JP2018188314A - Solidification restraining phosphate fertilizer and method of producing the same - Google Patents
Solidification restraining phosphate fertilizer and method of producing the same Download PDFInfo
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- JP2018188314A JP2018188314A JP2017089354A JP2017089354A JP2018188314A JP 2018188314 A JP2018188314 A JP 2018188314A JP 2017089354 A JP2017089354 A JP 2017089354A JP 2017089354 A JP2017089354 A JP 2017089354A JP 2018188314 A JP2018188314 A JP 2018188314A
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- 239000002686 phosphate fertilizer Substances 0.000 title claims abstract description 43
- 238000007711 solidification Methods 0.000 title abstract description 11
- 230000008023 solidification Effects 0.000 title abstract description 11
- 230000000452 restraining effect Effects 0.000 title abstract 5
- 238000000034 method Methods 0.000 title description 3
- 239000003337 fertilizer Substances 0.000 claims abstract description 80
- 239000011777 magnesium Substances 0.000 claims abstract description 55
- 239000011575 calcium Substances 0.000 claims abstract description 42
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000000292 calcium oxide Substances 0.000 claims abstract description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 78
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 26
- 238000007596 consolidation process Methods 0.000 claims description 21
- 230000001629 suppression Effects 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 230000002401 inhibitory effect Effects 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 9
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 9
- 239000004927 clay Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 238000010521 absorption reaction Methods 0.000 description 18
- 239000000741 silica gel Substances 0.000 description 17
- 229910002027 silica gel Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000001692 EU approved anti-caking agent Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 230000004720 fertilization Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 and further Chemical compound 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004889 fertilizer analysis Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
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Abstract
Description
本発明は、吸湿性が高く、バルクブレンド肥料において固結抑制機能を発揮するリン酸肥料に関する。 The present invention relates to a phosphate fertilizer having high hygroscopicity and exhibiting a caking suppression function in a bulk blend fertilizer.
バルクブレンド肥料（以下ＢＢ肥料）は、リン安、硫安、塩安、尿素、重過リン酸石灰、塩化カリ、硫酸カリなどの粒状肥料原料を、所望の成分になるように、２種類以上配合した固形配合肥料であり、粒状配合肥料とも云われている。 Bulk blend fertilizer (hereinafter referred to as BB fertilizer) is composed of two or more types of granular fertilizer raw materials such as phosphorous, ammonium sulfate, ammonium sulfate, urea, heavy superphosphate lime, potassium chloride, and potassium sulfate so as to become desired components. It is a solid compound fertilizer and is also called a granular compound fertilizer.
ＢＢ肥料について、従来から肥料の固結が問題になっている。肥料の固結は肥料粒子が塊状に固まることであり、従来から品質劣化の問題として提起されてきたが、機械による施肥が発達した現在においては、固結性に対する許容域が狭まり、軽い程度の固結でも施肥作業に支障をきたすため、従来に増して肥料の流動性が求められており、肥料の固結防止の要請が高まっている。 About BB fertilizer, solidification of the fertilizer has been a problem conventionally. Fertilizer consolidation is a solidification of fertilizer particles, and has been raised as a problem of quality degradation.However, with the development of fertilization by machine, the allowable range for solidification has become narrower and lighter. Since the fertilization work is hindered even in consolidation, the fluidity of fertilizer is required more than before, and the demand for prevention of consolidation of fertilizer is increasing.
肥料の固結防止手段として、肥料粒子を被覆することや、固結防止剤を添加することが従来から知られている。肥料粒子の被覆については、透湿度が特定範囲の膜を用いるもの（特許文献１）、糖類で被覆するもの（特許文献２）、樹脂で被覆するもの（特許文献３）、鉱産物粉末とポリオール化合物で被覆処理するもの（特許文献４）、鉱産物粉末とリン酸液等で被覆処理するもの（特許文献５）などが知られている。しかし、肥料粒子を被覆するのは製造に手間がかかり、製造コストが嵩む問題がある。また、固結防止効果も限定的である。 As means for preventing solidification of fertilizers, it has been conventionally known to coat fertilizer particles and to add an anti-caking agent. As for the coating of fertilizer particles, one using a membrane with a moisture permeability in a specific range (Patent Document 1), one coated with sugar (Patent Document 2), one coated with a resin (Patent Document 3), mineral powder and polyol Those that are coated with a compound (Patent Document 4), those that are coated with a mineral powder and a phosphoric acid solution (Patent Document 5), and the like are known. However, the coating of fertilizer particles is troublesome in production and increases the production cost. Moreover, the caking prevention effect is also limited.
固結防止剤の使用については、ゲル状シリカを用いるもの（特許文献６、７）が知られており、また固結防止剤として、無機系のシリカゲルのほかに、滑石粉末、クレー、シリカヒュームや、有機系の界面活性剤が尿素、硝安、化成肥料に対してよく使われている。 Regarding the use of anti-caking agents, those using gel silica (Patent Documents 6 and 7) are known. In addition to inorganic silica gel, anti-caking agents include talc powder, clay, and silica fume. Organic surfactants are often used for urea, ammonium nitrate, and chemical fertilizers.
しかし、ＢＢ肥料に使用できる固結防止剤は、法令(肥料取締法)によって種類が制限されており、シリカゲル、滑石粉末、クレー、珪石粉末、珪藻土、シリカヒューム、パーライト、および潤滑油に限られており、その添加量は、シリカゲルは６％以下、その他の粉末は３％以下、潤滑油は滑石粉末、クレー、珪藻土またはパーライトと併用されたものであって、０.３％以下に制限されている。そのため、固結防止剤による固結防止効果は十分ではない。さらに、粉末固結防止剤添加による肥料有効成分の低下、施肥時の粉塵飛散という問題が生じる場合がある。また、シリカゲルは高価であるため、この使用は肥料のコスト高になると云う問題もある。 However, anti-caking agents that can be used for BB fertilizers are restricted by law (fertilizer control law) and are limited to silica gel, talc powder, clay, silica powder, diatomaceous earth, silica fume, perlite, and lubricating oil. The amount added is 6% or less for silica gel, 3% or less for other powders, and the lubricating oil is used in combination with talc powder, clay, diatomaceous earth or pearlite, and is limited to 0.3% or less. ing. Therefore, the anti-caking effect by the anti-caking agent is not sufficient. Furthermore, the problem of the fall of the fertilizer active component by powder anti-caking additive addition and the dust scattering at the time of fertilization may arise. In addition, since silica gel is expensive, there is a problem that the use of it increases the cost of fertilizer.
本発明は、従来の上記課題を解決したものであり、バルクブレンド肥料において優れた固結抑制機能を発揮し、それ自体がリン酸肥料であって肥料効果が低下することのないリン酸肥料を提供する。 The present invention solves the above-mentioned conventional problems, and exhibits an excellent caking suppression function in a bulk blend fertilizer, and is a phosphate fertilizer that itself is a phosphate fertilizer and the fertilizer effect does not decrease. provide.
