JP4689217B2 - Compound fertilizer containing organic fertilizer - Google Patents
Compound fertilizer containing organic fertilizer Download PDFInfo
- Publication number
- JP4689217B2 JP4689217B2 JP2004259338A JP2004259338A JP4689217B2 JP 4689217 B2 JP4689217 B2 JP 4689217B2 JP 2004259338 A JP2004259338 A JP 2004259338A JP 2004259338 A JP2004259338 A JP 2004259338A JP 4689217 B2 JP4689217 B2 JP 4689217B2
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- JP
- Japan
- Prior art keywords
- fertilizer
- organic fertilizer
- water
- powder
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003895 organic fertilizer Substances 0.000 title claims description 129
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- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229940099402 potassium metaphosphate Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Landscapes
- Fertilizers (AREA)
Description
本発明は、有機肥料含有複合肥料に関する。詳しくは、土壌に施用された場合に、含有される有機肥料中の窒素成分の無機化が、有機肥料単独施用時に比べ促進される有機肥料含有複合肥料に関する。 The present invention relates to an organic fertilizer-containing composite fertilizer. Specifically, the present invention relates to an organic fertilizer-containing composite fertilizer that, when applied to soil, mineralization of nitrogen components in the contained organic fertilizer is promoted as compared to when organic fertilizer is applied alone.
有機肥料を土壌に施用すると、含有される有機肥料中の窒素成分は完全に無機化するわけではなく、およそ40〜80重量%が無機化した時点で無機化が非常に緩慢になることが知られている(例えば、非特許文献1参照)。これを解決するために、堆肥においては、異畜種の乾燥ふんを混合し、成型加工することで無機化速度を調節し、施用した堆肥が有効に利用される技術が開発されている(例えば、非特許文献2参照)。
しかし、この技術によっても、土壌に施用された堆肥中の窒素成分の無機化は十分ではなく、施用した有機肥料に含有される窒素成分の多くが栽培期間中に有効に活用されていないのが実状である。また、堆肥以外の有機肥料に関しては、無機化を促進する技術は無く、改善が求められている。
It is known that when organic fertilizer is applied to soil, the nitrogen component in the organic fertilizer contained is not completely mineralized, and mineralization becomes very slow when about 40 to 80% by weight is mineralized. (For example, refer nonpatent literature 1). In order to solve this, in compost, a technique has been developed that mixes dry dung of different species and adjusts the mineralization speed by molding and effectively uses the applied compost (for example, Non-patent document 2).
However, even with this technology, mineralization of nitrogen components in compost applied to soil is not sufficient, and most of the nitrogen components contained in applied organic fertilizers are not effectively utilized during the cultivation period. It's real. Moreover, regarding organic fertilizers other than compost, there is no technology for promoting mineralization, and improvements are required.
本発明は、土壌に施用された場合に、含有される有機肥料中の窒素成分の無機化が、有機肥料単独施用時に比べ促進される有機肥料含有複合肥料を提供することを課題とする。 This invention makes it a subject to provide the organic fertilizer containing composite fertilizer which mineralization of the nitrogen component in the organic fertilizer contained is accelerated compared with the time of an organic fertilizer independent application, when applied to soil.
本発明者らは前述の従来技術の課題に鑑み鋭意研究を重ねた。その結果、植物質含有有機肥料粒子と、難水溶性リン酸質肥料及び尿素−脂肪族アルデヒド縮合物を含有する粒子を混合して使用することによって、植物質含有有機肥料の無機化が促進され、前記課題が解決されることを見出し、この知見に基づいて本発明を完成させた。 The present inventors have intensively studied in view of the above-mentioned problems of the prior art. As a result, mineralization of plant-containing organic fertilizer is promoted by mixing and using plant-containing organic fertilizer particles, particles containing poorly water-soluble phosphate fertilizer and urea-aliphatic aldehyde condensate. The present inventors have found that the above problems can be solved, and have completed the present invention based on this finding.
本発明は下記の(1)〜(16)の構成を有する。
(1)20℃の水に対する溶解度が5g/100ml以下の難水溶性リン酸質肥料及び尿素−脂肪族アルデヒド縮合物を含有する粒子Aと、植物質含有有機肥料を含有する粒子Bとからなる複合肥料であって、下記式で示される無機化率の差が、10重量%以上である有機肥料含有複合肥料。
無機化率の差(重量%)=(粒子Aと粒子Bとからなる複合肥料を施用したときに粒子Bに含有される有機肥料中の窒素成分の60日無機化率)−(粒子Bを単独で施用したときの粒子Bに含有される有機肥料中の窒素成分の60日無機化率)
The present invention has the following configurations (1) to (16).
(1) Consists of particles A containing a poorly water-soluble phosphate fertilizer and urea-aliphatic aldehyde condensate having a solubility in water at 20 ° C. of 5 g / 100 ml or less, and particles B containing a plant-containing organic fertilizer An organic fertilizer-containing composite fertilizer that is a composite fertilizer and has a difference in mineralization rate represented by the following formula of 10% by weight or more.
Difference in mineralization rate (% by weight) = (60 day mineralization rate of nitrogen component in organic fertilizer contained in particle B when compound fertilizer consisting of particles A and particles B is applied) − (particle B 60-day mineralization rate of nitrogen component in organic fertilizer contained in particle B when applied alone)
(2)難水溶性リン酸質肥料が、その難水溶性リン酸質肥料を下記式で示される重量比で、30℃の2重量%クエン酸水溶液に浸漬後、含有するリン酸成分の80重量%が該クエン酸水溶液に溶出するのに要する時間が0.1〜2000分の範囲である前記(1)項記載の有機肥料含有複合肥料。
難水溶性リン酸質肥料/2重量%クエン酸水溶液(重量比)=0.013
(2) The poorly water-soluble phosphate fertilizer is 80% of the phosphate component contained after dipping the poorly water-soluble phosphate fertilizer in a 2% by weight citric acid aqueous solution at 30 ° C. in a weight ratio represented by the following formula: The organic fertilizer-containing composite fertilizer according to (1) above, wherein the time required for elution by weight of the citric acid aqueous solution is 0.1 to 2000 minutes.
Slightly water-soluble phosphate fertilizer / 2% by weight citric acid aqueous solution (weight ratio) = 0.013
(3)難水溶性リン酸質肥料が、リン鉱石、熔成リン肥、及び焼成リン肥から選ばれた1種以上である前記(1)または(2)項記載の有機肥料含有複合肥料。 (3) The organic fertilizer-containing composite fertilizer according to (1) or (2) above, wherein the poorly water-soluble phosphate fertilizer is at least one selected from phosphate rock ore, molten phosphorus fertilizer, and calcined phosphorus fertilizer.
(4)粒子Aにおける難水溶性リン酸質肥料の含有割合が、尿素−脂肪族アルデヒド縮合物に対してP2O5換算で0.01〜5重量%の範囲である前記(1)〜(3)項のいずれか1項記載の有機肥料含有複合肥料。 (4) The content ratio of the poorly water-soluble phosphate fertilizer in the particles A is in the range of 0.01 to 5% by weight in terms of P 2 O 5 with respect to the urea-aliphatic aldehyde condensate. The organic fertilizer-containing composite fertilizer according to any one of (3).
(5)尿素−脂肪族アルデヒド縮合物が、2−オキソ−4−メチル−6−ウレイドヘキサヒドロピリミジンである前記(1)〜(4)項のいずれか1項記載の有機肥料含有複合肥料。 (5) The organic fertilizer-containing composite fertilizer according to any one of (1) to (4), wherein the urea-aliphatic aldehyde condensate is 2-oxo-4-methyl-6-ureidohexahydropyrimidine.
(6)粒子Aにおける水溶性リン酸の含有割合が、尿素−脂肪族アルデヒド縮合物に対してP2O5換算で0.5重量%以下である前記(1)〜(5)項のいずれか1項記載の有機肥料含有複合肥料。 (6) The content ratio of the water-soluble phosphoric acid in the particles A is 0.5% by weight or less in terms of P 2 O 5 with respect to the urea-aliphatic aldehyde condensate, and any of the above items (1) to (5) 2. An organic fertilizer-containing composite fertilizer according to claim 1.
(7)粒子Bの炭素/窒素重量比が5.0以上であり、かつ粒子Bに含有される植物質含有有機肥料の炭素/窒素重量比が5.0以上である前記(1)〜(6)項のいずれか1項記載の有機肥料含有複合肥料。 (7) The carbon / nitrogen weight ratio of the particle B is 5.0 or more, and the carbon / nitrogen weight ratio of the plant-containing organic fertilizer contained in the particle B is 5.0 or more (1) to ( The organic fertilizer-containing composite fertilizer according to any one of items 6).
(8)粒子Bに含有される植物質含有有機肥料が、とうもろこし胚芽及びその粉末、大豆油粕及びその粉末、菜種油粕及びその粉末、わたみ油粕及びその粉末、落花生油粕及びその粉末、あまに油粕及びその粉末、ごま油粕及びその粉末、ひまし油粕及びその粉末、米ぬか油粕及びその粉末、その他の草本性植物油粕及びその粉末、とうもろこし胚芽油粕及びその粉末、カポック油粕及びその粉末、たばこくず肥料、甘草かす、豆腐かす乾燥肥料、およびえんじゅかすから選ばれた1種以上の植物粕類である前記(1)〜(7)項のいずれか1項記載の有機肥料含有複合肥料。 (8) The plant-containing organic fertilizer contained in the particle B includes corn germ and powder thereof, soybean oil cake and powder thereof, rapeseed oil cake and powder thereof, cotton oil cake and powder thereof, peanut oil cake and powder thereof, linseed oil cake and Powder, sesame oil cake and powder thereof, castor oil cake and powder thereof, rice bran oil cake and powder thereof, other herbaceous vegetable oil cake and powder thereof, corn germ oil cake and powder thereof, kapok oil cake and powder thereof, tobacco dust fertilizer, licorice waste Organic fertilizer-containing composite fertilizer according to any one of (1) to (7) above, wherein the fertilizer is one or more plant moss selected from dried tofu residue and enjuka .
