JP2020157247A - Water purification material - Google Patents
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- JP2020157247A JP2020157247A JP2019060822A JP2019060822A JP2020157247A JP 2020157247 A JP2020157247 A JP 2020157247A JP 2019060822 A JP2019060822 A JP 2019060822A JP 2019060822 A JP2019060822 A JP 2019060822A JP 2020157247 A JP2020157247 A JP 2020157247A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000000463 material Substances 0.000 title claims abstract description 110
- 238000000746 purification Methods 0.000 title claims abstract description 73
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000378 calcium silicate Substances 0.000 claims abstract description 37
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 37
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010457 zeolite Substances 0.000 claims abstract description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 33
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 230000037429 base substitution Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 16
- 238000009360 aquaculture Methods 0.000 claims description 11
- 244000144974 aquaculture Species 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 abstract description 16
- 239000006174 pH buffer Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 24
- 238000005259 measurement Methods 0.000 description 14
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000004567 concrete Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 241000206761 Bacillariophyta Species 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- -1 (plate-like form) Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000012773 agricultural material Substances 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 235000015170 shellfish Nutrition 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011381 foam concrete Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 241001669680 Dormitator maculatus Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- YKAIJSHGJPXTDY-CBDGTLMLSA-N α-cao Chemical group C([C@@H](N(CC1)C)C23C=CC4([C@H](C3)N(CCCl)CCCl)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YKAIJSHGJPXTDY-CBDGTLMLSA-N 0.000 description 1
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
Landscapes
- Farming Of Fish And Shellfish (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、水質浄化材に関する。 The present invention relates to a water purification material.
観賞や養殖を目的として、魚、海老等の水棲生物を、養殖池、水槽等の閉鎖水域で飼育する場合、水棲生物の排泄物や食べ残しの餌等によってアンモニアやリン酸が発生する等、水質が悪化するという問題がある。
特許文献１には、窒素やリンを含む汚水を浄化する方法として、合成樹脂モノフィラメント又はヤーンをラッシュ編みして、目巾を２〜１０ｍｍ程度とした短形の嚢袋に、粒径１５〜３０ｍｍのゼオライトと軽量気泡コンクリートを混合してなる浄化材を収納してなる浄化嚢を、排水溝の溝底から水面にまで積み上げて浄化堰を構築する汚水浄化方法が記載されている。
また、特許文献２には、クリノプチロライト及びモルデナイトを含むゼオライトと、ケイ酸カルシウムとを含み、前記クリノプチロライトの結晶子径が１５〜２６．５ｎｍ、前記モルデナイトの結晶子径が３９〜４８ｎｍであり、前記ゼオライトと前記ケイ酸カルシウムとの質量比が４．０：１〜１．１：１であることを特徴とする水処理材が記載されている。
When aquatic organisms such as fish and shrimp are bred in closed water areas such as fishponds and aquaculture tanks for the purpose of aquaculture and aquaculture, ammonia and phosphoric acid are generated by the excrement of aquatic organisms and leftover food. There is a problem that the water quality deteriorates.
According to Patent Document 1, as a method for purifying sewage containing nitrogen and phosphorus, a synthetic resin monofilament or yarn is rush-knitted into a short sac with a mesh width of about 2 to 10 mm and a particle size of 15 to 30 mm. A sewage purification method for constructing a purification weir by stacking purification bags made of a mixture of zeolite and lightweight bubble concrete from the bottom of a drainage ditch to the water surface is described.
Further, Patent Document 2 contains zeolite containing clinoptilolite and mordenite and calcium silicate, and the crystallite diameter of the clinoptilolite is 15 to 26.5 nm and the crystallite diameter of the mordenite is 39. A water treatment material having a diameter of about 48 nm and having a mass ratio of the zeolite to the calcium silicate of 4.0: 1 to 1.1: 1 is described.
本発明の目的は、アンモニア吸着性、リン酸吸着性、ｐＨ緩衝性、及びケイ酸供給性に優れた水質浄化材を提供することである。 An object of the present invention is to provide a water purification material having excellent ammonia adsorption property, phosphoric acid adsorption property, pH buffer property, and silicic acid supply property.
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、ケイ酸カルシウム含有材料とゼオライトを含み、塩基置換容量及びリン酸吸収係数が特定の数値以上である水質浄化材によれば、上記目的を達成できることを見出し、本発明を完成した。
すなわち、本発明は、以下の［１］〜［５］を提供するものである。
［１］ ケイ酸カルシウム含有材料とゼオライトを含む水質浄化材であって、塩基置換容量が９ｍｅｑ／１００ｇ以上であり、リン酸吸収係数が１３，０００ｍｇ／１００ｇ以上であることを特徴とする水質浄化材。
［２］ 上記水質浄化材中、可溶性ケイ酸の含有率が１０質量％以上であり、アルカリ分の含有率が１０質量％以上である前記［１］に記載の水質浄化材。
［３］ 上記ケイ酸カルシウム含有材料と上記ゼオライトの質量比（ケイ酸カルシウム含有材料／ゼオライト）が、５０／５０〜９９／１である前記［１］又は［２］に記載の水質浄化材。
［４］ 上記ケイ酸カルシウム含有材料は、粒度が６ｍｍ以下のものを７０質量％以上の割合で含むものであり、かつ、上記ゼオライトは、粒度が６ｍｍ以下のものを７０質量％以上の割合で含むものである、前記［１］〜［３］のいずれかに記載の水質浄化材。
［５］ 前記［１］〜［４］のいずれかに記載の水質浄化材を、水棲生物が生息している養殖用水域に供給して、水棲生物を養殖する水棲生物の養殖方法。
As a result of diligent studies to solve the above problems, the present inventor has described the above according to a water purification material containing a calcium silicate-containing material and zeolite and having a base substitution capacity and a phosphoric acid absorption coefficient of a specific value or more. The present invention has been completed by finding that the object can be achieved.
That is, the present invention provides the following [1] to [5].