本発明は、以下の構成によって上記課題を解決した、固結抑制リン酸肥料である。
〔１〕水溶性リン酸、水溶性酸化マグネシウム、水溶性酸化カルシウム、および水溶性酸化ナトリウムを含有し、さらにリン酸一苦土、リン酸一石灰、およびリン酸二水素ナトリウムからなる固結抑制成分を６.０質量％以上含有することを特徴とする固結抑制リン酸肥料。
〔２〕固結抑制成分が、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される請求項１に記載する固結抑制リン酸肥料。
〔３〕水溶性リン酸量８.０〜２１.０質量％、水溶性酸化マグネシウム２.０〜６.５質量％、水溶性酸化カルシム１.０〜３.２質量％、および水溶性酸化ナトリウム０.４〜１.３質量％を含有し、さらに、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される固結抑制成分を６.０〜５０.０質量％含有する請求項１または請求項２に記載する固結抑制リン酸肥料。
〔４〕(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される固結抑制成分が、相対湿度４０％の平衡水分が１０％以上であって、相対湿度５０％の平衡水分が１５％以上である吸湿性を有する請求項１〜請求項３の何れかに記載する固結抑制リン酸肥料。
〔５〕リン酸原料としてリン鉱石、リン酸液、焼成リン肥を用い、その他の原料として苦土原料および硫酸を用い、これらの原料粉体を、生成後のリン酸肥料中で、
水溶性リン酸量８.０〜２１.０質量％、水溶性酸化マグネシウム２.０〜６.５質量％、水溶性酸化カルシム１.０〜３.２質量％、および水溶性酸化ナトリウム０.４〜１.３質量％であって、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される固結抑制成分が６.０〜５０.０質量％になる配合にし、
まず、リン鉱石とリン酸液および硫酸をスラリー状態で加熱することにより反応させ、このスラリーと焼成リン肥および苦土原料を転動造粒機中にて造粒させながら反応させることによって固結抑制リン酸肥料を製造する方法。
The present invention is an anti-caking phosphate fertilizer that solves the above-described problems by the following configuration.
[1] Consolidation suppression comprising water-soluble phosphoric acid, water-soluble magnesium oxide, water-soluble calcium oxide, and water-soluble sodium oxide, and further comprising monobasic phosphate, monolime phosphate, and sodium dihydrogen phosphate An anti-caking phosphate fertilizer characterized by containing 6.0% by mass or more of components.
[2] The consolidation inhibitory component is represented by the formula of (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 The caking inhibitor phosphate fertilizer to describe.
[3] Water-soluble phosphoric acid amount 8.0 to 21.0% by mass, water-soluble magnesium oxide 2.0 to 6.5% by mass, water-soluble calcium oxide 1.0 to 3.2% by mass, and water-soluble oxidation It contains 0.4 to 1.3% by weight of sodium and is further represented by the formula of (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 The caking suppression phosphate fertilizer according to
[4] (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 represents a caking inhibitor component having a relative humidity of 40%. The caking suppression phosphate fertilizer according to any one of claims 1 to 3, which has a hygroscopicity in which the equilibrium moisture is 10% or more and the equilibrium moisture at a relative humidity of 50% is 15% or more.
[5] Phosphate ore, phosphoric acid solution, and calcined phosphorous fertilizer are used as the phosphoric acid raw material, and the raw material powder and sulfuric acid are used as the other raw materials.
Water-soluble phosphoric acid amount 8.0 to 21.0% by mass, water-soluble magnesium oxide 2.0 to 6.5% by mass, water-soluble calcium oxide 1.0 to 3.2% by mass, and water-soluble sodium oxide 0.0%. Consolidation represented by the formula of 4 to 1.3% by mass, (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 The inhibitory component is formulated to be 6.0 to 50.0% by mass,
First, the phosphorus ore, phosphoric acid solution and sulfuric acid are reacted by heating in a slurry state, and the slurry is calcined by reacting the calcined phosphorus fertilizer and the raw material of the clay with granulation in a rolling granulator. A method for producing a suppressed phosphate fertilizer.
本発明のリン酸肥料は、水溶性リン酸、水溶性酸化マグネシウム、水溶性酸化カルシウム、および水溶性酸化ナトリウムを含有し、さらにリン酸一苦土、リン酸一石灰、およびリン酸二水素ナトリウムからなる固結抑制成分を６.０質量％以上含有し、この固結抑制成分は(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表され、相対湿度４０％の平衡水分が１０％以上であって相対湿度５０％の平衡水分が１５％以上である高い吸湿性を有するので、周囲の環境下の水分を吸収して効果的に固結を抑制し防止することができる。 The phosphate fertilizer of the present invention contains water-soluble phosphoric acid, water-soluble magnesium oxide, water-soluble calcium oxide, and water-soluble sodium oxide, and further, phosphoric acid monoclay, phosphoric acid monolime, and sodium dihydrogen phosphate. The caking inhibitor component is 6.0% by mass or more, and the caking inhibitor component is (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH. 2 It is expressed by the formula of PO 4 and has a high hygroscopicity in which the equilibrium moisture at 40% relative humidity is 10% or more and the equilibrium moisture at 50% relative humidity is 15% or more. It can absorb and effectively suppress and prevent consolidation.
また、本発明のリン酸肥料に含まれる固結抑制成分は、リン酸一苦土、リン酸一石灰、およびリン酸二水素ナトリウムからなるリン酸肥料であり、従来のようなシリカゲルや非肥料成分の被膜を有するものではないので、肥料効果を低下させることが無い。 Further, the caking inhibitory component contained in the phosphate fertilizer of the present invention is a phosphate fertilizer composed of phosphate monoclay, phosphate monolime, and sodium dihydrogen phosphate, such as conventional silica gel and non-fertilizer. Since it does not have a component film, the fertilizer effect is not reduced.
さらに、本発明のリン酸肥料は、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウム、および焼成リン肥などのリン酸肥料原料を所定の割合になるように配合して反応させて製造することができ、シリカゲルなどの固結防止剤の添加や被膜形成を行う必要が無いので、低コストで容易に製造することができる。 Furthermore, the phosphate fertilizer of the present invention can be manufactured by blending and reacting phosphate fertilizer raw materials such as magnesium hydroxide, calcium hydroxide, sodium hydroxide, and calcined phosphorus fertilizer at a predetermined ratio. In addition, since it is not necessary to add an anti-caking agent such as silica gel or to form a film, it can be easily produced at low cost.
本発明のリン酸肥料は、優れた吸湿性を有するので、ＢＢ肥料に配合すると、肥料の固結を効果的に抑制することがきる。また、それ自体がリン酸肥料であるので、ＢＢ肥料に配合しても肥料成分量が低下しない。さらに、シリカゲルなどの固結防止剤の添加や被膜形成を行う必要が無いので、低コストで容易に製造することができる。 Since the phosphate fertilizer of the present invention has excellent hygroscopicity, when it is blended with the BB fertilizer, the solidification of the fertilizer can be effectively suppressed. Moreover, since it is a phosphate fertilizer itself, even if it mix | blends with BB fertilizer, the amount of fertilizer components does not fall. Furthermore, since it is not necessary to add an anti-caking agent such as silica gel or to form a film, it can be easily produced at low cost.
以下、本発明を実施例と共に具体的に説明する。なお、％は質量％である。
肥料の固結は、肥料粒子表面に水分（遊離水）が存在することにより起こる。この水分は、製造時の乾燥が不十分な場合や、梅雨や夏季のような高温多湿の条件で製造した場合に高くなりやすい。肥料粒子表面に遊離水が存在すると、肥料成分を溶解した飽和溶液となり、粒子間に液架橋を形成し、その後に温度や湿度の変化により水分が蒸発して再結晶が起こると、液架橋が固架橋に変化して肥料粒子が接着して固結する。単肥や化成肥料は主にこのようなメカニズムによって肥料粒子の固結が発生するが、ＢＢ肥料の場合は、上記メカニズムに加えて原料間の化学反応による反応生成物も固結を引き起こすので、単一の肥料に比べて問題はより深刻である。
Hereinafter, the present invention will be specifically described together with examples. In addition,% is the mass%.
