JP2000034481A - Inorganic composition, method for producing the same, fertilizer and soil modifier using the same - Google Patents
Inorganic composition, method for producing the same, fertilizer and soil modifier using the sameInfo
- Publication number
- JP2000034481A JP2000034481A JP20525798A JP20525798A JP2000034481A JP 2000034481 A JP2000034481 A JP 2000034481A JP 20525798 A JP20525798 A JP 20525798A JP 20525798 A JP20525798 A JP 20525798A JP 2000034481 A JP2000034481 A JP 2000034481A
- Authority
- JP
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- Prior art keywords
- sio
- inorganic composition
- weight
- fertilizer
- mgo
- Prior art date
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- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000003337 fertilizer Substances 0.000 title claims abstract description 38
- 239000002689 soil Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003607 modifier Substances 0.000 title claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims description 25
- 238000010828 elution Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000007979 citrate buffer Substances 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 41
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 5
- 235000009566 rice Nutrition 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000002893 slag Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000004111 Potassium silicate Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 6
- 229910052913 potassium silicate Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910000863 Ferronickel Inorganic materials 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000004720 fertilization Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940072033 potash Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011044 quartzite Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007974 sodium acetate buffer Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- -1 where again Chemical compound 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 229910021540 colemanite Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Fertilizers (AREA)
Abstract
(57)【要約】
【課題】稲作用に好適な酸可溶性ケイ酸の豊富な土壌改
質剤、肥料を提供する。
【解決手段】主成分がＭｇＯ、ＳｉＯ2、ＣａＯからな
り、ＭｇＯを１〜２０重量％、ＳｉＯ2を３０〜５０重
量％含有する非晶質の無機組成物であって、好ましく
は、モル換算したときの（ＣａＯ＋ＭｇＯ）／ＳｉＯ2
の比が、０．８〜２．５である無機組成物と、それを含
有する土壌改質剤と肥料。(57) [Problem] To provide a soil modifying agent and fertilizer rich in acid-soluble silicic acid suitable for rice action. A main component is MgO, a SiO 2, CaO, and MgO 1 to 20% by weight, an amorphous inorganic composition containing SiO 2 30 to 50 wt%, preferably, molar basis (CaO + MgO) / SiO 2
Is an inorganic composition having a ratio of 0.8 to 2.5, and a soil modifying agent and fertilizer containing the same.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、稲等の土壌中から
のケイ酸分を必要とする作物に有用な土づくり資材並び
に肥料として用いることのできる無機組成物、およびそ
の製造方法に関する。The present invention relates to an inorganic composition which can be used as a soil-making material and a fertilizer useful for crops requiring silicic acid from soil such as rice, and a method for producing the same.
【０００２】[0002]
【従来の技術】稲作に有用なケイ酸質肥料として、従来
からケイカル、並びにケイ酸カリ肥料が用いられてい
る。ケイカルはスラグを原料として製造され、Ｓｉ
Ｏ2、ＣａＯ、Ａｌ2Ｏ3を主成分とする、主としてアル
カリ分とケイ酸を補給するための土壌改質剤である。し
かしケイカルは塩酸可溶性ケイ酸分が３０重量％を越え
るものの、実際の土壌のｐＨに近い５〜７程度の領域で
は溶出量が極端に減少し、ケイ酸分の供給源としては非
常に効率の悪い資材である。2. Description of the Related Art Silica fertilizers and silica silicate fertilizers have been conventionally used as useful silicate fertilizers for rice cultivation. Keikal is made from slag,
It is a soil modifier containing O 2 , CaO, and Al 2 O 3 as main components and mainly for replenishing alkali content and silicic acid. However, silica has a hydrochloric acid-soluble silicic acid content of more than 30% by weight, but the elution amount is extremely reduced in a range of about 5 to 7 which is close to the actual soil pH, and is very efficient as a silicic acid source. Bad material.
【０００３】従って、実際に使用する場合も、田１０ａ
当たり２００ｋｇと大量に施肥しなくてはならず、それ
に要する労力が農家の大きな負担になっている。ケイカ
ルは肥料の三要素のいずれをも含まない資材であるた
め、他の肥料と混合して使用するのが一般的であり、例
えばようりん４０ｋｇをケイカル２００ｋｇと混合して
散布するのが広く用いられている処方である。ようりん
は、それに含まれるケイ酸分の中性に近いｐＨ域での溶
出性が高い事が知られており、燐酸質肥料であると同時
にケイ酸質の供給源となっていることが認められてい
る。Therefore, even when actually used, the field 10a
Fertilizer must be applied in a large amount of 200 kg per unit, and the labor required for the fertilization is a heavy burden on farmers. Keikal is a material that does not contain any of the three elements of fertilizers, so it is common to use it by mixing it with other fertilizers. It is a prescribed formula. Yorin is known to have a high dissolution property in the pH range near neutrality of the silicic acid content contained in it, and it is recognized that it is a phosphoric acid fertilizer and at the same time a source of siliceous material. Have been.
【０００４】また、ケイ酸カリ肥料のケイ酸溶出性は、
ケイカルに比べると高いと言われているが、ようりんに
比べるとｐＨ５〜７では劣っており十分とは言えない。
ケイ酸カリ肥料も、ケイカルの場合と同様に、ようりん
と混合して施肥されることが多く、ここでもようりんが
ケイ酸質の供給源としての役割を果たしている。[0004] The dissolution of potassium silicate from potassium silicate fertilizer is as follows.
It is said to be higher than Caical, but it is inferior to Yorin at pH 5-7 and is not sufficient.
Potassium silicate fertilizers are often fertilized in a mixture with iodine, as in the case of silicate, where again, iodine serves as a source of siliceous material.
【０００５】ケイカルの欠点であるケイ酸質溶出性を改
善するために各種の試みがなされ、中でもケイ酸カリ肥
料のケイ酸溶出性が比較的高いことに着目してカリ成分
を加える方法に基づいた、例えばケイ燐酸カリを主成分
とする新規肥料組成物（特公平１−２４７５９号公報）
や緩効性熔成ケイ酸カリ苦土肥料の製造法（特公平２−
２３５１４号公報）が開示されている。Various attempts have been made to improve the dissolution of siliceous material, which is a drawback of silica, based on a method of adding a potash component, focusing on the relatively high dissolution of silicic acid in potassium silicate fertilizers. For example, a novel fertilizer composition containing potassium silicate as a main component (Japanese Patent Publication No. 1-2759).
And production method of slow-release fused potash silicate fertilizer
No. 23514).