(9)植物粕類がとうもろこし胚芽油粕、大豆油粕、菜種油粕、わたみ油粕、米ぬか油粕から選ばれた1種以上である前記(8)項記載の有機肥料含有複合肥料。 (9) The organic fertilizer-containing composite fertilizer according to (8) above, wherein the plant meal is at least one selected from corn germ oil meal, soybean oil meal, rapeseed oil meal, cotton seed oil meal, and rice bran oil meal.
(10)植物粕類が菜種油粕である前記(8)項記載の有機肥料含有複合肥料。 (10) The organic fertilizer-containing composite fertilizer according to (8) above, wherein the plant meal is rapeseed oil meal.
(11)有機肥料含有複合肥料中の植物質含有有機肥料の含有量/尿素−脂肪族アルデヒド縮合物の含有量の重量比が15以下である前記(1)〜(10)項のいずれか1項記載の有機肥料含有複合肥料。 (11) Any one of the items (1) to (10), wherein the weight ratio of the content of the plant-containing organic fertilizer in the organic fertilizer-containing composite fertilizer / the content of the urea-aliphatic aldehyde condensate is 15 or less. Compound fertilizer containing organic fertilizer according to item.
(12)粒子Aが、更に撥水性物質を含有する前記(1)〜(11)項のいずれか1項記載の有機肥料含有複合肥料。 (12) The organic fertilizer-containing composite fertilizer according to any one of (1) to (11), wherein the particle A further contains a water-repellent substance.
(13)撥水性物質が60〜130℃の範囲の融点を有する前記(12)項記載の有機肥料含有複合肥料。 (13) The organic fertilizer-containing composite fertilizer according to (12), wherein the water-repellent substance has a melting point in the range of 60 to 130 ° C.
(14)撥水性物質が、天然ワックス及び合成ワックスから選ばれた1種以上である前記(12)または(13)項記載の有機肥料含有複合肥料。 (14) The organic fertilizer-containing composite fertilizer according to (12) or (13), wherein the water-repellent substance is at least one selected from natural wax and synthetic wax.
(15)天然ワックスが、硬化ひまし油及びその誘導体から選ばれた1種以上である前記(14)項記載の有機肥料含有複合肥料。 (15) The organic fertilizer-containing composite fertilizer according to (14), wherein the natural wax is one or more selected from hydrogenated castor oil and derivatives thereof.
(16)粒子A中の撥水性物質の含有割合が、0.1〜20重量%の範囲である前記(12)〜(15)項のいずれか1項記載の有機肥料含有複合肥料。 (16) The organic fertilizer-containing composite fertilizer according to any one of (12) to (15), wherein the content ratio of the water-repellent substance in the particles A is in the range of 0.1 to 20% by weight.
本発明の有機肥料含有複合肥料であれば、土壌に施用された場合に、該複合肥料に含まれる有機肥料中の窒素成分の60日無機化率が、有機肥料単独施用時に比べ10重量%以上促進される。これにより、施用された有機肥料に含有される窒素成分が、栽培期間中により有効に活用される。 In the case of the organic fertilizer-containing composite fertilizer of the present invention, when applied to the soil, the 60-day mineralization rate of the nitrogen component in the organic fertilizer contained in the composite fertilizer is 10% by weight or more as compared with the time when the organic fertilizer is applied alone. Promoted. Thereby, the nitrogen component contained in the applied organic fertilizer is utilized more effectively during the cultivation period.
本発明の有機肥料含有複合肥料は、難水溶性リン酸質肥料及び尿素−脂肪族アルデヒド縮合物を含有する粒子A(以下、単に粒子Aということがある)と、植物質含有有機肥料を含有する粒子B(以下、単に粒子Bということがある)とからなり、この構成により含有される有機肥料中の窒素成分の60日無機化率が有機肥料単独施用時に比べ10重量%以上促進される。 The organic fertilizer-containing composite fertilizer of the present invention contains particles A (hereinafter sometimes simply referred to as particles A) containing a poorly water-soluble phosphate fertilizer and a urea-aliphatic aldehyde condensate, and a plant-containing organic fertilizer. Particles B (hereinafter sometimes simply referred to as “particles B”), and the 60-day mineralization rate of the nitrogen component in the organic fertilizer contained by this configuration is promoted by 10% by weight or more as compared to when the organic fertilizer is applied alone. .
本発明において粒子Aに用いられる難水溶性リン酸質肥料は、水に難溶性で、植物に対してその正常な発育のために必要なリン酸成分を供給することが可能なものであれば特に限定されない。難水溶性リン酸質肥料は、溶解度の低いリン酸化合物を主成分とするものであっても良いが、水溶性のリン酸成分を固定化し難水溶性にしたもの、粒状のリン酸質肥料の表面を水不溶性あるいは疎水性の物質で被覆したもの、更には、リン酸質肥料の微粉末とリン酸質以外の物質であって、水不溶性あるいは疎水性の微粉末とを混合・造粒したもの等も挙げられる。 The poorly water-soluble phosphate fertilizer used for the particles A in the present invention is poorly soluble in water and can supply a phosphate component necessary for its normal growth to plants. There is no particular limitation. The slightly water-soluble phosphate fertilizer may be composed mainly of a phosphoric acid compound having low solubility, but the water-soluble phosphate component is fixed to make it slightly water-soluble, granular phosphate fertilizer Coated and granulated with a water-insoluble or hydrophobic substance coated with a fine powder of phosphate fertilizer and a non-phosphate substance that is water-insoluble or hydrophobic. And the like.
その中でも、溶解度の低いリン酸化合物は、比較的簡便に用いることができるので好ましい。具体的には、20℃の水に対する溶解度が5g/100ml以下の物質が望ましく、例えば、熔成リン肥、加工リン酸肥料、腐植酸混合リン肥、焼成リン肥、レナニアリン肥、副産リン酸二石灰、副産リン酸三石灰、トーマスリン肥、メタリン酸加里、メタリン酸石灰、メタリン酸苦土、メタリン酸加里苦土、リン鉱石等を挙げることができる。この中でも、熔成リン肥、焼成リン肥、リン鉱石は、特に水に対する溶解度が低いため、本発明に好ましく使用することができる。リン酸1アンモニウムやリン酸2アンモニウムなどの水溶性リン酸化合物は、本発明の効果を損なう場合がある。 Among them, a phosphoric acid compound having low solubility is preferable because it can be used relatively easily. Specifically, a substance having a solubility in water at 20 ° C. of 5 g / 100 ml or less is desirable. Examples thereof include dilime, tricalcium phosphate byproduct, Thomaslin fertilizer, potassium metaphosphate, lime metaphosphate, metaphosphoric acid clay, metaphosphoric acid potassium clay, and phosphate ore. Among these, molten phosphorous fertilizer, calcined phosphorous fertilizer, and phosphorus ore can be preferably used in the present invention because they have particularly low solubility in water. Water-soluble phosphoric acid compounds such as monoammonium phosphate and diammonium phosphate may impair the effects of the present invention.
また、本発明に使用される難水溶性リン酸質肥料は、その難水溶性リン酸質肥料を下記式で示される重量比で、30℃の2重量%クエン酸水溶液に浸漬後、含有するリン酸成分の80重量%が該クエン酸水溶液に溶出するのに要する時間(以下、溶出時間という)が0.1〜2000分の範囲である溶出特性を有するものであることが特に好ましい。
難水溶性リン酸質肥料/2重量%クエン酸水溶液(重量比)=0.013
The poorly water-soluble phosphate fertilizer used in the present invention contains the poorly water-soluble phosphate fertilizer after being immersed in a 2% by weight citric acid aqueous solution at 30 ° C. in a weight ratio represented by the following formula. It is particularly preferable that the time required for elution of 80% by weight of the phosphoric acid component into the aqueous citric acid solution (hereinafter referred to as elution time) is in the range of 0.1 to 2000 minutes.
Slightly water-soluble phosphate fertilizer / 2% by weight citric acid aqueous solution (weight ratio) = 0.013
該溶出時間は具体的には次のような方法で測定することができる。300ml容のポリ瓶に難水溶性リン酸質肥料2gと30℃に加熱した2重量%クエン酸水溶液150mlを入れ、30℃の振とう恒温槽で振とうする。経時的に該クエン酸水溶液の上澄みを少量ずつ取り、水で希釈後、希釈液中のリン酸成分をイオンクロマトグラフィーによって定量後、溶出曲線を作成することにより、該難水溶性リン酸質肥料が含有するリン酸成分の80重量%が溶出するまでに要した時間を求めることができる。 Specifically, the elution time can be measured by the following method. In a 300 ml plastic bottle, 2 g of poorly water-soluble phosphate fertilizer and 150 ml of 2 wt% aqueous citric acid solution heated to 30 ° C. are placed and shaken in a 30 ° C. shaking thermostat. Taking the supernatant of the aqueous citric acid solution little by little over time, diluting with water, quantifying the phosphoric acid component in the diluted liquid by ion chromatography, and then creating an elution curve, the poorly water-soluble phosphate fertilizer The time required until 80% by weight of the phosphoric acid component contained in can be eluted.
該溶出時間が0.1〜2000分の範囲であれば、有機肥料中の窒素成分の無機化を促進することが可能である。 When the elution time is in the range of 0.1 to 2000 minutes, it is possible to promote mineralization of the nitrogen component in the organic fertilizer.
該溶出時間が0.1〜2000分の範囲であるためには、該難水溶性リン酸質肥料は水に対する溶解度が低く、単一の結晶で構成されていることが好ましい。更に、形状が粒状である場合には粒内に空隙が少ないものであることが好ましい。 In order for the elution time to be in the range of 0.1 to 2000 minutes, the poorly water-soluble phosphate fertilizer preferably has a low solubility in water and is composed of a single crystal. Furthermore, when the shape is granular, it is preferable that there are few voids in the particles.
本発明に使用される難水溶性リン酸質肥料の溶出時間を0.1〜2000分の範囲に調節する方法は特に限定されないが、例えば、難水溶性リン酸質肥料を粒状とし、その粒径を調節する方法、粒状の難水溶性リン酸質肥料の表面を水不溶性または疎水性の物質で被覆する方法、及び、難水溶性リン酸質肥料の微粉末とリン酸質以外の物質であって、水不溶性または疎水性の微粉末とを混合し造粒する方法等を挙げることができる。 The method for adjusting the elution time of the poorly water-soluble phosphate fertilizer used in the present invention to a range of 0.1 to 2,000 minutes is not particularly limited. A method of adjusting the diameter, a method of coating the surface of a granular sparingly water-soluble phosphate fertilizer with a water-insoluble or hydrophobic substance, and a powder of sparingly water-soluble phosphate fertilizer and a substance other than phosphate And a method of mixing with water-insoluble or hydrophobic fine powder and granulating.
