JP2004352558A - Ammonium nitrate fertilizer excellent in preservation stability - Google Patents
Ammonium nitrate fertilizer excellent in preservation stability Download PDFInfo
- Publication number
- JP2004352558A JP2004352558A JP2003152128A JP2003152128A JP2004352558A JP 2004352558 A JP2004352558 A JP 2004352558A JP 2003152128 A JP2003152128 A JP 2003152128A JP 2003152128 A JP2003152128 A JP 2003152128A JP 2004352558 A JP2004352558 A JP 2004352558A
- Authority
- JP
- Japan
- Prior art keywords
- fertilizer
- ammonium nitrate
- weight
- granular
- nitrate
- 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.)
- Pending
Links
- 239000003337 fertilizer Substances 0.000 title claims abstract description 106
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004321 preservation Methods 0.000 title abstract 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011591 potassium Substances 0.000 claims abstract description 24
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003063 flame retardant Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 229910052602 gypsum Inorganic materials 0.000 description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 description 7
- 235000011151 potassium sulphates Nutrition 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004889 fertilizer analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- UUWDNZVBBUGKMK-UHFFFAOYSA-N dipotassium;dinitrate Chemical compound [K+].[K+].[O-][N+]([O-])=O.[O-][N+]([O-])=O UUWDNZVBBUGKMK-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- ZDDDSLALSKLVHS-UHFFFAOYSA-N potassium phosphoric acid nitrate Chemical compound [N+](=O)([O-])[O-].[K+].P(=O)(O)(O)O ZDDDSLALSKLVHS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- OUCNSFUASBNULY-UHFFFAOYSA-O [NH4+].[K].[O-][N+]([O-])=O Chemical compound [NH4+].[K].[O-][N+]([O-])=O OUCNSFUASBNULY-UHFFFAOYSA-O 0.000 description 1
- OBYUWBOIIKWGJI-UHFFFAOYSA-N [P].O[N+]([O-])=O Chemical compound [P].O[N+]([O-])=O OBYUWBOIIKWGJI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- UIGKOBGQTLLQBZ-UHFFFAOYSA-O tetraazanium;nitrate;phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-][N+]([O-])=O.[O-]P([O-])([O-])=O UIGKOBGQTLLQBZ-UHFFFAOYSA-O 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 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
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Fertilizers (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、化成肥料として重要な硝酸アンモニウムを主成分とする粒状肥料およびこの粒状肥料をポリオレフィン等の樹脂を含む被膜で被覆した被覆粒状硝安肥料に関するものである。
【０００２】
【従来の技術】
硝酸アンモニウム（以下硝安と略記）を主成分とする肥料は、窒素成分を多く含みかつ畑での吸収が速い硝酸態窒素を多く含むことから、土壌での硝酸化成の遅い寒冷地の畑作用の肥料として重要である。しかし、硝安は強力な酸化力を有する化合物であり、純度の高いものは少量の有機物の混合により爆発性を示すことから、多くの肥料では石膏等と混合造粒し難燃化して販売されている。硝安を主成分とする粒状肥料は、他の粒状窒素肥料、粒状カリ肥料、粒状燐酸肥料とブレンドし窒素、燐酸、カリウムを含む肥料のブレンド原料として使用されることが多く、硝安含量の高いものが求められる。