【０００６】カリウム成分は、一般に組成物をガラス化
しやすくし、ケイ酸質の溶出性を改善するが、その反
面、カリ原料が高価であるため得られた製品も高価にな
る、十分に高いケイ酸溶出性を確保するにはカリ含有量
を高くしなければらなず不経済である、カリウムが強ア
ルカリであるため製造設備の炉材を浸食する、カリを加
えると溶融物の粘度が上昇するため操業しにくく、それ
を下げようとして温度を上げるとカリが揮散する等の欠
点を有している。[0006] The potassium component generally makes the composition easy to vitrify and improves the dissolution of siliceous substances. On the other hand, the potassium product is expensive, and the resulting product is expensive. Potassium content must be increased to ensure acid dissolution, which is uneconomic. Potassium is a strong alkali, which erodes furnace materials of manufacturing equipment. Adding potassium increases the viscosity of the melt. Therefore, it is difficult to operate, and if the temperature is raised to lower it, potash is volatilized.
【０００７】一方、ようりんに含まれるケイ酸分は溶出
性が高く、植物吸収性が高い事が知られている。市販さ
れているようりんに含まれるＳｉＯ2は２０〜２５重量
％程度であるが、ケイ酸含有量を増やすとその溶出率が
低下する事が知られている。すなわち、溶成燐肥の一般
的な原料配合にケイ石を加えて加熱溶融・急冷して、２
％クエン酸水溶液へのケイ酸の溶出性を測定した試験例
（工業化学雑誌第６０巻１１０９頁１９５７年）によれ
ば、２％クエン酸溶液（ｐＨの初期値が２）へのケイ酸
溶出量は３０重量％程度で頭打ちになると記載されてい
る。On the other hand, it is known that the silicic acid component contained in yorin has a high elution property and a high plant absorbability. As is commercially available, the amount of SiO 2 contained in phosphorus is about 20 to 25% by weight, but it is known that the elution rate decreases as the content of silicic acid increases. That is, silica is added to a general raw material mixture of fused phosphorus fertilizer, heated, melted and quenched to obtain
According to a test example in which the dissolution property of silicic acid into an aqueous solution of 2% citric acid was measured (Industrial Chemistry Magazine Vol. 60, 1109, 1957), dissolution of silicic acid into a 2% citric acid solution (the initial value of pH was 2) The amount is stated to reach a plateau at about 30% by weight.
【０００８】又、特公平２−２３５１４号公報には、ｐ
Ｈが４の酢酸ソーダ緩衝液を用いた可溶性ケイ酸の評価
法が、植物吸収性との相関性が高いと記載されている
が、実際の土壌のｐＨはもっと中性に近く、たまたま試
験に使用した組成物のこの方法による溶出性が植物吸収
性と一致したと解釈するべきと思われる。ケイ酸質の溶
出性試験に関しては未だ公定法がなく、様々な方法が提
案されている。In Japanese Patent Publication No. 23514/1990, p.
Although the method for evaluating soluble silicic acid using sodium acetate buffer with H of 4 is described as having a high correlation with plant absorption, the actual soil pH is closer to neutral, and it happens to be a test. It is believed that the dissolution of the composition used by this method was consistent with plant absorbability. There is no official method for the dissolution test of siliceous substances, and various methods have been proposed.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、少量の施肥
で有効な、特に実際の土壌のｐＨ５〜７付近で溶出性の
高いＳｉＯ2を３０重量％以上含む無機組成物を提供す
ることにより、ケイ酸を主体として、アルカリ分を含む
資材を供給することを目的とする。更に、本発明は、通
常のようりん製造設備を用いて容易に製造することがで
き、カリを含んでいないので安価に製造できる、稲等の
土壌中にケイ酸分が必要とされる作物に用いられるケイ
酸質肥料並びに土壌改良剤を提供することを目的とす
る。[0008] The present invention, by providing a small amount of fertilizer in an efficient, inorganic compositions comprising high eluting SiO 2 30% by weight or more in the vicinity pH5~7 actual soil particularly It is intended to supply a material mainly containing silicic acid and containing an alkali component. Furthermore, the present invention is useful for crops that require silicic acid in the soil, such as rice, which can be easily produced using a conventional phosphorus production facility and can be produced at low cost because they do not contain potassium. It is an object to provide a siliceous fertilizer and a soil conditioner to be used.
【００１０】[0010]
【課題を解決するための手段】本発明は、ＭｇＯ、Ｓｉ
Ｏ2、ＣａＯを主成分とし、前記成分の総計中にＭｇＯ
を１〜２０重量％、ＳｉＯ2を３０〜５０重量％含有
し、しかも非晶質の無機組成物である。また、モル比
（ＣａＯ＋ＭｇＯ）／ＳｉＯ2が０．８〜２．５である
ことを特徴とする無機組成物である。更に、４重量％ク
エン酸ソーダ緩衝液（ｐＨの初期値が５．５）へのケイ
酸の溶出率が５０％以上であることを特徴とする無機組
成物であり、ＮＭＲ−29Ｓｉを測定した時にケミカルシ
フト値が−８０ｐｐｍ以上−７１ｐｐｍ以下であり、そ
の半値幅が１２ｐｐｍ以上２３ｐｐｍ以下であることを
特徴とする無機組成物である。SUMMARY OF THE INVENTION The present invention relates to a method for producing MgO, Si
O 2 and CaO as main components, and MgO in the total of the above components
1-20% by weight, the SiO 2 containing 30 to 50 wt%, yet is an amorphous inorganic composition. Further, the inorganic composition is characterized in that the molar ratio (CaO + MgO) / SiO 2 is 0.8 to 2.5. Further, an inorganic composition 4 wt% sodium citrate buffer (pH initial value 5.5) dissolution rate of silicic acid to is characterized in that at least 50%, measured NMR-29 Si The inorganic composition has a chemical shift value of -80 ppm or more and -71 ppm or less, and a half width of 12 ppm or more and 23 ppm or less.
【００１１】本発明は、原料を所望組成に配合し、加熱
溶融して得られる溶融物を、急冷することを特徴とする
前記の無機組成物の製造方法である。[0011] The present invention is the above-mentioned method for producing an inorganic composition, which comprises blending raw materials into a desired composition and rapidly cooling a melt obtained by heating and melting.
【００１２】また、本発明は前記の無機組成物を含有す
ることを特徴とする肥料、並びに土壌改質剤である。[0012] The present invention is also a fertilizer and a soil modifier containing the above-mentioned inorganic composition.
