JP6375550B2 - Method for producing amorphous fertilizer composition - Google Patents
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本発明は、熔成複合肥料に分類される非晶性粒子（非晶性肥料）を含む組成物とその製造方法に関する。 The present invention relates to a composition containing amorphous particles (amorphous fertilizer) classified as a molten composite fertilizer and a method for producing the same.
水稲等をはじめとする好けい酸植物では、ＳｉＯ２（ケイ酸成分）を多量に吸収する。肥料成分としてのＳｉＯ２は、例えば光合成の促進、根の酸化力の向上、耐病性の強化、対倒伏性の向上等に寄与しており、収量品質形成に関わっていることが知られている。収量品質形成に関しては、ＳｉＯ２のほかにも、リン、カリ等も必要不可欠な成分である。このため、特に好けい酸植物では、けい酸吸収性が高くなり、なおかつ、バランスのとれた肥料又は土壌改良材が必要とされている。 Silicic acid plants such as paddy rice absorb a large amount of SiO 2 (silicate component). SiO 2 as a fertilizer component contributes to, for example, promotion of photosynthesis, improvement of root oxidizing power, enhancement of disease resistance, improvement of lodging, etc., and is known to be involved in yield quality formation. . In addition to SiO 2 , phosphorus, potash and the like are indispensable components for yield quality formation. For this reason, especially a silicic acid plant has a high silicic acid absorptivity, and the balanced fertilizer or soil improvement material is required.
ここに、リン成分については、ようりん及び熔成けい酸りん肥が汎用されている。これは、りん鉱石等からなる原料組成物を加熱溶融した後に冷却して得られる熔成肥料であり、成分としてＰ２Ｏ５、ＳｉＯ２、ＣａＯ、ＭｇＯ等を含有している。ようりん及び熔成けい酸りん肥は、いわゆる土づくり肥料として、基肥に先立ち、あるいは基肥に合わせて、さらに追肥としても使用される。例えば、稲作用に好適な酸可溶性ケイ酸の豊富な土壌改質剤あるいは肥料として、主成分がＭｇＯ、ＳｉＯ２、ＣａＯ、Ｐ２Ｏ５からなり、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が知られている（特許文献１）。 Here, with respect to the phosphorus component, yorin and molten phosphorous silicate fertilizer are widely used. This is a molten fertilizer obtained by heating and melting a raw material composition composed of phosphate ore and the like, and contains P 2 O 5 , SiO 2 , CaO, MgO and the like as components. Yorin and molten phosphorous silicate fertilizer are used as so-called soil-making fertilizers, in addition to or in addition to the basic fertilizer. For example, as a soil modifier or fertilizer rich in acid-soluble silicic acid suitable for rice action, the main components are MgO, SiO 2 , CaO, P 2 O 5 , MgO 1-20 wt%, SiO 2 An inorganic composition containing 30 to 50% by weight and being amorphous is known (Patent Document 1).
しかし、このような肥料の製造にはリン供給源としてりん鉱石が従来から使用されているが、日本国内では工業的に利用可能なりん鉱石が産出されないため、その全量を海外からの輸入に頼っているのが現状である。ところが、近年において世界的なりん鉱石資源の枯渇が問題になっていることから、りん鉱石の使用量の削減を図るため、りん鉱石に替わるりん原料がりん肥料の製造においても要望されている。 However, in the production of such fertilizers, phosphate ore has been used as a source of phosphorus. However, since no industrially available phosphate ore is produced in Japan, the total amount depends on imports from overseas. This is the current situation. However, in recent years, worldwide depletion of phosphorus ore resources has become a problem, and in order to reduce the amount of phosphorus ore used, a phosphorus raw material replacing phosphorus ore is also demanded in the production of phosphorus fertilizer.
りん鉱石に替わるりん原料として、汚泥、都市ゴミ、産業廃棄物等の焼却灰を用いることを特徴とする熔成肥料の生産方法が提案されている。例えば、リンを含有する汚泥又はその他の焼却灰を原料とし、該原料を溶融し、その後に急冷してスラグ化する工程を含むことを特徴とする焼却灰を原料とする肥料の生産方法が知られている（特許文献２）。また例えば、リン成分を含んでいる汚泥焼却灰を還元性雰囲気の溶融炉内で加熱して、溶融金属と溶融スラグを溶融炉内に二液分離状態で共存させ、当該溶融スラグを水砕処理によって粒状化させることを特徴とするリン肥料製造方法がある（特許文献３）。 There has been proposed a method for producing a molten fertilizer characterized by using incinerated ash such as sludge, municipal waste, and industrial waste as a phosphorus raw material to replace phosphorus ore. For example, a method for producing fertilizer using incinerated ash as a raw material is known, which includes a step of using sludge containing phosphorus or other incinerated ash as a raw material, melting the raw material, and then rapidly cooling to slag. (Patent Document 2). Also, for example, incineration sludge ash containing phosphorus components is heated in a melting furnace in a reducing atmosphere so that the molten metal and molten slag coexist in the melting furnace in a two-part separation state, and the molten slag is subjected to a water granulation treatment. There is a phosphorus fertilizer manufacturing method characterized by granulating by (Patent Document 3).
ところが、これらの製造方法では、汚泥焼却灰等を原料として使用することから、有毒な成分（水銀、ヒ素、カドミウム等）が肥料中に比較的多量に混入するおそれがあるほか、組成が安定しないので所望の肥料成分をバランス良く含有させることが困難である。 However, in these production methods, sludge incineration ash etc. are used as raw materials, so toxic components (mercury, arsenic, cadmium, etc.) may be mixed in the fertilizer in a relatively large amount, and the composition is not stable. Therefore, it is difficult to contain a desired fertilizer component in a balanced manner.
これに対し、鶏糞をリン供給源として使用する方法がある。特に、鶏糞を専用鶏糞ボイラー等で燃焼させて得られる鶏糞燃焼灰がある。鶏糞燃焼灰は、１）燃焼（加熱処理）により減容化されている、２）感染性病原菌等が滅菌されている、３）ほとんど臭気がない、４）Ｐ２Ｏ５のほか、Ｋ２Ｏ、ＣａＯ等も含有している、５）他の肥料原料より比較的安価である、等の理由で肥料原料として有用である。 On the other hand, there is a method of using chicken manure as a phosphorus supply source. In particular, there is chicken manure burning ash obtained by burning chicken manure with a dedicated chicken manure boiler or the like. Chicken manure combustion ash is 1) reduced in volume by combustion (heat treatment), 2) infectious pathogens are sterilized, 3) almost no odor, 4) P 2 O 5 and K 2 It contains O, CaO, etc. 5) It is useful as a fertilizer raw material because it is relatively cheaper than other fertilizer raw materials.
しかし、鶏糞燃焼灰は、使用場面によってはそのまま直接肥料として用いることができるものの、アルカリ性が強いだけでなく、燃焼灰のリン成分の大部分が水に不溶性であり、かつ、一部は肥効価値の低い化合物となっており、肥料としての適用範囲が限られている。このため、硫酸、リン酸等の鉱酸類を鶏糞燃焼灰に添加し、燃焼灰中のリン成分の一部を水溶性に変化させた肥料が提案されている（例えば特許文献４〜６参照）。 However, although poultry manure ash can be used directly as a fertilizer depending on the usage situation, it is not only strongly alkaline, but most of the phosphorus component of the combustion ash is insoluble in water, and some of it is fertilizer It is a low-value compound and its application range as a fertilizer is limited. For this reason, the fertilizer which added mineral acids, such as a sulfuric acid and phosphoric acid, to chicken manure combustion ash, and changed some phosphorus components in combustion ash to water solubility is proposed (for example, refer patent documents 4-6). .
さらに、鶏糞燃焼灰を用いて熔成りん肥を製造する際における硫酸根又は塩酸根による問題を解決するため、鶏糞燃焼灰を水洗処理し、脱水することで得られる鶏糞燃焼灰精製物であって、当該鶏糞燃焼灰精製物中に含まれる硫酸根及び塩酸根の割合（重量換算）が、前記鶏糞燃焼灰中に含まれる硫酸根及び塩酸根それぞれの割合（重量換算）よりも少ないことを特徴とする鶏糞燃焼灰精製物が提案されている（特許文献７）。 Furthermore, in order to solve the problems caused by sulfate radicals or hydrochloric acid roots in the production of molten manure using chicken manure combustion ash, it is a purified product of chicken manure combustion ash obtained by washing and dehydrating chicken manure combustion ash. The ratio of sulfate radicals and hydrochloric acid radicals (weight conversion) contained in the purified chicken dung combustion ash is less than the ratio (weight conversion) of each sulfate radical and hydrochloric acid radical contained in the chicken dung combustion ash. A purified chicken manure combustion ash product has been proposed (Patent Document 7).