【０００３】
硝安含量が約９０重量％程度の肥料は、酸化性物質として貯蔵、混合の制限を受けるものでありその取り扱いに細心の注意が必要であり、難燃性の高い肥料とはいえないものである。
【０００４】
難燃性で硝安含量の高い肥料としては、硝安含量が７１〜８０重量％、燐酸がＰ２Ｏ５として３〜５重量％、および石膏等を含む粒状肥料が国内で製造販売されている。また、輸入肥料として硝酸アンモニア石灰との名称で、硝安含量が７１〜７７重量％、石膏をＣａＯとして１０重量％程度含む粒状肥料が販売されており、これらは酸化性物質としての危険性は少ないものである。
【０００５】
これら硝安を主成分とする粒状肥料のもう一つの欠点は、長期間保存すると粒が膨潤し粉粉になることである。この現象については古くから検討がなされており、いくつかの報告がある。非特許文献１によれば、この硝安の膨潤、粉化は硝安の４型結晶から３型結晶への３２．５℃における結晶転移によるものであり、硝安にＭｇＯを０．２５％とＣａＯを０．３４％添加したり、硝安に３％程度の硝酸カリウムを添加することなどで防止できると記載されている。
【０００６】
しかし、これらの効果は硝安含量が８５％を超える純度のものであり、また、硝安の膨潤、粉化防止期間としても２０サイクル以下の短い期間であった。現実の難燃化した硝安肥料は前述のように燐酸や石膏を含んでおり、また、膨潤、粉化が２年〜３年の期間起こらない安定した肥料が求められている。このような肥料を工業的に生産、販売することは困難であった。
【０００７】
また、硝安を主成分とする被覆粒状肥料は硝安の欠点である肥効の短さと窒素成分の流亡を改善した肥料として、広く使用されている。被覆粒状肥料の製造については、特許文献１、特許文献２等に記載されている。
しかしながら、硝安系の被覆粒状肥料において使用する原肥が膨潤すると被覆被膜に亀裂が発生し、被覆効果を損なうため大きな問題を起こす。現実に販売されている肥料は２年程度の保管で比較的高温にさらされている部分が膨潤を起こし、被膜に亀裂が発生することが多い。この原因について、原肥として使用している硝安を主成分とする粒状肥料の問題と関連づけて検討を行った報告はなかった。
尚、硝安含量の少ない肥料では多くの場合かなりの量の燐酸成分やカリウム成分が添加されており、上記の膨潤、粉化が起こることは観察されていない。
【０００８】
【特許文献１】
特公昭５４−３１０４号公報
【特許文献２】
特公昭６０−２１９５２号
【非特許文献１】
安藤淳平著「化学肥料の研究」、株式会社日進出版発行（１９６５年）
【０００９】
【発明が解決しようとする課題】
本発明が解決しようとする課題は上述したように難燃性で長期間保存しても膨潤、粉化しない硝安を主成分とする粒状肥料および被覆粒状肥料を供給することである。
【００１０】
【発明を解決するための手段】
本発明者らは上記問題点について鋭意検討した結果、硝安に特定量のカリウム成分と特定量の燐酸成分を添加することにより、硝安の含量が高くても難燃性と保存安定性に優れた粒状肥料および被覆粒状肥料が得られるとの知見を得て、本発明を完成するに至った。
【００１１】
即ち本発明は、次の（１）、（２）である。
（１）安定剤としてカリウム成分をＫ２Ｏとして０．５〜５重量％、難燃性付与剤として燐酸成分をＰ２Ｏ５として２〜５重量％、および硝酸アンモニウムを７０〜８５重量％含むことを特徴とする難燃性と保存安定性に優れた粒状硝安肥料。
（２）上記（１）に記載の粒状硝安肥料１００重量部を樹脂含有被膜１〜３０重量部で被覆したことを特徴とする難燃性と保存安定性に優れた被覆粒状硝安肥料。
【００１２】
【発明の実施の形態】
本発明における粒状硝安肥料とは、硝安を主成分とするものであり、具体的には硝安を７０〜８５重量％含むものである。即ち、硝酸態窒素およびアンモニア態窒素を窒素として各々１２．２５〜１４．８８重量％含む。また、硝酸カリウムや硝酸カルシウムなどの硝酸態窒素含量はそれぞれ１３．８、１７．１重量％であり、硫酸アンモニウム、塩化アンモニウムのアンモニア態窒素含量はそれぞれ２１．２、２６．２重量％であるので、アンモニア態窒素を含まない硝酸カルシウムや硝酸カリウムと硝酸態窒素を含まない塩安、硫安等の混合物では硝酸態窒素およびアンモニア態窒素の両者が１２．２５重量％以上になることはない。
【００１３】
本発明において安定剤として使用するカリウム成分は、水溶性のカリウムを含むものであればいずれでも良く、例えば硝酸カリウム、塩化カリウム、硫酸カリウム、燐酸水素二カリウム、燐酸二水素カリウム等肥料に混合可能なカリウム塩が使用できる。カリウム成分の含量は肥料分析法における水溶性Ｋ２Ｏとして、０．５〜５重量％が必要である。カリウム含量がこの範囲よりも少ないと、長期に亘る膨潤、粉化防止効果を達成できなくなり、また、多い場合には窒素、燐酸、カリウムの保証成分に対する余裕が少なくなり製造時の合格率の低下や経済的な問題が発生する。
【００１４】
本発明において難燃性付与剤として使用する燐酸成分は、肥料分析法における苦溶性リンまたは水溶性リンであればいずれのものも使用できる。一例をあげれば、燐酸二水素アンモニウム、燐酸水素二アンモニウム、燐酸水素二カリウム、燐酸水素カルシウム、燐酸カルシウム等の化合物を単独または混合して使用することができる。燐酸成分の含量はＰ２Ｏ５として２〜５重量％が好ましく、この含量よりも少ないと難燃性付与が充分でなく還元性物質との接触、混合により引火することがある。また、この量よりも多い場合には、窒素、燐酸、カリウムの保証成分に対する余裕が少なくなり製造時の合格率の低下や経済的な問題が発生する。
【００１５】
本発明の粒状硝安肥料には、上記の成分以外に造粒助剤として少量の石膏、カオリン、タルクなどの難水溶性の無機物、造粒バインダーとしての少量の糖蜜、デンプン糊やポリビニールアルコールなどを含んでいても良い。
【００１６】