【００１３】[0013]
【発明の実施の形態】本発明は、本発明者らが、ｐＨ＝
５以上の高いｐＨ域で高い溶出性を持つＳｉＯ2を含む
組成を探求した結果、同じ組成であってもその結晶性に
よって、溶出性が大きく変化すること、そして、特定組
成を有する非晶質の組成物が前記高ｐＨ域でケイ酸溶出
性を示すことを見い出し、なされたものであるDETAILED DESCRIPTION OF THE INVENTION The present invention relates to
As a result of exploring a composition containing SiO 2 having a high dissolution property in a high pH range of 5 or more, the dissolution property is largely changed by the crystallinity even if the composition is the same, and an amorphous material having a specific composition is obtained. Have been found to exhibit silicic acid elution properties in the high pH range, and have been made.
【００１４】本発明は、主成分がＭｇＯ、ＳｉＯ2、Ｃ
ａＯからなり、ＭｇＯを１〜２０重量％、ＳｉＯ2を３
０〜５０重量％含有し、しかも非晶質であることを特徴
とする無機組成物である。本発明において、無機組成物
の主成分は、ＭｇＯ、ＳｉＯ 2、ＣａＯから構成され、
その合計量は８７重量％以上、好ましくは９０重量％以
上あれば良い。従来公知のケイ酸溶出性を有するものの
多くは、例えばケイ酸カリ肥料の如くに、カリウムを主
成分として含有するのに対し、本願発明の無機組成物は
これを主成分として有しない特徴がある。これにより、
製品価格が高くなる、製造設備の炉材を浸食する、操業
しにくい等の欠点を解消することが出来る。According to the present invention, the main components are MgO, SiOTwo, C
aO, MgO of 1 to 20% by weight, SiOTwo3
It is characterized by containing 0 to 50% by weight and being amorphous
It is an inorganic composition. In the present invention, the inorganic composition
Is mainly composed of MgO, SiO Two, CaO,
The total amount is 87% by weight or more, preferably 90% by weight or less.
I just want to go up. Although it has a conventionally known silicic acid elution property,
Many use potassium mainly, for example, potassium silicate fertilizers.
In contrast to containing as an ingredient, the inorganic composition of the present invention is
There is a feature not having this as a main component. This allows
Higher product prices, erosion of furnace materials in manufacturing facilities, operations
It is possible to eliminate disadvantages such as difficulty in carrying out.
【００１５】本発明の無機組成物はケイ酸の溶出性を高
めるために非晶質であることが必須である。非晶質の程
度については、本発明者らの実験的検討結果によれば、
ＮＭＲ−29Ｓｉのケミカルシフト値（以下、単にＮＭＲ
−Ｓｉという）について、半値幅が１０ｐｐｍ以上の拡
がりを有するものであれば充分である。It is essential that the inorganic composition of the present invention is amorphous in order to enhance the dissolution of silicic acid. Regarding the degree of amorphousness, according to the experimental study results of the present inventors,
NMR-29 Si chemical shift value (hereinafter, simply NMR
-Si), it is sufficient that the half width has a spread of 10 ppm or more.
【００１６】本発明の無機組成物は、ＳｉＯ2含有量が
３０重量％以上である。これより少ないと、十分なケイ
酸溶出量が確保できず、ケイ酸質資材或いは肥料として
の価値が減少する。５０重量％を越えると大幅にＳｉＯ
2溶出性が下がり、中性に近い領域での溶出性が悪くな
る。３２〜４５重量％が好ましい範囲である。The inorganic composition of the present invention has a SiO 2 content of 30% by weight or more. If the amount is less than this, a sufficient amount of silicic acid elution cannot be secured, and the value as siliceous material or fertilizer decreases. If it exceeds 50% by weight, SiO
(2) The elution property decreases, and the elution property in a region near neutrality deteriorates. A preferred range is 32 to 45% by weight.
【００１７】ＭｇＯは、無機組成物の溶融温度を下げる
効果やケイ酸溶出率を増大させる効果があり、また肥料
成分としても有効なので、適当量含有させる必要があ
る。１重量％以下ではこれらの効果が十分ではなく、２
０重量％をこえると施用した植物の肥効成分の吸収性に
拮抗作用を生じ、不都合である。上記バランスから、７
〜１８重量％が好ましい範囲である。Since MgO has the effect of lowering the melting temperature of the inorganic composition and the effect of increasing the dissolution rate of silicic acid, and is also effective as a fertilizer component, it must be contained in an appropriate amount. Below 1% by weight, these effects are not sufficient,
If the amount is more than 0% by weight, the absorption of the fertilizing component of the applied plant is antagonized, which is inconvenient. From the above balance, 7
-18% by weight is a preferred range.
【００１８】また、本発明の無機組成物について、モル
換算した（ＣａＯ＋ＭｇＯ）／ＳｉＯ2比が０．８〜
２．５であることが好ましい。前記比が０．８より小さ
くなるとＳｉＯ2溶出量が減少する一方、２．５を超え
るとＳｉＯ2含有量の低下や融点の上昇とＳｉＯ2溶出性
の低下が起こることがある。１．１〜２．０が好ましい
範囲である。The inorganic composition of the present invention has a molar ratio (CaO + MgO) / SiO 2 ratio of 0.8 to 0.8.
It is preferably 2.5. If the ratio is less than 0.8, the amount of SiO 2 eluted decreases, while if it exceeds 2.5, the SiO 2 content may decrease, the melting point may increase, and the SiO 2 elution property may decrease. 1.1 to 2.0 is a preferable range.
【００１９】本発明の無機組成物において、主成分を構
成する前記成分の他に、微量成分として有効な硼素やマ
ンガンを含有させることもできる。硼素やマンガンの存
在は、後述する製造方法において、溶融温度の低下や溶
融物の流動性の増加の効果があるし、得られる無機組成
物の非晶質化を促し、ケイ酸の溶出性を助長するという
効果もある。また、不可避的に混入する鉄酸化物やアル
ミニウムの酸化物などが含まれてもよい。しかし、アル
ミニウムについては、肥料効果が無く、有効成分の含有
量を低下させ、また、量が多くなるとケイ酸分の溶出性
に悪影響を及ぼすので、Ａｌ2Ｏ3の量は２重量％以下に
抑制することが好ましい。In the inorganic composition of the present invention, boron or manganese which is effective as a minor component may be contained in addition to the components constituting the main component. The presence of boron or manganese has the effect of lowering the melting temperature or increasing the fluidity of the melt in the production method described below, promotes the amorphousization of the obtained inorganic composition, and increases the dissolution of silicic acid. There is also an effect of promoting. In addition, iron oxide or aluminum oxide that is unavoidably mixed may be included. However, aluminum does not have a fertilizer effect, reduces the content of the active ingredient, and an increase in the amount adversely affects the dissolution of silicic acid, so that the amount of Al 2 O 3 is 2% by weight or less. Preferably, it is suppressed.