そのうち、難水溶性リン酸質肥料を粒状とし、その粒子径を調節する方法は、比較的簡便に実施可能であり好ましい。その際の粒子径は使用する難水溶性リン酸質肥料の種類や、要求される溶出時間によって異なるが、製造の面から0.1〜2mmの範囲であることが好ましい。 Among them, the method of making the slightly water-soluble phosphate fertilizer granular and adjusting its particle size is preferable because it can be carried out relatively easily. The particle diameter at that time varies depending on the kind of poorly water-soluble phosphate fertilizer used and the required elution time, but is preferably in the range of 0.1 to 2 mm from the viewpoint of production.
粒子Aにおける難水溶性リン酸質肥料の添加割合は特に限定されないが、尿素−脂肪族アルデヒド縮合物に対しP2O5換算で0.01〜5重量%の範囲であることが好ましい。難水溶性リン酸質肥料の添加割合がこの範囲内であれば、有機肥料中の窒素成分の無機化の促進を効果的に行うことが可能である。 The addition ratio of the poorly water-soluble phosphate fertilizer in the particles A is not particularly limited, but is preferably in the range of 0.01 to 5% by weight in terms of P 2 O 5 with respect to the urea-aliphatic aldehyde condensate. If the addition ratio of the poorly water-soluble phosphate fertilizer is within this range, it is possible to effectively promote the mineralization of the nitrogen component in the organic fertilizer.
本発明において粒子Aに用いられる尿素−脂肪族アルデヒド縮合物は特に限定されるものではなく、直鎖状、分岐のある鎖状、環状等の何れの分子構造を持つ尿素−脂肪族アルデヒド縮合物であっても使用することができる。具体的には、尿素−ホルムアルデヒド縮合物、尿素−アセトアルデヒド縮合物、尿素−イソブチルアルデヒド縮合物等を挙げることができる。本発明においてはそれらのうち1種以上を任意に選択し使用すればよい。 The urea-aliphatic aldehyde condensate used for the particles A in the present invention is not particularly limited, and the urea-aliphatic aldehyde condensate having any molecular structure such as linear, branched chain, and cyclic. Can even be used. Specific examples include urea-formaldehyde condensates, urea-acetaldehyde condensates, urea-isobutyraldehyde condensates, and the like. In the present invention, one or more of them may be arbitrarily selected and used.
前述の尿素−脂肪族アルデヒド縮合物のうち、尿素−アセトアルデヒド縮合物である2−オキソ−4−メチル−6−ウレイドヘキサヒドロピリミジン(以下「CDU」と記述する。)を本発明に使用した場合には、本発明の効果がより顕著である。 Among the aforementioned urea-aliphatic aldehyde condensates, urea-acetaldehyde condensate 2-oxo-4-methyl-6-ureidohexahydropyrimidine (hereinafter referred to as “CDU”) is used in the present invention. The effect of the present invention is more remarkable.
尿素−脂肪族アルデヒド縮合物が粉状である場合の粒径は、製造時の取り扱いの面、他原料との混合性、造粒性の面から1〜200μmの範囲であることが好ましい。 The particle size when the urea-aliphatic aldehyde condensate is powdery is preferably in the range of 1 to 200 μm from the viewpoint of handling during production, miscibility with other raw materials, and granulation.
粒子Aに含有される尿素−脂肪族アルデヒド縮合物の割合は、特に限定されないが、好ましくは50〜99.98重量%、より好ましくは75〜99.98重量%の範囲である。 The ratio of the urea-aliphatic aldehyde condensate contained in the particles A is not particularly limited, but is preferably in the range of 50 to 99.98% by weight, more preferably 75 to 99.98% by weight.
尚、水溶性リン酸が粒子A中にある程度以上存在すると、本発明の効果を損なう場合があるため、粒子A中の水溶性リン酸の含有割合は、尿素−脂肪族アルデヒド縮合物に対して、P2O5換算で0.5重量%以下であることが好ましい。この観点から、本発明に使用する難水溶性リン酸質肥料はリン鉱石、熔成リン肥、焼成リン肥から選ばれた1種以上であることが好ましい。 If the water-soluble phosphoric acid is present in the particles A to some extent, the effect of the present invention may be impaired. Therefore, the content ratio of the water-soluble phosphoric acid in the particles A is based on the urea-aliphatic aldehyde condensate. In terms of P 2 O 5 , it is preferably 0.5% by weight or less. From this viewpoint, it is preferable that the poorly water-soluble phosphate fertilizer used in the present invention is at least one selected from phosphorus ore, molten phosphorus fertilizer, and calcined phosphorus fertilizer.
粒子Aの製造方法は、特に限定されないが、具体的には、スラリー状、粒状、顆粒状、粉状、塊状の何れかの状態である尿素−アルデヒド縮合物に、難水溶性リン酸質肥料を添加し、混合した後、造粒することによって得ることができる。その際に使用する尿素−脂肪族アルデヒド縮合物は、難水溶性リン酸質肥料との均一分散の面から粉状であることが好ましい。 The production method of the particles A is not particularly limited, and specifically, a slightly water-soluble phosphate fertilizer is added to the urea-aldehyde condensate in a slurry state, granular state, granular state, powder state, or bulk state. Can be obtained by adding, mixing, and granulating. The urea-aliphatic aldehyde condensate used at that time is preferably in the form of powder from the viewpoint of uniform dispersion with the poorly water-soluble phosphate fertilizer.
一方、尿素−脂肪族アルデヒド縮合物に添加混合する難水溶性リン酸質肥料は、混合における均一性の面では顆粒状である方が好ましい。反面、その場合、土壌中で溶解しやすく、微粒状難水溶性リン酸質肥料の大きさによっては尿素−脂肪族アルデヒド縮合物の無機化を必要以上に促進することがあり、難水溶性リン酸質肥料はある程度の大きさの粒である方が好ましい。 On the other hand, the poorly water-soluble phosphate fertilizer to be added to and mixed with the urea-aliphatic aldehyde condensate is preferably granular in terms of uniformity in mixing. On the other hand, in that case, it is easy to dissolve in the soil, and depending on the size of the finely divided slightly water-soluble phosphate fertilizer, mineralization of the urea-aliphatic aldehyde condensate may be promoted more than necessary. The acid fertilizer is preferably a grain of a certain size.
土壌中における難水溶性リン酸質肥料の溶解速度はその種類や結晶構造等によって異なるため、難水溶性リン酸質肥料粒の粒径は一概に限定することは困難であるが、製造時の混合均一性から通常0.15〜2mmの範囲、好ましくは0.15〜1mmの範囲が良好である場合が多い。 Since the dissolution rate of poorly water-soluble phosphate fertilizer in soil varies depending on the type and crystal structure, it is difficult to limit the particle size of poorly water-soluble phosphate fertilizer grains. From the mixing uniformity, the range of usually 0.15 to 2 mm, preferably 0.15 to 1 mm is often good.
粒子Aの粒子径は、特に限定されないが、好ましくは1〜20mm、より好ましくは1.5〜10mmの範囲である。この範囲であれば本発明の効果が顕著である。 The particle diameter of the particles A is not particularly limited, but is preferably 1 to 20 mm, more preferably 1.5 to 10 mm. Within this range, the effect of the present invention is remarkable.
粒子Bの粒子径は、特に限定されないが、好ましくは20mm以下、より好ましくは10mm以下、さらに好ましくは1mm以下である。粒子Bの粒子径が20mm以下であれば、無機化が促進されやすく、1mm以下であればさらに無機化が促進されやすい。 The particle diameter of the particles B is not particularly limited, but is preferably 20 mm or less, more preferably 10 mm or less, and even more preferably 1 mm or less. If the particle diameter of the particle B is 20 mm or less, mineralization is easily promoted, and if it is 1 mm or less, mineralization is further facilitated.
粒子A及び粒子Bの造粒方法としては、転動造粒法、圧縮型造粒法、攪拌型造粒法、押出造粒法、破砕型造粒法、流動層及び流動層多機能型造粒法、噴霧乾燥造粒法、真空凍結造粒法、液中造粒法等を挙げることができる。本発明においてはその中でも、転動造粒法、圧縮型造粒法、攪拌型造粒法、及び押出造粒法を好ましい造粒方法として挙げることができる。 As granulation methods of particles A and particles B, rolling granulation method, compression granulation method, stirring granulation method, extrusion granulation method, crushing granulation method, fluidized bed and fluidized bed multifunctional type granulation Examples thereof include a granulation method, a spray-drying granulation method, a vacuum freeze granulation method, and a submerged granulation method. Among them, the rolling granulation method, the compression granulation method, the stirring granulation method, and the extrusion granulation method can be cited as preferable granulation methods in the present invention.