Fertilizer consolidation is caused by the presence of moisture (free water) on the fertilizer particle surface. This moisture tends to be high when drying at the time of manufacture is insufficient or when it is manufactured under conditions of high temperature and high humidity such as rainy season or summer. When free water is present on the fertilizer particle surface, it becomes a saturated solution in which the fertilizer components are dissolved, and liquid bridges are formed between the particles.After that, when water is evaporated due to changes in temperature and humidity, recrystallization occurs. The fertilizer particles are bonded and solidified by changing to solid crosslinking. In simple fertilizers and chemical fertilizers, solidification of fertilizer particles occurs mainly due to such a mechanism, but in the case of BB fertilizers, in addition to the above mechanism, reaction products due to chemical reactions between raw materials also cause consolidation. The problem is more serious than a single fertilizer.
従来から、ある種のリン酸肥料はＢＢ肥料に配合すると固結を抑制する作用があることが経験的に知られていた。この作用は、乾燥剤のシリカゲルと同じように、リン酸肥料は水分吸着力が大きく、肥料袋中の湿度を低下させることから、固結が抑制されると考えられていた。しかし、リン酸肥料中のどの成分がそのような作用を有するのかは必ずしも明確ではなかった。 Conventionally, it has been empirically known that certain types of phosphate fertilizers have an action of suppressing caking when blended with BB fertilizers. This action, like silica gel as a desiccant, was considered to suppress caking because phosphoric acid fertilizer has a high moisture adsorption capacity and lowers the humidity in the fertilizer bag. However, it has not always been clear which component in phosphate fertilizer has such an effect.
本発明は、リン酸肥料の固結抑制作用について検討を進め、リン酸一苦土、リン酸一石灰、およびリン酸二水素ナトリウムの組合せが優れた固結抑制作用を有することを見出し、これらの３成分を含む固結抑制成分を含有させたリン酸肥料を提供する。
具体的には、本発明のリン酸肥料は、水溶性リン酸、水溶性酸化マグネシウム、水溶性酸化カルシウム、および水溶性酸化ナトリウムを含有し、さらにリン酸一苦土、リン酸一石灰、およびリン酸二水素ナトリウムからなる固結抑制成分を６.０質量％以上含有することを特徴とする固結抑制リン酸肥料である。
上記固結抑制成分は、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される高吸湿性を有するリン酸成分である。
The present invention has proceeded with studies on the caking inhibitory action of phosphate fertilizer, and found that the combination of phosphate monoclay, monocalcium phosphate, and sodium dihydrogen phosphate has an excellent caking inhibitory action. A phosphate fertilizer containing an anti-caking component containing these three components is provided.
Specifically, the phosphate fertilizer of the present invention contains water-soluble phosphoric acid, water-soluble magnesium oxide, water-soluble calcium oxide, and water-soluble sodium oxide, and further phosphoric acid monoclay, phosphoric acid monolime, and It is a caking suppression phosphoric acid fertilizer characterized by containing 6.0 mass% or more of the caking suppression component which consists of sodium dihydrogen phosphate.
The above-mentioned consolidation inhibitory component is phosphorus having high hygroscopicity represented by the formula of (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4. It is an acid component.
本発明のリン酸肥料は、好ましくは、表１に示すように、水溶性リン酸量８.０〜２１.０質量％、水溶性酸化マグネシウム２.０〜６.５質量％、水溶性酸化カルシム１.０〜３.２質量％、および水溶性酸化ナトリウム０.４〜１.３質量％を含有する。 As shown in Table 1, the phosphate fertilizer of the present invention preferably has a water-soluble phosphoric acid content of 8.0 to 21.0% by mass, water-soluble magnesium oxide of 2.0 to 6.5% by mass, and water-soluble oxidation. It contains 1.0 to 3.2% by weight of calsim and 0.4 to 1.3% by weight of water-soluble sodium oxide.
本発明のリン酸肥料は、好ましくは、表５に示すように、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される固結抑制成分を６.０〜５０.０質量％含有する。上記式によって表される固結抑制成分は、図２に示すように、例えば、相対湿度４０％の平衡水分が１０％以上であって相対湿度５０％の平衡水分が１５％以上である高い吸湿性を有する。この高い吸湿性によって肥料の固結を効果的に抑制する。 As shown in Table 5, the phosphate fertilizer of the present invention is preferably (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 It contains 6.0 to 50.0% by mass of a caking inhibitory component represented by the formula. As shown in FIG. 2, the anti-caking component represented by the above formula is, for example, a high moisture absorption having an equilibrium moisture of 40% relative humidity of 10% or more and an equilibrium moisture of 50% relative humidity of 15% or more. Have sex. This high hygroscopicity effectively suppresses fertilizer consolidation.
〔製造方法〕
本発明のリン酸肥料は、原料としてリン酸原料の他に、苦土原料、および焼成リン肥等のナトリウムを含む原料を用い、リン酸一苦土〔Ｍｇ(Ｈ２ＰＯ４)２〕、リン酸一石灰〔Ｃａ(Ｈ２ＰＯ４)２〕、およびリン酸二水素ナトリウム〔ＮａＨ２ＰＯ４〕からなる固結抑制成分を含有するように配合して製造することができる。
〔Production method〕
The phosphate fertilizer of the present invention uses a raw material containing sodium, such as a bitter earth raw material and a calcined phosphorous fertilizer, in addition to the phosphoric acid raw material as a raw material, and phosphoric acid one bitumen [Mg (H 2 PO 4 ) 2 ], it can be prepared by blending to contain caking suppressing component consisting of monocalcium phosphate of lime [Ca (H 2 PO 4) 2], and sodium dihydrogen phosphate [NaH 2 PO 4].
具体的には、例えば、リン酸原料としてリン鉱石、リン酸液、焼成リン肥を用い、その他の原料として苦土原料および硫酸を用い、これらの原料粉体を、生成後のリン酸肥料中で、水溶性リン酸量８.０〜２１.０質量％、水溶性酸化マグネシウム２.０〜６.５質量％、水溶性酸化カルシム１.０〜３.２質量％、および水溶性酸化ナトリウム０.４〜１.３質量％であって、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される固結抑制成分が６.０〜５０.０質量％になる配合にし、
まず、リン鉱石とリン酸液および硫酸をスラリー状態で加熱することにより反応させ、このスラリーと焼成リン肥および苦土原料を転動造粒機中にて造粒させながら反応させることによって固結抑制リン酸肥料を製造することができる。
Specifically, for example, phosphate ore, phosphoric acid solution, and calcined phosphorus fertilizer are used as the phosphoric acid raw material, and the raw material powder and sulfuric acid are used as the other raw materials. Water-soluble phosphoric acid amount 8.0 to 21.0% by weight, water-soluble magnesium oxide 2.0 to 6.5% by weight, water-soluble calcium oxide 1.0 to 3.2% by weight, and water-soluble sodium oxide 0.4 to 1.3% by mass, represented by the formula of (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 The composition is such that the caking inhibitor component is 6.0 to 50.0% by mass,
First, the phosphorus ore, phosphoric acid solution and sulfuric acid are reacted by heating in a slurry state, and the slurry is calcined by reacting the calcined phosphorus fertilizer and the raw material of the clay with granulation in a rolling granulator. A suppressed phosphate fertilizer can be produced.