例えば特許文献７に開示されているような鶏糞燃焼灰又はその精製物を含む原料を溶融・急冷することによって製造される熔成複合肥料は、肥料成分がガラス化されていることから、優れた緩効性を発揮できるという点で有用な肥料である。 For example, the molten composite fertilizer manufactured by melting and quenching raw materials containing chicken manure burning ash or purified product thereof as disclosed in Patent Document 7 is excellent because the fertilizer component is vitrified. It is a fertilizer that is useful in that it can exert its slow effect.
しかしながら、これらの鶏糞燃焼灰を用いた熔成複合肥料においても、以下の点においてさらなる改善の余地がある。 However, there is room for further improvement in the following points also in the molten composite fertilizer using these chicken manure burning ash.
すなわち、熔成複合肥料において、けい酸吸収性の改善が必要である。特に好けい酸植物を栽培する場合等においては、けい酸がより吸収され易い性能（けい酸吸収性）を有する熔成複合肥料が要求される。前述の通り、肥料成分としてのＳｉＯ２は、光合成の促進等の役割を果たすものであり、肥料のけい酸吸収性を向上させることは品質の高い農産物を効率良く生産する上で極めて重要である。加えて、リン成分のほか、カリウム成分等の栄養分もバランス良く含まれていることも必要である。ところが、そのようなけい酸吸収性に優れ、栄養バランスのとれた熔成複合肥料は、未だ開発されるに至っていないのが現状である。 That is, it is necessary to improve silicic acid absorption in the molten composite fertilizer. In particular, when cultivating silicic acid plants, a molten composite fertilizer having a performance (silicic acid absorbability) in which silicic acid is more easily absorbed is required. As described above, SiO 2 as a fertilizer component plays a role such as promotion of photosynthesis, and improving the silicic acid absorbability of the fertilizer is extremely important for efficiently producing high-quality agricultural products. . In addition to the phosphorus component, nutrients such as the potassium component must be contained in a well-balanced manner. However, at present, such a fused compound fertilizer having excellent silicic acid absorption and nutritional balance has not yet been developed.
従って、本発明の主な目的は、特にけい酸吸収性に優れ、なおかつ、栄養バランスのとれた熔成複合肥料を提供することを目的とする。 Therefore, the main object of the present invention is to provide a molten composite fertilizer that is particularly excellent in silicic acid absorption and has a well-balanced nutritional balance.
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定の肥料組成を採用することにより上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by employing a specific fertilizer composition, and has completed the present invention.
すなわち、本発明は、下記の非晶性肥料組成の製造方法に係る。
１． 非晶性粒子を肥料成分として含有する肥料組成物を製造する方法であって、鶏糞燃焼灰及びフェロニッケルスラグを含む出発原料を溶融することにより溶融物を製造する工程及び前記溶融物を冷却してガラス化することにより非晶性粒子を得る工程を含み、
前記非晶性粒子は、前記非晶性粒子１００重量％中、
（１）２重量％クエン酸水溶液に溶けるリン成分をＰ２Ｏ５換算で６〜１６重量％、
（２）２重量％クエン酸水溶液に溶けるカリウム成分をＫ２Ｏ換算で３〜１０重量％、
（３）０．５モル／リットルの塩酸水溶液に溶けるケイ素成分をＳｉＯ２換算で２０〜４０重量％、
（４）２重量％クエン酸液に溶けるマグネシウム成分をＭｇＯ換算で１０〜３０重量％、
（５）０．５モル／リットルの塩酸水溶液に溶けるカルシウム成分をＣａＯ換算で５〜３０重量％含有し、かつ、
（６）前記ＭｇＯ／ＳｉＯ２をモル換算した時の値が０．６５以上である、
ことを特徴とする非晶性肥料組成物の製造方法。
２． フェロニッケルスラグがＳｉＯ２を４６〜５８重量％含有し、ＭｇＯを２８〜３８重量％含有する、前記項１に記載の製造方法。
３． 冷却に際し、溶融物を水と接触させるとともに微細化して急冷する、前記項１又は２に記載の製造方法。
That is, this invention concerns on the manufacturing method of the following amorphous fertilizer composition.
1. A method for producing a fertilizer composition containing amorphous particles as a fertilizer component, the step of producing a melt by melting starting materials including chicken manure combustion ash and ferronickel slag, and cooling the melt A step of obtaining amorphous particles by vitrification,
The amorphous particles are 100% by weight of the amorphous particles,
(1) Phosphorus component soluble in 2% by weight citric acid aqueous solution is 6 to 16% by weight in terms of P 2 O 5 ,
(2) 3 to 10% by weight of a potassium component dissolved in 2% by weight citric acid aqueous solution in terms of K 2 O,
(3) 20-40% by weight of a silicon component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution in terms of SiO 2 ;
(4) Magnesium component soluble in 2 wt% citric acid solution is 10 to 30 wt% in terms of MgO,
(5) containing 5 to 30% by weight of a calcium component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution in terms of CaO, and
(6) When the MgO / SiO 2 is converted into a mole, the value is 0.65 or more.
The manufacturing method of the amorphous fertilizer composition characterized by the above-mentioned.
2. Item 2. The method according to Item 1 , wherein the ferronickel slag contains 46 to 58% by weight of SiO 2 and 28 to 38% by weight of MgO.
3. Item 3. The method according to Item 1 or 2 , wherein the cooling is performed by bringing the melt into contact with water and miniaturizing and rapidly cooling.
本発明の肥料組成物によれば、特定の成分が一定の比率で含有されている非晶性粒子を有効成分としているので、けい酸吸収性に優れ、なおかつ、栄養バランスのとれた肥料として有効である。 According to the fertilizer composition of the present invention, amorphous particles containing a specific component in a certain ratio are used as active ingredients, so that they are excellent in silicic acid absorption and effective as a fertilizer with a balanced nutrition. It is.
特に、本発明組成物では、Ｍｇ成分及びＳｉ成分について、酸化物換算のモル比ＭｇＯ／ＳｉＯ２が０．６５以上に制御されていることから、優れたけい酸吸収性を発揮できる結果、植物がＳｉ成分を吸収しやすい肥料として好適に用いることができる。また同時に、非晶質成分の形状が粒子状とすることができる結果、肥料製造時のハンドリング性（作業性）を高めることができる。鶏糞燃焼灰又はその精製物を含む原料を溶融・急冷することによって得られる生成物（すなわち、本発明の非晶性粒子）は、工業的規模での生産においては、その後の工程（移動・搬送工程、他の添加剤等の配合工程等）に支障を来さない程度の流動性を有することが望ましく、その点において非晶性粒子が粒状である本発明組成物は好適である。 In particular, in the composition of the present invention, the Mg component and the Si component are controlled to have an oxide equivalent molar ratio MgO / SiO 2 of 0.65 or more. Can be suitably used as a fertilizer that easily absorbs Si components. At the same time, the shape of the amorphous component can be made particulate, so that the handling property (workability) at the time of fertilizer production can be improved. The product obtained by melting and quenching raw material containing chicken manure combustion ash or purified product thereof (that is, the amorphous particles of the present invention) is a subsequent process (moving / transporting) in production on an industrial scale. It is desirable that the composition has fluidity that does not hinder the process and other additives and the like, and the composition of the present invention in which the amorphous particles are granular is preferable.
また、本発明組成物では、栄養バランスという点においても、植物の生長に必要なリン成分、カリウム成分、ケイ素成分、マグネシウム成分及びカルシウム成分が非晶性粒子に含まれており、なおかつ、非晶性粒子はガラス質であるので優れた緩効性（持続性）を発揮することができる。すなわち、１つの非晶性粒子がリン成分、カリウム成分、ケイ素成分、マグネシウム成分及びカルシウム成分を含むガラス質で構成されているので、良好な栄養バランスと優れた緩効性とを同時に実現することができる。 Further, in the composition of the present invention, also in terms of nutritional balance, the phosphorus component, potassium component, silicon component, magnesium component and calcium component necessary for plant growth are contained in the amorphous particles, and the amorphous particle Since the conductive particles are glassy, they can exhibit excellent slow-acting properties (sustainability). In other words, since one amorphous particle is composed of a glassy material containing a phosphorus component, a potassium component, a silicon component, a magnesium component, and a calcium component, a good nutritional balance and an excellent slow-release property can be realized at the same time. Can do.