[1] A water purification material containing a calcium silicate-containing material and zeolite, which has a base substitution capacity of 9 meq / 100 g or more and a phosphoric acid absorption coefficient of 13,000 mg / 100 g or more. Material.
[2] The water purification material according to the above [1], wherein the content of soluble silicic acid is 10% by mass or more and the content of alkali content is 10% by mass or more in the water purification material.
[3] The water purification material according to the above [1] or [2], wherein the mass ratio of the calcium silicate-containing material to the zeolite (calcium silicate-containing material / zeolite) is 50/50 to 99/1.
[4] The calcium silicate-containing material contains a material having a particle size of 6 mm or less at a ratio of 70% by mass or more, and the zeolite contains a material having a particle size of 6 mm or less at a ratio of 70% by mass or more. The water purification material according to any one of the above [1] to [3], which comprises.
[5] A method for cultivating aquatic organisms by supplying the water purification material according to any one of the above [1] to [4] to aquaculture water area where aquatic organisms inhabit.
本発明の水質浄化材は、アンモニア吸着性（水中のアンモニア（アンモニア態窒素）を吸着する能力）、及び、リン酸吸着性（水中のリン酸を吸着する能力）に優れているため、養殖池、水槽等の閉鎖水域に投入することによって、閉鎖水域における水質を良好にすることができる。
また、本発明の水質浄化材は、ｐＨ緩衝性（水のｐＨを緩衝する能力）に優れているため、餌の食べ残し等に起因する有機酸の生成による水のｐＨの過度の変動を抑制し、ｐＨを一定に維持することができる。
さらに、本発明の水質浄化材は、ケイ酸供給性（水中にケイ酸を供給する能力）に優れているため、水中の珪藻の増殖が促進され、珪藻を餌とする甲殻類、貝類、動物プランクトン等の増殖や成長を良好にすることができる。
The water purification material of the present invention is excellent in ammonia adsorption (ability to adsorb ammonia (ammonia-like nitrogen) in water) and phosphoric acid adsorption (ability to adsorb phosphoric acid in water). , The water quality in the closed water area can be improved by putting it in a closed water area such as a water tank.
Further, since the water purification material of the present invention is excellent in pH buffering property (ability to buffer the pH of water), it suppresses excessive fluctuation of the pH of water due to the generation of organic acid due to leftover food and the like. However, the pH can be kept constant.
Furthermore, since the water purification material of the present invention has excellent silicic acid supply (capacity to supply silicic acid into water), the growth of diatoms in water is promoted, and crustaceans, shellfish, and animals that feed on diatoms are promoted. It is possible to improve the growth and growth of plankton and the like.
本発明の水質浄化材は、ケイ酸カルシウム含有材料とゼオライトを含む水質浄化材であって、塩基置換容量が９ｍｅｑ／１００ｇ以上であり、かつ、リン酸吸収係数が１３，０００ｍｇ／１００ｇ以上であるものである。
本発明で用いられるケイ酸カルシウム含有材料の例としては、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、及び、ウォラストナイト等が挙げられる。これらは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
トバモライトとは、結晶性のケイ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。
ゾノトライトとは、結晶性のケイ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ゲルとは、αＣａＯ・βＳｉＯ2・γＨ2Ｏ（ただし、α／β＝０．７〜２．３、γ／β＝１．２〜２．７である。）の化学組成を有するものである。具体的には、３ＣａＯ・２ＳｉＯ2・３Ｈ2Ｏの化学組成を有するケイ酸カルシウム水和物等が挙げられる。
フォシャジャイトとは、Ｃａ４（ＳｉＯ３）３（ＯＨ）２等の化学組成を有するものである。
ジャイロライトとは、（ＮａＣａ２）Ｃａ１４（Ｓｉ２３Ａｌ）Ｏ６０（ＯＨ）８・１４Ｈ２Ｏ等の化学組成を有するものである。
ヒレブランダイトとは、Ｃａ２ＳｉＯ３（ＯＨ）２等の化学組成を有するものである。
ウォラストナイトとは、ＣａＯ・ＳｉＯ２（繊維状又は柱状の形態）等の化学組成を有するものである。
The water purification material of the present invention is a water purification material containing a calcium silicate-containing material and zeolite, and has a base substitution capacity of 9 meq / 100 g or more and a phosphoric acid absorption coefficient of 13,000 mg / 100 g or more. It is a thing.
Examples of the calcium silicate-containing material used in the present invention include tovamorite, zonotrite, CSH gel, foschagit, gyrolite, finbrandite, and wollastonite. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Tovamorite is a crystalline calcium silicate hydrate, 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 having a chemical composition such as Ca 6 , (Si 6 O 17 ), (OH) 2 (fibrous form).
The CSH gel, those having a chemical composition of αCaO · βSiO 2 · γH 2 O ( provided that, alpha / beta = 0.7 to 2.3, a γ / β = 1.2~2.7.) is there. Specifically, calcium silicate hydrate or the like having a chemical composition of 3CaO · 2SiO 2 · 3H 2 O and the like.
The fossilite has a chemical composition such as Ca 4 (SiO 3 ) 3 (OH) 2 .
The gyro light, those having a (NaCa 2) Ca 14 (Si 23 Al) O 60 (OH) 8 · 14H 2 O The chemical composition of such.
The fillet brandite has a chemical composition such as Ca 2 SiO 3 (OH) 2 .
Wollastonite has a chemical composition such as CaO · SiO 2 (fibrous or columnar form).