以下、本発明の実施例を比較例と共に示す。
〔試料No.Ａ〜Ｈの調製〕
本発明のリン酸肥料について、リン酸原料としてリン鉱石、リン酸液、および焼成リン肥を用い、その他の成分として苦土原料および硫酸を用い、表１に示す肥料成分を有する試料Ａ〜Ｅを調製した。具体的な製造方法としては、まず、リン鉱石とリン酸液および硫酸をスラリー状態で加熱することにより反応させ、このスラリーと焼成リン肥および苦土原料を転動造粒機中にて造粒させながら反応させて粒状肥料とした。苦土原料は橄欖岩、ニッケルスラグ、マグネシア、水酸化マグネシウム等である。比較試料Ｆについては、上記試料Ａ〜Ｅと同様な製造方法にて、苦土原料を原料として用いずに製造した。比較試料Ｇについては、フェロニッケルスラグを硫酸とリン酸の混酸で分解し、そのスラリーに苦土原料と重過石を添加、造粒することで製造した。比較試料Ｈについては、リン鉱石にリン酸液および硫酸を混和することで製造した。
一般的な肥料と同様に、肥料粒子の粒度は１mm以上〜４mm未満とした。ク溶性リン酸（Ｃ−Ｐ２Ｏ５）、水溶性リン酸（Ｗ−Ｐ２Ｏ５）等の肥料成分は、肥料分析法に基づき分析した。また、水溶性カルシウム（Ｗ−ＣａＯ）と水溶性ナトリウム（Ｗ−Ｎａ２Ｏ）は、水溶性リン酸の供試液を用いて、原子吸光光度法により分析した。
Examples of the present invention are shown below together with comparative examples.
[Preparation of sample Nos. A to H]
About the phosphate fertilizer of this invention, the sample AE which has a fertilizer component shown in Table 1 using a phosphorous ore, a phosphoric acid liquid, and a baking phosphorous fertilizer as a phosphoric acid raw material, and using a bitter earth raw material and a sulfuric acid as another component. Was prepared. As a specific production method, first, the phosphate ore, phosphoric acid solution and sulfuric acid are reacted by heating in a slurry state, and the slurry, the calcined phosphorus fertilizer and the bitter earth material are granulated in a tumbling granulator. It was made to react, making it a granular fertilizer. The raw materials for the clay are nepheline, nickel slag, magnesia, magnesium hydroxide and the like. About the comparative sample F, it manufactured with the manufacturing method similar to the said samples A-E, without using a bitter clay raw material as a raw material. Comparative sample G was produced by decomposing ferronickel slag with a mixed acid of sulfuric acid and phosphoric acid, adding a bitter earth material and bitumen to the slurry, and granulating it. The comparative sample H was manufactured by mixing a phosphoric acid solution and sulfuric acid into a phosphate rock.
Similar to general fertilizers, the fertilizer particles had a particle size of 1 mm to less than 4 mm. Fertilizer components such as water-soluble phosphoric acid (C—P 2 O 5 ) and water-soluble phosphoric acid (W—P 2 O 5 ) were analyzed based on a fertilizer analysis method. Water-soluble calcium (W—CaO) and water-soluble sodium (W—Na 2 O) were analyzed by atomic absorption spectrophotometry using a test solution of water-soluble phosphoric acid.
〔堆積試験〕
調製したリン酸肥料（No.Ａ〜Ｈ）について、ＢＢ肥料に対する固結抑制効果を把握するために堆積試験を行った。この堆積試験は、ＢＢ肥料の成分を、硫安、リン酸二安（ＤＡＰ）、および塩化カリとし、これら各肥料成分の粒状原料を各２２５ｇ混合して、あらかじめ３０℃、７５％ＲＨの条件で重量増が３.５ｇになるまで吸湿させた。この吸湿原料に、乾燥させた表１のリン酸肥料（No.Ａ〜Ｈ）を７５ｇ混合し、ポリエチレン製袋（２００×１５０×０.１５mm）に封入した（試料No.１〜８）。また、比較試料９として、シリカゲルの粉末（粒径250〜1000μｍ）７.５ｇを固結抑制剤として用いた。さらに対照として、試料No.Ａ〜Ｈおよびシリカゲル粉末を混合しない水準を設けた。
[Deposition test]
The prepared phosphate fertilizer (No. A to H) was subjected to a deposition test in order to grasp the caking suppression effect on the BB fertilizer. In this sedimentation test, the components of BB fertilizer are ammonium sulfate, dibasic phosphate (DAP), and potassium chloride, and 225 g of each of these fertilizer components is mixed in advance at 30 ° C. and 75% RH. Moisture absorption was performed until the weight gain was 3.5 g. 75 g of the dried phosphate fertilizer (No. A to H) in Table 1 was mixed with this moisture-absorbing raw material, and sealed in a polyethylene bag (200 × 150 × 0.15 mm) (Sample Nos. 1 to 8). Moreover, as a comparative sample 9, 7.5 g of silica gel powder (particle size: 250 to 1000 μm) was used as a caking inhibitor. Furthermore, as a control, a level at which sample Nos. A to H and silica gel powder were not mixed was provided.
これらの肥料袋を１水準について１袋用意し、４段積みにして６０kgの加重を掛け（200ｇ/cm２）、常温常湿の室内にて３０日間静置した。堆積試験終了後、袋を解袋し、固結が生じた肥料については、固結部分を手でより分けて重量割合を測定した。また、固結部分については山中式土壌硬度計にて５ヵ所の硬度を測定し、その平均値を固結強度とした。ＢＢ肥料の成分配合量と、使用したリン酸肥料の種類（No.Ａ〜Ｈ）と配合量、固結割合および固結強度を表２に示す。 One bag of these fertilizer bags was prepared for one level, stacked in four layers, applied with a weight of 60 kg (200 g / cm 2 ), and allowed to stand for 30 days in a room temperature and humidity room. After completion of the deposition test, the bags were unpacked, and for the fertilizer in which consolidation occurred, the consolidated portion was divided by hand and the weight ratio was measured. Moreover, about the consolidation part, the hardness of five places was measured with the Yamanaka type soil hardness meter, and the average value was made into the consolidation strength. Table 2 shows the component blending amount of BB fertilizer, the type (No. A to H) of phosphoric acid fertilizer used, the blending amount, the consolidation ratio, and the consolidation strength.
表２に示すように、本発明のリン酸肥料（No.Ａ〜Ｅ）を配合した試料No.１〜５は、固結割合が７６％未満、固結強度が２.１kg/cm２未満であり、対照試験に比べて固結割合が低く、また固結強度は大幅に小さく、しかも固結強度はシリカゲルを用いた試料No.９よりも格段に小さく、優れた固結抑制効果が確認された。 As shown in Table 2, Sample Nos. 1 to 5 containing the phosphate fertilizer (No. A to E) of the present invention have a consolidation ratio of less than 76% and a consolidation strength of less than 2.1 kg / cm 2. Compared to the control test, the caking ratio is lower, the caking strength is significantly smaller, and the caking strength is much smaller than that of sample No. 9 using silica gel, confirming the excellent caking suppression effect. It was done.