しかも、本発明組成物では、特に汚泥等を原料として使用しなくて済む上、減容化・滅菌化処理された鶏糞燃焼灰を使用することから、有毒成分の混入が効果的に抑制ないしは防止された肥料を提供することができる。しかも、未焼成の鶏糞による悪臭、衛生害虫の発生源等の問題を解消することもでき、環境面においても大いに貢献することができる。 Moreover, in the composition of the present invention, it is not necessary to use sludge or the like as a raw material in particular, and the use of chicken dung burning ash that has been reduced in volume and sterilized effectively suppresses or prevents the mixing of toxic components. Fertilizer can be provided. In addition, problems such as bad odor caused by unburned chicken manure and the source of sanitary pests can be solved, which can greatly contribute to the environment.
このような特徴を有する本発明の肥料組成物は、例えば水稲等の好けい酸植物をはじめ、麦類、サトウキビ、各種野菜類、各種果樹類等の様々な植物（農作物）の肥料として好適に用いることができる。 The fertilizer composition of the present invention having such characteristics is suitable as a fertilizer for various plants (agricultural crops) such as silicate plants such as paddy rice, wheat, sugarcane, various vegetables, and various fruit trees. Can be used.
１．非晶性肥料組成物
本発明の非晶性肥料組成物（本発明組成物）は、少なくとも非晶性粒子を肥料成分として含有する肥料組成物であって、前記非晶性粒子１００重量％中、
（１）２重量％クエン酸水溶液に溶けるリン成分をＰ２Ｏ５換算で６〜１６重量％、
（２）２重量％クエン酸水溶液に溶けるカリウム成分をＫ２Ｏ換算で３〜１０重量％、
（３）０．５モル／リットルの塩酸水溶液に溶けるケイ素成分をＳｉＯ２換算で２０〜４０重量％、
（４）２重量％クエン酸液に溶けるマグネシウム成分をＭｇＯ換算で１０〜３０重量％、
（５）０．５モル／リットルの塩酸水溶液に溶けるカルシウム成分をＣａＯ換算で５〜３０重量％含有し、かつ、
（６）前記ＭｇＯ／ＳｉＯ２をモル換算した時の値が０．６５以上である、
ことを特徴とする。
1. Amorphous fertilizer composition The amorphous fertilizer composition of the present invention (the composition of the present invention) is a fertilizer composition containing at least amorphous particles as a fertilizer component, and is contained in 100% by weight of the amorphous particles. ,
(1) Phosphorus component soluble in 2% by weight citric acid aqueous solution is 6 to 16% by weight in terms of P 2 O 5 ,
(2) 3 to 10% by weight of a potassium component dissolved in 2% by weight citric acid aqueous solution in terms of K 2 O,
(3) 20-40% by weight of a silicon component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution in terms of SiO 2 ;
(4) Magnesium component soluble in 2 wt% citric acid solution is 10 to 30 wt% in terms of MgO,
(5) containing 5 to 30% by weight of a calcium component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution in terms of CaO, and
(6) When the MgO / SiO 2 is converted into a mole, the value is 0.65 or more.
It is characterized by that.
本発明の非晶性肥料組成物（本発明組成物）は、少なくとも非晶性粒子を肥料成分として含有する。本発明組成物中における非晶性粒子の含有量は限定的ではないが、通常は５０〜１００重量％程度とし、好ましくは７０〜１００重量％、より好ましくは８０〜１００重量％とすれば良い。 The amorphous fertilizer composition of the present invention (the composition of the present invention) contains at least amorphous particles as a fertilizer component. The content of the amorphous particles in the composition of the present invention is not limited, but is usually about 50 to 100% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight. .
（ａ）非晶性粒子
本発明組成物の主成分となる非晶性粒子は、所定の成分を含む非晶質（ガラス質）の物質であり、本発明組成物の有効成分（肥料成分）となるものである。施肥された非晶性粒子は、非晶質であることから、植物の根から分泌される根酸（有機酸）により徐々に溶けることにより、緩効性を発揮する結果、長期間にわたり植物に栄養分を送り続けることができる。本発明において、非晶質成分は、例えば鶏糞燃焼灰とフェロニッケルスラグを含む溶融物に由来するものであることが好ましい。従って、非晶質粒子は、以下に示すような成分を特定量含有することが好ましい。
(A) Amorphous Particles Amorphous particles as a main component of the composition of the present invention are amorphous (glassy) substances containing a predetermined component, and the active ingredients (fertilizer components) of the composition of the present invention. It will be. Since the fertilized amorphous particles are amorphous, they are gradually dissolved by the root acid (organic acid) secreted from the roots of the plant, and as a result, they exhibit a slow effect. Can continue to feed nutrients. In the present invention, the amorphous component is preferably derived from a melt containing, for example, chicken manure combustion ash and ferronickel slag. Accordingly, the amorphous particles preferably contain a specific amount of components as shown below.
リン成分
非晶質粒子は、２重量％クエン酸水溶液に溶けるリン成分をＰ２Ｏ５換算で６〜１６重量％、好ましくは６〜１５重量％含有する。リン成分の含有量がＰ２Ｏ５換算で６重量％未満の場合は肥効が期待できなくなるので好ましくない。リン成分の含有量がＰ２Ｏ５換算で１６重量％を超える場合は、組成上ほかの成分の含有量が相対的に低くなって、肥料としてのバランスが悪くなることがあるので好ましくない。
Phosphorous component The amorphous particles contain 6 to 16% by weight, preferably 6 to 15% by weight, of a phosphorus component that is soluble in 2% by weight citric acid aqueous solution in terms of P 2 O 5 . When the content of the phosphorus component is less than 6% by weight in terms of P 2 O 5 , it is not preferable because fertilization effect cannot be expected. When the content of the phosphorus component exceeds 16% by weight in terms of P 2 O 5 , the content of other components in the composition is relatively low, and the balance as a fertilizer may be deteriorated.
カリウム成分
非晶性粒子は、２重量％クエン酸水溶液に溶けるカリウム成分をＫ２Ｏ換算で３〜１０重量％、好ましくは３〜８重量％含有する。カリウム成分の含有量がＫ２Ｏ換算で３重量％未満の場合は肥効が期待できなくなるので好ましくない。カリウム成分の含有量がＫ２Ｏ換算で１０重量％を超える場合は、組成上ほかの成分含有量が相対的に低くなって、肥料としてのバランスが悪くなることがあるので好ましくない。
Potassium component Amorphous particles contain 3 to 10% by weight, preferably 3 to 8% by weight, in terms of K 2 O, of a potassium component that is soluble in a 2% by weight citric acid aqueous solution. When the content of the potassium component is less than 3% by weight in terms of K 2 O, fertilization cannot be expected, which is not preferable. When the content of the potassium component exceeds 10% by weight in terms of K 2 O, the content of other components in the composition is relatively low, and the balance as a fertilizer may be deteriorated.
ケイ素成分
非晶性粒子は、０．５モル／リットルの塩酸水溶液に溶けるケイ素成分をＳｉＯ２換算で２０〜４０重量％、好ましくは２０〜３６重量％含有する。ケイ素成分の含有量がＳｉＯ２換算で２０重量％未満の場合は肥効が期待できなくなるので好ましくない。ケイ素の含有量がＳｉＯ２換算で４０重量％を超える場合は、組成上ほかの成分含有量が相対的に低くなり、肥料としてのバランスが悪くなることがあって好ましくない。
Silicon component The amorphous particles contain 20 to 40% by weight, preferably 20 to 36% by weight, of a silicon component dissolved in a 0.5 mol / liter hydrochloric acid aqueous solution in terms of SiO 2 . Undesirable content of silicon component can not be expected fertilizing effect in the case of less than 20% by weight in terms of SiO 2. When the silicon content exceeds 40% by weight in terms of SiO 2 , the content of other components is relatively low in terms of composition, and the balance as a fertilizer may be deteriorated.