本発明の有機肥料含有複合肥料に含有される粒子Bに用いられる植物質含有有機肥料としては、肥料取締法で規定される有機質肥料及び特殊肥料のうち植物質を含有するものである。ここで言う植物質は、リグニン、セルロースなどの難分解性の多糖類で構成される細胞壁を有する生物、該生物遺体、及びその構成成分であり、植物以外に細胞壁を有する微生物も含まれ、デンプンなどの易分解性多糖類のみで構成されるものは除く。具体的には、植物質含有有機質肥料としては、とうもろこし胚芽及びその粉末、大豆油粕及びその粉末、菜種油粕及びその粉末、わたみ油粕及びその粉末、落花生油粕及びその粉末、あまに油粕及びその粉末、ごま油粕及びその粉末、ひまし油粕及びその粉末、米ぬか油粕及びその粉末、その他の草本性植物油粕及びその粉末、とうもろこし胚芽油粕及びその粉末、カポック油粕及びその粉末、たばこくず肥料、甘草かす、豆腐かす乾燥肥料、えんじゅかす等の植物粕類、乾燥菌体肥料、副産植物質肥料、混合有機質肥料が挙げられる。特殊肥料としては、米ぬか、はっこう米ぬか、はっこうかす、くず植物油粕及びその粉末、草本性植物種子皮殻油粕及びその粉末、木の実油粕及びその粉末、コーヒーかす、くず大豆及びその粉末、たばこくず肥料及びその粉末、乾燥藻及びその粉末、落棉分離かす肥料、よもぎかすが挙げられる。この中でも、植物粕類は、本発明の複合肥料に用いたときに無機化の促進度合が大きいことから望ましい。植物粕類の中でも、とうもろこし胚芽油粕、大豆油粕、菜種油粕、わたみ油粕、米ぬか油粕が好ましく、特に菜種油粕及びその粉末が好ましい。 The plant-containing organic fertilizer used for the particles B contained in the organic fertilizer-containing composite fertilizer of the present invention contains plant matter among organic fertilizers and special fertilizers defined by the Fertilizer Control Law. The plant substance mentioned here is an organism having a cell wall composed of a hardly-degradable polysaccharide such as lignin and cellulose, the biological body, and its constituent components, including microorganisms having a cell wall in addition to plants, Excluding those composed only of easily degradable polysaccharides such as Specifically, the plant-containing organic fertilizer includes corn germ and powder thereof, soybean oil cake and powder thereof, rapeseed oil cake and powder thereof, cotton seed oil cake and powder thereof, peanut oil cake and powder thereof, linseed oil cake and powder thereof, Sesame oil cake and its powder, castor oil cake and its powder, rice bran oil cake and its powder, other herbaceous vegetable oil cake and its powder, corn germ oil cake and its powder, Kapok oil cake and its powder, tobacco waste fertilizer, licorice meal, tofu residue Plant fertilizers such as dry fertilizers, enjukas, dry cell fertilizers, by-product plant fertilizers , and mixed organic fertilizers. Special fertilizers include rice bran, bran rice bran, ground bran, waste vegetable oil cake and powder thereof, herbaceous plant seed shell oil cake and powder thereof, nut oil and powder thereof, coffee grounds, waste soybean and powder thereof, tobacco waste fertilizer and the powder, dried algae and powders,落棉separated cake fertilizers include mugwort dregs. Among these, plant meals are desirable because they have a high degree of promotion of mineralization when used in the composite fertilizer of the present invention. Among plant meals, corn germ oil meal, soybean oil meal, rapeseed oil meal, cottonseed oil meal, and rice bran oil meal are preferable, and rapeseed oil meal and powder thereof are particularly preferable.
一般的に、有機物の分解について論じられるとき、炭素/窒素重量比が重要である。炭素/窒素重量比が大きい有機物が分解される速さは遅く、炭素/窒素重量比が小さい有機物が分解される速さは早いことが多い。炭素/窒素重量比は、粒子Bまたは該植物質含有有機肥料に含有される炭素量と窒素量を測定することにより求められる。両物質とも炭素窒素同時分析法(博友社 土壌環境分析法 p222−p233に記載の方法)で測定される。 In general, the carbon / nitrogen weight ratio is important when discussing the decomposition of organics. An organic substance having a large carbon / nitrogen weight ratio is decomposed at a low speed, and an organic substance having a small carbon / nitrogen weight ratio is often decomposed at a high speed. The carbon / nitrogen weight ratio is determined by measuring the amount of carbon and the amount of nitrogen contained in the particle B or the plant-containing organic fertilizer. Both substances are measured by a simultaneous carbon nitrogen analysis method (method described in Hirotosha soil environment analysis method p222-p233).
本発明において、粒子Bの炭素/窒素重量比は、特に限定はされないが、5.0以上が好ましく、5.5〜80がより好ましい。また、粒子Bに含有される植物質含有有機肥料の炭素/窒素重量比も、特に限定はされないが、5.0以上が好ましく、5.5〜80がより好ましい。粒子Bの炭素/窒素重量比が上記範囲であり、粒子Bに含有される植物質含有有機肥料の炭素/窒素重量比が上記範囲であれば、該複合肥料に含有される植物質含有有機肥料の無機化が促進されやすい。 In the present invention, the carbon / nitrogen weight ratio of the particles B is not particularly limited, but is preferably 5.0 or more, more preferably 5.5 to 80. Moreover, the carbon / nitrogen weight ratio of the plant-containing organic fertilizer contained in the particle B is not particularly limited, but is preferably 5.0 or more, and more preferably 5.5 to 80. If the carbon / nitrogen weight ratio of the particle B is in the above range, and the carbon / nitrogen weight ratio of the plant-containing organic fertilizer contained in the particle B is in the above range, the plant-containing organic fertilizer contained in the composite fertilizer It is easy to promote mineralization.
本発明の有機肥料含有複合肥料は、粒子Aと粒子Bを混合することによって製造される。その際の混合割合は、有機肥料含有複合肥料中の有機肥料の含有量/尿素−脂肪族アルデヒド縮合物の含有量の重量比が15以下であることが望ましい。重量比が15以下であれば、発明の効果が十分であるからである。 The organic fertilizer-containing composite fertilizer of the present invention is produced by mixing particles A and particles B. As for the mixing ratio in that case, it is desirable that the weight ratio of the content of the organic fertilizer in the organic fertilizer-containing composite fertilizer / the content of the urea-aliphatic aldehyde condensate is 15 or less. If the weight ratio is 15 or less, the effect of the invention is sufficient.
本発明の有機肥料含有複合肥料においては、本発明の効果を損なわない範囲であれば、本発明の必須成分である難水溶性リン酸質肥料、尿素−脂肪族アルデヒド縮合物、有機肥料以外の成分を、本発明の原料として使用することができる。該成分としては肥料、各種造粒助剤、結合材等を挙げることができる。該成分は、それぞれの粒子を製造する際に添加しても良いし、それぞれの粒子とは別の粒子として複合肥料中に混合しても良い。ただし、炭素成分、窒素成分を含有するものを粒子Bに添加する際には、粒子Bに含まれる炭素/窒素重量比が5.0以上になるように添加するのが好ましい。 In the organic fertilizer-containing composite fertilizer of the present invention, as long as the effects of the present invention are not impaired, the water-soluble phosphate fertilizer, urea-aliphatic aldehyde condensate, which is an essential component of the present invention, other than organic fertilizer Ingredients can be used as raw materials for the present invention. Examples of the component include fertilizers, various granulation aids, and binders. The component may be added when each particle is produced, or may be mixed in the composite fertilizer as a particle different from each particle. However, when the carbon component and the nitrogen component are added to the particle B, the carbon / nitrogen weight ratio contained in the particle B is preferably 5.0 or more.
前記肥料としては、尿素、硫安、塩安、硝安、石灰窒素、腐植酸アンモニア等の窒素質肥料、リン酸1アンモニウム、リン酸2アンモニウム、過燐酸石灰、重過燐酸石灰、重焼リン、苦土重焼リン等のリン酸質肥料、硫酸グアニル尿素、オキサミド、グリコールウレア等の化学合成系緩効性肥料、硫酸加里、塩化加里、重炭酸加里、腐植酸加里、珪酸加里等の加里肥料、普通化成肥料、二成分複合化成肥料、高度化成肥料、石灰質肥料、苦土質肥料、ケイ酸質肥料、及び微量要素肥料等を挙げることができる。本発明においては必要に応じてそれら肥料の中から1種以上を選択して用いればよい。 Examples of the fertilizer include urea, ammonium sulfate, ammonium chloride, ammonium nitrate, lime nitrogen, ammonia humic acid, and other nitrogenous fertilizers, monoammonium phosphate, diammonium phosphate, lime perphosphate, heavy superphosphate lime, heavy burnt phosphorus, bitterness Phosphoric fertilizers such as earthen baked phosphorus, chemical synthetic slow-release fertilizers such as guanyl urea sulfate, oxamide, glycol urea, potassium fertilizers such as potassium sulfate, potassium chloride, bicarbonate potassium, humic acid potassium, silicic acid potassium, Examples include ordinary chemical fertilizers, two-component compound fertilizers, advanced chemical fertilizers, calcareous fertilizers, mafic fertilizers, siliceous fertilizers, and trace element fertilizers. In the present invention, one or more fertilizers may be selected and used as necessary.
そのうちリン酸質肥料、普通化成肥料、二成分複合化成肥料、高度化成肥料等のリン酸成分を含有する肥料を用いるときは、含有するリン酸成分の溶出時間と含有量を考慮して使用することが好ましい。 Among them, when using fertilizers containing phosphate components such as phosphate fertilizers, ordinary chemical fertilizers, two-component compound fertilizers, and advanced chemical fertilizers, use them in consideration of the elution time and content of the phosphate components. It is preferable.
造粒助剤としては、ベントナイト、クレイ、カオリン、セリサイト、タルク、酸性白土、軽石、珪砂、珪石、ゼオライト、パーライト、バーミキュライト等の鉱物質、モミガラ、オガクズ、木質粉、パルプフロック、大豆粉等の植物質等を挙げることができる。本発明においては必要に応じてそれら造粒助剤の中から1種以上を選択して用いればよい。 Granulation aids include bentonite, clay, kaolin, sericite, talc, acid clay, pumice, quartz sand, quartzite, zeolite, perlite, vermiculite, and other minerals, rice straw, sawdust, wood flour, pulp floc, soybean flour, etc. The plant substance of this can be mentioned. In the present invention, one or more kinds of granulation aids may be selected and used as necessary.
結合材としては、アラビアゴム、アルギン酸ナトリウム、グリセリン、ゼラチン、糖蜜、微結晶セルロース、ピッチ、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ポリアクリル酸ナトリウム、ポリビニルピロリドン、アルミナゾル、セメント、ポリリン酸ナトリウム、リグニンスルホン酸塩、ポリビニルアルコール、ポリエチレングリコール、界面活性剤、デンプン、熱硬化性樹脂原料等を挙げることができる。本発明においては必要に応じてそれら結合材の中から1種以上を選択して用いればよい。 Binders include gum arabic, sodium alginate, glycerin, gelatin, molasses, microcrystalline cellulose, pitch, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium polyacrylate, polyvinylpyrrolidone, alumina sol, cement, sodium polyphosphate, lignin Examples thereof include sulfonates, polyvinyl alcohol, polyethylene glycol, surfactants, starch, thermosetting resin raw materials, and the like. In the present invention, one or more of these binders may be selected and used as necessary.