本発明の粒状硝安肥料の製造方法は、高濃度の硝酸液に上記のカリウム成分や燐酸成分を溶解または分散させてアンモニアで中和し、濃縮し、回転ドラム造粒機や圧縮造粒機等で１〜１０ｍｍの粒度に造粒し、乾燥後冷却する方法や、カリウム成分や燐酸成分の粉末に濃厚硝安液をスプレーして１〜１０ｍｍの粒度に造粒し、乾燥後冷却する方法等の通常の方法が用いられる。カリウム成分や燐酸成分を粉末のまま使用する場合や分散させて使用する場合には、その粒度を０．２ｍｍ以下の微粉末として使用することが好ましい。また、カリウム成分や燐酸成分を溶解させて使用する方法が、成分の均一性を保てることから特に好ましい。
また、粒状硝安肥料の形状は、球状、ラグビーボール状、小型円柱状などであって、その球相当径が１〜１０ｍｍの範囲であればよい。被覆粒状硝安肥料の原料とするものは、角がなく表面が滑らかな球状に近い形状のものが好ましい。
【００１７】
本発明の被覆粒状硝安肥料は、上記の粒状硝安肥料を樹脂含有被膜で被覆し、肥料成分が長期に亘りゆっくりと溶け出すようにしたものであり、他の被覆肥料の製造と同様な被膜組成で、同様な方法で製造することができる。
【００１８】
被覆に使用する被膜材とは、樹脂を含むものであり、溶出速度を調整するためのノニオン系界面活性剤や無機系および有機系充填剤を含有していてもよい。被膜材の樹脂としては従来の被覆肥料に使用されているものと同様な樹脂が使用できる。樹脂の種類としてはポリエチレン、ポリエチレンワックス、ポリプロピレン、エチレン−酢酸ビニル共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリ（メタ）アクリル酸エステル、ポリカプロラクトン、ポリ乳酸、アルキレングリコールと脂肪酸ジカルボン酸からなる脂肪族ポリエステル等の熱可塑性樹脂、ポリウレタン、アルキッド樹脂などの熱硬化性樹脂などが使用できる。
【００１９】
被膜材の樹脂として、熱可塑性樹脂を使用する場合には、内容物の溶出速度を調節するために、「低透湿性ポリマー」と「高透湿性ポリマー」とを混合して使用することが好ましい。低透湿性ポリマーとは、厚さ２００μｍの該ポリマーのフィルム状成型物について、ＡＳＴＭ Ｅ９６記載のＥ法にて測定された透湿度が２０ｇ／２４ｈ／ｍ２未満のポリマーであり、例えばポリエチレン、ポリプロピレン、ポリブテンおよびこれらの共重合体などである。高透湿性ポリマーとは、厚さ２００μｍの該ポリマーのフィルム状成型物について、ＡＳＴＭ−Ｅ９６記載のＥ法にて測定された透湿度が２０ｇ／２４ｈ／ｍ２以上のポリマーであり、例えばエチレン−酢酸ビニル共重合体、ポリ（メタ）アクリル酸エステル、エチレン−アクリル酸共重合体、ポリカプロラクトン、ポリ乳酸、ポリエステルなどである。
【００２０】
また、溶出速度を高めるためにノニオン系の界面活性剤、ポリエチレングリコール、ポリアクリル酸等の水溶性ポリマー等を少量添加することもできる。ただし、これらの配合量はポリマー１００重量部に対して１０重量部以下が好ましい。この量より多いと被膜の強度が大幅に低下する。また、溶出速度を調節するためにタルク、クレー、カオリン、ベントナイト等の無機系充填剤および／または澱粉、寒天、キトサン、架橋ポリスチレン等の有機充填剤を使用することができる。これらの充填剤の配合量は、ポリマー１００重量部に対して１２０重量部以下が好ましい。この量よりも多いと、バインダーとしてのポリマー量が不足し強度の大幅な低下と溶出が著しく速くなり、被覆の効果が減少する。
【００２１】
粒状硝安肥料を被覆する被膜の重量は粒状肥料１００重量部に対し１〜３０重量部であり、好ましくは、３〜２０重量部、さらに好ましくは、５〜１５重量部である。この下限を逸脱すると、肥料としての溶出成分のコントロールが困難となる。また、この上限を逸脱すると、肥料としての品位の低下という問題が生じる。
【００２２】
本発明の被覆粒状硝安肥料の粒子径に特に制限はないが、通常１〜１０ｍｍである。被覆粒状肥料の形状は原肥の形状にも依存するが、球状に近いことが好ましく、凹凸のない滑らかな真球状に近いものが特に好ましい。
【００２３】
本発明の被覆肥料は従来公知の方法で製造することができる。即ち、噴流ないしは転動装置に粒状肥料を導入し、次にこの装置を所定温度に保持しながら、所定の物質を所定量含有する分散（溶）液を供給することにより目的のものを製造することができる。以下にその製造方法について述べる。
【００２４】
噴流装置ないし転動装置は従来公知のものを使用することができる。これらの装置については、例えば、前記特許文献１に開示されている。即ち、噴流塔や転動槽本体に、熱風を送風するためのブロアー、被覆用分散（溶）液を送液するための溶液ポンプ、及びスプレーノズル、温度計などを取り付けた装置である。該装置内に被覆しようとする粒状肥料を導入し、ブロアー等から所定の温度のガスを送風する。噴流塔の場合には装置内で肥料の噴流が安定に起こるように調整する。装置内が所望の温度になったら、スプレーノズルから所定の分散（溶）液を供給することにより粒状肥料の表面に被膜を形成させることができる。
【００２５】
【実施例】
以下に本発明の実施例、及び比較例を具体的に示す。なお、実施例、比較例中の試験は下記の方法によった。
【００２６】
＜被覆肥料の溶出試験＞
５重量部の被覆粒状肥料を最大容水量の６０％に調製した富士市新藤間土壌２００重量部に分散して埋設した。このサンプルは同一の要領で調製したものを複数個準備し、２５℃の恒温槽に保管した。一定時間経過毎に肥料粒子を土壌から回収し、残留している肥料成分を肥料分析法に基づいて測定した。溶出率は、もとの被覆肥料に含まれていた肥料成分に対する溶出してきた成分の百分率で表示する。
【００２７】
［実施例１］
硝安系肥料（くみあい燐硝安２９０３（成分保証値：アンモニア態窒素１４．９％、硝酸態窒素１４．１％、燐酸成分３．０％含有）旭化成（株）製）を粉砕し、硫酸カリウム（試薬１級）を硝安系肥料１００ｇに対して各々１，２，４，８ｇを２００ｍｌのビーカー中で添加、混合した。その後、各々のビーカーに水を２０ｍｌ添加し、１００℃まで加熱、スラリー状とし、１５時間水分が蒸発しないように蓋をし、温度を維持した。その後、蓋を外し、１２０℃の温度で濃縮、乾燥した。乾燥品を取り出し、粉砕して得た各々の混合物粉末を内径６ｍｍ、長さ５０ｍｍの穴のあいたステンレスブロックの穴に各々０．５ｇずつ投入し、ピストンを挿入し、上部から５００ｋｇの荷重をかけ５分間放置後、荷重を外し、成型品を取り出した。このようにして、直径６ｍｍの小型円柱状成型品を硫酸カリウム添加量毎に１０本作った。成型品の水分は０．３〜０．６重量％と低かった。