本発明のリン酸肥料の成分であるＭｇ(Ｈ２ＰＯ４)２、Ｃａ(Ｈ２ＰＯ４)２、ＮａＨ２ＰＯ４は全て水溶性であり、肥料の水溶性成分のＷ−ＭｇＯがＭｇ(Ｈ２ＰＯ４)２に、Ｗ−ＣａＯがＣａ(Ｈ２ＰＯ４)２に、Ｗ−Ｎａ２ＯがＮａＨ２ＰＯ４によって供給される。また、本発明のリン酸肥料は、表１の試料Ａ〜Ｅに示すように、Ｗ−ＭｇＯを２.４４％以上、Ｗ−ＣａＯを１.１１％以上、Ｗ−Ｎａ２Ｏを０.４１％以上含有しており、吸湿性能の高いＭｇ(Ｈ２ＰＯ４)２とＣａ(Ｈ２ＰＯ４)２とＮａＨ２ＰＯ４との３成分を含有するので、高い吸湿性を有している。 Mg (H 2 PO 4 ) 2 , Ca (H 2 PO 4 ) 2 and NaH 2 PO 4 which are components of the phosphate fertilizer of the present invention are all water-soluble, and W-MgO which is a water-soluble component of the fertilizer is Mg. the (H 2 PO 4) 2, W-CaO within Ca (H 2 PO 4) 2 , W-Na 2 O is supplied by the NaH 2 PO 4. Further, phosphate fertilizer of the present invention, as shown in the sample A~E in Table 1, W-MgO 2.44% or more, the W-CaO 1.11% or more, the W-Na 2 O 0. Since it contains 41% or more and contains three components of Mg (H 2 PO 4 ) 2 , Ca (H 2 PO 4 ) 2 and NaH 2 PO 4 with high moisture absorption performance, it has high moisture absorption. Yes.
一方、表１の試料Ｆは、Ｗ−ＭｇＯが０.８０％と低く、Ｍｇ(Ｈ２ＰＯ４)２の含有量が少ない。試料Ｇは、Ｗ−Ｎａ２Ｏが０.１２％と低く、ＮａＨ２ＰＯ４の含有量が少ない。試料Ｈは、Ｗ−ＭｇＯが０.７９％、Ｗ−Ｎａ２Ｏが０.２２％と低く、Ｍｇ(Ｈ２ＰＯ４)２およびＮａＨ２ＰＯ４の何れも少なく、吸湿性が低い。
これらのリン酸肥料（No.Ｆ、Ｇ、Ｈ）を配合した試料No.６、７、８は何れも対照試験より固結割合が多く、試料No.７、８は固結強度も大きく、固結抑制効果は認められない。
On the other hand, Sample F in Table 1 has a low W-MgO content of 0.80% and a low content of Mg (H 2 PO 4 ) 2 . Sample G, W-Na 2 O is as low as 0.12%, the content of NaH 2 PO 4 is small. Sample H is, W-MgO is 0.79%, W-Na 2 O is as low as 0.22%, Mg (H 2 PO 4) both less of 2 and NaH 2 PO 4, less hygroscopic.
Samples Nos. 6, 7, and 8 blended with these phosphate fertilizers (No. F, G, and H) all have a higher consolidation ratio than the control test, and sample Nos. 7 and 8 have a larger consolidation strength. No caking suppression effect is observed.
〔吸湿試験〕
ＢＢ肥料の堆積試験において、固結抑制効果を有する試料No.Ａ〜Ｅはその高い水分吸収能力によって肥料袋中の相対湿度を低下させ、それにより固結を抑制したと考えられる。そこで、試料No.Ａ〜Ｅに含まれるどの成分が吸湿能力を発揮したのかを明らかにするために、吸湿試験を行った。一般に成分固有の臨界湿度を越えると吸湿を開始し、吸湿が進むとその表面に遊離水を生じて濡れた状態になる。遊離水には吸湿した成分が溶解し、その成分の飽和溶液となる。すなわち、その吸湿液の成分は、吸湿に関与している成分であることから、吸湿液の成分を調べることにより、試料No.Ａ〜Ｅに含まれる水分吸収能力の高い成分を特定することができる。
[Hygroscopic test]
In the BB fertilizer deposition test, it is considered that Samples Nos. A to E having a caking suppression effect lowered the relative humidity in the fertilizer bag due to its high water absorption ability, thereby suppressing caking. Therefore, in order to clarify which component contained in Sample Nos. A to E exhibited the moisture absorption capability, a moisture absorption test was performed. In general, when the critical humidity specific to the component is exceeded, moisture absorption starts, and when moisture absorption proceeds, free water is generated on the surface and the surface becomes wet. The component that has absorbed moisture is dissolved in the free water, and a saturated solution of the component is obtained. That is, since the component of the hygroscopic liquid is a component involved in moisture absorption, it is possible to identify a component having a high water absorption capability contained in the sample Nos. A to E by examining the components of the hygroscopic liquid. it can.
試料No.Ａ、Ｂ、Ｃ、Ｄ、Ｅと、比較試料Ｆ、Ｇ、Ｈについて、各１０.０ｇを粒状のまま秤量瓶に計り取り、蓋を開けた状態で２５℃、９０％ＲＨの恒温恒湿槽中で２０時間吸湿させた。次に、ガラス濾過器に網を設置して網上に吸湿した肥料粒子を置き、（１＋１）エタノール１００mlで洗浄した。この洗浄後の溶液を加熱濃縮してエタノールを揮散除去した後に、肥料分析法に従って溶液中に含まれるＰ２Ｏ５、ＣａＯ、ＭｇＯ、Ｎａ２Ｏを分析した。吸湿させていない肥料粒子についても同様な操作を行い、空試験とした。試験は各肥料について２回ずつ行い、その平均を分析値とした。この結果を表３に示す。なお、表中の吸湿液濃度は、空試験の値を補正した数値である。また、吸湿液の成分のモル比は、モル濃度が一番低いＣａのモル濃度を基準としたモル比である。 For Sample Nos. A, B, C, D, E and Comparative Samples F, G, H, each 10.0 g was weighed into a weighing bottle in the form of granules, and at 25 ° C. and 90% RH with the lid open. Moisture was absorbed for 20 hours in a constant temperature and humidity chamber. Next, a net was placed on a glass filter and fertilizer particles that had absorbed moisture were placed on the net, and washed with 100 ml of (1 + 1) ethanol. The washed solution was concentrated by heating to volatilize and remove ethanol, and then analyzed for P 2 O 5 , CaO, MgO, and Na 2 O contained in the solution according to the fertilizer analysis method. The same operation was performed on fertilizer particles that had not been absorbed by moisture, and a blank test was performed. The test was performed twice for each fertilizer, and the average was taken as the analytical value. The results are shown in Table 3. The hygroscopic liquid concentration in the table is a numerical value obtained by correcting the blank test value. The molar ratio of the components of the hygroscopic liquid is a molar ratio based on the molar concentration of Ca having the lowest molar concentration.
表３に示すように、試料No.Ａ、Ｂ、Ｃ、Ｄについて、吸湿液のモル比はほぼ等しく、Ｍｇ：Ｃａ：Ｎａモル比は、概ね５：１：１．２〜３である。試料No.Ｅについては、Ｃａ：Ｎａのモル比は試料No.Ａ、Ｂ、Ｃ、Ｄとほぼ同じであるが、Ｍｇのモル比は１３.１であり格段に大きい。 As shown in Table 3, for sample Nos. A, B, C, and D, the molar ratio of the hygroscopic liquid is substantially equal, and the molar ratio of Mg: Ca: Na is approximately 5: 1: 1.2-3. For sample No. E, the molar ratio of Ca: Na is almost the same as that of samples No. A, B, C, and D, but the molar ratio of Mg is 13.1, which is much larger.
