Examples 1 to 10 using the purifying materials 1 to 10 (water purification material of the present invention) obtained by mixing the granule A and the granule B at a mass ratio of 10:90 to 90:10. Then, the content of phosphate ions was greatly reduced from 1,633 mg / liter to less than 300 mg / liter, and the concentration of ammonium ions was greatly reduced from 350 mg / liter to less than 120 mg / liter.
On the other hand, in Comparative Example 1 using the purification material 11 consisting only of the granular material A and Comparative Example 3 using the purification material 13 obtained by mixing the granular material A and the granular material B at a mass ratio of 95: 5, The concentration of ammonium ions greatly exceeded 120 mg / liter even after treatment.
Moreover, in the comparative example 2 using the purification | cleaning material 12 which consists only of the granule B, the content rate of the phosphate ion exceeded 300 mg / liter greatly even after the process.

Claims (8)

  1. 　粒度が０．０１ｍｍ以上、１．０ｍｍ未満であり、かつ珪酸カルシウム水和物を主成分として含む粒体Ａ、および、粒度が１．０ｍｍ以上、４．０ｍｍ以下であり、かつ珪酸カルシウム水和物を主成分として含む多孔質の粒体Ｂを含み、かつ、粒体Ａと粒体Ｂの合計量中の粒体Ｂの割合が１０～９５質量％であることを特徴とする水質浄化材。 Granule A having a particle size of 0.01 mm or more and less than 1.0 mm and containing calcium silicate hydrate as a main component, and a particle size of 1.0 mm or more and 4.0 mm or less, and calcium silicate hydration A water purification material comprising a porous granule B containing a substance as a main component, and the proportion of the granule B in the total amount of the granule A and the granule B is 10 to 95% by mass .
  2. 　上記水質浄化材は、魚介類の養殖場の飼育水に散布して用いるためのものである請求項１に記載の水質浄化材。 The water purification material according to claim 1, wherein the water purification material is used by being sprayed on the breeding water of a seafood farm.
  3. 　粒体Ｂが、５０％以上の空隙率を有する粒体からなる請求項１又は２に記載の水質浄化材。 The water purification material according to claim 1 or 2, wherein the granule B comprises a granule having a porosity of 50% or more.
  4. 　粒体Ａと粒体Ｂの合計量中、粒度が０．０１ｍｍ以上、０．１ｍｍ未満の粒体の割合が、０～４０質量％であり、粒度が０．１ｍｍ以上、０．５ｍｍ未満の粒体の割合が、０～５０質量％であり、粒度が０．５ｍｍ以上、１．０ｍｍ未満の粒体の割合が、０～５０質量％であり、粒度が１．０ｍｍ以上、２．５ｍｍ未満の粒体の割合が、０～７０質量％であり、粒度が２．５ｍｍ以上、４．０ｍｍ以下の粒体の割合が、０～７０質量％である請求項１～３のいずれか１項に記載の水質浄化材。 In the total amount of the granule A and the granule B, the proportion of the granule having a particle size of 0.01 mm or more and less than 0.1 mm is 0 to 40% by mass, and the particle size is 0.1 mm or more and less than 0.5 mm. The proportion of granules is 0-50% by mass, the proportion of granules having a particle size of 0.5 mm or more and less than 1.0 mm is 0-50% by mass, the particle size is 1.0 mm or more, 2.5 mm. The proportion of granules having a particle size of less than 0 to 70% by mass and the proportion of granules having a particle size of 2.5 mm or greater and 4.0 mm or less is 0 to 70% by mass. The water purification material as described in the paragraph.
  5. 　粒体Ａおよび粒体Ｂが、軽量気泡コンクリートの廃材からなる請求項１～４のいずれか１項に記載の水質浄化材。 The water purification material according to any one of claims 1 to 4, wherein the granule A and the granule B are made of a lightweight cellular concrete waste material.
  6. 　請求項１～５のいずれか１項に記載の水質浄化材を、魚介類の養殖場の飼育水に散布することを特徴とする魚介類の養殖場の水質の浄化方法。 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.
  7. 　上記水質浄化材の散布量が、魚介類の養殖場の飼育水１００質量部当たり、０．１～５質量部である請求項６に記載の魚介類の養殖場の水質の浄化方法。 The method for purifying the water quality of a seafood farm according to claim 6, wherein the amount of the water purification material sprayed is 0.1 to 5 parts by mass per 100 parts by mass of the breeding water of the seafood farm.
  8. 　上記養殖場の飼育水への上記水質浄化材の散布が、上記飼育水に魚介類が存在しない状態で行われる請求項６又は７に記載の魚介類の養殖池の水質の浄化方法。 The method for purifying the water quality of a fishery pond according to claim 6 or 7, wherein the water purification material is sprayed onto the breeding water of the aquaculture farm in a state where there is no seafood in the breeding water.
PCT/JP2013/074337 2013-07-16 2013-09-10 Water quality purification material and method for purifying water quality of fish and shellfish farm WO2015008397A1 (en)

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