【００２８】
硫酸カリウム添加品を吸湿防止のためポリエチレンの袋に入れ、４５℃×１２時間その後２０℃×１２時間の温度に設定したヒートサイクル試験装置の中にいれ、一定時間毎にサンプルを取り出し、棒状加圧成型品の外観および直径を測定した。
結果を表１に示す。尚、直径は１０本の平均値である。
【００２９】
【表１】
【００３０】
［比較例１］
実施例１で使用した硫酸カリウムの替わりに、硫酸カルシウム２水塩（試薬１級、以下石膏と略記）を使用した以外は同様の試験を行った。結果を表２に示す。
【００３１】
【表２】
【００３２】
［実施例２］
硝酸アンモニウム（試薬１級）、燐酸二水素アンモニウム（試薬１級）、硫酸カリウム（試薬１級）各々を１ｍｍのスクリーンを有する奈良式粉砕機で粉砕し、０．２５ｍｍの目開きの篩で篩い、０．２５ｍｍ以下の微粉末を得た。硝酸アンモニウム微粉末８３重量部と燐酸二水素アンモニウム微粉末６重量部と硫酸カリウム微粉末２重量部と石膏２水塩（試薬１級）４重量部およびカオリン（はく陶土、試薬）５重量部とを造粒機（アイリッヒミキサーを使用）に投入し、攪拌混合後、攪拌しながら約５重量部の水を徐々に加え造粒した。粒径が２〜４ｍｍ程度になった時点で攪拌を止め、粒状肥料を造粒機より取り出し、１２０℃の乾燥機で一晩乾燥した。乾燥後、粒状肥料を篩いにかけ粒径が２〜４ｍｍの燐硝安カリ粒状肥料５２重量部を得た。水分率によりヒートサイクルによる粉化の発生率、大量燃焼性試験による危険性判断が異なるので水分率は１％に調整した。また、粒度の異なる肥料は粉砕し再造粒することができる。
【００３３】
得られた燐硝安カリ粒状肥料について実施例１と同じ条件のヒートサイクル試験を行い、１００サイクル目の粉化率を測定した。粉化率は１ｍｍの目開きの篩いに試料を入れ５分間篩い１ｍｍ以下の粉の重量を篩いに入れた重量で割り求めた。また、消防法に規定される危険物１類（酸化性固体）に該当するかを判定するために、「大量燃焼性試験」を実施した。「大量燃焼性試験」については、「危険物確認試験実施マニュアル」新日本法規出版発行、に基づき実施した。結果を表３に示す。
【００３４】
［比較例２］
燐酸二水素アンモニウム微粉末を使用せず、カオリンを１１重量部とした以外は実施例２と同様にし、粒径が２〜４ｍｍの硝安カリ粒状肥料４６重量部を得た。
得られた硝安カリ粒状肥料を実施例１と同じ条件のヒートサイクル試験を行い、１００サイクル目の粉化率を測定した。また、消防法に規定される危険物１類（酸化性固体）に該当するかを判定するために、「大量燃焼性試験」を実施した。結果を表３に纏めて示す。
【００３５】
［比較例３］
硫酸カリウム微粉末を使用せず、カオリンを７重量部とした以外は実施例２と同様にし、粒径が２〜４ｍｍの燐硝安粒状肥料を５８重量部得た。
得られた燐硝安粒状肥料を実施例１と同じ条件のヒートサイクル試験を行い、１００サイクル目の粉化率を測定した。また、消防法に規定される危険物１類（酸化性固体）に該当するかを判定するために、「大量燃焼性試験」を実施した。結果を表３にまとめて示す。
【００３６】
【表３】
【００３７】
［実施例３］
実施例２と同様にして製造した燐硝安カリ粒状肥料を原料とし被覆粒状硝安肥料を製造した。即ち、エチレン・酢酸ビニル共重合体（商品名 エバフレックス３１０、三井デュポンポリケミカル（株）製）１．５重量部、ポリエチレン（商品名 サンテック２２７０、旭化成（株）製）２．０重量部に２００重量部のテトラクロルエチレンを加え、該溶剤の沸点まで加熱リフラックスさせてこれらを溶解した。さらにこの溶液にタルク４．０重量部を加え、十分攪拌して分散液を調整した。実施例２の粒状硝安系肥料（Ｎ、Ｐ２Ｏ５、Ｋ２Ｏ成分は各々２９．５％、３．６％、１．１％）１００重量部を噴流装置に投入し、熱風を送風して装置内の温度が６０℃で安定な噴流状態を起こさせた。次に、上記で調製した分散液を送液ポンプによりスプレーノズルから１０分を要して噴流装置に供給した。この間、噴流装置内は６５±２℃となるよう熱風の温度を調節した。その後、熱風を冷風に切り替え、３５℃以下になった時点で噴流装置から内容物を取り出した。
【００３８】
製造された被覆肥料は１０７．５重量部であり、供給された固形分のほぼ全量が、被覆されていることがわかった。この被覆粒状硝安肥料溶出率を測定したところ、２５℃の土壌中では含まれる肥料成分の８０％が溶出する日数は１００日であった。
得られた被覆粒状硝安系肥料を実施例１と同様にポリエチレンの袋に入れ同条件のヒートサイクル試験機で保存性を評価した。結果を表４に示す。
【００３９】
［比較例４］
比較例３と同様にして製造した燐硝安粒状肥料を使用し、実施例３と同様な条件で被覆粒状硝安肥料を製造した。得られた被覆肥料は１０７．５重量部であり、２５℃の土壌中では含まれる肥料成分の８０％が溶出する日数は９８日であった。
得られた被覆粒状硝安系肥料を実施例１と同様にポリエチレンの袋に入れ同条件のヒートサイクル試験機で保存性を評価した。結果を表４に示す。
【００４０】
【表４】
【００４１】
【発明の効果】
以上述べたように本発明によれば、硝安を主成分とする肥料に所定量のカリウム成分と所定量の燐酸成分を添加することにより、有機肥料等の有機物を混合しても混合危険性の少なく、また温度変化の大きい屋外に保存しても保存安定性に優れた粒状硝安肥料を提供することが可能である。また、同様にカリウム成分と燐酸成分を添加した粒状硝安肥料を樹脂含有被膜で被覆することにより、危険性の少ない保存安定性に優れた被覆粒状硝安肥料を提供することが可能である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a granular fertilizer mainly containing ammonium nitrate, which is important as a chemical fertilizer, and a coated granular ammonium fertilizer obtained by coating the granular fertilizer with a film containing a resin such as polyolefin.