マグネシウム成分
非晶性粒子は、２重量％クエン酸液に溶けるマグネシウム成分をＭｇＯ換算で１０〜３０重量％、好ましくは１０〜２５重量％含有する。マグネシウム成分の含有量がＭｇＯ換算で１０重量％未満の場合は肥効が期待できなくなるので好ましくない。マグネシウム成分の含有量がＭｇＯ換算で３０重量％を超える場合は、組成上ほかの成分含有量が相対的に低くなり、肥料としてのバランスが悪くなることがあるので好ましくない。
Magnesium component The amorphous particles contain 10 to 30% by weight, preferably 10 to 25% by weight, in terms of MgO, of a magnesium component dissolved in a 2% by weight citric acid solution. When the content of the magnesium component is less than 10% by weight in terms of MgO, it is not preferable because fertilization effect cannot be expected. When the content of the magnesium component exceeds 30% by weight in terms of MgO, the content of other components is relatively low in terms of composition, and the balance as a fertilizer may be unfavorable.
カルシウム成分
非晶性粒子は、０．５モル／リットルの塩酸水溶液に溶けるカルシウム成分をＣａＯ換算で５〜３０重量％、好ましくは８〜３０重量％含有する。カルシウム成分の含有量がＣａＯ換算で５重量％未満の場合は、肥効が期待できなくなるので好ましくない。カルシウム成分の含有量がＣａＯ換算で３０重量％を超える場合は、組成上ほかの成分含有量が相対的に低くなって肥料としてのバランスが悪くなることがあるので好ましくない。
Calcium component Amorphous particles contain 5 to 30% by weight, preferably 8 to 30% by weight, of Ca component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution in terms of CaO. When the content of the calcium component is less than 5% by weight in terms of CaO, the fertilization effect cannot be expected, which is not preferable. When the content of the calcium component exceeds 30% by weight in terms of CaO, the content of other components is relatively low in composition, and the balance as a fertilizer may be deteriorated, which is not preferable.
ＭｇＯ／ＳｉＯ２モル比
非晶質粒子において、前記ＭｇＯ／ＳｉＯ２をモル換算した時の値が０．６５以上である。すなわち、２重量％クエン酸液に溶けるマグネシウム成分をＭｇＯ換算した時の含有量Ｍ（モル％）を、０．５モル／リットルの塩酸水溶液に溶けるケイ素成分をＳｉＯ２換算した時の含有量Ｓ（モル％）で割ったときの値（Ｍ／Ｓ）が０．６５以上であり、好ましくは０．７０以上である。前記値（Ｍ／Ｓ）が０．６５未満の場合は、所望のけい酸吸収性が得られなくなることがあるほか、水砕後の形状として針金状の固まりが大量に生成することがあり、流動性が悪くなる。なお、前記値（Ｍ／Ｓ）の上限値は限定的ではないが、通常は０．９７程度とすれば良い。
MgO / SiO 2 molar ratio In the amorphous particles, the MgO / SiO 2 molar conversion is 0.65 or more. That is, the content M (mol%) of the magnesium component dissolved in 2 wt% citric acid solution when converted to MgO, and the content S of the silicon component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution converted to SiO 2 The value (M / S) when divided by (mol%) is 0.65 or more, preferably 0.70 or more. When the value (M / S) is less than 0.65, the desired silicic acid absorptivity may not be obtained, and a large amount of wire-like mass may be generated as a shape after water granulation, The fluidity becomes worse. The upper limit value of the value (M / S) is not limited, but is usually about 0.97.
非晶性粒子中に含まれる他の成分
本発明組成物の非晶性粒子中には、本発明の効果を妨げない範囲内で他の成分が含まれていても良い。他の成分としては、例えば鉄、マンガン、ホウ素等が挙げられる。その他にも、出発原料として用いた鶏糞燃焼灰、フェロニッケルスラグ等に由来する成分が含まれていても良い。
Other components contained in amorphous particles Other components may be contained in the amorphous particles of the composition of the present invention within a range not impeding the effects of the present invention. Examples of other components include iron, manganese, and boron. In addition, components derived from chicken manure combustion ash, ferronickel slag and the like used as starting materials may be included.
非晶性粒子の性状
非晶性粒子の性状は限定的ではないが、通常は粒子状（砂状）の形態で存在する。粒子形状は限定的ではない。特に、非晶性粒子は、後記「２．本発明組成物の製造方法」に示す製造方法で得られるものであることが好ましい。かかる製造方法によって、より確実に粒子状（砂状）の非晶質粒子として得ることができる。砂状の形態である場合は、流動性に優れるため、後工程又は後処理を円滑に進めることが可能となる。
Properties of Amorphous Particles The properties of the amorphous particles are not limited, but usually exist in the form of particles (sand). The particle shape is not critical. In particular, the amorphous particles are preferably those obtained by the production method described later in “2. Production method of the composition of the present invention ”. By such a production method, it is possible to more reliably obtain particulate (sandy) amorphous particles. Since it is excellent in fluidity | liquidity when it is a sand-like form, it becomes possible to advance a post process or a post-process smoothly.
また、非晶性粒子が砂状である場合、その平均粒径は限定的ではないが、ハンドリング性等の見地より、通常０．１〜５ｍｍ程度の範囲内であることが好ましい。 In addition, when the amorphous particles are sandy, the average particle diameter is not limited, but it is usually preferably in the range of about 0.1 to 5 mm from the viewpoint of handling properties.
（ｂ）非晶性粒子以外の成分
本発明組成物では、必要に応じて非晶性粒子以外の成分が含まれていても良い。例えば、肥料成分のほか、非晶性粒子を造粒する場合はバインダー等が含まれていても良い。
(B) Components other than amorphous particles In the composition of the present invention, components other than amorphous particles may be included as necessary. For example, in addition to the fertilizer component, when amorphous particles are granulated, a binder or the like may be included.
上記肥料成分としては、例えば窒素質肥料、りん酸質肥料、加里質肥料、有機質肥料、複合肥料、石灰質肥料、けい酸質肥料、苦土肥料、マンガン質肥料、ほう素質肥料、微量要素複合肥料等を混合することができる。非晶性粒子と肥料成分との混合の形態としては、特に制限はなく、例えばａ）粉末ないし砂状品どうしの混合、ｂ）造粒物どうしの混合、ｃ）粉末混合後の造粒等から適宜選択できる。また、これらの肥料とは種々のタイミングで混合でき、例えばａ）予め混合した混合物として供給する、ｂ）使用者（農家等）が使用直前に混合して施肥する等のタイミングを挙げることができる。 Examples of the fertilizer components include nitrogenous fertilizer, phosphate fertilizer, calcareous fertilizer, organic fertilizer, composite fertilizer, calcareous fertilizer, siliceous fertilizer, bitter fertilizer, manganese fertilizer, boron fertilizer, and trace element composite fertilizer Etc. can be mixed. The form of mixing the amorphous particles and the fertilizer component is not particularly limited. For example, a) mixing of powders or sandy products, b) mixing of granulated products, c) granulation after mixing of powders, etc. Can be selected as appropriate. In addition, these fertilizers can be mixed at various timings, for example, a) supplied as a premixed mixture, b) a user (farmer, etc.) mixes and fertilizes immediately before use. .
非晶性粒子を造粒する場合は、その造粒方法、用いるバインダー等については、後記２．において詳述する。 In the case of granulating amorphous particles, the granulation method, the binder to be used, etc. are described later in 2. Will be described in detail.
２．本発明組成物の製造方法
本発明組成物の製造方法は特に制限されないが、以下の方法によって好適に製造することができる。すなわち、少なくとも非晶性粒子を肥料成分として含有する肥料組成物を製造する方法であって、鶏糞燃焼灰及びフェロニッケルスラグを含む出発原料を溶融することにより溶融物を製造する工程（溶融工程）及び前記溶融物を冷却してガラス化することにより非晶性粒子を得る工程（冷却工程）を含むことを特徴とする製造方法を採用することが望ましい。
2. Production method of the composition of the present invention The production method of the composition of the present invention is not particularly limited, but can be suitably produced by the following method. That is, a method for producing a fertilizer composition containing at least amorphous particles as a fertilizer component, the step of producing a melt by melting a starting material containing chicken manure combustion ash and ferronickel slag (melting step) It is desirable to employ a production method characterized by including a step (cooling step) of obtaining amorphous particles by cooling and vitrifying the melt.