中でも、入手の容易性および経済性の観点から、トバモライトが好適である。トバモライトとしては、天然の鉱物を用いてもよいが、入手の容易性の観点から、トバモライトを主成分とする軽量気泡コンクリート（ＡＬＣ）を用いることが好ましい。また、廃材の利用促進の観点から、軽量気泡コンクリートの製造工程や建設現場で発生する軽量気泡コンクリートの端材を用いることが、より好ましい。
ここで、軽量気泡コンクリートとは、トバモライト、および、未反応の珪石からなるものであり、かつ、８０体積％程度の空隙率を有するものである。ここで、空隙率とは、コンクリートの全体積中の、空隙の体積の合計の割合をいう。
軽量気泡コンクリート中のトバモライトの割合は、軽量気泡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、通常、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。
Of these, tobamolite is preferable from the viewpoint of availability and economy. As the tobamolite, a natural mineral may be used, but from the viewpoint of easy availability, it is preferable to use lightweight cellular concrete (ALC) containing tobamolite as a main component. Further, from the viewpoint of promoting the use of waste materials, it is more preferable to use the scraps of lightweight aerated concrete generated in the manufacturing process of lightweight aerated concrete or at a construction site.
Here, the lightweight aerated concrete is made of tobermorite and unreacted silica stone, and has a porosity of about 80% by volume. Here, the porosity refers to the ratio of the total volume of voids in the total volume of concrete.
The ratio of tovamorite in the lightweight aerated concrete is usually about 65 to 80% by volume, assuming that the entire solid phase excluding the void portion inside the lightweight aerated concrete is 100% by volume.
Lightweight cellular concrete can be obtained by autoclaving a raw material (for example, a cured product consisting of a mixture thereof) containing, for example, siliceous stone powder, cement, quicklime powder, foaming agent (for example, aluminum powder), water and the like. ..
ケイ酸カルシウム含有材料のリン酸吸収係数は、好ましくは１３，０００ｍｇ／１００ｇ以上、より好ましくは１４，０００〜４０，０００ｍｇ／１００ｇ、さらに好ましくは１６，０００〜３５，０００ｍｇ／１００ｇ、特に好ましくは１８，０００〜３０，０００ｍｇ／１００ｇである。該係数が１３，０００ｍｇ／１００ｇ以上であれば、水質浄化材のリン酸吸着性をより向上させることができる。該係数が４０，０００ｍｇ／１００ｇを超えるものは入手が困難である。
なお、リン酸吸収係数は、「土壌標準分析・測定法（土壌標準分析 測定法委員会編） リン酸アンモニウム液法（１：５０抽出）」に記載された方法に準拠して測定することができる。
The phosphoric acid absorption coefficient of the calcium silicate-containing material is preferably 13,000 mg / 100 g or more, more preferably 14,000 to 40,000 mg / 100 g, still more preferably 16,000 to 35,000 mg / 100 g, and particularly preferably. It is 18,000 to 30,000 mg / 100 g. When the coefficient is 13,000 mg / 100 g or more, the phosphoric acid adsorption property of the water purification material can be further improved. Those having the coefficient exceeding 40,000 mg / 100 g are difficult to obtain.
The phosphate absorption coefficient can be measured in accordance with the method described in "Soil Standard Analysis / Measurement Method (Soil Standard Analysis and Measurement Method Committee) Ammonium Phosphate Solution Method (1:50 Extraction)". it can.
ケイ酸カルシウム含有材料の可溶性ケイ酸の含有率は、好ましくは１０質量％以上、より好ましくは１２〜３５質量％、さらに好ましくは１４〜３０質量％、特に好ましくは１６〜２５質量％である。該含有率が１０質量％以上であれば、水質浄化材のケイ酸供給性をより向上させることができる。該含有率が３５質量％を超えるものは入手が困難である。
なお、可溶性ケイ酸の含有率は、独立行政法人農林水産消費安全技術センター（ＦＡＭＩＣ）が監修した「肥料等試験法（２０１８）４．４．１．ａ ふっ化カリウム法」に記載された方法に準拠して測定することができる。
The content of soluble silicic acid in the calcium silicate-containing material is preferably 10% by mass or more, more preferably 12 to 35% by mass, still more preferably 14 to 30% by mass, and particularly preferably 16 to 25% by mass. When the content is 10% by mass or more, the silicic acid supply property of the water purification material can be further improved. Those having a content of more than 35% by mass are difficult to obtain.
The content of soluble silicic acid is the method described in "Fertilizer Test Method (2018) 4.4.1.a Potassium Fluoride Method" supervised by the Food and Agricultural Materials Safety Technology Center (FAMIC). Can be measured according to.
ケイ酸カルシウム含有材料のアルカリ分の含有率は、好ましくは１０質量％以上、より好ましくは１２〜３５質量％、さらに好ましくは１４〜３０質量％、特に好ましくは１６〜２５質量％である。該含有率が１０質量％以上であれば、水質浄化材のｐＨ緩衝性をより向上させることができる。該含有率が３５質量％を超えるものは入手が困難である。
なお、アルカリ分の含有率は、独立行政法人農林水産消費安全技術センター（ＦＡＭＩＣ）が監修した「肥料等試験法（２０１８）４．５．４ アルカリ分」に記載された方法に準拠して測定することができる。
The alkali content of the calcium silicate-containing material is preferably 10% by mass or more, more preferably 12 to 35% by mass, still more preferably 14 to 30% by mass, and particularly preferably 16 to 25% by mass. When the content is 10% by mass or more, the pH buffering property of the water purification material can be further improved. Those having a content of more than 35% by mass are difficult to obtain.
The alkali content is measured in accordance with the method described in "Fertilizer Test Method (2018) 4.5.4 Alkali Content" supervised by the Food and Agricultural Materials Safety Technology Center (FAMIC). can do.
ケイ酸カルシウム含有材料は多孔質であることが好ましい。ケイ酸カルシウム含有材料が多孔質であれば、ケイ酸カルシウム含有材料からのケイ酸の溶出量がより大きくなるため、水中の珪藻の増殖をより促進することができる。また、本発明の水質浄化材を水中に添加した際に、ケイ酸カルシウム含有材料の多孔質部分に存在する空気が、水中に連行されることによって、水中の溶存酸素量の低下を防ぐことができる。 The calcium silicate-containing material is preferably porous. When the calcium silicate-containing material is porous, the amount of silicic acid eluted from the calcium silicate-containing material is larger, so that the growth of diatoms in water can be further promoted. Further, when the water purification material of the present invention is added to water, the air existing in the porous portion of the calcium silicate-containing material can be taken into the water to prevent a decrease in the amount of dissolved oxygen in the water. it can.