[0002]
[Prior art]
Fertilizers containing ammonium nitrate (hereinafter abbreviated as ammonium nitrate) as a main component contain a large amount of nitrogen components and a large amount of nitrate nitrogen which is rapidly absorbed in the field, so that the fertilizer is a field effect in a cold region where nitrification in soil is slow. As important. However, ammonium nitrate is a compound with strong oxidizing power, and high-purity compounds show explosive properties by mixing a small amount of organic substances. I have. Granular fertilizer mainly composed of ammonium nitrate is blended with other granular nitrogen fertilizers, granular potassium fertilizers, and granular phosphate fertilizers, and is often used as a raw material for blending fertilizers containing nitrogen, phosphoric acid, and potassium. Desired.
[0003]
Fertilizers with a nitrate content of about 90% by weight are subject to restrictions on storage and mixing as oxidizing substances, require careful handling, and cannot be said to be highly flame-retardant fertilizers. .
[0004]
The high ammonium nitrate content manure flame retardant, ammonium nitrate content of 71 to 80 wt%, phosphoric acid 3-5% by weight as P 2 O 5, and granular fertilizer containing gypsum manufactured and sold domestically. In addition, granular fertilizers containing ammonium nitrate content of 71 to 77% by weight and gypsum of about 10% by weight as CaO are sold as imported fertilizers under the name of ammonium nitrate lime, and these are less dangerous as oxidizing substances. Things.
[0005]
Another disadvantage of these particulate fertilizers based on ammonium nitrate is that when stored for a long period of time, the particles swell and turn into powder. This phenomenon has been studied for a long time, and there are several reports. According to Non-Patent Document 1, this swelling and pulverization of ammonium nitrate is due to a crystal transition at 32.5 ° C. from a type 4 crystal to a type 3 crystal of ammonium nitrate. It is described that it can be prevented by adding 0.34% or adding about 3% potassium nitrate to ammonium nitrate.
[0006]
However, these effects were those having a purity of more than 85% ammonium nitrate, and also had a short period of 20 cycles or less as a period for preventing swelling and powdering of ammonium nitrate. The actual flame-retardant nitric acid fertilizer contains phosphoric acid or gypsum as described above, and a stable fertilizer that does not swell or powder for a period of two to three years is required. It was difficult to industrially produce and sell such fertilizers.
[0007]
In addition, coated granular fertilizer containing ammonium nitrate as a main component is widely used as a fertilizer in which the shortcoming of fertilizer which is a disadvantage of ammonium nitrate and the elimination of nitrogen component are improved. The production of coated granular fertilizer is described in Patent Documents 1 and 2, and the like.
However, when the raw fertilizer used in the nitrate-based coated granular fertilizer swells, a crack is generated in the coated film, which impairs the coating effect, causing a serious problem. In fertilizers actually sold, portions that are exposed to relatively high temperatures after storage for about two years often swell, and cracks often occur in the coating. There was no report that examined the cause in connection with the problem of granular fertilizers mainly composed of ammonium nitrate used as raw manure.
In many cases, fertilizers having a small amount of ammonium nitrate contain a considerable amount of a phosphoric acid component or a potassium component, and the above-mentioned swelling and powdering are not observed.
[0008]
[Patent Document 1]
Japanese Patent Publication No. 54-3104 [Patent Document 2]
Japanese Patent Publication No. 60-19552 [Non-Patent Document 1]
Junpei Ando, "Research on Chemical Fertilizers", published by Nisshin Shuppan Co., Ltd. (1965)
[0009]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to supply a granular fertilizer and a coated granular fertilizer containing ammonium nitrate as a main component, which is flame-retardant and does not swell or powder even after long storage as described above.
[0010]
[Means for Solving the Invention]
The present inventors have conducted intensive studies on the above problems, and as a result, by adding a specific amount of a potassium component and a specific amount of a phosphoric acid component to ammonium nitrate, excellent flame retardancy and storage stability even at a high ammonium nitrate content. The knowledge that granular fertilizers and coated granular fertilizers can be obtained has led to the completion of the present invention.