【００２０】本発明の無機組成物は、４重量％クエン酸
緩衝液（ｐＨの初期値が５．５）へのケイ酸の溶出率は
５０％以上、好ましい組成範囲の無機組成物では７０％
以上であるという特徴を有し、また、ＮＭＲによる29Ｓ
ｉの結合状態の測定結果によれば、−８０ｐｐｍ以上−
７１ｐｐｍ以下にケミカルシフト値が見られ、またその
半値幅は１２ｐｐｍ以上２３ｐｐｍ以下を示す。ここ
で、本発明の溶出率とは、前記クエン酸緩衝液中に溶出
したケイ酸に相当するＳｉＯ2量を、無機組成物中の全
ＳｉＯ2量に対して百分率で表したものである。The inorganic composition of the present invention has an elution rate of silicic acid of 50% or more in a 4% by weight citrate buffer (initial pH value is 5.5), and 70% in an inorganic composition having a preferable composition range.
And 29 S by NMR.
According to the measurement result of the bonding state of i, -80 ppm or more-
A chemical shift value is observed at 71 ppm or less, and its half width is 12 ppm to 23 ppm. Here, the dissolution rate of the present invention, the SiO 2 amount corresponding to silicic acid eluted in the citrate buffer, which was expressed in percentage relative to the total amount of SiO 2 of the inorganic composition.
【００２１】無機組成物、特に肥料、土壌改質剤等のケ
イ酸分の溶出性を調べる方法としては、前記したとおり
に、２％クエン酸水溶液（ｐＨが約２）を用いる方法、
ｐＨの初期値が４の酢酸ソーダ緩衝液を用いる方法が知
られているが、いずれも溶出時のｐＨが低く、土壌のｐ
Ｈに近いｐＨ＝５〜７付近でのケイ酸の溶出性の評価方
法としては不適切である。本発明者らは、いろいろ検討
した結果、４重量％クエン酸緩衝液（ｐＨの初期値が
５．５）を用いる方法が好適であることを見出したもの
である。この方法により、肥料、土壌改質剤の土壌への
ケイ酸分の溶出性について、その評価が可能となる。As a method for examining the dissolution property of a silicic acid component of an inorganic composition, particularly a fertilizer, a soil modifier, etc., as described above, a method using a 2% citric acid aqueous solution (pH: about 2),
A method using a sodium acetate buffer having an initial pH of 4 is known.
It is not suitable as a method for evaluating the dissolution property of silicic acid at pH close to H = 5 to 7. As a result of various studies, the present inventors have found that a method using a 4% by weight citrate buffer (the initial value of pH is 5.5) is suitable. With this method, it is possible to evaluate the dissolution of silicic acid into soil by the fertilizer and the soil modifier.
【００２２】本発明における可溶性ケイ酸の評価方法
は、４重量％クエン酸緩衝液（ｐＨの初期値が５．５）
を用いることを特徴とし、次に例示するように行えば良
い。即ち、多量の肥料或いは土壌改質剤の場合につい
て、前記の肥料或いは土壌改質剤より約１００ｇのサン
プルを従来公知の方法で採取し、前記サンプルを振動ミ
ルで粉砕し、目開き１５０ミクロンの篩下とし、可溶性
ケイ酸の評価試料とする。前記評価試料を１ｇはかりと
り、クエン酸水溶液に２Ｎ水酸化ナトリウム水溶液を加
えてｐＨを５．５に調整した４重量％クエン酸ソーダ緩
衝液１５０ｍｌを加えて、３０℃水浴中で１時間揺動す
る。前記溶液をろ紙でろ過して得られるろ液を純水で希
釈した後、ろ液中に含まれるＳｉＯ2量をＩＣＰ（誘導
結合プラズマ発光分光法）で測定する。In the method for evaluating soluble silicic acid in the present invention, a 4% by weight citrate buffer (the initial pH value is 5.5)
The following is an example. That is, in the case of a large amount of fertilizer or soil modifying agent, a sample of about 100 g from the fertilizer or soil modifying agent is collected by a conventionally known method, and the sample is pulverized by a vibration mill to obtain a 150 μm mesh. The sample is placed under a sieve and used as an evaluation sample for soluble silicic acid. Weigh 1 g of the evaluation sample, add 150 ml of a 4% by weight sodium citrate buffer adjusted to pH 5.5 by adding a 2N aqueous sodium hydroxide solution to the aqueous citric acid solution, and rock for 1 hour in a 30 ° C. water bath. I do. After the filtrate obtained by filtering the solution with filter paper is diluted with pure water, the amount of SiO 2 contained in the filtrate is measured by ICP (inductively coupled plasma emission spectroscopy).
【００２３】また、ＮＭＲ−29Ｓｉの測定は、無機組成
物を振動ミルで粉砕して、目開き１５０ミクロンの篩下
とし、例えば、日本電子製ＧＸ２７０を用いて、マジッ
クアングルスピニング下にハイパワーデカップリングを
組み合わせたモードで１０秒間隔に約８０００回の積算
を行い、ケミカルシフトの調整としてポリジメチルシラ
ンを−３３．８ｐｐｍとして、測定すればよい。尚、ア
ダマンタンを用いて13Ｃの高磁場側共鳴ピークの半値幅
が０．１４７〜０．０７２ｐｐｍとなる様に調整し、こ
の条件下で調整したときに、単結晶シリコンの半値幅は
０．７ｐｐｍであった。本発明の無機組成物は、前記条
件で測定したときに、得られるＮＭＲ− 29Ｓｉが−８０
ｐｐｍ以上−７１ｐｐｍ以下にケミカルシフト値を示
し、その半値幅が１２〜２３ｐｐｍの間で様々な値を示
す。Also, NMR-29Si measurement is based on inorganic composition
The material is pulverized with a vibration mill and sieved with a sieve with an aperture of 150 microns.
For example, using JEOL GX270, magic
High power decoupling under angle spinning
Approximately 8,000 accumulations at 10-second intervals in combined mode
To adjust the chemical shift
The measurement may be performed with -33.8 ppm. In addition,
With damantan13Half width of the high magnetic field side resonance peak of C
Is adjusted to be 0.147 to 0.072 ppm.
When adjusted under the conditions of
0.7 ppm. The inorganic composition of the present invention,
NMR- 29Si is -80
Chemical shift value is shown in the range from ppm to -71 ppm.