ケイ酸カルシウム含有材料は、粉粒状物（粉状物あるいは粒状物）であることが好ましい。ケイ酸カルシウム含有材料の粒度は、該材料に含まれるケイ酸の水への溶出量をより多くする観点から、好ましくは６ｍｍ以下、より好ましくは４ｍｍ以下、さらに好ましくは３ｍｍ以下、さらに好ましくは２ｍｍ以下、特に好ましくは１ｍｍ以下である。該粒度の下限値は、粉砕に要するエネルギーの削減や、水質浄化材の水への供給を容易にする等の観点から、好ましくは０．００１ｍｍ、より好ましくは０．００５ｍｍ、特に好ましくは０．０１ｍｍである。
なお、ケイ酸の溶出量が多くなれば、水中の珪藻の成育がより安定し、その増殖がより促進される。
ケイ酸カルシウム含有材料の粒度分布は、ケイ酸の溶出量をより多くする観点から、好ましくは６ｍｍ以下（より好ましくは４ｍｍ以下、さらに好ましくは３ｍｍ以下、さらに好ましくは２ｍｍ以下、特に好ましくは１ｍｍ以下）の粒度を有する粒体を７０質量％以上（好ましくは８０質量％以上、より好ましくは９０質量％以上）の割合で含むものである。
なお、本明細書中、粒度の値は、篩の目開き寸法に対応する値である。
The calcium silicate-containing material is preferably a powder or granular material (powder or granular material). The particle size of the calcium silicate-containing material is preferably 6 mm or less, more preferably 4 mm or less, still more preferably 3 mm or less, still more preferably 2 mm, from the viewpoint of increasing the amount of silicic acid contained in the material eluted into water. Below, it is particularly preferably 1 mm or less. The lower limit of the particle size is preferably 0.001 mm, more preferably 0.005 mm, and particularly preferably 0., from the viewpoint of reducing the energy required for pulverization and facilitating the supply of the water purification material to water. It is 01 mm.
The larger the amount of silicic acid eluted, the more stable the growth of diatoms in water and the more promoted their growth.
The particle size distribution of the calcium silicate-containing material is preferably 6 mm or less (more preferably 4 mm or less, further preferably 3 mm or less, still more preferably 2 mm or less, particularly preferably 1 mm or less, from the viewpoint of increasing the elution amount of silicic acid. ) Is contained in a proportion of 70% by mass or more (preferably 80% by mass or more, more preferably 90% by mass or more).
In the present specification, the particle size value is a value corresponding to the opening size of the sieve.
本発明で用いられるゼオライトとしては、天然で産出されるもの（ゼオライト鉱物）でもよく、工業的に製造されるもの（合成ゼオライト）でもよい。中でも、原料にかかるコストを低減する観点から、天然で産出されるものが好ましい。ゼオライト鉱物の例としては、ゼオライト（狭義のもの；天然ゼオライト）、モルデナイト、クリノブチライト等が挙げられる。
ゼオライトの塩基置換容量（ＣＥＣ：Ｃａｔｉｏｎ Ｅｘｃｈａｎｇｅ Ｃａｐａｃｉｔｙ、陽イオン交換容量ともいう。）は、好ましくは２０ｍｅｑ／１００ｇ以上、より好ましくは５０〜２００ｍｅｑ／１００ｇ、さらに好ましくは１００〜１８０ｍｅｑ／１００ｇ、特に好ましくは１２０〜１６０ｍｅｑ／１００ｇである。該量が２０ｍｅｑ／１００ｇ以上であれば、水質浄化材のアンモニア吸着性をより向上させることができる。該量が２００ｍｅｑ／１００ｇを超えるものは入手が困難である。
The zeolite used in the present invention may be a naturally produced zeolite (zeolite mineral) or an industrially produced zeolite (synthetic zeolite). Among them, those produced naturally are preferable from the viewpoint of reducing the cost of raw materials. Examples of zeolite minerals include zeolite (narrowly defined; natural zeolite), mordenite, clinobtilite and the like.
The base substitution capacity (CEC: Cation Exchange Capacity, also referred to as cation exchange capacity) of zeolite is preferably 20 meq / 100 g or more, more preferably 50 to 200 meq / 100 g, still more preferably 100 to 180 meq / 100 g, and particularly preferably 100 to 180 meq / 100 g. It is 120 to 160 meq / 100 g. When the amount is 20 meq / 100 g or more, the ammonia adsorption property of the water purification material can be further improved. Those having the amount exceeding 200 meq / 100 g are difficult to obtain.
ゼオライトの粒度は、水質浄化材のアンモニア吸着性をより向上させる観点から、好ましくは６ｍｍ以下、より好ましくは４ｍｍ以下、さらに好ましくは３ｍｍ以下、さらに好ましくは２ｍｍ以下、特に好ましくは１ｍｍ以下である。該粒度の下限値は、粉砕に要するエネルギーの削減や、水質浄化材の水への供給を容易にする等の観点から、好ましくは０．００１ｍｍ、より好ましくは０．００５ｍｍ、特に好ましくは０．０１ｍｍである。
ゼオライトの粒度分布は、水質浄化材のアンモニア吸着性をより向上させる観点から、好ましくは６ｍｍ以下（より好ましくは４ｍｍ以下、さらに好ましくは３ｍｍ以下、さらに好ましくは２ｍｍ以下、特に好ましくは１ｍｍ以下）の粒度を有する粒体を７０質量％以上（好ましくは８０質量％以上、より好ましくは９０質量％以上）の割合で含むものである。
The particle size of the zeolite is preferably 6 mm or less, more preferably 4 mm or less, further preferably 3 mm or less, further preferably 2 mm or less, and particularly preferably 1 mm or less, from the viewpoint of further improving the ammonia adsorption property of the water purification material. The lower limit of the particle size is preferably 0.001 mm, more preferably 0.005 mm, and particularly preferably 0., from the viewpoint of reducing the energy required for pulverization and facilitating the supply of the water purification material to water. It is 01 mm.