一方、Ｍｇをほとんど含まない試料No.Ｆの吸湿液は組成が大きく異なり、Ｍｇ：Ｃａ：Ｎａのモル比は概ね１：１：２である。また、Ｎａをほとんど含まない試料No.Ｇの吸湿液のＭｇ：Ｃａ：Ｎａのモル比は５.６：１.０：０.１であり、ＭｇとＮａをほとんど含まない試料No.Ｈの吸湿液のＭｇ：Ｃａ：Ｎａのモル比は０.６：１.０：０.１である。 On the other hand, the moisture absorption liquid of sample No. F containing almost no Mg has a greatly different composition, and the molar ratio of Mg: Ca: Na is approximately 1: 1: 2. Further, the molar ratio of Mg: Ca: Na in the moisture absorption liquid of sample No. G containing almost no Na is 5.6: 1.0: 0.1, and the sample No. H containing almost no Mg and Na. The molar ratio of Mg: Ca: Na in the hygroscopic liquid is 0.6: 1.0: 0.1.
ここで、固結抑制効果の高い試料No.Ａ〜Ｅの(２Ｍｇ＋２Ｃａ＋Ｎａ)／Ｐモル比はほぼ１であり、一方、比較試料No.Ｆ〜Ｈは固結抑制効果が殆ど無いことから、吸湿性の高い成分は、リン酸一苦土〔Ｍｇ(Ｈ２ＰＯ４)２〕、リン酸一石灰〔Ｃａ(Ｈ２ＰＯ４)２〕、およびリン酸二水素ナトリウム〔ＮａＨ２ＰＯ４〕の３成分であると考えられる。これらのことから、試料No.Ａ、Ｂ、Ｃ、Ｄ、Ｅについて、高い吸湿性能を有する成分は、その肥料中に含有される(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４によって表される成分であると考えられる。 Here, (2Mg + 2Ca + Na) / P molar ratio of sample Nos. A to E having a high caking suppression effect is almost 1, while comparative samples No. F to H have almost no caking suppression effect. The highly soluble component is composed of monobasic phosphate [Mg (H 2 PO 4 ) 2 ], monolime phosphate [Ca (H 2 PO 4 ) 2 ], and sodium dihydrogen phosphate [NaH 2 PO 4 ]. It is considered to be a three component. For these reasons, the sample No. A, B, C, D, for E, components having high hygroscopicity is contained in its fertilizer (5~13) Mg (H 2 PO 4) 2 + Ca (H 2 PO 4 ) 2 + (1-3) is considered to be a component represented by NaH 2 PO 4 .
〔吸湿性の確認〕
本発明のリン酸肥料は、上記検討に基づき、リン酸一苦土〔Ｍｇ(Ｈ２ＰＯ４)２〕、リン酸一石灰〔Ｃａ(Ｈ２ＰＯ４)２〕、およびリン酸二水素ナトリウム〔ＮａＨ２ＰＯ４〕の各成分を特定の割合で含有することによって、高い吸湿性によって優れた固結抑制機能を有すると考えられる。そこで、これら３種類の純物質を合成し、どの成分あるいは組み合わせが最も吸湿性に優れているのかを明らかにするための試験を行った。
[Confirmation of hygroscopicity]
Based on the above study, the phosphate fertilizer of the present invention is based on phosphoric acid monomite [Mg (H 2 PO 4 ) 2 ], phosphoric acid monolime [Ca (H 2 PO 4 ) 2 ], and sodium dihydrogen phosphate. By containing each component of [NaH 2 PO 4 ] at a specific ratio, it is considered that it has an excellent caking suppression function due to high hygroscopicity. Therefore, these three kinds of pure substances were synthesized, and a test was conducted to clarify which component or combination has the best hygroscopicity.
〔試料No. １１〜１６の調製〕
試薬のＭｇ(ＯＨ)２、Ｃａ(ＯＨ)２、ＮａＯＨ、焼成リン肥、Ｈ３ＰＯ４を表４に示す割合で配合した粉体原料に水を加えて全体をスラリーにし、常温で８５％Ｈ３ＰＯ４を表４に示す割合で添加、撹拌して反応させた。反応後はウォーターバス上で濃縮し、その後１１０℃で乾燥して試料１１〜１６を調製した。
試料１１〜１６の分析結果を表４に示した。モル比はＣａを基準にしたモル比である。また、Ｘ線回折の結果を図１に示す。試料No.１１はＭｇ(Ｈ２ＰＯ４)２が同定され、ピークもシャープに現れている。試料１２〜１６については、Ｍｇ(Ｈ２ＰＯ４)２、Ｃａ(Ｈ２ＰＯ４)２・Ｈ２Ｏ、ＮａＨ２ＰＯ４・２Ｈ２Ｏ、および縮合塩などの種々の物質が同定された。
[Preparation of Sample Nos. 11-16]
Water is added to the powder raw material in which the reagents Mg (OH) 2 , Ca (OH) 2 , NaOH, calcined phosphorous fertilizer, and H 3 PO 4 are blended in the proportions shown in Table 4 to make the whole slurry, and 85% at room temperature. H 3 PO 4 was added at the ratio shown in Table 4 and stirred to react. After the reaction, the sample was concentrated on a water bath and then dried at 110 ° C. to prepare Samples 11 to 16.
The analysis results of Samples 11 to 16 are shown in Table 4. The molar ratio is a molar ratio based on Ca. The results of X-ray diffraction are shown in FIG. In sample No. 11, Mg (H 2 PO 4 ) 2 was identified, and the peak appeared sharply. For Samples 12-16, various substances such as Mg (H 2 PO 4 ) 2 , Ca (H 2 PO 4 ) 2 .H 2 O, NaH 2 PO 4 .2H 2 O, and condensed salts were identified. .
試料No.１１の成分はＭｇ(Ｈ２ＰＯ４)２単独であり、Ｃａ(Ｈ２ＰＯ４)２、ＮａＨ２ＰＯ４が加わった試料No.１３、１４では、試料No.１１に比べて、Ｍｇ(Ｈ２ＰＯ４)２のピークの強度が大幅に低下している。 The component of sample No. 11 is Mg (H 2 PO 4 ) 2 alone, and sample Nos. 13 and 14 to which Ca (H 2 PO 4 ) 2 and NaH 2 PO 4 are added are compared to sample No. 11 , Mg (H 2 PO 4 ) 2 peak intensity is greatly reduced.
〔吸湿試験〕
試料No.１１〜１６について吸湿試験を行い、平衡水分を測定して平衡水分曲線を求めた。測定試料２.０ｇを秤量瓶に精秤し、３０℃、相対湿度３０％（以下３０％ＲＨという）に設定した恒温恒湿槽に入れ、恒量に達するまで静置し（１９日間）、重量を測定した。その後、３０℃、４０％ＲＨ、５０％ＲＨ、６０％ＲＨ、７０％ＲＨ、８０％ＲＨについて、順次同じ操作を繰り返し（吸湿時間は１０日〜３０日間）、重量増から含水率（平衡水分）を計算して平衡水分曲線を作成した。この結果を図２に示す。また、比較として、試薬のＭｇ(Ｈ２ＰＯ４)２、肥料の固結抑制剤として用いられているシリカゲルの平衡水分曲線を示した。
[Hygroscopic test]
A moisture absorption test was performed on Samples Nos. 11 to 16, and the equilibrium moisture curve was determined by measuring the equilibrium moisture. 2.0 g of a measurement sample is precisely weighed in a weighing bottle, placed in a constant temperature and humidity chamber set at 30 ° C. and a relative humidity of 30% (hereinafter referred to as 30% RH), and left to reach a constant weight (19 days). Was measured. Thereafter, the same operation was repeated for 30 ° C., 40% RH, 50% RH, 60% RH, 70% RH, and 80% RH in order (moisture absorption time was 10 to 30 days). ) Was calculated to create an equilibrium moisture curve. The result is shown in FIG. For comparison, an equilibrium moisture curve of the reagent Mg (H 2 PO 4 ) 2 and silica gel used as a fertilizer caking inhibitor is shown.