粒子Aに原料として更に撥水性物質を含有させれば、該粒子の土壌中における溶解を抑制することができ、有機肥料中の窒素成分の無機化を促進するだけでなく、無機化速度を調節することが可能である。 If the particle A further contains a water-repellent substance as a raw material, dissolution of the particle in the soil can be suppressed, not only promoting the mineralization of the nitrogen component in the organic fertilizer, but also adjusting the mineralization rate. Is possible.
本発明に使用する撥水性物質は、防湿性、防水性を有する撥水性物質であれば特に限定されないが、その中でも融点が好ましくは60〜130℃の範囲、より好ましくは60〜100℃の範囲である撥水性物質が望ましい。 The water-repellent substance used in the present invention is not particularly limited as long as it is a moisture-repellent and waterproof water-repellent substance. Among them, the melting point is preferably in the range of 60 to 130 ° C, more preferably in the range of 60 to 100 ° C. A water repellent material is desirable.
該撥水性物質の融点が60℃以上であれば、本発明の有機肥料含有複合肥料の夏季における保存性が安定し、該融点が130℃以下であれば、本発明の有機肥料含有複合肥料の製造時に物温が130℃を超えるような熱処理を行う必要がなく、尿素−脂肪族アルデヒド縮合物の製造時における分解が生じにくい。 If the water repellent material has a melting point of 60 ° C. or higher, the storage stability in the summer of the organic fertilizer-containing composite fertilizer of the present invention is stable, and if the melting point is 130 ° C. or lower, the organic fertilizer-containing composite fertilizer of the present invention It is not necessary to perform a heat treatment such that the temperature of the product exceeds 130 ° C. during the production, and decomposition during the production of the urea-aliphatic aldehyde condensate hardly occurs.
本発明においては、撥水性物質として天然ワックス、合成ワックスから選ばれた1種以上を適宜使用するのが好ましい。天然ワックスとしては、キャデリンワックス、カルナウバワックス、ライスワックス、木ろう、ホホバ油等の植物系ワックス、みつろう、ラノリン、鯨ろう等の動物系ワックス、モンタンワックス、オゾケライト、セレシン等の鉱物系ワックス、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタム等の石油ワックスが挙げられ、合成ワックスとしては、フィッシャー・トロプシュワックス、ポリエチレンワックス、ポリプロピレンワックス等の合成炭化水素、モンタンワックス誘導体、パラフィンワックス誘導体、マイクロクリスタリンワックス誘導体等の変性ワックス、硬化ひまし油、硬化ひまし油誘導体等の水素化ワックス、12−ヒドロキシステアリン酸、ステアリン酸アミド、無水フタル酸イミド、塩素化炭化水素等が挙げられる。この中でも、硬化ひまし油及びその誘導体が本発明に効果的である。 In the present invention, it is preferable to appropriately use at least one selected from natural wax and synthetic wax as the water repellent substance. Natural waxes include plant waxes such as cadrine wax, carnauba wax, rice wax, wax, jojoba oil, animal waxes such as beeswax, lanolin, and sperm wax, and mineral waxes such as montan wax, ozokerite, and ceresin. , Paraffin wax, microcrystalline wax, petroleum wax such as petrolatum, and synthetic waxes include synthetic hydrocarbons such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives Denatured wax, hydrogenated wax such as hardened castor oil, hardened castor oil derivative, 12-hydroxystearic acid, stearamide, phthalic anhydride, chlorinated hydrocarbon And the like. Among these, hydrogenated castor oil and derivatives thereof are effective in the present invention.
本発明において撥水性物質の含有割合は、粒子Aに対して好ましくは0.1〜20重量%、更に好ましくは1〜15重量%の範囲である。該含有割合が上記の範囲内であれば、撥水性物質の効果が十分で、製造コストに見合う効果が得られる。 In the present invention, the content of the water-repellent substance is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight with respect to the particles A. When the content ratio is within the above range, the effect of the water repellent substance is sufficient, and an effect commensurate with the manufacturing cost can be obtained.
原料として更に撥水性物質を含有する、粒子Aの製造方法は特に限定されるものではないが、撥水性物質、難水溶性リン酸質肥料、尿素−脂肪族アルデヒド縮合物、及び水を原料とする粒子を造粒し(造粒工程)、次いで該撥水性物質の融点以上500℃以下の温度である気体を用いて該粒子の乾燥を行う(乾燥工程)製造方法を挙げることができる。 The method for producing the particles A further containing a water repellent material as a raw material is not particularly limited, but the water repellent material, the poorly water-soluble phosphate fertilizer, the urea-aliphatic aldehyde condensate, and water are used as the raw material. Examples of the production method include granulating the particles to be granulated (granulating step), and then drying the particles using a gas having a temperature not lower than the melting point of the water-repellent substance and not higher than 500 ° C. (drying step).
該造粒工程においては、先ず原料となる撥水性物質、難水溶性リン酸質肥料、尿素−脂肪族アルデヒド縮合物、及び水の混合を行い、この混合物を所定の形状に造粒するのであるが、その際の混合方法としては、コンクリートミキサー等の回転容器型混合装置による対流混合や、攪拌混合造粒機等の固定容器型混合装置による攪拌等が挙げられ、状況に応じて適宜選択すれば良い。 In the granulation step, first, a water-repellent material, a poorly water-soluble phosphate fertilizer, a urea-aliphatic aldehyde condensate, and water are mixed, and the mixture is granulated into a predetermined shape. However, the mixing method at that time includes convection mixing with a rotating container type mixing apparatus such as a concrete mixer, stirring with a fixed container type mixing apparatus such as a stirring and mixing granulator, etc., and may be appropriately selected according to the situation. It ’s fine.
混合の際、該撥水性物質の状態は、スラリー状、粒状、粉状、塊状、溶融状態、または溶液状態の何れかの状態であっても良いが、混合物の均一性の面から粉状、溶融状態、或いは溶液状態であることが好ましく、その中でも特に製造時の取り扱い面や製造コストの面から粉状であることが好ましい。 At the time of mixing, the state of the water-repellent substance may be any of a slurry state, a granular state, a powder state, a lump shape, a molten state, or a solution state, but in terms of the uniformity of the mixture, It is preferably in a molten state or in a solution state, and in particular, it is preferably in a powder form from the viewpoint of handling during production and production cost.
該撥水性物質が粉状である場合の粒径は、製造時の取り扱い面、他原料との混合性、造粒性の面から0.005〜1mmの範囲であることが好ましい。 The particle size when the water repellent material is powdery is preferably in the range of 0.005 to 1 mm from the viewpoint of handling during production, miscibility with other raw materials, and granulation.
混合後の造粒方法は特に限定されるものではないが、転動造粒法、圧縮型造粒法、攪拌型造粒法、押出造粒法、破砕型造粒法、流動層及び流動層多機能型造粒法等を挙げることができ、本発明においては、転動造粒法、圧縮型造粒法、攪拌型混合造粒法、押出造粒法等によって造粒することが好ましい。 The granulation method after mixing is not particularly limited, but rolling granulation method, compression granulation method, stirring granulation method, extrusion granulation method, crushing granulation method, fluidized bed and fluidized bed A multifunctional granulation method and the like can be mentioned. In the present invention, granulation is preferably performed by a rolling granulation method, a compression granulation method, a stirring type mixing granulation method, an extrusion granulation method, or the like.
その中でも攪拌型混合造粒法は、混合及び造粒を1つの装置で行うことができ、更に温度条件の設定が容易なため、本発明に好ましく使用することができる。該攪拌混合造粒機は、原料が適度に混合され造粒が可能な装置であれば特に限定されないが、本発明においては、パドル型、アンカー型、ゲート型、ダブルモーションパドル型、リボン型、スクリュー型から選ばれた攪拌羽根を持つ装置が特に好ましく使用することができる。 Among them, the stirring type mixing granulation method can be preferably used in the present invention because mixing and granulation can be performed with one apparatus and the temperature condition can be easily set. The stirring and mixing granulator is not particularly limited as long as the raw materials are appropriately mixed and granulated, but in the present invention, a paddle type, an anchor type, a gate type, a double motion paddle type, a ribbon type, An apparatus having a stirring blade selected from a screw type can be particularly preferably used.
造粒工程において、撥水性物質、難水溶性リン酸質肥料、尿素−脂肪族アルデヒド縮合物、及び水等の原料の温度は特に限定されないが、融点が60〜130℃の範囲内である撥水性物質を用いる場合において、該温度は該撥水性物質の融点より0〜40℃低い温度であることが好ましい。該温度はこの範囲である場合には、乾燥工程を経て得られる肥料粒子内において撥水性物質が良好に拡散する。 In the granulation step, the temperature of the raw materials such as water repellent material, poorly water-soluble phosphate fertilizer, urea-aliphatic aldehyde condensate, and water is not particularly limited, but the melting point is in the range of 60 to 130 ° C. In the case of using an aqueous material, the temperature is preferably 0 to 40 ° C. lower than the melting point of the water-repellent material. When the temperature is within this range, the water repellent material diffuses well in the fertilizer particles obtained through the drying step.
乾燥工程において使用する気体は特に限定されるものではなく、空気、窒素、ヘリウム、アルゴン等を挙げることができ、その中でも空気は製造コストの面から好ましく本発明に使用することができる。 The gas used in the drying step is not particularly limited, and examples thereof include air, nitrogen, helium, and argon. Among these, air is preferable from the viewpoint of production cost and can be used in the present invention.
気体の温度は、用いる撥水性物資の融点以上であることが必須である。該融点以上の温度の気体を用いることにより、粒子に含まれる撥水性物質が溶融し、該粒子内において撥水性物質が更に拡散され、撥水性物質の添加量に対する効率が良い。更に該気体の温度は高くとも500℃以下である。該温度が500℃以下であれば、混合する尿素−脂肪族アルデヒド縮合物が分解しにくい。 It is essential that the gas temperature is equal to or higher than the melting point of the water-repellent material to be used. By using a gas having a temperature equal to or higher than the melting point, the water-repellent substance contained in the particles is melted, and the water-repellent substance is further diffused in the particles, so that the efficiency with respect to the added amount of the water-repellent substance is good. Furthermore, the temperature of the gas is at most 500 ° C. or less. If this temperature is 500 degrees C or less, the urea-aliphatic aldehyde condensate to mix will not decompose | disassemble easily.