The particle size distribution of the zeolite is preferably 6 mm or less (more preferably 4 mm or less, further preferably 3 mm or less, still more preferably 2 mm or less, particularly preferably 1 mm or less) from the viewpoint of further improving the ammonia adsorption property of the water purification material. It contains particles having a particle size in a proportion of 70% by mass or more (preferably 80% by mass or more, more preferably 90% by mass or more).
本発明の水質浄化材は、上述したケイ酸カルシウム含有材料とゼオライトを混合することで得ることができる。
水質浄化材において、ケイ酸カルシウム含有材料とゼオライトの質量比（ケイ酸カルシウム含有材料／ゼオライト）は、リン酸吸着性、ケイ酸供給性、及びｐＨ緩衝性をより向上させる観点からは、好ましくは５０／５０以上、より好ましくは６０／４０以上、さらに好ましくは７０／３０以上、特に好ましくは８０／２０以上である。また、アンモニア吸着性をより向上させる観点からは、好ましくは９９／１以下、より好ましくは９５／５以下である。
The water purification material of the present invention can be obtained by mixing the above-mentioned calcium silicate-containing material and zeolite.
In the water purification material, the mass ratio of calcium silicate-containing material to zeolite (calcium silicate-containing material / zeolite) is preferable from the viewpoint of further improving phosphoric acid adsorption, silicic acid supply, and pH buffering. It is 50/50 or more, more preferably 60/40 or more, still more preferably 70/30 or more, and particularly preferably 80/20 or more. Further, from the viewpoint of further improving the ammonia adsorption property, it is preferably 99/1 or less, more preferably 95/5 or less.
水質浄化材の塩基置換容量は、水質浄化材のアンモニア吸着性をより向上する観点からは、９ｍｅｑ／１００ｇ以上、好ましくは１２ｍｅｑ／１００ｇ以上、より好ましくは１８ｍｅｑ／１００ｇ以上、さらに好ましくは３０ｍｅｑ／１００ｇ以上、特に好ましくは５０ｍｅｑ／１００ｇ以上である。また、水質浄化材の塩基置換容量は、相対的にケイ酸カルシウム含有材料の量が少なくなり、水質浄化材のリン酸吸収係数、可溶性ケイ酸の含有率、及びアルカリ分の含有率が小さくなることを防ぐ観点からは、好ましくは２００ｍｅｑ／１００ｇ以下、より好ましくは１５０ｍｅｑ／１００ｇ以下、さらに好ましくは１２０ｍｅｑ／１００ｇ以下、さらに好ましくは１００ｍｅｑ／１００ｇ以下、特に好ましくは９０ｍｅｑ／１００ｇ以下である。 The base substitution capacity of the water purification material is 9 meq / 100 g or more, preferably 12 meq / 100 g or more, more preferably 18 meq / 100 g or more, still more preferably 30 meq / 100 g, from the viewpoint of further improving the ammonia adsorption property of the water purification material. As mentioned above, it is particularly preferably 50 meq / 100 g or more. In addition, the base substitution capacity of the water purification material is such that the amount of the calcium silicate-containing material is relatively small, and the phosphoric acid absorption coefficient, the soluble silicic acid content, and the alkali content of the water purification material are small. From the viewpoint of preventing this, it is preferably 200 meq / 100 g or less, more preferably 150 meq / 100 g or less, still more preferably 120 meq / 100 g or less, still more preferably 100 meq / 100 g or less, and particularly preferably 90 meq / 100 g or less.
水質浄化材のリン酸吸収係数は、水質浄化材のリン酸吸着性をより向上させる観点からは、１３，０００ｍｇ／１００ｇ以上、好ましくは１３，２００ｍｇ／１００ｇ以上、よりに好ましくは１５，０００ｍｇ／１００ｇ以上、特に好ましくは１８，０００ｍｇ／１００ｇ以上である。該係数は、相対的にゼオライトの量が少なくなり、水質浄化材のアンモニア吸着性が低下することを防ぐ観点からは、好ましくは４０，０００ｍｇ／１００ｇ以下、好ましくは３０，０００ｍｇ／１００ｇ以下、よりに好ましくは２５，０００ｍｇ／１００ｇ以下、特に好ましくは２０，０００ｍｇ／１００ｇ以下である。 The phosphoric acid absorption coefficient of the water purification material is 13,000 mg / 100 g or more, preferably 13,200 mg / 100 g or more, more preferably 15,000 mg / g, from the viewpoint of further improving the phosphoric acid adsorption property of the water purification material. It is 100 g or more, particularly preferably 18,000 mg / 100 g or more. The coefficient is preferably 40,000 mg / 100 g or less, preferably 30,000 mg / 100 g or less, from the viewpoint of preventing the amount of zeolite from being relatively small and the ammonia adsorption property of the water purification material from being lowered. It is preferably 25,000 mg / 100 g or less, and particularly preferably 20,000 mg / 100 g or less.
水質浄化材の可溶性ケイ酸の含有率は、水質浄化材のケイ酸供給性をより向上させる観点からは、好ましくは１０質量％以上、より好ましくは１２質量％以上、さらに好ましくは１４質量％以上、特に好ましくは１６質量％以上である。該含有率は、相対的にゼオライトの量が少なくなり、水質浄化材のアンモニア吸着性が低下することを防ぐ観点からは、好ましくは３５質量％以下、より好ましくは３０質量％以下、さらに好ましくは２５質量％以下、さらに好ましくは２０質量％以下、特に好ましくは１８質量％以下である。 The content of soluble silicic acid in the water purification material is preferably 10% by mass or more, more preferably 12% by mass or more, still more preferably 14% by mass or more, from the viewpoint of further improving the silicic acid supply property of the water purification material. , Particularly preferably 16% by mass or more. The content is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 30% by mass or less, from the viewpoint of preventing the amount of zeolite from being relatively small and the ammonia adsorption property of the water purification material from being lowered. It is 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 18% by mass or less.