[0011]
That is, the present invention includes the following (1) and (2).
(1) 0.5 to 5% by weight of a potassium component as K 2 O as a stabilizer, 2 to 5% by weight of a phosphoric acid component as P 2 O 5 as a flame retardant, and 70 to 85% by weight of ammonium nitrate A granular ammonium fertilizer having excellent flame retardancy and storage stability.
(2) A coated granular ammonium fertilizer excellent in flame retardancy and storage stability, characterized in that 100 parts by weight of the granular nitrate fertilizer described in (1) above is coated with 1 to 30 parts by weight of a resin-containing coating.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The granular nitric acid fertilizer in the present invention contains ammonium nitrate as a main component, and specifically contains 70 to 85% by weight of ammonium nitrate. That is, each contains 12.25 to 14.88% by weight of nitrate nitrogen and ammonia nitrogen as nitrogen. The nitrate nitrogen contents of potassium nitrate and calcium nitrate are 13.8 and 17.1% by weight, respectively, and the ammonium nitrogen contents of ammonium sulfate and ammonium chloride are 21.2 and 26.2% by weight, respectively. In a mixture of calcium nitrate or potassium nitrate not containing ammonium nitrogen and ammonium salt or ammonium sulfate not containing nitrate nitrogen, both nitrate nitrogen and ammonia nitrogen do not exceed 12.25% by weight.
[0013]
The potassium component used as a stabilizer in the present invention may be any one containing water-soluble potassium, and can be mixed with fertilizers such as potassium nitrate, potassium chloride, potassium sulfate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate. Potassium salts can be used. The content of potassium component as a water-soluble K 2 O in the fertilizer analysis, it is necessary 0.5 to 5 wt%. If the potassium content is less than this range, swelling and powdering prevention effects cannot be achieved for a long period of time, and if it is too large, there is less room for guaranteed components of nitrogen, phosphoric acid, and potassium, and the pass rate during production decreases. And economic problems arise.
[0014]
As the phosphoric acid component used as the flame retardant in the present invention, any of phosphorus-soluble or water-soluble phosphorus in a fertilizer analysis method can be used. For example, compounds such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate and calcium phosphate can be used alone or in combination. The content of the phosphoric acid component is preferably 2 to 5% by weight as P 2 O 5. If the content is less than this, the flame retardancy may not be sufficiently imparted, and the mixture may be ignited by contact with or mixing with a reducing substance. On the other hand, if the amount is larger than the above, there is less room for the guaranteed components of nitrogen, phosphoric acid, and potassium, which lowers the pass rate at the time of production and causes economic problems.
[0015]
In the granular nitric acid fertilizer of the present invention, in addition to the above components, a small amount of gypsum as a granulation aid, a poorly water-soluble inorganic substance such as kaolin, talc, a small amount of molasses as a granulation binder, starch paste and polyvinyl alcohol, etc. May be included.
[0016]
The method for producing a granular ammonium nitrate fertilizer according to the present invention comprises dissolving or dispersing the potassium component or the phosphoric acid component in a high-concentration nitric acid solution, neutralizing with ammonia, and concentrating the concentrated nitric acid solution. A method of granulating to a particle size of 1 to 10 mm, cooling after drying, a method of spraying a concentrated ammonium nitrate solution on a powder of a potassium component or a phosphoric acid component, granulating to a particle size of 1 to 10 mm, cooling after drying, and the like. Normal methods are used. When the potassium component or the phosphoric acid component is used as it is or in a dispersed state, it is preferable to use the powder as a fine powder having a particle size of 0.2 mm or less. Further, a method of dissolving and using a potassium component or a phosphoric acid component is particularly preferable because the uniformity of the components can be maintained.
The shape of the granular nitrate fertilizer may be a sphere, a rugby ball, a small column, or the like, and the equivalent diameter of the sphere may be in the range of 1 to 10 mm. It is preferable that the raw material of the coated granular nitrate fertilizer has a shape close to a spherical shape with no corners and a smooth surface.
[0017]
The coated granular nitric acid fertilizer of the present invention is obtained by coating the above-mentioned granular nitric acid fertilizer with a resin-containing coating so that the fertilizer component slowly dissolves over a long period of time, and has the same coating composition as in the production of other coated fertilizers. Then, it can be manufactured by a similar method.
[0018]
The coating material used for coating contains a resin, and may contain a nonionic surfactant or an inorganic or organic filler for adjusting the dissolution rate. As the resin of the coating material, the same resin as that used in the conventional coated fertilizer can be used. Examples of resins include polyethylene, polyethylene wax, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, poly (meth) acrylate, polycaprolactone, polylactic acid, alkylene glycol and fatty acid dicarboxylic acid. A thermoplastic resin such as an aliphatic polyester made of, or a thermosetting resin such as a polyurethane or an alkyd resin can be used.
[0019]
When using a thermoplastic resin as the resin of the coating material, it is preferable to use a mixture of “low moisture permeable polymer” and “high moisture permeable polymer” in order to adjust the dissolution rate of the contents. . The low moisture permeable polymer is a polymer having a moisture permeability of less than 20 g / 24 h / m 2 as measured by a method E described in ASTM E96 for a film-shaped molded product of the polymer having a thickness of 200 μm. , Polybutene and copolymers thereof. The high moisture polymer, the film-like molded product of the polymer of the thickness 200 [mu] m, an ASTM-E96 moisture permeability 20g / 24h / m 2 or more polymers as measured by Method E described, for example, ethylene - Examples include vinyl acetate copolymer, poly (meth) acrylate, ethylene-acrylic acid copolymer, polycaprolactone, polylactic acid, and polyester.