溶融工程
溶融工程では、鶏糞燃焼灰及びフェロニッケルスラグを含む出発原料を溶融することにより溶融物を製造する。
Melting process In the melting process, a melt is produced by melting starting raw materials including chicken manure combustion ash and ferronickel slag.
鶏糞燃焼灰は、養鶏業等から排出される鶏糞を燃焼して得られる灰であれば良く、公知の方法によって製造される鶏糞燃焼灰を使用することもできる。また、鶏糞としては、例えば産卵鶏、育成鶏、ブロイラー等のいずれの鶏の排泄物も使用することができる。本発明では、必要に応じて鶏糞に牛糞、豚糞等を混合して得られた混合物を燃焼した鶏糞燃焼灰も使用することができる。この場合、混合物中における鶏糞の含有量は、特にリン成分の濃度等を高く維持できるという見地より、通常３０〜１００重量％、好ましくは５０〜１００重量％、より好ましくは８０〜１００重量％とすれば良い。 The chicken manure burning ash may be an ash obtained by burning chicken manure discharged from the poultry industry or the like, and chicken manure burning ash produced by a known method can also be used. Further, as chicken dung, excrement of any chicken such as laying hen, breeding chicken, broiler and the like can be used. In the present invention, chicken dung burning ash obtained by burning a mixture obtained by mixing cow dung, pig dung, and the like with chicken dung can be used as necessary. In this case, the content of chicken manure in the mixture is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 80 to 100% by weight, from the viewpoint that the concentration of the phosphorus component and the like can be maintained high. Just do it.
鶏糞燃焼灰は必要に応じて粉体のまま用いることもできるが、必要に応じて種々の造粒法により造粒・成形して使用することもできる。造粒法に制限はなく、例えば転動造粒法、押出し造粒法、圧縮造粒法、攪拌造粒法等を挙げることができる。造粒する際の粒径も適宜調節することができるが、好ましくは１〜３０ｍｍ程度の範囲内とすれば良い。なお、造粒の際に、後述の各種バインダー、各種造粒助剤等を適宜用いることも可能である。 The poultry manure ash can be used as it is, if necessary, but can also be granulated and molded by various granulation methods if necessary. There is no restriction | limiting in the granulation method, For example, a rolling granulation method, an extrusion granulation method, a compression granulation method, a stirring granulation method etc. can be mentioned. Although the particle diameter at the time of granulation can also be adjusted suitably, it should just be in the range of about 1-30 mm preferably. In the granulation, various binders described later, various granulation aids, and the like can be appropriately used.
フェロニッケルスラグは、ステンレス鋼等の原料であるフェロニッケルを精錬する際に電気炉より出滓されるスラグであり、主成分としてＳｉＯ２を４６〜５８％程度、ＭｇＯを２８〜３８％程度含有している。種々のスラグ類の中でフェロニッケルスラグは、高濃度でＳｉＯ２及びＭｇＯを含有するものであり、なおかつ、比較的安価であるため、本発明組成物の原料として最適である。本発明では、フェロニッケルスラグは、砂状粒子の形態で好適に用いることができる。従って、例えば出滓後に高圧水で水砕して得られた砂状粒子も好適に用いることができる。フェロニッケルスラグの砂状粒子の平均粒径は限定的ではないが、通常は５ｍｍ未満程度の範囲内とすれば良い。 Ferronickel slag is slag extracted from an electric furnace when refining ferronickel, which is a raw material such as stainless steel, and contains about 46 to 58% of SiO 2 and about 28 to 38% of MgO as main components. doing. Among various slags, ferronickel slag contains SiO 2 and MgO at a high concentration and is relatively inexpensive, and is therefore optimal as a raw material for the composition of the present invention. In the present invention, ferronickel slag can be suitably used in the form of sand-like particles. Therefore, for example, sandy particles obtained by water granulation with high-pressure water after brewing can be suitably used. The average particle size of the ferronickel slag sand-like particles is not limited, but is usually within a range of less than 5 mm.
本発明では、出発原料中に必要に応じて他の成分（副原料）を配合することもできる。例えば、副原料としては、りん鉱石、各種アパタイト等のＰ２Ｏ５源；けい石、シリカゲル等のＳｉＯ２源、高炉スラグ（高炉さい）等のＳｉＯ２・ＭｇＯ・アルカリ源；生石灰、石灰石、炭酸カルシウム等のＣａＯ源；重焼マグネシア、軽焼マグネシア、軽炭粕等のＭｇＯ源のほか、各種肥料及びこれらの混合物等を挙げることができる。さらに、微量要素であるマンガン又はホウ素源として、例えばマンガン鉱石、マンガンスラグ、コレマナイト、ＨＣスラグ、ボラックス、ホウ砂等を配合することができる。 In the present invention, other components (sub-materials) can be blended in the starting material as necessary. For example, as auxiliary materials, P 2 O 5 sources such as phosphate ore and various apatites; SiO 2 sources such as silica and silica gel; SiO 2 / MgO / alkali sources such as blast furnace slag (blast furnace slag); quick lime, limestone, In addition to CaO sources such as calcium carbonate; MgO sources such as heavy calcined magnesia, light calcined magnesia, and light charcoal lees, various fertilizers and mixtures thereof can be exemplified. Furthermore, as a trace element manganese or boron source, for example, manganese ore, manganese slag, colemanite, HC slag, borax, borax and the like can be blended.
出発原料における鶏糞燃焼灰、フェロニッケルスラグ及び前記副原料の配合割合は、用いる鶏糞燃焼灰の組成等に応じて、前記非晶性粒子の組成となるように適宜調整すれば良い。特に、所定の栄養分をバランス良くかつ効率的に配合し、非晶質成分（ガラス成分）を効果的に形成するという見地より、鶏糞燃焼灰とフェロニッケルスラグの合計量が出発原料中５０〜１００重量％程度とし、好ましくは６０〜１００重量％とし、より好ましくは７０〜１００重量％とすれば良い。 The mixing ratio of the chicken manure combustion ash, ferronickel slag and the auxiliary material in the starting material may be appropriately adjusted so as to be the composition of the amorphous particles according to the composition of the chicken manure combustion ash used. In particular, the total amount of chicken manure burning ash and ferronickel slag is 50 to 100 in the starting material from the viewpoint of blending predetermined nutrients in a balanced and efficient manner and effectively forming an amorphous component (glass component). It may be about wt%, preferably 60 to 100 wt%, more preferably 70 to 100 wt%.
本発明では、鶏糞燃焼灰、フェロニッケルスラグ及び必要に応じて各種副原料を混合して得られた出発原料を溶融する。溶融方法は限定的でなく、例えば電気炉、平炉等の公知又は市販の溶融炉を使用して実施すれば良い。加熱温度は、溶融温度以上であれば良く、特に１２００〜１５００℃の範囲が好ましい。所定の温度で一定時間保持することによって溶融物（溶融スラグ）となる。 In the present invention, the starting material obtained by mixing chicken manure combustion ash, ferronickel slag and various auxiliary materials as required is melted. The melting method is not limited. For example, a known or commercially available melting furnace such as an electric furnace or a flat furnace may be used. The heating temperature should just be more than melting temperature, and the range of 1200-1500 degreeC is especially preferable. A melt (molten slag) is obtained by holding at a predetermined temperature for a certain period of time.
冷却工程
冷却工程では、前記溶融物を冷却してガラス化することにより非晶性粒子を得る。溶融物の冷却方法はガラス化が可能である限りは特に制限はないが、特に水との接触による冷却（急冷）を実施することが望ましい。特に、溶融物を水と接触させるとともに微細化して急冷する方法を好適に採用することができる。このような急冷方法としては、例えば水中への流し込み、高圧水による水砕、吹き飛ばし後の水による冷却等を挙げることができる。この場合、用いる水の温度は限定的ではないが、、好ましくは０℃〜６０℃程度の範囲から選択でき、さらに好ましくは０℃〜５０℃程度の範囲から選択できる。このようにして、溶融物がガラス化することによって非晶性粒子が得られる。
Cooling step In the cooling step, the melt is cooled and vitrified to obtain amorphous particles. Although there is no restriction | limiting in particular as long as vitrification is possible for the cooling method of a melt, It is desirable to implement especially cooling (rapid cooling) by contact with water. In particular, a method of bringing the melt into contact with water and miniaturizing and rapidly cooling can be suitably employed. Examples of such a rapid cooling method include pouring into water, granulation with high-pressure water, and cooling with water after blowing off. In this case, the temperature of the water to be used is not limited, but can be preferably selected from the range of about 0 ° C to 60 ° C, more preferably from the range of about 0 ° C to 50 ° C. In this way, amorphous particles are obtained by vitrification of the melt.