水質浄化材のアルカリ分の含有率は、水質浄化材のｐＨ緩衝性をより向上させる観点からは、好ましくは１０質量％以上、より好ましくは１２質量％以上、さらに好ましくは１４質量％以上、特に好ましくは１６質量％以上である。該含有率は、相対的にゼオライトの量が少なくなり、水質浄化材のアンモニア吸着性が低下することを防ぐ観点からは、好ましくは３５質量％以下、より好ましくは３０質量％以下、さらに好ましくは２５質量％以下、さらに好ましくは２２質量％以下、特に好ましくは１８質量％以下である。 From the viewpoint of further improving the pH buffering property of the water purification material, the alkali content of the water purification material is preferably 10% by mass or more, more preferably 12% by mass or more, still more preferably 14% by mass or more, particularly. It is preferably 16% by mass or more. The content is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 30% by mass or less, from the viewpoint of preventing the amount of zeolite from being relatively small and the ammonia adsorption property of the water purification material from being lowered. It is 25% by mass or less, more preferably 22% by mass or less, and particularly preferably 18% by mass or less.
水棲生物（養殖の対象となる水棲生物を含む）が生息している養殖池や水槽等の養殖用水域に、本発明の水質浄化材を散布し落下させて、水中に供給するという簡易な方法によって、養殖用水域の水質を良好に維持することができ、水棲生物（珪藻、動物プランクトンや、養殖の対象となる魚類、甲殻類、貝類等）の増殖や成長を良好なものにすることができる。
水質浄化材は、長期間にわたって水質を良好なものにする観点から、時間的間隔を置いて繰り返し供給してもよい。水質浄化材を繰り返し供給する間隔は、好ましくは１〜３０日間、より好ましくは２〜１５日間、特に好ましくは３〜１０日間である。
また、上記水質浄化材は、徐々に溶けて、最終的には消滅することから、使用後の回収や除去が不要であり、管理が容易である。
A simple method of spraying the water purification material of the present invention on aquaculture water bodies such as aquaculture ponds and aquaculture tanks where aquaculture organisms (including aquaculture organisms to be cultivated) inhabit, dropping them, and supplying them into the water. This makes it possible to maintain good water quality in aquaculture areas and improve the growth and growth of aquatic organisms (diaphores, zooplankton, fish, shellfish, shellfish, etc. to be cultivated). it can.
The water purification material may be repeatedly supplied at time intervals from the viewpoint of improving the water quality over a long period of time. The interval for repeatedly supplying the water purification material is preferably 1 to 30 days, more preferably 2 to 15 days, and particularly preferably 3 to 10 days.
Further, since the water quality purification material gradually dissolves and finally disappears, it is not necessary to collect or remove it after use, and it is easy to manage.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
［使用材料］
（１）ケイ酸カルシウム含有材料；トバモライトを含む軽量気泡コンクリート（ＡＬＣ）を破砕した粉粒状物、１ｍｍ以下の粒度のものの含有率：９０質量％以上
（２）ゼオライト；１ｍｍ以下の粒度のものの含有率：９０質量％以上、ジークライト社製、商品名「ＳＧＷ−Ｂ４」
上記ケイ酸カルシウム含有材料及び上記ゼオライトの物性値を、以下の方法で測定した。結果を表１に示す。
［塩素置換容量の測定］
「土壌環境分析法（土壌環境分析法編集委員会編）Ｖ．６ セミミクロ・ショレンベルガー（Ｓｃｈｏｌｌｅｎｂｅｒｇｅｒ）法」に記載された方法に準拠して測定した。
［リン酸吸収係数の測定］
「土壌標準分析・測定法（土壌標準分析 測定法委員会編） リン酸アンモニウム液法（１：５０抽出）」に記載された方法に準拠して測定した。
［可溶性ケイ酸の測定］
独立行政法人農林水産消費安全技術センター（ＦＡＭＩＣ）が監修した「肥料等試験法（２０１８）４．４．１．ａ ふっ化カリウム法」に記載された方法に準拠して測定した。
［アルカリ分の測定］
独立行政法人農林水産消費安全技術センター（ＦＡＭＩＣ）が監修した「肥料等試験法（２０１８）４．５．４アルカリ分」に記載された方法に準拠して測定した。
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
[Material used]
(1) Calcium silicate-containing material; powder granules of crushed lightweight aerated concrete (ALC) containing tovamorite, content of 1 mm or less particle size: 90% by mass or more (2) Zeolite; 1 mm or less particle size Rate: 90% by mass or more, manufactured by Siegrite, trade name "SGW-B4"
The physical property values of the calcium silicate-containing material and the zeolite were measured by the following methods. The results are shown in Table 1.
[Measurement of chlorine replacement capacity]
The measurement was performed according to the method described in "Soil environment analysis method (edited by the editorial board of the soil environment analysis method) V.6 Semi-micro Scholenberger method".
[Measurement of phosphate absorption coefficient]
Measurement was performed in accordance with the method described in "Soil Standard Analysis / Measurement Method (Soil Standard Analysis / Measurement Method Committee) Ammonium Phosphate Solution Method (1:50 Extraction)".
[Measurement of soluble silicic acid]
The measurement was performed in accordance with the method described in "Fertilizer Test Method (2018) 4.4.1.a Potassium Fluoride Method" supervised by the Food and Agricultural Materials Safety Technology Center (FAMIC).
[Measurement of alkali content]
The measurement was performed in accordance with the method described in "Fertilizer Test Method (2018) 4.5.4 Alkaline Content" supervised by the Food and Agricultural Materials Safety Technology Center (FAMIC).