And its half-value width shows various values between 12 and 23 ppm.
You.
【００２４】本発明の無機組成物のＮＭＲ−Ｓｉについ
て、そのチャート上のピーク形状は略組成によって決ま
るが、製造方法によっても影響される。特に、後述する
本発明の製造方法によれば、同じ組成物であってもより
ピークの半値幅の大きいものが得られる。Regarding the NMR-Si of the inorganic composition of the present invention, the peak shape on the chart is substantially determined by the composition, but is also affected by the manufacturing method. In particular, according to the production method of the present invention described below, even with the same composition, a composition having a larger half width of the peak can be obtained.
【００２５】更に、本発明者らは、無機組成物のケイ酸
の溶出率とＮＭＲ−Ｓｉのケミカルシフト値が相関する
事を見いだしたものであり、具体的には、−８０ｐｐｍ
以上−７１ｐｐｍ以下にケミカルシフト値を有し、その
半値幅が１２ｐｐｍ以上２３ｐｐｍ以下である無機組成
物は、ケイ酸分のｐＨの初期値が５．５のクエン酸緩衝
液溶出率が７０％以上である。Further, the present inventors have found that the elution rate of silicic acid in the inorganic composition and the chemical shift value of NMR-Si are correlated, and specifically, -80 ppm.
The inorganic composition having a chemical shift value of not less than -71 ppm or less and a half value width of not less than 12 ppm and not more than 23 ppm has a citrate buffer elution rate of 70% or more when the initial value of the pH of silicic acid is 5.5. It is.
【００２６】前記の相関性を用い、試料の固体ＭＮＲ測
定を行うことのみで、前記溶出率を容易に推定すること
ができ、手間のかかる可溶性ケイ酸の評価を省略するこ
ともできる。クエン酸溶液を用いるケイ酸の溶出性の測
定においては、溶液中の共存イオンの影響や、溶出後の
溶液のｐＨの変化、溶出したケイ酸の再重合等分析上の
いろいろな問題が生じるが、ＮＭＲ−Ｓｉの測定におい
ては前記煩わしさがない。The elution rate can be easily estimated only by performing solid-state MNR measurement of the sample using the above-mentioned correlation, and the troublesome evaluation of soluble silicic acid can be omitted. In the measurement of dissolution of silicic acid using a citric acid solution, there are various analytical problems such as the effect of coexisting ions in the solution, changes in the pH of the solution after elution, and repolymerization of the eluted silicic acid. And in the measurement of NMR-Si, there is no such inconvenience.
【００２７】ＮＭＲ−Ｓｉに基づく可溶性ケイ酸の評価
の方法に関しては、従来公知の方法に比較して、正確性
においても優れているという効果を有している。即ち、
ＮＭＲ−Ｓｉのケミカルシフト値はＳｉＯ4の４面体構
造のつながりの状態を反映し、半値幅は原子配置のラン
ダムさを表していると考えられる。原子配置のランダム
さ、すなわち非晶質状態を判別する方法としては、一般
にＸ線回折装置を用いて回折パターンを見る方法があ
る。しかし、同じ組成の試料でＸ線回折で同じ様なブロ
ードなパターンが得られた試料であっても、ケイ酸の溶
出性が異なっている場合があった。また、他のガラス化
状態の判別法として、光学顕微鏡を用いブロモホルムを
滴下し透過光下で試料粒子一個一個の状態を調べて、そ
の個数からガラス化状態を定量的に把握する方法が知ら
れている（工業化学雑誌６３巻４７７頁１９６０年）
が、この方法は非常に手間のかかる方法であった。The method for evaluating soluble silicic acid based on NMR-Si has the effect of being superior in accuracy as compared with conventionally known methods. That is,
It is considered that the chemical shift value of NMR-Si reflects the connected state of the tetrahedral structure of SiO 4 , and the half-value width represents the randomness of the atom arrangement. As a method of determining the randomness of the atomic arrangement, that is, the amorphous state, there is generally a method of observing a diffraction pattern using an X-ray diffractometer. However, even in a sample having the same composition and a similar broad pattern obtained by X-ray diffraction, the elution property of silicic acid was sometimes different. As another method for determining the vitrification state, a method is known in which bromoform is dropped using an optical microscope, the state of each sample particle is examined under transmitted light, and the vitrification state is quantitatively grasped from the number. (Industrial Chemistry Magazine Vol. 63, p. 477, 1960)
However, this method was very time-consuming.
【００２８】本発明の無機組成物を得る方法に関して
は、原料として、蛇紋岩、ケイ石、石灰石、フェロニッ
ケル鉱滓、フェロマンガン鉱滓、各種高炉滓、各種製鋼
滓、製リンスラグ、フライアッシュ等のＣａＯ、Ｍｇ
Ｏ、或いはＳｉＯ2を含有する通常の原料類を利用する
ことができる。上記原料の中にはアルミナ分（Ａｌ
2Ｏ3）を含むものもあるが、Ａｌ2Ｏ3の存在はケイ酸溶
出率を悪化させ、またＡｌ2Ｏ3含有量が増加すると他の
成分の含有量が実質的に減るので、Ａｌ2Ｏ3含有量の増
大は好ましくない。Ａｌ2Ｏ3が含まれていない原料を使
用するか、またはＡｌ2Ｏ3が含まれている原料は少量に
限定して使用し、得られる無機組成物中のＡｌ2Ｏ3含有
量が２重量％以下とすることが好ましい。With regard to the method for obtaining the inorganic composition of the present invention, as raw materials, CaO such as serpentine, quartzite, limestone, ferronickel slag, ferromanganese slag, various blast furnace slags, various steelmaking slags, rinse slag, fly ash, etc. , Mg
Ordinary raw materials containing O or SiO 2 can be used. Among the above raw materials, an alumina component (Al
Some contain Al 2 O 3 ), but the presence of Al 2 O 3 deteriorates the dissolution rate of silicic acid, and when the content of Al 2 O 3 increases, the content of other components substantially decreases. An increase in the 2 O 3 content is not preferred. Al 2 O 3 or to use a material that does not contain, or Al 2 materials O 3 is included is used is limited to small amounts, Al 2 O 3 content of the inorganic composition obtained is 2 % By weight or less.