上記のように、溶融物を水と接触させるとともに微細化して急冷する方法において、本発明の所定の組成では砂状の形態からなる非晶性粒子を得ることができる。これに対し、本発明の所定の組成の範囲外では、例えば針金状の固まりが大量に生成することがあり、流動性が低くなる。 As described above, in the method of bringing the melt into contact with water and miniaturizing and quenching, amorphous particles having a sandy form can be obtained with the predetermined composition of the present invention. On the other hand, outside the range of the predetermined composition of the present invention, for example, a large amount of wire-like lumps may be generated, resulting in low fluidity.
得られた非晶性粒子は、水との接触により濡れた状態であるため、必要に応じて種々の方法で乾燥することが好ましい。乾燥方法には特に制限はなく、種々の方法を用いることができる。例えば風乾、天日干し等の自然乾燥、加熱乾燥、熱風乾燥、真空乾燥、流動乾燥、ロータリーキルン等の種々の装置による乾燥（強制乾燥）を用いることができる。乾燥後の含水率は、最終製品の用途等に応じて適宜選択できる。 Since the obtained amorphous particles are wet by contact with water, they are preferably dried by various methods as necessary. There is no particular limitation on the drying method, and various methods can be used. For example, natural drying such as air drying and sun drying, heat drying, hot air drying, vacuum drying, fluidized drying, and drying (forced drying) using various apparatuses such as a rotary kiln can be used. The moisture content after drying can be appropriately selected depending on the use of the final product.
得られた非晶性粒子は、そのままでも肥料又は土壌改良材として使用できるが、必要に応じて粉砕、篩分け又は造粒をすることによって種々の形態で供給できる。この場合、粉砕又は篩分けの程度、すなわち粒子径の範囲は目的に応じて適宜選択できる。 The obtained amorphous particles can be used as they are as a fertilizer or a soil improver, but can be supplied in various forms by pulverizing, sieving or granulating as necessary. In this case, the degree of pulverization or sieving, that is, the range of the particle diameter can be appropriately selected according to the purpose.
特に、造粒する場合、その造粒方法に制限はなく、例えば転動造粒法、押出し造粒法、圧縮造粒法、攪拌造粒法等を挙げることができる。造粒する際の粒径も適宜選択することができるが、好ましくは１〜１０ｍｍ程度の範囲から選択できる。 In particular, when granulating, the granulating method is not limited, and examples thereof include a rolling granulation method, an extrusion granulation method, a compression granulation method, and a stirring granulation method. Although the particle diameter at the time of granulation can also be selected suitably, Preferably it can select from the range of about 1-10 mm.
造粒に際してバインダーを使用する場合、そのバインダーの種類も特に限定されず、種々のものを用いることができる。例えば、各種スターチ類、でんぷん類、キサンタンガム等のガム類、廃糖蜜類、廃酵母液、アルコール醗酵廃液濃縮液、ステフェン廃水濃縮液、ポリビニルアルコール（ＰＶＡ）類、ポリビニルピロリドン類、リグニンスルホン酸塩類、カルボキシメチルセルロース（ＣＭＣ）類等を挙げることができる。さらに、各種造粒助剤についても特に制限はなく、種々のものを用いることができる。例えば、珪藻土、ベントナイト、モンモリロナイト、ヘクトライト、サポナイト、スチブンサイト、バイデライト等の各種粘土鉱物類、膨潤性雲母、バーミキュライト、ゼオライト、二水石膏、半水石膏、無水石膏等を挙げることができる。 When a binder is used for granulation, the type of the binder is not particularly limited, and various types can be used. For example, various starches, starches, gums such as xanthan gum, molasses, waste yeast liquid, alcohol fermentation waste liquid concentrate, stefen wastewater concentrate, polyvinyl alcohol (PVA), polyvinyl pyrrolidones, lignin sulfonates, Examples thereof include carboxymethyl cellulose (CMC). Furthermore, there are no particular limitations on the various granulation aids, and various types can be used. Examples thereof include various clay minerals such as diatomaceous earth, bentonite, montmorillonite, hectorite, saponite, stevensite, beidellite, swelling mica, vermiculite, zeolite, dihydrate gypsum, hemihydrate gypsum, and anhydrous gypsum.
３．非晶性肥料組成物の使用
本発明に係る非晶性肥料組成物は、公知又は市販の肥料と同様の使用方法に従って用いることができる。例えば、植物を育成する土壌に本発明組成物をそのまま付与しても良い。また、本発明組成物は、例えば基肥（元肥）又は追肥のいずれの形態でも使用することができる。
3. Use of Amorphous Fertilizer Composition The amorphous fertilizer composition according to the present invention can be used according to the same method of use as known or commercially available fertilizers. For example, you may provide the composition of this invention as it is to the soil which grows a plant. In addition, the composition of the present invention can be used in any form of, for example, basic fertilizer (top fertilizer) or top dressing.
さらに、本発明に係る非晶性肥料組成物は、土壌改良材としても使用することができる。従って、例えば未だ植物が植えられていない土壌（農地）に本発明組成物を適用し、土質を改善することができる。より具体的には、本発明組成物とともにその土地の土と混合する方法等によって実施することができる。 Furthermore, the amorphous fertilizer composition according to the present invention can also be used as a soil conditioner. Therefore, for example, the composition of the present invention can be applied to soil (agricultural land) in which no plants have been planted to improve the soil quality. More specifically, it can be carried out by a method of mixing with the soil of the land together with the composition of the present invention.
以下に実施例及び比較例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。 The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.
出発原料
実施例及び比較例で用いた出発原料（鶏糞燃焼灰、フェロニッケルスラグ、副原料類）の組成を表１に示す。鶏糞燃焼灰、フェロニッケルスラグ及び各副原料類は、トップグラインダーで粉砕均一化して分析し、実施例及び比較例で用いた。各成分は、肥料分析法（農林水産省農業環境技術研究所法）−１９９２年版−の各成分における全量分析の方法で分析した。
The starting materials used in the starting material in Example and Comparative Example (poultry manure combustion ash, ferronickel slag, secondary raw material such) a composition shown in Table 1. The chicken manure combustion ash, ferronickel slag and each auxiliary material were pulverized and homogenized with a top grinder and analyzed, and used in Examples and Comparative Examples. Each component was analyzed by a method for analyzing the total amount of each component of the fertilizer analysis method (Agricultural Environment Technology Laboratory Method, Ministry of Agriculture, Forestry and Fisheries) -1992.
実施例１
鶏糞燃焼灰１：４０４重量部及びフェロニッケルスラグ１：６８３重量部を秤量して十分に混合した。得られた混合物６０ｇを容量１００ｍｌの１６００℃耐熱性アルミナルツボに入れ、高速昇温炉にて１５００℃まで加熱し、その温度を１０分間保持した。溶融物を２５℃の水中に投入して冷却し、固形分を水から取り出し、１００℃で乾燥することにより実施例１の試料を得た。
Example 1
Chicken dung burning ash 1: 404 parts by weight and ferronickel slag 1: 683 parts by weight were weighed and mixed thoroughly. 60 g of the obtained mixture was put in a 1600 ° C. heat-resistant alumina crucible having a capacity of 100 ml, heated to 1500 ° C. in a high-speed heating furnace, and the temperature was maintained for 10 minutes. The melt was poured into 25 ° C. water and cooled, and the solid content was taken out of the water and dried at 100 ° C. to obtain a sample of Example 1.
実施例２
鶏糞燃焼灰１：５７０重量部及びフェロニッケルスラグ１：５７０重量部を秤量して十分に混合したほかは、実施例１と同様の操作により実施例２の試料を得た。
Example 2
A sample of Example 2 was obtained in the same manner as in Example 1, except that 1: 570 parts by weight of chicken manure ash and 1: 570 parts by weight of ferronickel slag were weighed and mixed thoroughly.