［実施例１〜４、比較例１〜４］
ケイ酸カルシウム含有材料とゼオライトを、水質浄化材中の各含有率が表２に示す含有率となる量で混合して、水質浄化材を調製した。
得られた水質浄化材の、塩基置換容量、リン酸吸収係数、可溶性ケイ酸、及びアルカリ分を上述した方法で測定した。結果を表２に示す。
[Examples 1 to 4, Comparative Examples 1 to 4]
A water purification material was prepared by mixing a calcium silicate-containing material and zeolite in an amount such that each content in the water purification material becomes the content shown in Table 2.
The base substitution capacity, phosphoric acid absorption coefficient, soluble silicic acid, and alkali content of the obtained water purification material were measured by the methods described above. The results are shown in Table 2.
［水質浄化材のｐＨ緩衝性の評価］
水道水に、硝酸（関東化学社製、特級試薬）を添加して、硝酸濃度が、０、１０、３０、１００、３００ｐｐｍ（質量基準）となるように調整した硝酸水溶液を得た。得られた硝酸水溶液を模擬水として、各々の模擬水１００ミリリットルと水質浄化材１ｇを、１００ミリリットルのポリプロピレン製の容器に入れて、振とう機を用いて、７日間振とうした。次いで、模擬水のｐＨを、複合型ガラス電極（堀場製作所社製、型番：９６２５−１０Ｄ）を用いて測定した。
また、参考例１として、上記硝酸水溶液（水質浄化材を添加しなかったもの）のｐＨを測定した。
結果を表３に示す。
[Evaluation of pH buffering property of water purification material]
Nitric acid (manufactured by Kanto Chemical Co., Inc., a special grade reagent) was added to tap water to obtain an aqueous nitric acid solution adjusted so that the nitric acid concentration was 0, 10, 30, 100, or 300 ppm (mass basis). Using the obtained nitric acid aqueous solution as simulated water, 100 ml of each simulated water and 1 g of a water purification material were placed in a 100 ml polypropylene container and shaken for 7 days using a shaker. Next, the pH of the simulated water was measured using a composite glass electrode (manufactured by HORIBA, Ltd., model number: 9625-10D).
In addition, as Reference Example 1, the pH of the above-mentioned aqueous nitric acid solution (without the addition of a water purification material) was measured.
The results are shown in Table 3.
各々の水質浄化材について、以下の方法を用いて、物性の評価を行った。
［アンモニアおよびリン酸吸着性の評価］
リン酸水素二アンモニウム（関東化学社製、特級試薬）０．０９４４ｇを蒸留水に加えて、模擬水２リットルを調製した。該模擬水中、アンモニア態窒素の濃度は１０ｍｇ／リットル、リン酸濃度は３３．９ｍｇ／リットルであった。
上記模擬水１００ミリリットルと水質浄化材１ｇを、１００ミリリットルのポリプロピレン製の容器に入れて、振とう機を用いて、７日間振とうした。次いで、孔径が０．４５μｍであるＰＴＦＥ（ポリテトラフルオロエチレン）製のメンブレンフィルターを用いて、模擬水をろ過して、ろ液を得た。
The physical properties of each water purification material were evaluated using the following methods.
[Evaluation of ammonia and phosphate adsorption]
0.0944 g of diammonium hydrogen phosphate (manufactured by Kanto Chemical Co., Inc., a special grade reagent) was added to distilled water to prepare 2 liters of simulated water. In the simulated water, the concentration of ammonia nitrogen was 10 mg / liter and the concentration of phosphoric acid was 33.9 mg / liter.
The simulated water (100 ml) and 1 g of the water purification material were placed in a 100 ml polypropylene container and shaken for 7 days using a shaker. Next, the simulated water was filtered using a membrane filter made of PTFE (polytetrafluoroethylene) having a pore size of 0.45 μm to obtain a filtrate.
ろ液のアンモニア態窒素、リン酸、及び、ケイ酸の濃度を、以下の方法で測定した。
［アンモニア態窒素濃度（表４中、「ＮＨ４−Ｎ」と示す。）の測定］
インドフェノール青比色法を用いたデジタルパックテスト（共立理化学研究所社製、商品名「デジタルパックテスト・マルチ、型式：ＤＰＭ−ＭＴ」を用いて測定した。
［リン酸濃度の測定］
モリブデン青比色法を用いたデジタルパックテスト（共立理化学研究所社製、商品名「デジタルパックテスト・マルチ、型式：ＤＰＭ−ＭＴ」を用いて測定した。
［ケイ酸濃度の測定］
ＩＣＰ発光分析装置（堀場製作所社製、商品名「ＵＬＴＩＭＡ ＩＩ」）を用いて測定した。
また、水質浄化材のアンモニア吸着性及びリン酸吸着性の指標として、アンモニア態窒素及びリン酸の吸着率（％）を、以下の式を用いて算出した。
アンモニア態窒素の吸着率（％）＝（振とう前の模擬水のアンモニア態窒素の濃度−振とう後のろ液のアンモニア態窒素の濃度）／振とう前の模擬水のアンモニア態窒素の濃度×１００
リン酸の吸着率（％）＝（振とう前の模擬水のリン酸の濃度−振とう後のろ液のリン酸の濃度）／振とう前の模擬水のリン酸の濃度×１００
結果を表４に示す。
なお、アンモニア態窒素及びリン酸の濃度は、小さいほど水質が良好である。また、アンモニア態窒素及びリン酸の吸着率は、水質を良好にする観点から、大きい方が好ましい。
また、ケイ酸濃度は、珪藻の増殖を促進することができる観点から、大きいほうが好ましい。
The concentrations of ammonia nitrogen, phosphoric acid, and silicic acid in the filtrate were measured by the following methods.
[Measurement of ammonia nitrogen concentration (indicated as "NH 4- N" in Table 4)]
The measurement was performed using a digital pack test using the indophenol blue colorimetric method (manufactured by Kyoritsu RIKEN, trade name "Digital Pack Test Multi, model: DPM-MT".