【００２９】前記原料を、揮発分の量等を考慮し、生成
物が所望組成となるように、即ち、ＭｇＯを１〜２０重
量％、ＳｉＯ2を３０〜５０重量％含有するように、好
ましくは、モル比（ＣａＯ＋ＭｇＯ）／ＳｉＯ2が０．
８〜２．５となるように、配合し、高温で溶融する。Considering the amount of volatile components and the like, the raw material is preferably adjusted so that the product has a desired composition, that is, contains 1 to 20% by weight of MgO and 30 to 50% by weight of SiO 2. Has a molar ratio (CaO + MgO) / SiO 2 of 0.1.
It is blended so as to be 8 to 2.5 and melted at a high temperature.
【００３０】前記溶融に用いる炉（溶融炉）は、外熱式
電気炉、アーク炉、高周波加熱炉等の電気炉、或いは平
炉を初めとするいろいろな燃焼ガス炉等が使用できる。
溶融温度は、組成にもよるが１３５０℃以上が望まし
い。目標とする組成を有する原料が完全に溶融する温度
より、およそ１５０℃以上高い温度で溶融すると、溶融
温度から結晶化の進まない温度までの間で十分な冷却速
度がとれるため好ましい。前記溶融炉のうち、後述する
とおりに、溶融液を急冷することができ、非晶質化した
無機組成物を容易に得ることができることから電気炉、
並びに平炉が選択される。As the furnace (melting furnace) used for the above-mentioned melting, an electric furnace such as an external heating electric furnace, an arc furnace, a high-frequency heating furnace or the like, or various combustion gas furnaces including a flat furnace can be used.
The melting temperature is desirably 1350 ° C. or higher, depending on the composition. It is preferable to melt at a temperature about 150 ° C. or more higher than the temperature at which the raw material having the target composition is completely melted, since a sufficient cooling rate can be obtained from the melting temperature to a temperature at which crystallization does not proceed. Among the melting furnaces, as described below, the melt can be quenched, and an electric furnace can be obtained easily because an amorphous inorganic composition can be obtained.
And the open hearth is selected.
【００３１】溶融液の急冷は、得られる無機組成物の非
晶質化を達成し、ケイ酸の溶出性を高めるために必須で
ある。急冷は、一般には、炉から抜き出した溶融液に溶
融液の２０〜４０倍の重量の水を吹き付ける方法や、多
量の水中に浸漬する方法等を適用することによって行わ
れる。本発明の無機組成物を得る際の冷却方法として
は、溶融温度から１００℃までの所要時間は２０秒以下
好ましくは１０秒以下とすることがよく、特に、原料が
完全に溶融する温度の上下２００℃の間を５秒以内とす
る事が望ましいので、このため、ジェット水流を当てて
冷却する方法が好ましい。更に、ジェット水流を用いる
冷却方法は、溶融液より砂状物を直接に得られ、後工程
としての粉砕を省略することもできるという効果も得ら
れる。The quenching of the melt is indispensable in order to attain the amorphous composition of the obtained inorganic composition and to enhance the dissolution of silicic acid. The quenching is generally performed by applying a method of spraying water having a weight 20 to 40 times the weight of the molten liquid to the molten liquid extracted from the furnace, or a method of immersing the molten liquid in a large amount of water. As a cooling method for obtaining the inorganic composition of the present invention, the time required from the melting temperature to 100 ° C. is preferably 20 seconds or less, and more preferably 10 seconds or less. Since it is desirable to keep the temperature between 200 ° C. within 5 seconds, a method of cooling by applying a jet water stream is preferable. Further, the cooling method using the jet water stream has an effect that a sandy substance can be directly obtained from the molten liquid, and the pulverization as a subsequent step can be omitted.
【００３２】得られた砂状物はそのままでも肥料、土壌
改質剤として利用できるが、更に、必要に応じて粉砕や
造粒をすることにより、施肥の際に取り扱い易くした形
態にして供給することもできる。また、必要に応じて、
窒素、カリなどの他の肥料を混合して、所望の組成の複
合肥料とすることもできる。The obtained sandy substance can be used as it is as a fertilizer or a soil modifier, but is further supplied by pulverizing or granulating as necessary so that it can be easily handled during fertilization. You can also. Also, if necessary,
Other fertilizers such as nitrogen and potash can be mixed into a composite fertilizer having a desired composition.
【００３３】[0033]
【実施例】以下、実施例及び比較例に基づいて、本発明
を更に詳細に説明する。The present invention will be described below in more detail with reference to Examples and Comparative Examples.
【００３４】〔実施例１〕蛇紋岩、フェロニッケル鉱
滓、ケイ石、炭酸カルシウム（和光純薬製）を、それぞ
れ２．１６ｇ、０．３４ｇ、３．２５ｇ、８．０６ｇ混
合し、白金坩堝に入れて、シリコニット電気炉内に置き
１５５０℃で加熱溶融した。電気炉から取り出した溶融
物をすばやく水中に投入して組成物を得た。Example 1 2.16 g, 0.34 g, 3.25 g, and 8.06 g of serpentine, ferronickel slag, quartzite, and calcium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and placed in a platinum crucible. It was placed in a siliconite electric furnace and heated and melted at 1550 ° C. The melt taken out of the electric furnace was quickly poured into water to obtain a composition.
【００３５】この組成物は、ＳｉＯ2、ＭｇＯ、ＣａＯ
をそれぞれ４２．２重量％、９．８重量％、４５．６重
量％含んでいた。従って、モル比（ＣａＯ＋ＭｇＯ）／
ＳｉＯ2は１．５０である。This composition comprises SiO 2 , MgO, CaO
Was 42.2% by weight, 9.8% by weight, and 45.6% by weight, respectively. Therefore, the molar ratio (CaO + MgO) /
SiO 2 is 1.50.
【００３６】前記組成物を粉砕・分級して１５０ミクロ
ン下の粉として、以下の評価に用いた。４％クエン酸ソ
ーダ緩衝液（ｐＨの初期値が５．５）への溶出ケイ酸量
（以下、Ｃ−ＳｉＯ2量と呼ぶ）は３１．２％、溶出率
（以下、ク溶率と呼ぶ）は７４％だった。ＮＭＲ−Ｓｉ
の測定を行ったところ、ピーク位置は−７５．３ｐｐ
ｍ、半値幅は１６．０ｐｐｍだった。The above composition was pulverized and classified and used as powder having a size of 150 μm or less in the following evaluation. 4% sodium citrate buffer eluted silicate amount (initial value of pH 5.5) to (hereinafter, referred to as C-SiO 2 weight) 31.2%, the dissolution rate (hereinafter, referred to as click溶率) Was 74%. NMR-Si
Was measured, the peak position was -75.3 pp.
m, and the half width was 16.0 ppm.