本発明の有機肥料含有複合肥料は、粒子Aと、粒子Bを混合することによって製造される。混合方法は特に限定されないが、それぞれの粒子が均一に分散するような混合方法が望ましい。 The organic fertilizer-containing composite fertilizer of the present invention is produced by mixing particles A and particles B. The mixing method is not particularly limited, but a mixing method in which each particle is uniformly dispersed is desirable.
本発明の有機肥料含有複合肥料あれば、含有される有機肥料の窒素成分の無機化を促進することが可能である。無機化率は、2L容の容器に2mmの篩いを通った風乾土壌を1kg入れ、そこに該複合肥料を全窒素で1.0g相当量、水を最大容水量の60%になるように入れ混合し、該容器の上縁をポリエチレンフィルムで覆い25℃の恒温室に静置し、定期的に生成した無機態窒素を測定することにより得られる値から、別途計測しておいた粒子Aの無機化率を差し引くことによって得られる。粒子Aの無機化量は複合肥料中の窒素成分の無機化率と同様の方法で測定される。一般的に無機化率は、土壌量に対する該肥料投入量、土壌の種類、水添加量、静置環境条件等により異なる場合がある。 With the organic fertilizer-containing composite fertilizer of the present invention, it is possible to promote mineralization of the nitrogen component of the organic fertilizer contained. The mineralization rate is 1 kg of air-dried soil that passed through a 2 mm sieve in a 2 L container, and the composite fertilizer is added in an amount equivalent to 1.0 g of total nitrogen and water to 60% of the maximum volume. From the value obtained by covering the upper edge of the container with a polyethylene film, leaving it in a constant temperature room at 25 ° C., and measuring the inorganic nitrogen produced periodically, the particles A previously measured It is obtained by subtracting the mineralization rate. The mineralization amount of the particles A is measured by the same method as the mineralization rate of the nitrogen component in the composite fertilizer. In general, the mineralization rate may vary depending on the amount of fertilizer input relative to the amount of soil, the type of soil, the amount of water added, the static environment conditions, and the like.
本発明の有機肥料含有複合肥料を土壌に施用する際、含有される有機肥料の窒素成分の無機化を効率良く促進するためには、連続する土壌中あるいは土壌表面において、粒子Aと粒子Bの距離が10cm以下になるように施用するのが好ましい。10cmを超えるような場合、無機化促進度合が低下することがある。 When the organic fertilizer-containing composite fertilizer of the present invention is applied to soil, in order to efficiently promote mineralization of the nitrogen component of the organic fertilizer contained, the particles A and B in the continuous soil or the soil surface It is preferable to apply so that the distance is 10 cm or less. When it exceeds 10 cm, the degree of mineralization promotion may be reduced.
以下実施例によって本発明を説明するが、本発明はこれら実施例により限定されるものではない。尚、以下の実施例における「%」は特に断りがない限り「重量%」である。
1.粒子A−1の製造
下記「難水溶性リン酸質肥料粒の取得と、得られた難水溶性リン酸質肥料粒のリン酸溶出時間測定」で得られた難水溶性リン酸質肥料粒(熔成リン肥)と、CDU粉粒体(150μmの篩いを通ったもの)とを、表1の粒子A−1に示した割合で投入量の合計が20kgとなるように、容量50Lの球形混合機に投入し5分間混合した。
ついで、該混合物1kgを直径120cmの回転皿型パン造粒機に入れ、40rpmの回転速度で該混合物を転動させながら水及び混合物を少量ずつ添加し、平均粒径が2.5mm程度になるまで造粒した。造粒後、熱風循環乾燥機を用い120℃の条件下で6時間乾燥し、更に、振動篩で分級して粒子径が2.36〜3.35mmの粒子A−1を得た。
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following examples, “%” is “% by weight” unless otherwise specified.
1. Production of Particle A-1 Slightly water-soluble phosphate fertilizer granules obtained in the following “Acquisition of poorly water-soluble phosphate fertilizer granules and measurement of phosphate elution time of the obtained poorly water-soluble phosphate fertilizer granules” (Fused phosphorus fertilizer) and CDU powder (through a sieve of 150 μm) with a capacity of 50 L so that the total amount of input is 20 kg at the ratio shown in particle A-1 in Table 1 It put into the spherical mixer and mixed for 5 minutes.
Next, 1 kg of the mixture is put into a rotating dish pan granulator having a diameter of 120 cm, and water and the mixture are added little by little while rolling the mixture at a rotation speed of 40 rpm, so that the average particle diameter becomes about 2.5 mm. Until granulated. After granulation, it was dried for 6 hours at 120 ° C. using a hot air circulating dryer, and further classified with a vibrating sieve to obtain particles A-1 having a particle size of 2.36 to 3.35 mm.
「難水溶性リン酸質肥料粒の取得と、得られた難水溶性リン酸質肥料粒のリン酸溶出時間測定」
熔成リン肥(南九州化学工業(株)製 くみあい熔リン20−15−20(商品名))を振動篩で分級して粒径が600〜710μmの該難水溶性リン酸質肥料粒を得た。また、重焼リン(小野田化学工業(株)製、46重焼リン(商品名))を振動篩で分級して粒径が0.15〜0.5mmの該難水溶性リン酸質肥料粒を得た。
分級によって得られた該難水溶性リン酸質肥料粒2gと、30℃に加熱した2重量%クエン酸水溶液150mlとを、300ml容のポリ瓶に入れ、30℃の振とう恒温槽で振とうした。経時的に上澄みを少量取り、水で希釈後、希釈液中のリン酸成分をイオンクロマトグラフィーによって定量した。測定値から溶出曲線を作成し、グラフからリン酸溶出時間を算出した。その結果、80%溶出するのに要する時間は熔成リン肥が600分、重焼リンが35分であることが示された。
"Acquisition of poorly water-soluble phosphate fertilizer granules and measurement of phosphate dissolution time of the obtained poorly water-soluble phosphate fertilizer granules"
Molten phosphorus fertilizer (Kumai Molten 20-15-20 (trade name) manufactured by Minami Kyushu Chemical Industry Co., Ltd.) is classified with a vibrating sieve, and the poorly water-soluble phosphate fertilizer grains having a particle size of 600 to 710 μm are classified. Obtained. In addition, the poorly water-soluble phosphate fertilizer granules having a particle size of 0.15 to 0.5 mm obtained by classifying heavy burnt phosphorus (onoda chemical industry, 46 heavy burn phosphorus (trade name)) with a vibrating sieve. Got.
2 g of the poorly water-soluble phosphate fertilizer particles obtained by classification and 150 ml of 2 wt% aqueous citric acid solution heated to 30 ° C. are placed in a 300 ml plastic bottle and shaken in a 30 ° C. shaking thermostat. did. A small amount of the supernatant was collected over time, diluted with water, and the phosphate component in the diluted solution was quantified by ion chromatography. An elution curve was created from the measured values, and the phosphate elution time was calculated from the graph. As a result, it was shown that the time required for 80% elution was 600 minutes for molten phosphorus fertilizer and 35 minutes for heavy burnt phosphorus.
2.有機肥料含有複合肥料の製造
表2の実施例1に示した組成の有機肥料含有複合肥料を下記の方法にて製造した。
前記粒子A−1に、粒子Bとして5.3抽出菜種油粕((株)サンアンドホープ製、1.0mmの篩いを通り、100μmの篩いを通らないもの、炭素/窒素重量比7.6)を、表2に示した割合で加え、たらいで、均一に混ざるまで手でよく混合し、有機肥料含有複合肥料を製造した。
2. Manufacture of organic fertilizer-containing composite fertilizer An organic fertilizer-containing composite fertilizer having the composition shown in Example 1 in Table 2 was manufactured by the following method.
5.3 particles of rapeseed oil cake as particle B (made by Sun and Hope Co., Ltd., passing through a 1.0 mm sieve and not passing through a 100 μm sieve, carbon / nitrogen weight ratio 7.6) Were added in the ratio shown in Table 2 and mixed well by hand until mixed uniformly to produce an organic fertilizer-containing composite fertilizer.
3.土壌中における無機化率測定試験
2L容の容器に2mmの篩いを通った風乾土壌(熊本県植木町で採取した黒ボク土)を1kg入れ、そこに実施例1の複合肥料を全窒素で1.0g相当量、水を最大容水量の60%になるように入れ混合し無機化土壌サンプルを作成した。
該無機化土壌サンプルが入った容器の上縁をポリエチレンフィルムで覆い25℃の恒温室に静置した。所定の期間経過後に土壌を全て回収し、よく混合した後、そのうち10gを採取した。
採取した土壌中の無機態窒素量をアンモニア態、亜硝酸態、硝酸態窒素の同時浸出測定法(養賢堂 土壌養分測定法 p197−p200に記載の方法)で測定した。
試験は全て3反復制とし、供試土壌に元来含まれていた無機態窒素量を測定するために、肥料を施用していない試験区も設けた。無機態窒素量の測定値から、下記式に従って菜種油粕の無機化率を算出した。
菜種油粕の無機化率(%)=(n日培養後の複合肥料施用土壌の無機態窒素量−n日培養後の粒子A施用土壌の無機態窒素量)/施用前の菜種油粕に含まれる窒素量×100
n:施用後日数
結果を表3に示した。
3. Measurement test for mineralization rate in soil 1 kg of air-dried soil (black soil collected in Ueki-cho, Kumamoto Prefecture) passed through a 2 mm sieve in a 2 L container, and 1% of the combined fertilizer of Example 1 with total nitrogen A mineralized soil sample was prepared by mixing and mixing 0.0 g equivalent water with 60% of the maximum volume of water.
The upper edge of the container containing the mineralized soil sample was covered with a polyethylene film and allowed to stand in a thermostatic chamber at 25 ° C. After a predetermined period of time, all of the soil was collected and mixed well, and 10 g of that was collected.