[0020]
In order to increase the dissolution rate, a small amount of a nonionic surfactant, a water-soluble polymer such as polyethylene glycol or polyacrylic acid can be added. However, the amount of these compounds is preferably 10 parts by weight or less based on 100 parts by weight of the polymer. If the amount is more than this, the strength of the coating is greatly reduced. In order to control the dissolution rate, an inorganic filler such as talc, clay, kaolin, bentonite and / or an organic filler such as starch, agar, chitosan and cross-linked polystyrene can be used. The amount of these fillers is preferably 120 parts by weight or less based on 100 parts by weight of the polymer. If the amount is larger than this amount, the amount of the polymer as the binder is insufficient, so that the strength is greatly reduced and the elution is remarkably accelerated, and the effect of coating is reduced.
[0021]
The weight of the coating covering the granular ammonium fertilizer is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and more preferably 5 to 15 parts by weight based on 100 parts by weight of the granular fertilizer. Exceeding this lower limit makes it difficult to control the eluted components as fertilizer. In addition, when the value exceeds the upper limit, there is a problem that the quality of the fertilizer decreases.
[0022]
Although the particle size of the coated granular ammonium fertilizer of the present invention is not particularly limited, it is usually 1 to 10 mm. The shape of the coated granular fertilizer also depends on the shape of the raw fertilizer, but is preferably close to a sphere, particularly preferably a smooth true sphere without irregularities.
[0023]
The coated fertilizer of the present invention can be produced by a conventionally known method. That is, a granular fertilizer is introduced into a jet or tumbling device, and then a dispersion (solution) containing a predetermined amount of a predetermined substance is supplied while maintaining the device at a predetermined temperature to produce a desired product. be able to. The manufacturing method will be described below.
[0024]
A conventionally known jet device or rolling device can be used. These devices are disclosed, for example, in Patent Document 1. That is, it is a device in which a blower for sending hot air, a solution pump for sending a dispersion (solution) solution for coating, a spray nozzle, a thermometer, and the like are attached to the jet tower and the rolling tank body. A granular fertilizer to be coated is introduced into the device, and a gas at a predetermined temperature is blown from a blower or the like. In the case of a spout tower, it is adjusted so that a spout of fertilizer occurs stably in the apparatus. When the temperature inside the device reaches a desired temperature, a coating film can be formed on the surface of the granular fertilizer by supplying a predetermined dispersion (solution) solution from a spray nozzle.
[0025]
【Example】
Hereinafter, examples of the present invention and comparative examples will be specifically described. In addition, the test in an Example and a comparative example was based on the following method.
[0026]
<Dissolution test of coated fertilizer>
5 parts by weight of the coated granular fertilizer was dispersed and buried in 200 parts by weight of Shintoma soil in Fuji City, which was adjusted to 60% of the maximum water capacity. A plurality of samples prepared in the same manner were prepared and stored in a thermostat at 25 ° C. Fertilizer particles were collected from the soil at regular intervals, and the remaining fertilizer components were measured based on the fertilizer analysis method. The elution rate is expressed as a percentage of the eluted component relative to the fertilizer component contained in the original coated fertilizer.
[0027]
[Example 1]
Nitrate fertilizer (Kumiai Phosphorus Nitric Acid 2903 (guaranteed component: ammonia nitrogen 14.9%, nitrate nitrogen 14.1%, phosphoric acid component 3.0%) manufactured by Asahi Kasei Corporation) was pulverized and potassium sulfate ( Reagent 1) was added and mixed in a 200 ml beaker with 1, 2, 4, 8 g each to 100 g of ammonium nitrate fertilizer. Thereafter, 20 ml of water was added to each beaker, heated to 100 ° C. to form a slurry, and covered for 15 hours to prevent evaporation of water, and the temperature was maintained. Thereafter, the lid was removed, and the mixture was concentrated and dried at a temperature of 120 ° C. The dried product was taken out, pulverized, and each mixed powder obtained was put into a hole of a stainless steel block having an inner diameter of 6 mm and a length of 50 mm by 0.5 g each, a piston was inserted, and a 500 kg load was applied from above. After standing for 5 minutes, the load was removed and the molded product was taken out. In this way, 10 small cylindrical molded articles having a diameter of 6 mm were prepared for each amount of added potassium sulfate. The water content of the molded product was as low as 0.3 to 0.6% by weight.
[0028]
The potassium sulfate-added product was placed in a polyethylene bag to prevent moisture absorption, placed in a heat cycle test apparatus set at 45 ° C x 12 hours, and then set at a temperature of 20 ° C x 12 hours. The appearance and diameter of the pressed product were measured.
Table 1 shows the results. The diameter is an average value of 10 pieces.
[0029]
[Table 1]
[0030]
[Comparative Example 1]
A similar test was performed except that calcium sulfate dihydrate (reagent first grade, hereinafter abbreviated as gypsum) was used instead of potassium sulfate used in Example 1. Table 2 shows the results.