【００３７】〔実施例２〕蛇紋岩、フェロニッケル鉱
滓、ケイ石、炭酸カルシウム（和光純薬製）を、それぞ
れ３．３２ｇ、０．３４ｇ、２．８１ｇ、６．９６ｇ混
合し、実施例１と同じ操作により組成物を得た。Example 2 3.31 g, 0.34 g, 2.81 g and 6.96 g of serpentine, ferronickel slag, quartzite and calcium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, respectively. A composition was obtained by the same operation as described above.
【００３８】この組成物は、ＳｉＯ2、ＭｇＯ、ＣａＯ
をそれぞれ４２．２重量％、１４．３重量％、３９．４
重量％含んでいた。従って、モル比（ＣａＯ＋ＭｇＯ）
／ＳｉＯ2は１．５１である。This composition is composed of SiO 2 , MgO, CaO
Of 42.2% by weight, 14.3% by weight, 39.4%
% By weight. Therefore, the molar ratio (CaO + MgO)
/ SiO 2 is 1.51.
【００３９】この組成物を粉砕・分級して１５０ミクロ
ン下の粉を以下の評価に用いた。Ｃ−ＳｉＯ2量は３
８．１％、ク溶率は９０％だった。ＮＭＲ−Ｓｉのピー
ク位置は−７３．５ｐｐｍ、半値幅は１６．７ｐｐｍだ
った。This composition was pulverized and classified, and a powder having a size of 150 microns was used for the following evaluation. The amount of C-SiO 2 is 3
The dissolution rate was 8.1% and the dissolution rate was 90%. The peak position of NMR-Si was -73.5 ppm, and the half width was 16.7 ppm.
【００４０】〔実施例３〕蛇紋岩、フェロニッケル鉱
滓、ケイ石、石灰岩、コレマナイト、マンガンスラグ
を、それぞれ３１．１ｋｇ、３．４ｋｇ、２５．１ｋ
ｇ、６７．５ｋｇ、１．６ｋｇ、４．７ｋｇ混合し、１
００ｋＶＡの直流アーク式電気炉に投入し通電して加熱
溶融した。電気炉のタップ口から流れ出た溶融物にジェ
ット水流を吹き付け、急冷し、水砕した。Example 3 Serpentine, ferronickel slag, quartzite, limestone, colemanite, and manganese slag were respectively 31.1 kg, 3.4 kg, and 25.1 k.
g, 67.5 kg, 1.6 kg, 4.7 kg
It was charged into a 00 kVA DC arc type electric furnace, energized, and heated and melted. A jet stream was sprayed on the melt flowing out of the tap of the electric furnace, rapidly cooled, and granulated.
【００４１】この水砕物は、ＳｉＯ2、ＭｇＯ、ＣａＯ
をそれぞれ４１．０重量％、１３．７重量％、３８．３
重量％含んでいた。従って、モル比（ＣａＯ＋ＭｇＯ）
／ＳｉＯ2は１．５０である。The granulated product is made of SiO 2 , MgO, CaO
Of 41.0% by weight, 13.7% by weight and 38.3% by weight, respectively.
% By weight. Therefore, the molar ratio (CaO + MgO)
/ SiO 2 is 1.50.
【００４２】この水砕物を粉砕・分級して１５０ミクロ
ン下の粉を以下の分析に用いた。Ｃ−ＳｉＯ2量は３
３．８％、ク溶率は８５％だった。ＮＭＲ−Ｓｉのピー
ク位置は−７５．０ｐｐｍ、半値幅は２０．０ｐｐｍだ
った。The granulated product was pulverized and classified, and a powder having a size of 150 μm was used for the following analysis. The amount of C-SiO 2 is 3
3.8%, and the dissolution rate was 85%. The peak position of NMR-Si was -75.0 ppm, and the half width was 20.0 ppm.
【００４３】〔比較例〕蛇紋岩、フェロニッケル鉱滓、
ケイ石、炭酸カルシウム（和光純薬製）を、それぞれ
０．９７ｇ、０．３４ｇ、５．７４ｇ、５．６１ｇ混合
し、実施例１と同じ操作により組成物を得た。Comparative Example Serpentine, ferronickel slag,
0.97 g, 0.34 g, 5.74 g, and 5.61 g of silica stone and calcium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and a composition was obtained in the same manner as in Example 1.
【００４４】この組成物は、ＳｉＯ2、ＭｇＯ、ＣａＯ
をそれぞれ６１．５重量％、５．０重量％、３１．９重
量％含んでいた。従って、モル比（ＣａＯ＋ＭｇＯ）／
ＳｉＯ2は０．６８である。This composition comprises SiO 2 , MgO, CaO
Of 61.5% by weight, 5.0% by weight and 31.9% by weight, respectively. Therefore, the molar ratio (CaO + MgO) /
SiO 2 is 0.68.
【００４５】この組成物を粉砕・分級して１５０ミクロ
ン下の粉を以下の評価に用いた。Ｃ−ＳｉＯ2量は０．
７％、ク溶率は１％だった。This composition was pulverized and classified, and the powder having a size of 150 microns was used for the following evaluation. The amount of C-SiO 2 is 0.1.
The dissolution rate was 7%.
【００４６】[0046]
【発明の効果】本発明の無機組成物は、全ＳｉＯ2中の
４重量％クエン酸緩衝液（ｐＨの初期値が５．５）への
溶出率が５０％以上であり、土壌中への可溶性ケイ酸を
多く含むという特徴を有し、しかもその組成中にはカリ
ウム等のアルカリ金属元素を含有しないので製造しやす
いという特徴を有するので、土壌中のケイ酸分が有用な
働きをする作物、特に稲作用の土づくり資材あるいは肥
料として有用である。The inorganic composition of the present invention has an elution rate of 50% or more in a 4% by weight citrate buffer (the initial pH value is 5.5) in total SiO 2 , Crops that have a feature that they contain a lot of soluble silicic acid, and that they do not contain alkali metal elements such as potassium in their composition, making them easy to produce. It is especially useful as a soil-making material or fertilizer for rice action.