図２に示すように、試料No.１２〜１５は、４０％ＲＨ〜８０％ＲＨの全域にかけて、シリカゲルより平衡水分が高く、特に試料No.１２、１３はシリカゲルの１.５倍〜２倍の平衡水分を示し、きわめて高い吸湿能力を示した。一方、試料No.１１は、６０％ＲＨ〜８０％ＲＨの領域では平衡水分が急激に上昇してシリカゲルよりも高くなるが、３０％ＲＨ〜５０％ＲＨの領域では平衡水分がシリカゲルよりも低い。この結果から、４０％ＲＨ〜８０％ＲＨの全域にかけて高い吸湿性を有するには、試料No.１２〜１５のように、Ｍｇ(Ｈ２ＰＯ４)２の他に、Ｃａ(Ｈ２ＰＯ４)２、ＮａＨ２ＰＯ４を含有するものが好ましい。また、試料No.１６は、Ｍｇ(Ｈ２ＰＯ４)２およびＣａ(Ｈ２ＰＯ４)２を含有するが、試料No.１２〜１５よりもＭｇのモル比が少なく、３０％ＲＨ〜７０％ＲＨの領域でシリカゲルよりも平衡水分が少なく吸湿性が低い。 As shown in FIG. 2, Samples Nos. 12 to 15 have a higher equilibrium moisture content than silica gel over the entire range of 40% RH to 80% RH, and Samples Nos. 12 and 13 are particularly 1.5 to 2 times that of silica gel. Showed an extremely high moisture absorption capacity. On the other hand, in sample No. 11, the equilibrium moisture rises rapidly in the region of 60% RH to 80% RH and is higher than that of silica gel, but the equilibrium moisture is lower than that of silica gel in the region of 30% RH to 50% RH. . From this result, in order to have high hygroscopicity over the entire region of 40% RH to 80% RH, as in Sample Nos. 12 to 15, in addition to Mg (H 2 PO 4 ) 2 , Ca (H 2 PO 4 ) 2 and those containing NaH 2 PO 4 are preferred. Sample No. 16 contains Mg (H 2 PO 4 ) 2 and Ca (H 2 PO 4 ) 2 , but has a lower molar ratio of Mg than sample Nos. 12 to 15 and 30% RH to 70%. In the% RH region, it has less equilibrium moisture content than silica gel, and its hygroscopicity is lower.
比較のために、試薬のＭｇ(Ｈ２ＰＯ４)２について平衡水分曲線を測定したところ、図２に示すように、６０％ＲＨまでは１％未満の平衡水分であり、吸湿性は極端に低い。ところが、合成した試料No.１１はＭｇ(Ｈ２ＰＯ４)２でも、試薬のＭｇ(Ｈ２ＰＯ４)２に比べるとかなり高い吸湿性を有している。一方、前述のように、試料No.１１よりも試料No.１２，１３はさらに高い吸湿性を有している。ここで、試料No. １３と試料No.１１のＸ線回折チャートを比較すると、試料No. １３は、Ｍｇ(Ｈ２ＰＯ４)２のピーク強度は試料No.１１の約１７分の１であり、結晶性が非常に低い。試料No. １３はＭｇ(Ｈ２ＰＯ４)２と共にＣａ(Ｈ２ＰＯ４)２、およびＮａＨ２ＰＯ４を含有することと、結晶性が非常に低いことも高い吸湿性を有する原因であるように推察される。 For comparison, the equilibrium moisture curve was measured for the reagent Mg (H 2 PO 4 ) 2. As shown in FIG. 2, the equilibrium moisture was less than 1% up to 60% RH, and the hygroscopicity was extremely low. Low. However, even when the synthesized sample No. 11 is Mg (H 2 PO 4 ) 2, it has a considerably higher hygroscopicity than the reagent Mg (H 2 PO 4 ) 2 . On the other hand, as described above, Sample Nos. 12 and 13 have higher hygroscopicity than Sample No. 11. Here, comparing the X-ray diffraction charts of sample No. 13 and sample No. 11, sample No. 13 has a peak intensity of Mg (H 2 PO 4 ) 2 of about 17 times that of sample No. 11. Yes, crystallinity is very low. Sample No. 13 contains Ca (H 2 PO 4 ) 2 and Mg (H 2 PO 4 ) 2 and NaH 2 PO 4 together with Mg (H 2 PO 4 ) 2 , and the fact that the crystallinity is very low is also a cause of high hygroscopicity It is guessed as follows.
これらの結果から、４０％ＲＨ〜８０％ＲＨの全域にかけて高い吸湿性を有するには、Ｃａ１モルに対して、Ｍｇを２.０〜１４.０モル、およびＮａを１〜３.０モル含有するものが好ましく、Ｍｇ５.０〜１４.０モル、およびＮａ１.０〜３.０モルの範囲がより好ましいことが確認された。このことから、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４によって表される組成の成分を含有するリン酸肥料は、高い吸湿性能を有することが確かめられた。
From these results, in order to have a high hygroscopicity over the entire range of 40% RH to 80% RH, 2.0 to 14.0 mol of Mg and 1 to 3.0 mol of Na are contained with respect to 1 mol of Ca. It was confirmed that Mg 5.0 to 14.0 mol and Na 1.0 to 3.0 mol are more preferable. Therefore, (5~13) Mg (H 2 PO 4) 2 + Ca (
このように、本発明のリン酸肥料に含まれる高い吸湿性能を有する成分のＭｇ、Ｎａ、Ｃａのモル比は、Ｃａ１モルに対して、Ｍｇ２.０〜１４.０モル、およびＮａ１.０〜３.０モルの範囲が好ましく、Ｍｇ５.０〜１４.０モル、およびＮａ１.０〜３.０モルの範囲がより好ましい。Ｃａ１モルに対して、Ｍｇが２.０モル未満であるとリン酸一苦土の含有量が少なくなるので吸湿性が低下し、Ｍｇが１４.０モルを超えると相対的にリン酸一石灰およびリン酸二水素ナトリウムの含有量が少なくなり、Ｎａが１.０モル未満ではリン酸二水素ナトリウムの含有量が少なくなり、Ｎａが３.０モルを超えると相対的にリン酸一苦土やリン酸一石灰の含有量が少なくなり、何れの場合も吸湿性が低下するので好ましくない。 Thus, the molar ratio of Mg, Na, and Ca, which is a component having high moisture absorption performance included in the phosphate fertilizer of the present invention, is Mg 2.0 to 14.0 mol and Na 1.0 to Ca 1 mol. The range of 3.0 mol is preferable, and the range of Mg 5.0 to 14.0 mol and Na 1.0 to 3.0 mol is more preferable. If the Mg content is less than 2.0 mol with respect to 1 mol of Ca, the hygroscopicity is reduced because the content of monobasic phosphate is reduced, and if the Mg content exceeds 14.0 mol, it is relatively monolithic phosphate. The content of sodium dihydrogen phosphate is reduced, the content of sodium dihydrogen phosphate is reduced when Na is less than 1.0 mol, and the content of sodium phosphate is relatively low when Na is more than 3.0 mol. In addition, the content of phosphorous monolime is reduced, and in any case, the hygroscopicity is lowered, which is not preferable.