実施例３
鶏糞燃焼灰１：４００重量部、フェロニッケルスラグ１：５８０重量部及び生石灰：１５０重量部を秤量して十分に混合したほかは、実施例１と同様の操作によって実施例３の試料を得た。
Example 3
A sample of Example 3 was obtained in the same manner as in Example 1 except that 1: 400 parts by weight of chicken manure burning ash, 1: 580 parts by weight of ferronickel slag and 150 parts by weight of quicklime were mixed and mixed thoroughly. .
実施例４
鶏糞燃焼灰１：４００重量部、フェロニッケルスラグ１：４１０重量部、生石灰：２２０重量部及びケイ石：１００重量部を秤量して十分に混合したほかは、実施例１と同様の操作により実施例４の試料を得た。
Example 4
Poultry manure ash 1: 400 parts by weight, ferronickel slag 1: 410 parts by weight, quicklime: 220 parts by weight, and quartzite: 100 parts by weight The sample of Example 4 was obtained.
実施例５
鶏糞燃焼灰１：４００重量部、フェロニッケルスラグ１：３９０重量部及び高炉スラグ：３２０重量部を秤量して十分に混合したほかは、実施例１と同様の操作により実施例５の試料を得た。
Example 5
A sample of Example 5 was obtained in the same manner as in Example 1 except that 1: 400 parts by weight of chicken ash combustion ash, 1: 390 parts by weight of ferronickel slag and 320 parts by weight of blast furnace slag were weighed and mixed thoroughly. It was.
実施例６
鶏糞燃焼灰２：３２４重量部、フェロニッケルスラグ２：５８７重量部及びりん鉱石１：１８２重量部を秤量して十分に混合したほかは、実施例１と同様の操作により実施例６の試料を得た。
Example 6
The sample of Example 6 was prepared in the same manner as in Example 1 except that 324 parts by weight of poultry manure ash, 2: 5 parts by weight of ferronickel slag, and 1: 182 parts by weight of phosphate ore were weighed and mixed thoroughly. Obtained.
実施例７
鶏糞燃焼灰３：５０７重量部、フェロニッケルスラグ２：５７３重量部及びりん鉱石１：５６重量部を秤量して十分に混合したほかは、実施例１と同様の操作により実施例７の試料を得た。
Example 7
The sample of Example 7 was prepared in the same manner as in Example 1 except that 3: 507 parts by weight of chicken manure burning ash, 2: 573 parts by weight of ferronickel slag and 1:56 parts by weight of phosphate ore were weighed and mixed thoroughly. Obtained.
実施例８
鶏糞燃焼灰３：４０７重量部、フェロニッケルスラグ２：５９０重量部及びりん鉱石１：１１５重量部を秤量して十分に混合したほかは、実施例１と同様の操作により実施例８の試料を得た。
Example 8
The sample of Example 8 was prepared in the same manner as in Example 1 except that 407 parts by weight of poultry manure ash, 2: 590 parts by weight of ferronickel slag, and 1: 115 parts by weight of phosphate ore were weighed and mixed thoroughly. Obtained.
実施例９
鶏糞燃焼灰３：３１４重量部、フェロニッケルスラグ２：６０６重量部及びりん鉱石１：１６９重量部を秤量して十分に混合したほかは、実施例１と同様の操作により実施例９の試料を得た。
Example 9
The sample of Example 9 was prepared in the same manner as in Example 1 except that 3: 314 parts by weight of chicken manure burning ash, 2: 606 parts by weight of ferronickel slag and 1: 169 parts by weight of phosphate ore were weighed and mixed thoroughly. Obtained.
実施例１０
鶏糞燃焼灰３：７．６ｋｇ、フェロニッケルスラグ１：１３．１ｋｇ及びりん鉱石２：５．３ｋｇを秤量して十分に混合し、その約１／４を小型電気炉に投入して通電し、溶融状態とした。溶融状態を確認しながら残りの全ての原料を投入した後、１５００℃にて５分間保持し、小型電気炉より流下させると同時に２５℃の高圧水で冷却した。次いで、固形分を水から取り出し、１００℃で乾燥することにより実施例１０の試料を得た。
Example 10
Chicken dung burning ash 3: 7.6 kg, Ferronickel slag 1: 13.1 kg and Phosphate ore 2: 5.3 kg are weighed and mixed thoroughly, about 1/4 of which is put into a small electric furnace and energized. It was made into a molten state. All the remaining raw materials were added while confirming the molten state, and then kept at 1500 ° C. for 5 minutes, and then allowed to flow down from a small electric furnace and simultaneously cooled with high-pressure water at 25 ° C. Subsequently, the sample of Example 10 was obtained by taking out solid content from water and drying at 100 degreeC.
実施例１１
鶏糞燃焼灰１：１６．２ｋｇ及びフェロニッケルスラグ１：１４．７ｋｇを秤量して十分に混合したほかは、実施例１０と同様の操作により実施例１１の試料を得た。
Example 11
A sample of Example 11 was obtained in the same manner as in Example 10 except that weighed and fully mixed chicken dung burning ash 1: 16.2 kg and ferronickel slag 1: 14.7 kg.
実施例１２
鶏糞燃焼灰１：１１．７ｋｇ、フェロニッケルスラグ２：１０．９ｋｇ及び高炉スラグ：８．０ｋｇを秤量して十分に混合したほかは、実施例１０と同様の操作により実施例１２の試料を得た。
Example 12
The sample of Example 12 was obtained in the same manner as in Example 10 except that 11.7 kg of chicken manure burning ash, 10.9 kg of ferronickel slag and 8.0 kg of blast furnace slag were weighed and mixed thoroughly. It was.
比較例１
鶏糞燃焼灰１：４０４重量部と、フェロニッケルスラグ１：３５３重量部、生石灰：２００重量部及びケイ石：１５０重量部を秤量して十分に混合したほかは、実施例１と同様の操作により比較例１の試料を得た。
Comparative Example 1
The same operation as in Example 1 except that 1: 404 parts by weight of chicken manure ash, 1: 353 parts by weight of ferronickel slag, 200 parts by weight of quicklime, and 150 parts by weight of quartzite were thoroughly mixed. A sample of Comparative Example 1 was obtained.
比較例２
鶏糞燃焼灰１：４２０重量部、フェロニッケルスラグ１：３６０重量部、生石灰：１５０重量部及びケイ石：１８０重量部を秤量して十分に混合したほかは、実施例１と同様の操作を行うことにより比較例２の試料を得た。
Comparative Example 2
The same operations as in Example 1 were performed except that 1: 420 parts by weight of chicken manure burning ash, 1: 360 parts by weight of ferronickel slag, 150 parts by weight of quicklime and 180 parts by weight of quartzite were weighed and mixed thoroughly. Thus, a sample of Comparative Example 2 was obtained.
試験例１
（１）成分分析
実施例１〜１１及び比較例１〜２で得られた各試料について、乳鉢にて粉砕し、前記肥料分析法にて各成分を分析した。また、得られた分析値に基づいて、２重量％クエン酸液に溶けるＭｇＯと０．５モル／リットルの塩酸に溶けるＳｉＯ２のモル換算した時の比（モル比）を計算で得た。その結果を表２に示す。なお、表２中において、「Ｃ−」は２重量％クエン酸液に溶ける各成分量を示し、「Ｓ−」は０．５モル／リットルの塩酸に溶ける各成分量を示す。
（２）性状観察
実施例１〜１１及び比較例１〜２において、溶融物を水中で冷却した際の性状（外観）を目視にて観察した。その結果を表２（水砕状況）に示す。
（３）結晶性
実施例１及び比較例１で得られた試料の結晶性をＸ線回折分析により調べた。その結果を図１及び図２にそれぞれ示す。これらの図からも明らかなように、いずれの成分も非晶質であることがわかる。
Test example 1
(1) Component analysis About each sample obtained in Examples 1-11 and Comparative Examples 1-2, it grind | pulverized in the mortar and analyzed each component with the said fertilizer analysis method. Moreover, based on the obtained analytical value, the ratio (molar ratio) in terms of mole of MgO dissolved in 2 wt% citric acid solution and SiO 2 dissolved in 0.5 mol / liter hydrochloric acid was obtained by calculation. The results are shown in Table 2. In Table 2, “C-” represents the amount of each component dissolved in 2% by weight citric acid solution, and “S-” represents the amount of each component dissolved in 0.5 mol / liter hydrochloric acid.
(2) Property observation In Examples 1-11 and Comparative Examples 1-2, the property (appearance) at the time of cooling a melt in water was observed visually. The results are shown in Table 2 (Branched condition).