[Measurement of phosphoric acid concentration]
The measurement was performed using a digital pack test using the molybdenum blue colorimetric method (manufactured by Kyoritsu RIKEN, trade name "Digital Pack Test Multi, model: DPM-MT".
[Measurement of silicic acid concentration]
The measurement was performed using an ICP emission spectrometer (manufactured by HORIBA, Ltd., trade name "ULTIMA II").
In addition, the adsorption rate (%) of ammonia nitrogen and phosphoric acid was calculated using the following formula as an index of ammonia adsorption property and phosphoric acid adsorption property of the water purification material.
Adsorption rate of ammonia nitrogen (%) = (Concentration of ammonia nitrogen in simulated water before shaking-Concentration of ammonia nitrogen in filtrate after shaking) / Concentration of ammonia nitrogen in simulated water before shaking × 100
Phosphoric acid adsorption rate (%) = (Phosphoric acid concentration in simulated water before shaking-Phosphoric acid concentration in filtrate after shaking) / Phosphoric acid concentration in simulated water before shaking x 100
The results are shown in Table 4.
The smaller the concentration of ammonia nitrogen and phosphoric acid, the better the water quality. Further, the adsorption rate of ammonia nitrogen and phosphoric acid is preferably large from the viewpoint of improving the water quality.
Further, the silicic acid concentration is preferably high from the viewpoint of promoting the growth of diatoms.
表３から、実施例１〜４において、硝酸濃度が３００ｐｐｍである模擬水に本発明の水質浄化材を添加した場合、模擬水のｐＨは８．７７〜９．１０であった。一方、比較例２〜４において、硝酸濃度が３００ｐｐｍである模擬水に水質浄化材（リン酸吸収係数が６，０００〜１２，０００ｍｇ／１００ｇであり、アルカリ分が１〜９質量％であるもの）を添加した場合、模擬水のｐＨは、２．７４〜８．１５であった。これらのこと等から、本発明の水質浄化材を用いることで、ｐＨの低下をより抑制しうることがわかる。 From Table 3, in Examples 1 to 4, when the water purification material of the present invention was added to the simulated water having a nitric acid concentration of 300 ppm, the pH of the simulated water was 8.77 to 9.10. On the other hand, in Comparative Examples 2 to 4, a water purification material (phosphoric acid absorption coefficient of 6,000 to 12,000 mg / 100 g and alkali content of 1 to 9% by mass) was added to simulated water having a nitric acid concentration of 300 ppm. ) Was added, the pH of the simulated water was 2.74 to 8.15. From these facts, it can be seen that the decrease in pH can be further suppressed by using the water purification material of the present invention.
また、表４から、実施例１〜４において、アンモニア態窒素の濃度は３．４〜６．９ｍｇ／リットルであり、比較例１におけるアンモニア態窒素の濃度（９．１ｍｇ／リットル）よりも小さいことがわかる。このことから、本発明の水質浄化材（実施例１〜４）は、ケイ酸カルシウム含有材料のみを用いた水質浄化材（比較例１）よりも、アンモニア吸着性に優れていることがわかる。
また、実施例１〜４において、リン酸の濃度は０．０〜０．３ｍｇ／リットルであり、比較例２〜４におけるリン酸の濃度（１．１〜３３．８ｍｇ／リットル）よりも小さいことがわかる。このことから、本発明の水質浄化材（実施例１〜４）は、リン酸吸収係数が６，０００〜１２，０００ｍｇ／１００ｇであり、アルカリ分が１〜９質量％である水質浄化材（比較例２〜４）よりも、リン酸吸着性に優れていることがわかる。
さらに、実施例１〜４において、ケイ酸の濃度は８９．２〜１０５．３ｍｇ／リットルであり、比較例２〜４におけるケイ酸の濃度（２２．０〜７８．８ｍｇ／リットル）よりも大きいことがわかる。このことから、本発明の水質浄化材（実施例１〜４）は、ケイ酸供給性に優れていることがわかる。
Further, from Table 4, in Examples 1 to 4, the concentration of ammonia nitrogen was 3.4 to 6.9 mg / liter, which was smaller than the concentration of ammonia nitrogen in Comparative Example 1 (9.1 mg / liter). You can see that. From this, it can be seen that the water purification material of the present invention (Examples 1 to 4) is superior in ammonia adsorption property to the water quality purification material (Comparative Example 1) using only the calcium silicate-containing material.
Further, in Examples 1 to 4, the concentration of phosphoric acid was 0.0 to 0.3 mg / liter, which was smaller than the concentration of phosphoric acid in Comparative Examples 2 to 4 (1.1 to 33.8 mg / liter). You can see that. From this, the water purification material of the present invention (Examples 1 to 4) has a phosphoric acid absorption coefficient of 6,000 to 12,000 mg / 100 g and an alkali content of 1 to 9% by mass. It can be seen that the phosphoric acid adsorption property is superior to that of Comparative Examples 2 to 4).
Further, in Examples 1 to 4, the concentration of silicic acid is 89.2 to 105.3 mg / liter, which is higher than the concentration of silicic acid in Comparative Examples 2 to 4 (22.0 to 78.8 mg / liter). You can see that. From this, it can be seen that the water purification material of the present invention (Examples 1 to 4) is excellent in silicic acid supply.
Claims (5)
塩基置換容量が９ｍｅｑ／１００ｇ以上であり、かつ、リン酸吸収係数が１３，０００ｍｇ／１００ｇ以上であることを特徴とする水質浄化材。 A water purification material containing calcium silicate-containing material and zeolite.
A water purification material having a base substitution capacity of 9 meq / 100 g or more and a phosphoric acid absorption coefficient of 13,000 mg / 100 g or more.
A method for cultivating aquatic organisms by supplying the water purification material according to any one of claims 1 to 4 to an aquaculture area in which aquatic organisms inhabit.
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