【００４７】本発明の肥料、土壌改質剤はいずれも、土
壌中への可溶性ケイ酸を多く含むので、少ない施肥量で
充分であり農家の省力化が可能となる特徴がある。ま
た、燐酸分を含まない、若しくは少量であることから、
各種単肥との混合散布により個々の土地に適した施肥が
可能であること、ケイ酸質の土壌への吸収性が良く作物
の病虫害の発生が抑制されること、各種の肥料成分の吸
収を助長し、作物の収量を増加させることができるこ
と、緩効性であり肥あたりを起こさないこと、水には難
溶性であるので雨水に流亡せず肥料散布の回数を減らす
ことができる等の数々の利点を有する。Since both the fertilizer and the soil modifier of the present invention contain a large amount of soluble silicic acid in the soil, a small amount of fertilization is sufficient and the labor of the farmer can be saved. In addition, since it does not contain phosphoric acid or is a small amount,
It is possible to apply fertilizer suitable for individual land by mixing and spraying with various single fertilizers, absorb silicic acid well to the soil, suppress the occurrence of pests and diseases of crops, and absorb various fertilizer components. It can promote and increase crop yields, is slow-acting and does not cause fertilization, and is hardly soluble in water, so it can be run down to rainwater and the number of times of fertilizer application can be reduced. Has the advantage of
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０５Ｄ 3:00 5:00） Ｃ０９Ｋ 101:00 (72)発明者 古川 洋一郎 東京都町田市旭町３丁目５番１号 電気化 学工業株式会社総合研究所内 (72)発明者 冨田 誠 東京都町田市旭町３丁目５番１号 電気化 学工業株式会社総合研究所内 Ｆターム(参考） 4H026 AA01 AA04 AA06 AB04 4H061 AA01 AA02 AA10 CC02 CC12 CC17 DD14 EE01 EE12 EE14 GG18 GG20 GG23 GG41 HH04 HH11 KK01 LL14 LL22 LL25 LL26 Continuation of the front page (51) Int.Cl. 7 Identification code FI Theme coat II (reference) C05D 3:00 5:00) C09K 101: 00 (72) Inventor Yoichiro Furukawa 3-5-1 Asahicho, Machida-shi, Tokyo No. Within the Research Institute of Denki Kagaku Kogyo Co., Ltd. (72) Inventor Makoto Tomita 3-5-1 Asahicho, Machida-shi, Tokyo F-term within the Research Institute of Denki Kagaku Kogyo Co., Ltd. 4H026 AA01 AA04 AA06 AB04 4H061 AA01 AA02 AA10 CC02 CC12 CC17 DD14 EE01 EE12 EE14 GG18 GG20 GG23 GG41 HH04 HH11 KK01 LL14 LL22 LL25 LL26
Claims (7)
り、ＭｇＯを１〜２０重量％、ＳｉＯ2を３０〜５０重
量％含有し、しかも非晶質であることを特徴とする無機
組成物。1. A main component MgO, consists SiO 2, CaO, and MgO 1 to 20% by weight, the SiO 2 containing 30 to 50 wt%, yet mineral composition characterized in that it is amorphous .
ＳｉＯ2の比が、０．８〜２．５であることを特徴とす
る請求項１記載の無機組成物。2. (CaO + MgO) /
The ratio of SiO 2 is an inorganic composition of claim 1, wherein it is 0.8 to 2.5.
（ｐＨの初期値が５．５）への溶出率が５０％以上であ
ることを特徴とする請求項１又は請求項２記載の無機組
成物。3. The method according to claim 1, wherein the elution ratio to a 4% by weight citrate buffer solution in the total SiO 2 (the initial value of the pH is 5.5) is 50% or more. Inorganic composition.
が−８０ｐｐｍ以上−７１ｐｐｍ以下であり、かつ半値
幅が１２ｐｐｍ以上２３ｐｐｍ以下であることを特徴と
する請求項１、請求項２又は請求項３記載の無機組成
物。4. NMR-29 Si chemical shift values at the time of measurement is less -71ppm than -80 ppm, and claim 1, the half width is equal to or less than 23ppm or 12 ppm, claim 2 or claim 3. The inorganic composition according to 3.
られる溶融物を急冷することを特徴とする請求項１、請
求項２、請求項３又は請求項４記載の無機組成物の製造
方法。5. The inorganic composition according to claim 1, wherein the raw material is blended into a desired composition, and a melt obtained by heating and melting is rapidly cooled. Production method.
４記載の無機組成物を含有することを特徴とする肥料。6. A fertilizer comprising the inorganic composition according to claim 1, 2, 3, or 4.
４記載の無機組成物を含有することを特徴とする土壌改
質剤。7. A soil modifier comprising the inorganic composition according to claim 1, 2, 3, or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20525798A JP4141538B2 (en) | 1998-07-21 | 1998-07-21 | Fertilizer or soil conditioner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20525798A JP4141538B2 (en) | 1998-07-21 | 1998-07-21 | Fertilizer or soil conditioner |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000146281A Division JP2001026487A (en) | 2000-01-01 | 2000-05-18 | Inorganic composition, fertilizer and soil modifier using the same |
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| Publication Number | Publication Date |
|---|---|
| JP2000034481A true JP2000034481A (en) | 2000-02-02 |
| JP4141538B2 JP4141538B2 (en) | 2008-08-27 |
Family
ID=16504000
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000034185A (en) * | 1998-07-21 | 2000-02-02 | Denki Kagaku Kogyo Kk | Inorganic composition, method for producing the same, fertilizer and soil modifier using the same |
| WO2002066402A1 (en) * | 2001-02-21 | 2002-08-29 | Nkk Corporation | Process for producing slow-release potassium fertilizer and slow-release potassium fertilizers |
| WO2003037825A1 (en) * | 2001-10-31 | 2003-05-08 | Jfe Steel Corporation | Raw material for silicate fertilizer and method for production thereof |
| JP2015137213A (en) * | 2014-01-23 | 2015-07-30 | 南九州化学工業株式会社 | Amorphous fertilizer composition and manufacturing method therefor |
-
1998
- 1998-07-21 JP JP20525798A patent/JP4141538B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000034185A (en) * | 1998-07-21 | 2000-02-02 | Denki Kagaku Kogyo Kk | Inorganic composition, method for producing the same, fertilizer and soil modifier using the same |
| WO2002066402A1 (en) * | 2001-02-21 | 2002-08-29 | Nkk Corporation | Process for producing slow-release potassium fertilizer and slow-release potassium fertilizers |
| WO2003037825A1 (en) * | 2001-10-31 | 2003-05-08 | Jfe Steel Corporation | Raw material for silicate fertilizer and method for production thereof |
| JPWO2003037825A1 (en) * | 2001-10-31 | 2005-02-17 | Ｊｆｅスチール株式会社 | Silica fertilizer raw material and method for producing the same |
| JP2015137213A (en) * | 2014-01-23 | 2015-07-30 | 南九州化学工業株式会社 | Amorphous fertilizer composition and manufacturing method therefor |
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| Publication number | Publication date |
|---|---|
| JP4141538B2 (en) | 2008-08-27 |
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