The amount of inorganic nitrogen in the collected soil was measured by a simultaneous leaching measurement method for ammonia, nitrite, and nitrate nitrogen (method described in Yokendo soil nutrient measurement method p197-p200).
All tests were repeated three times, and in order to measure the amount of inorganic nitrogen originally contained in the test soil, a test plot without fertilizer was also provided. From the measured value of the amount of inorganic nitrogen, the mineralization rate of the rapeseed oil cake was calculated according to the following formula.
Rapeseed oil meal mineralization rate (%) = (inorganic nitrogen content of soil applied with compound fertilizer after n-day culture-inorganic nitrogen content of soil applied with particle A after n-day culture) / included in rapeseed oil cake before application Nitrogen content x 100
n: Days after application The results are shown in Table 3.
難水溶性リン酸質肥料粒(熔成リン肥)と、CDU粉粒体(150μmの篩いを通ったもの)とを、表1の粒子A−2に示した割合で投入量の合計が20kgとなるようにした以外は、実施例1と同様の方法で粒子A−2を製造し、表2の実施例2に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。 Slightly water-soluble phosphate fertilizer granules (molten phosphorus fertilizer) and CDU granules (through a 150 μm sieve) at a rate shown in particle A-2 in Table 1, the total input amount is 20 kg. The particles A-2 were produced in the same manner as in Example 1 except that the organic fertilizer-containing composite fertilizer having the composition shown in Example 2 in Table 2 was produced in the same manner as in Example 1. did. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
前記の粒子A−2を用い、表2の実施例3に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。 Using the particle A-2, an organic fertilizer-containing composite fertilizer having the composition shown in Example 3 in Table 2 was produced in the same manner as in Example 1. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
前記の粒子A−2を用い、表2の実施例4に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。 Using the particle A-2, an organic fertilizer-containing composite fertilizer having the composition shown in Example 4 in Table 2 was produced in the same manner as in Example 1. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
難水溶性リン酸質肥料粒(熔成リン肥)と、CDU粉粒体(150μmの篩いを通ったもの)とを、表1の粒子A−3に示した割合で投入量の合計が20kgとなるようにした以外は、実施例1と同様の方法で粒子A−3を製造し、表2の実施例5に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。 A total amount of input of 20 kg of poorly water-soluble phosphate fertilizer granules (fused phosphorus fertilizer) and CDU powder (passed through a 150 μm sieve) at the ratio shown in Particle A-3 of Table 1 The particles A-3 were produced in the same manner as in Example 1 except that the organic fertilizer-containing composite fertilizer having the composition shown in Example 5 in Table 2 was produced in the same manner as in Example 1. did. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
難水溶性リン酸質肥料粒として、前述の粒径が0.15〜0.5mmの46重焼リン(商品名、小野田化学工業(株)製)を用い、これと、CDU粉粒体(150μmの篩いを通ったもの)とを、表1の粒子A−4に示した割合で投入量の合計が20kgとなるようにした以外は、実施例1と同様の方法で粒子A−4を製造した。
粒子A−4には、水溶性リン酸がCDU100重量部に対して0.48重量部含まれていた。表2の実施例6に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。
As the poorly water-soluble phosphate fertilizer granules, 46 heavy burned phosphorus (trade name, manufactured by Onoda Chemical Co., Ltd.) having a particle size of 0.15 to 0.5 mm is used. The particles A-4 were passed through the same method as in Example 1 except that the total amount of input was 20 kg at the ratio shown in the particles A-4 in Table 1. Manufactured.
Particle A-4 contained 0.48 parts by weight of water-soluble phosphoric acid with respect to 100 parts by weight of CDU. An organic fertilizer-containing composite fertilizer having the composition shown in Example 6 in Table 2 was produced in the same manner as in Example 1. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
難水溶性リン酸質肥料粒(熔成リン肥)、CDU粉粒体(150μmの篩いを通ったもの)、及び撥水性物質としてカスターワックスF−P(商品名、小倉合成工業(株)製硬化ひまし油)を、表1の粒子A−5に示した割合で投入量の合計が20kgとなるようにした以外は、実施例1と同様の方法で粒子A−5を製造し、表2の実施例7に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。 Slightly water-soluble phosphate fertilizer grains (molten phosphorus fertilizer), CDU powder (through a 150 μm sieve), and castor wax FP (trade name, manufactured by Kokura Gosei Kogyo Co., Ltd.) as a water-repellent substance Cured castor oil) was produced in the same manner as in Example 1 except that the total amount of input was 20 kg at the ratio shown in Particle A-5 in Table 1, An organic fertilizer-containing composite fertilizer having the composition shown in Example 7 was produced in the same manner as in Example 1. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
実施例2と同様の方法で粒子A−2を製造し、粒子Bとして大豆油粕(不二製油(株)製、1.0mmの篩いを通り、100μmの篩いを通らないもの、炭素/窒素重量比5.3)を、表2の実施例8に示した割合で加え、たらいで、均一に混ざるまで手でよく混合し、有機肥料含有複合肥料を製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表4に示した。 Particle A-2 was produced in the same manner as in Example 2, and soybean oil cake (produced by Fuji Oil Co., Ltd., passing through a 1.0 mm sieve, not passing through a 100 μm sieve, as carbon particle / weight) The ratio 5.3) was added in the ratio shown in Example 8 in Table 2, and the mixture was mixed well by hand until it was uniformly mixed to produce an organic fertilizer-containing composite fertilizer. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 4.
(比較例1)
CDU粉粒体(150μmの篩いを通ったもの)のみを20kg投入した以外は、実施例1と同様の方法で粒子A−6を製造し、表2の比較例1に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。
(Comparative Example 1)
Organic fertilizer having the composition shown in Comparative Example 1 in Table 2 was produced by producing particles A-6 in the same manner as in Example 1 except that 20 kg of only CDU granular material (through a 150 μm sieve) was added. The contained composite fertilizer was produced in the same manner as in Example 1. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
(比較例2)
リン酸質肥料粒として、MAP(リン酸1アンモニウム。和光純薬工業(株)製特級試薬を乳鉢で微粉砕し、45μmの篩いを通ったもの)を用い、これと、CDU粉粒体(150μmの篩いを通ったもの)とを、表1の粒子A−7に示した割合で投入量の合計が20kgとなるようにした以外は、実施例1と同様の方法で粒子A−7を製造した。上述の「難水溶性リン酸質肥料粒の取得と、得られた難水溶性リン酸質肥料粒のリン酸溶出時間測定」に記載の方法と同様の方法でMAPのリン酸溶出時間を測定したところ、浸とう開始5秒後には、リン酸溶出率が100%に達していた。粒子A−7には、水溶性リン酸がCDU100重量部に対して1.23重量部含まれていた。表2の比較例2に示した組成の有機肥料含有複合肥料を実施例1と同様の方法で製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。
(Comparative Example 2)
As phosphate fertilizer granules, MAP (monoammonium phosphate, a fine reagent manufactured by Wako Pure Chemical Industries, Ltd. was finely pulverized in a mortar and passed through a 45 μm sieve) was used. The particles A-7 were passed through the same method as in Example 1 except that the total charge was 20 kg at the ratio shown in Particle A-7 in Table 1. Manufactured. Measure the phosphate elution time of MAP by the same method as described in “Acquisition of poorly water-soluble phosphate fertilizer granules and measurement of phosphate elution time of the obtained poorly water-soluble phosphate fertilizer granules”. As a result, the phosphoric acid elution rate reached 100% 5 seconds after the start of immersion. Particle A-7 contained 1.23 parts by weight of water-soluble phosphoric acid based on 100 parts by weight of CDU. An organic fertilizer-containing composite fertilizer having the composition shown in Comparative Example 2 in Table 2 was produced in the same manner as in Example 1. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
(比較例3)
粒子Aを用いずに、表2の比較例3に示した有機肥料について、土壌中における無機化率測定試験を行なった。結果を表3に示した。
(Comparative Example 3)
Without using the particles A, the organic fertilizer shown in Comparative Example 3 in Table 2 was subjected to a mineralization rate measurement test in soil. The results are shown in Table 3.
(比較例4)
粒子Aを用いずに、表2の比較例4に示した有機肥料について、土壌中における無機化率測定試験を行なった。結果を表4に示した
(Comparative Example 4)
Without using particles A, the organic fertilizer shown in Comparative Example 4 in Table 2 was subjected to a mineralization rate measurement test in soil. The results are shown in Table 4.
(比較例5)
実施例2と同様の方法で粒子A−2を製造し、粒子Bとしてフェザーミール(蒸製毛粉、南国興産(株)製)を、表2の比較例5に示した割合で加え、たらいで、均一に混ざるまで手でよく混合し、有機肥料含有複合肥料を製造した。得られた有機肥料含有複合肥料について、土壌中における無機化率測定試験を行なった。結果を表5に示した。
(Comparative Example 5)
Particle A-2 was produced in the same manner as in Example 2, and Feather Meal (Steaming Flour, manufactured by Nankoku Kosan Co., Ltd.) was added as Particle B in the proportion shown in Comparative Example 5 in Table 2, Mix well by hand until evenly mixed to produce a complex fertilizer containing organic fertilizer. The obtained organic fertilizer-containing composite fertilizer was subjected to a mineralization rate measurement test in soil. The results are shown in Table 5.
(比較例6)
粒子Aを用いずに、表2の比較例6に示した有機肥料について、土壌中における無機化率測定試験を行なった。結果を表5に示した。
(Comparative Example 6)
Without using the particles A, the organic fertilizer shown in Comparative Example 6 in Table 2 was subjected to a mineralization rate measurement test in soil. The results are shown in Table 5.