(3) Crystallinity The crystallinity of the samples obtained in Example 1 and Comparative Example 1 was examined by X-ray diffraction analysis. The results are shown in FIGS. 1 and 2, respectively. As is apparent from these figures, it can be seen that all components are amorphous.
表２の結果からも明らかなように、Ｃ−ＭｇＯとＳ−ＳｉＯ２のモル比が０．６５未満の場合、加熱溶融後に水中へ流し込んで冷却すると、各粒子が針金状に固化していた。この状態では、製品化に際して、ハンドリング上好ましくない、粉砕工程が大掛かりになって経済性が損なわれる等の問題が生じる。 As is clear from the results in Table 2, when the molar ratio of C—MgO and S—SiO 2 was less than 0.65, each particle was solidified in a wire shape when poured into water after cooling by heating and cooling. . In this state, there are problems such as unfavorable handling in commercialization, and the pulverization process becomes large and the economy is impaired.
一方、実施例１〜１１のように、Ｃ−ＭｇＯとＳ−ＳｉＯ２のモル比が０．６５以上の場合は、溶融物を水中へ流し込んで冷却した際に、針金状ではなく、各粒子が砂状となって固化しており、ハンドリング及び粉砕工程で特に問題がないことを確認した。 On the other hand, when the molar ratio of C—MgO and S—SiO 2 is 0.65 or more as in Examples 1 to 11, when the melt is poured into water and cooled, each particle is not in the form of a wire. It was confirmed that there was no particular problem in the handling and pulverization process.
このように、実施例で製造した本発明組成物は、鶏糞燃焼灰にフェロニッケルスラグを加え、さらに必要に応じて副原料を混合した組成物を加熱溶融した後に冷却して得られるものであり、りん鉱石の代替ないしりん鉱石の使用量の削減を可能とした肥料として有用であり、しかも粉砕工程が簡易で工業化時の経済性に優れている。 Thus, the composition of the present invention produced in the example is obtained by adding ferronickel slag to chicken manure burning ash, and further cooling the composition after heating and melting the composition mixed with auxiliary materials as necessary. It is useful as a fertilizer that can replace the phosphate ore or reduce the amount of phosphate ore, and has a simple pulverization process and is economical at the time of industrialization.
実施例１３〜１６、比較例３及び参考例１
１／４０００ａワグネルポットに水田土壌を充填し、水を加えて混和し、代掻き状態とし、ビニールハウス内に静置した。上記実施例で得られた本発明物及び比較例で得られた非晶性肥料組成物を、それぞれ乳鉢にて粉砕してポット当り３．３ｇ散布し、さらに基肥として硫安を４．８ｇ、塩化カリウムを１．７ｇ、重過燐酸石灰を２．５ｇ散布した。参考例として基肥のみの区も設けた。表層土壌を混和して２ｃｍの湛水状態とした。３日後に３葉期の水稲苗（コシヒカリ）をポット当たり２本３株植えで移植し、その後はビニールハウス内にて湛水状態を維持した。試験は２連で実施した。収穫期に地上部を刈り取り、風乾後にわら重及び玄米重を測定し、さらに茎葉中のけい酸濃度を硝酸過塩素酸分解−重量法（「土壌，水質及び植物体分析法」２５９〜２６０頁、平成１３年３月、財団法人日本土壌協会発行）にて測定した。その結果を表３に示す。なお、茎葉中のけい酸濃度は、乾物当たりＳｉＯ２濃度（％）で示した。
Examples 13 to 16, Comparative Example 3 and Reference Example 1
A 1 / 4000a Wagner pot was filled with paddy field soil, water was added and mixed to make a scraped state, and the mixture was allowed to stand in a greenhouse. The present invention obtained in the above examples and the amorphous fertilizer composition obtained in the comparative example were each pulverized in a mortar and sprayed with 3.3 g per pot. Further, 4.8 g of ammonium sulfate as a basic fertilizer, chloride 1.7 g of potassium and 2.5 g of heavy superphosphate were sprayed. As a reference example, a base-only section was also provided. The surface soil was mixed to make a 2 cm flooded state. Three days later, three-leaf rice seedlings (Koshihikari) were transplanted by transplanting two to three plants per pot, and then maintained in a flooded state in the greenhouse. The test was performed in duplicate. The above-ground part is cut off during the harvest period, and the weight of straw and brown rice is measured after air drying. Further, the silicic acid concentration in the foliage is determined by the perchloric acid decomposition-weight method ("Soil, Water Quality and Plant Analysis" pages 259-260). , March 2001, published by the Japan Soil Association). The results are shown in Table 3. Incidentally, silicic acid concentration in the foliage showed a dry matter per SiO 2 concentration (%).
表３の結果からも明らかなように、本発明物を使用した肥料を施肥した実施例１３〜１５は、比較例と比較して生育が優れていた。また、茎葉中のけい酸濃度が高く、すなわち作物のけい酸吸収量が多く、健全な生育が認められた。 As is clear from the results in Table 3, Examples 13 to 15 fertilized with the fertilizer using the present invention were excellent in growth as compared with the comparative example. Moreover, the silicic acid concentration in the foliage was high, that is, the amount of silicic acid absorbed by the crop was large, and healthy growth was observed.
本発明は、鶏糞燃焼灰とフェロニッケルスラグ由来の非晶性肥料組成物であり、その肥料成分としての非晶性粒子は、鶏糞燃焼灰にフェロニッケルスラグを加え、さらに必要に応じて副原料を混合した組成物を加熱溶融した後に冷却して得られる。本発明の非晶性肥料組成物は、りん鉱石の代替ないしりん鉱石の使用量の削減を可能とした肥料であり、また粉砕工程が簡易で工業化時の経済性に優れ、さらに作物へのけい酸吸収量が多く、特に緩効性肥料として有用である。 The present invention is an amorphous fertilizer composition derived from chicken manure burning ash and ferronickel slag, and the amorphous particles as the fertilizer component are added ferronickel slag to chicken manure burning ash, and if necessary, an auxiliary material It is obtained by cooling after heating and melting the composition mixed with. The amorphous fertilizer composition of the present invention is a fertilizer capable of substituting for phosphate ore or reducing the amount of phosphate ore used, has a simple grinding process, is economical at the time of industrialization, and is suitable for crops. It has a large amount of acid absorption and is particularly useful as a slow release fertilizer.
Claims (3)
前記非晶性粒子は、前記非晶性粒子１００重量％中、
（１）２重量％クエン酸水溶液に溶けるリン成分をＰ２Ｏ５換算で６〜１６重量％、
（２）２重量％クエン酸水溶液に溶けるカリウム成分をＫ２Ｏ換算で３〜１０重量％、
（３）０．５モル／リットルの塩酸水溶液に溶けるケイ素成分をＳｉＯ２換算で２０〜４０重量％、
（４）２重量％クエン酸液に溶けるマグネシウム成分をＭｇＯ換算で１０〜３０重量％、
（５）０．５モル／リットルの塩酸水溶液に溶けるカルシウム成分をＣａＯ換算で５〜３０重量％含有し、かつ、
（６）前記ＭｇＯ／ＳｉＯ２をモル換算した時の値が０．６５以上である、
ことを特徴とする非晶性肥料組成物の製造方法。 A method for producing a fertilizer composition containing amorphous particles as a fertilizer component, the step of producing a melt by melting starting materials including chicken manure combustion ash and ferronickel slag, and cooling the melt A step of obtaining amorphous particles by vitrification,
The amorphous particles are 100% by weight of the amorphous particles,
(1) Phosphorus component soluble in 2% by weight citric acid aqueous solution is 6 to 16% by weight in terms of P 2 O 5 ,
(2) 3 to 10% by weight of a potassium component dissolved in 2% by weight citric acid aqueous solution in terms of K 2 O,
(3) 20-40% by weight of a silicon component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution in terms of SiO 2 ;
(4) Magnesium component soluble in 2 wt% citric acid solution is 10 to 30 wt% in terms of MgO,
(5) containing 5 to 30% by weight of a calcium component dissolved in 0.5 mol / liter hydrochloric acid aqueous solution in terms of CaO, and
(6) When the MgO / SiO 2 is converted into a mole, the value is 0.65 or more.
The manufacturing method of the amorphous fertilizer composition characterized by the above-mentioned.
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