さらに、この成分の(２Ｍｇ＋２Ｃａ＋Ｎａ)／Ｐモル比については、１前後であることが好ましい。その理由は、(２Ｍｇ＋２Ｃａ＋Ｎａ)／Ｐモル比が１前後であれば、高い吸湿性を有するＭｇ(Ｈ２ＰＯ４)２、Ｃａ(Ｈ２ＰＯ４)２、ＮａＨ２ＰＯ４の三成分の組み合わせとなるからである。 Furthermore, the (2Mg + 2Ca + Na) / P molar ratio of this component is preferably around 1. The reason is that if the (2Mg + 2Ca + Na) / P molar ratio is around 1, a combination of three components of Mg (H 2 PO 4 ) 2 , Ca (H 2 PO 4 ) 2 and NaH 2 PO 4 having high hygroscopicity. Because it becomes.
〔固形抑制成分の含有量〕
上記(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式で表される固形抑制成分の肥料中の含有量について、吸湿性能が高い試料No.１３を例にして試料A~Hに含まれる固形抑制成分No.１３の含有量を算出した。
試料１３の水溶性成分量は、Ｗ−Ｐ２Ｏ５（６２.７９％）、Ｗ−ＭｇＯ（１３.６２％）、Ｗ−ＣａＯ（３.３０％）、Ｗ−Ｎａ２Ｏ（２.３３％）である。試料Ａ〜Ｈの水溶性成分量は表１に示すとおりであるので、制限要素となるＷ−ＭｇＯを基準として、試料Ａ〜Ｈの試料１３含有量を計算する。例えば、試料ＡのＷ−ＭｇＯは２.４４％であるので、試料Ａに含まれる試料１３の含有量は、２.４４/１３.６２×１００＝１７.９％である。同様にして算出した試料Ａ〜Ｆ，Ｈに含まれる試料１３含有量を表５に示す。なお、試料No.ＧはＷ−ＭｇＯが多く、Ｗ−Ｎａ２Ｏが少ないため、Ｗ−Ｎａ２Ｏを基準として計算した。
[Content of solid suppression component]
About the content in the fertilizer of the solid suppression component represented by the formula (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 Using the sample No. 13 with high performance as an example, the content of the solid suppression component No. 13 contained in the samples A to H was calculated.
Water-soluble components of the sample 13, W-P 2 O 5 ( 62.79%), W-MgO (13.62%), W-CaO (3.30%), W-Na 2 O (2. 33%). Since the amounts of water-soluble components of Samples A to H are as shown in Table 1, the content of Sample 13 of Samples A to H is calculated based on W-MgO as a limiting factor. For example, since W-MgO of sample A is 2.44%, the content of sample 13 included in sample A is 2.44 / 13.62 × 100 = 17.9%. Table 5 shows the content of Sample 13 contained in Samples A to F and H calculated in the same manner. Incidentally, the sample No.G are often W-MgO, for W-Na 2 O is less, calculated based on the W-Na 2 O.
表５に示すように、本発明のリン酸肥料（試料No.Ａ〜Ｅ）は、吸湿性が高い試料No.１３を１７％〜４５％含有している。一方、比較試料Ｆ、Ｇ、Ｈに含まれる試料１３の含量は５％台であり大幅に低い。このことから、本発明のリン酸肥料に含まれる固形抑制成分〔(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４〕の含有量は６.０〜５０.０％が好ましいことがかわる。 As shown in Table 5, the phosphate fertilizer of the present invention (sample Nos. A to E) contains 17% to 45% of sample No. 13 having high hygroscopicity. On the other hand, the content of the sample 13 contained in the comparative samples F, G, and H is on the order of 5% and is significantly low. From this, the solid suppression component [(5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 ] contained in the phosphate fertilizer of the present invention. The content is preferably 6.0 to 50.0%.
Claims (5)
水溶性リン酸量８.０〜２１.０質量％、水溶性酸化マグネシウム２．０〜６.５質量％、水溶性酸化カルシム１.０〜３.２質量％、および水溶性酸化ナトリウム０.４〜１.３質量％であって、(５〜１３)Ｍｇ(Ｈ２ＰＯ４)２＋Ｃａ(Ｈ２ＰＯ４)２＋(１〜３)ＮａＨ２ＰＯ４の式によって表される固結抑制成分が６.０〜５０.０質量％になる配合にし、
まず、リン鉱石とリン酸液および硫酸をスラリー状態で加熱することにより反応させ、このスラリーと焼成リン肥および苦土原料を転動造粒機中にて造粒させながら反応させることによって固結抑制リン酸肥料を製造する方法。
Phosphate ore, phosphoric acid solution, and calcined phosphorus fertilizer are used as the phosphoric acid raw material, and the raw material powder and sulfuric acid are used as the other raw materials.
Water-soluble phosphoric acid amount 8.0 to 21.0% by mass, water-soluble magnesium oxide 2.0 to 6.5% by mass, water-soluble calcium oxide 1.0 to 3.2% by mass, and water-soluble sodium oxide 0.0%. Consolidation represented by the formula of 4 to 1.3% by mass, (5-13) Mg (H 2 PO 4 ) 2 + Ca (H 2 PO 4 ) 2 + (1-3) NaH 2 PO 4 The inhibitory component is formulated to be 6.0 to 50.0% by mass,
First, the phosphorus ore, phosphoric acid solution and sulfuric acid are reacted by heating in a slurry state, and the slurry is calcined by reacting the calcined phosphorus fertilizer and the raw material of the clay with granulation in a rolling granulator. A method for producing a suppressed phosphate fertilizer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5216365A (en) * | 1975-07-18 | 1977-02-07 | Onoda Chem Ind Co Ltd | Process for producing quick and slack effective phosphate fertilizers |
| JPS5860686A (en) * | 1981-10-05 | 1983-04-11 | 村樫石灰工業株式会社 | Manufacture of phosphatic fertilizer |
| JPS59213696A (en) * | 1983-05-17 | 1984-12-03 | 住友化学工業株式会社 | Solidification prevention for granular composite fertilizer |
| JPH0624885A (en) * | 1992-05-30 | 1994-02-01 | Kokura Gosei Kogyo Kk | Consolidation preventive agent and granular fertilizer formed by using this agent |
| US5782951A (en) * | 1997-02-20 | 1998-07-21 | Western Industrial Clay Products, Inc. | Particulate urea with finely divided inorganic material incorporated for hardness nonfriability and anti-caking |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5216365A (en) * | 1975-07-18 | 1977-02-07 | Onoda Chem Ind Co Ltd | Process for producing quick and slack effective phosphate fertilizers |
| JPS5860686A (en) * | 1981-10-05 | 1983-04-11 | 村樫石灰工業株式会社 | Manufacture of phosphatic fertilizer |
| JPS59213696A (en) * | 1983-05-17 | 1984-12-03 | 住友化学工業株式会社 | Solidification prevention for granular composite fertilizer |
| JPH0624885A (en) * | 1992-05-30 | 1994-02-01 | Kokura Gosei Kogyo Kk | Consolidation preventive agent and granular fertilizer formed by using this agent |
| US5782951A (en) * | 1997-02-20 | 1998-07-21 | Western Industrial Clay Products, Inc. | Particulate urea with finely divided inorganic material incorporated for hardness nonfriability and anti-caking |
Non-Patent Citations (1)
| Title |
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| 洗 幸夫, 「肥料加工学」固結防止, JPN6021008257, 3 September 2016 (2016-09-03), pages 1 - 10, ISSN: 0004461314 * |
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