(表1)
粒子Aの組成
・熔成リン肥、重焼リン、MAPの値はP2O5換算値
・CDUに対する水溶性リン酸の含有割合はCDUを100としたときの重量比
(Table 1)
Composition of particle A
・ The values of molten phosphorus fertilizer, heavy burned phosphorus, and MAP are P 2 O 5 equivalent values ・ The content ratio of water-soluble phosphoric acid to CDU is weight ratio when CDU is 100
熔成リン肥:南九州化学工業(株)製、くみあい熔リン20−15−20(商品名)の篩分品(710μmの篩いを通り、600μmの篩いを通らないもの)。
重焼リン:小野田化学工業(株)製、46重焼リン(商品名)の篩分品(0.5mmの篩いを通り、150μmの篩いを通らないもの)。
MAP:リン酸1アンモニウム、和光純薬工業(株)製、特級試薬(乳鉢で微粉砕し、45μmの篩いを通ったもの)
CDU:チッソ(株)製、2−オキソ−4−メチル−6−ウレイドヘキサヒドロピリミジン紛粒体の150μmの篩いを通ったもの。
硬化ひまし油:カスターワックスF−P(商品名)、小倉合成工業(株)製、硬化ひまし油、融点81℃。
Molten phosphorus fertilizer: Kumiai phosphorus 20-15-20 (trade name), manufactured by Minamikyushu Chemical Co., Ltd. (through a 710 μm sieve and not through a 600 μm sieve).
Heavy burned phosphorus: A sieved product of 46 heavy burned phosphorus (trade name) manufactured by Onoda Chemical Co., Ltd. (through 0.5 mm sieve and not through 150 μm sieve).
MAP: Ammonium phosphate, manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent (pulverized in a mortar and passed through a 45 μm sieve)
CDU: manufactured by Chisso Corporation, passed through a 150 μm sieve of 2-oxo-4-methyl-6-ureidohexahydropyrimidine powder.
Hardened castor oil: Custer wax FP (trade name), manufactured by Ogura Gosei Kogyo Co., Ltd., hardened castor oil, melting point 81 ° C.
(表2)
有機肥料含有複合肥料の組成
含有比:有機肥料の含有量/CDUの含有量の重量比
菜種油粕:(株)サンアンドホープ製、5.3抽出菜種油粕の篩分品(1.0mmの篩いを通り、100μmの篩いを通らないもの、炭素/窒素重量比7.6)。
大豆油粕:不二製油(株)製、1.0mmの篩いを通り、100μmの篩いを通らないもの、炭素/窒素重量比5.3。
フェザーミール:南国興産(株)製の蒸製毛粉(動物質)。
(Table 2)
Composition of organic fertilizer-containing compound fertilizer
Content ratio: Weight ratio of organic fertilizer content / CDU content Rapeseed oil cake: manufactured by Sun and Hope Co., Ltd., 5.3 Extracted rapeseed oil cake (through a 1.0 mm sieve, a 100 μm sieve) Unable to pass, carbon / nitrogen weight ratio 7.6).
Soybean oil lees: manufactured by Fuji Oil Co., Ltd., passing through a 1.0 mm sieve and not passing through a 100 μm sieve, carbon / nitrogen weight ratio 5.3.
Feather Meal: Steamed hair powder (animal) manufactured by Nangoku Kosan Co., Ltd.
(表3)
土壌中における無機化率測定試験結果
(菜種油粕中の窒素成分の無機化率(%)と無機化率の差(%))
無機化率の差=(粒子Aと粒子Bとからなる複合肥料を施用したときに粒子Bに含有される有機肥料中の窒素成分の60日無機化率)−(粒子Bを単独で施用したときの粒子Bに含有される有機肥料中の窒素成分の60日無機化率)
(Table 3)
Results of mineralization rate measurement test in soil (mineralization rate of nitrogen component in rapeseed oil cake (%) and difference between mineralization rate (%))
Difference in mineralization rate = (60-day mineralization rate of nitrogen component in organic fertilizer contained in particle B when compound fertilizer consisting of particles A and particles B is applied) − (particle B was applied alone) 60-day mineralization rate of nitrogen component in organic fertilizer contained in particles B
(表4)
土壌中における無機化率測定試験結果
(大豆油粕中の窒素成分の無機化率(%)と無機化率の差(%))
無機化率の差=(粒子Aと粒子Bとからなる複合肥料を施用したときに粒子Bに含有される有機肥料中の窒素成分の60日無機化率)−(粒子Bを単独で施用したときの粒子Bに含有される有機肥料中の窒素成分の60日無機化率)
(Table 4)
Test result of mineralization rate measurement in soil (difference between mineralization rate (%) and mineralization rate of nitrogen component in soybean oil lees (%))
Difference in mineralization rate = (60-day mineralization rate of nitrogen component in organic fertilizer contained in particle B when compound fertilizer consisting of particles A and particles B is applied) − (particle B was applied alone) 60-day mineralization rate of nitrogen component in organic fertilizer contained in particles B
(表5)
土壌中における無機化率測定試験結果
(フェザーミール中の窒素成分の無機化率(%)と無機化率の差(%))
無機化率の差=(粒子Aと粒子Bとからなる複合肥料を施用したときに粒子Bに含有される有機肥料中の窒素成分の60日無機化率)−(粒子Bを単独で施用したときの粒子Bに含有される有機肥料中の窒素成分の60日無機化率)
(Table 5)
Results of mineralization rate measurement test in soil (mineralization rate of nitrogen component in feather meal (%) and difference between mineralization rate (%))
Difference in mineralization rate = (60-day mineralization rate of nitrogen component in organic fertilizer contained in particle B when compound fertilizer consisting of particles A and particles B is applied) − (particle B was applied alone) 60-day mineralization rate of nitrogen component in organic fertilizer contained in particles B
以上の結果から、難水溶性リン酸質肥料及び尿素−脂肪族アルデヒド縮合物を含有する粒子Aと、植物質含有有機肥料を含有する粒子Bとからなる複合肥料であれば、無機化率の差が10重量%以上であることが明らかである。特に、表5から、粒子Bに植物質が含有されていない場合は無機化促進効果が見られないと言える。望ましい植物質含有有機肥料としては、植物粕、特に菜種油粕であることが分かる。さらに、該粒子Aに含有される難水溶性リン酸質肥料の含有割合が尿素−脂肪族アルデヒド縮合物に対してP2O5換算で0.01〜5重量%の範囲であるのが適当と言える。また、粒子Aに撥水性物質を含有する場合に粒子Bの無機化促進効果が顕著である。表4から、粒子Bの炭素/窒素重量比が5.0以上であり、かつ粒子Bに含有される植物質含有有機肥料の炭素/窒素重量比が5.0以上であれば、無機化促進効果が大きいことが分かる。有機肥料含有複合肥料中の植物質含有有機肥料の含有量/尿素−脂肪族アルデヒド縮合物の含有量の重量比については、15以下が好ましい。 From the above results, if the compound fertilizer is composed of the particle A containing the poorly water-soluble phosphate fertilizer and the urea-aliphatic aldehyde condensate and the particle B containing the plant-containing organic fertilizer, the mineralization rate It is clear that the difference is 10% by weight or more. In particular, from Table 5, it can be said that the mineralization promoting effect is not seen when the particle B does not contain plant matter. It can be seen that a desirable plant-containing organic fertilizer is a plant meal, especially a rapeseed oil meal. Furthermore, the content ratio of the poorly water-soluble phosphate fertilizer contained in the particles A is suitably in the range of 0.01 to 5% by weight in terms of P 2 O 5 with respect to the urea-aliphatic aldehyde condensate. It can be said. Further, when the particle A contains a water-repellent substance, the effect of promoting the mineralization of the particle B is remarkable. From Table 4, if the carbon / nitrogen weight ratio of the particle B is 5.0 or more and the carbon / nitrogen weight ratio of the plant-containing organic fertilizer contained in the particle B is 5.0 or more, mineralization is promoted. It turns out that the effect is great. The weight ratio of the content of the plant-containing organic fertilizer in the organic fertilizer-containing composite fertilizer / the content of the urea-aliphatic aldehyde condensate is preferably 15 or less.
野菜、果樹、花卉等の栽培に広く利用でき、有機肥料を有効に利用することができる。 It can be widely used for cultivation of vegetables, fruit trees, flower buds, etc., and organic fertilizer can be used effectively.
Claims (16)
無機化率の差(重量%)=(粒子Aと粒子Bとからなる複合肥料を施用したときに粒子Bに含有される有機肥料中の窒素成分の60日無機化率)−(粒子Bを単独で施用したときの粒子Bに含有される有機肥料中の窒素成分の60日無機化率) A composite fertilizer comprising particles A containing a poorly water-soluble phosphate fertilizer having a solubility in water at 20 ° C. of 5 g / 100 ml or less and a urea-aliphatic aldehyde condensate and particles B containing a plant-containing organic fertilizer And the organic fertilizer containing compound fertilizer whose difference of the mineralization rate shown by a following formula is 10 weight% or more.
Difference in mineralization rate (% by weight) = (60 day mineralization rate of nitrogen component in organic fertilizer contained in particle B when compound fertilizer consisting of particles A and particles B is applied) − (particle B 60-day mineralization rate of nitrogen component in organic fertilizer contained in particle B when applied alone)
難水溶性リン酸質肥料/2重量%クエン酸水溶液(重量比)=0.013 When the slightly water-soluble phosphate fertilizer is immersed in a 2 wt% citric acid aqueous solution at 30 ° C. in a weight ratio represented by the following formula, 80 wt% of the phosphoric acid component contained The organic fertilizer-containing composite fertilizer according to claim 1, wherein the time required for elution into the citric acid aqueous solution is in the range of 0.1 to 2000 minutes.
Slightly water-soluble phosphate fertilizer / 2% by weight citric acid aqueous solution (weight ratio) = 0.013
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02102447U (en) * | 1989-02-02 | 1990-08-15 | ||
JPH02208276A (en) * | 1989-02-06 | 1990-08-17 | Tosoh Corp | Humification-promoting agent and production thereof |
JP2003212682A (en) * | 2000-12-05 | 2003-07-30 | Chisso Corp | Fertilizer, method of manufacturing fertilizer, method of controlling mineralization rate of urea-aliphatic aldehyde condensate and method of cultivating crop |
-
2004
- 2004-09-07 JP JP2004259338A patent/JP4689217B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02102447U (en) * | 1989-02-02 | 1990-08-15 | ||
JPH02208276A (en) * | 1989-02-06 | 1990-08-17 | Tosoh Corp | Humification-promoting agent and production thereof |
JP2003212682A (en) * | 2000-12-05 | 2003-07-30 | Chisso Corp | Fertilizer, method of manufacturing fertilizer, method of controlling mineralization rate of urea-aliphatic aldehyde condensate and method of cultivating crop |
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