[0031]
[Table 2]
[0032]
[Example 2]
Each of ammonium nitrate (reagent first grade), ammonium dihydrogen phosphate (reagent first grade), and potassium sulfate (reagent first grade) is pulverized with a Nara type pulverizer having a 1 mm screen, and sieved with a 0.25 mm mesh sieve. A fine powder of 0.25 mm or less was obtained. 83 parts by weight of ammonium nitrate fine powder, 6 parts by weight of ammonium dihydrogen phosphate fine powder, 2 parts by weight of potassium sulfate fine powder, 4 parts by weight of gypsum dihydrate (reagent first grade) and 5 parts by weight of kaolin (removable clay, reagent) Was charged into a granulator (using an Erich mixer), and after stirring and mixing, about 5 parts by weight of water was gradually added while stirring to granulate. When the particle size became about 2 to 4 mm, the stirring was stopped, the granular fertilizer was taken out of the granulator, and dried overnight in a dryer at 120 ° C. After drying, the granular fertilizer was sieved to obtain 52 parts by weight of potassium phosphate nitrate granular fertilizer having a particle size of 2 to 4 mm. The moisture content was adjusted to 1% because the occurrence rate of powdering by the heat cycle and the risk judgment by the mass flammability test differed depending on the moisture content. Further, fertilizers having different particle sizes can be crushed and re-granulated.
[0033]
A heat cycle test was performed on the obtained phosphoric acid nitrate potassium granular fertilizer under the same conditions as in Example 1, and the powdering rate at the 100th cycle was measured. The powdering ratio was determined by placing a sample on a sieve having a mesh opening of 1 mm, sieving for 5 minutes, and dividing the weight of the powder having a size of 1 mm or less by the weight of the sieve. In addition, a "mass flammability test" was performed to determine whether the substance falls under the category of dangerous substances (oxidizing solid) specified by the Fire Service Law. The "mass flammability test" was carried out based on the "Dangerous Goods Confirmation Test Implementation Manual" published by New Japan Law. Table 3 shows the results.
[0034]
[Comparative Example 2]
46 parts by weight of potassium nitrate potassium nitrate having a particle size of 2 to 4 mm were obtained in the same manner as in Example 2 except that 11 parts by weight of kaolin was used without using fine ammonium dihydrogen phosphate powder.
The obtained potassium nitrate potassium granular fertilizer was subjected to a heat cycle test under the same conditions as in Example 1, and the powdering rate at the 100th cycle was measured. In addition, a "mass flammability test" was performed to determine whether the substance falls under the category of dangerous substances (oxidizing solid) specified by the Fire Service Law. The results are summarized in Table 3.
[0035]
[Comparative Example 3]
58 parts by weight of an ammonium phosphate nitrate granular fertilizer having a particle size of 2 to 4 mm were obtained in the same manner as in Example 2 except that kaolin was used in an amount of 7 parts by weight without using the potassium sulfate fine powder.
The obtained phosphoric acid nitrate granular fertilizer was subjected to a heat cycle test under the same conditions as in Example 1, and the powdering rate at the 100th cycle was measured. In addition, a "mass flammability test" was performed to determine whether the substance falls under the category of dangerous substances (oxidizing solid) specified by the Fire Service Law. The results are summarized in Table 3.
[0036]
[Table 3]
[0037]
[Example 3]
A coated granular ammonium nitrate fertilizer was produced using a granular ammonium nitrate potassium fertilizer produced in the same manner as in Example 2. That is, 1.5 parts by weight of an ethylene / vinyl acetate copolymer (trade name: Evaflex 310, manufactured by Mitsui DuPont Polychemicals Co., Ltd.) and 2.0 parts by weight of polyethylene (trade name: Suntec 2270, manufactured by Asahi Kasei Corporation) 200 parts by weight of tetrachloroethylene were added, and these were dissolved by heating and refluxing to the boiling point of the solvent. Further, 4.0 parts by weight of talc was added to the solution, and the mixture was sufficiently stirred to prepare a dispersion. 100 parts by weight of the granular ammonium nitrate fertilizer of Example 2 (N, P 2 O 5 , and K 2 O components are 29.5%, 3.6%, and 1.1%, respectively) are charged into a jet apparatus, and hot air is blown. Then, a stable jet state was generated at a temperature of 60 ° C. in the apparatus. Next, the dispersion liquid prepared above was supplied to the jet apparatus by the liquid feed pump from the spray nozzle in 10 minutes. During this time, the temperature of the hot air was adjusted so that the inside of the jet apparatus became 65 ± 2 ° C. Thereafter, the hot air was switched to cold air, and when the temperature became 35 ° C. or less, the contents were taken out from the jet device.
[0038]
The produced coated fertilizer was 107.5 parts by weight, and it was found that almost all of the supplied solid matter was coated. When the dissolution rate of the coated granular nitrate fertilizer was measured, the number of days in which 80% of the contained fertilizer component was dissolved in the soil at 25 ° C. was 100 days.
The obtained coated granular ammonium nitrate fertilizer was put in a polyethylene bag in the same manner as in Example 1, and the storage stability was evaluated using a heat cycle tester under the same conditions. Table 4 shows the results.
[0039]
[Comparative Example 4]
A coated granular ammonium nitrate fertilizer was produced under the same conditions as in Example 3 using the phosphoric acid nitrate granular fertilizer produced in the same manner as in Comparative Example 3. The obtained coated fertilizer was 107.5 parts by weight, and the number of days that 80% of the contained fertilizer component eluted in the soil at 25 ° C was 98 days.
The obtained coated granular nitrate-based fertilizer was placed in a polyethylene bag in the same manner as in Example 1, and the storage stability was evaluated using a heat cycle tester under the same conditions. Table 4 shows the results.
[0040]
[Table 4]
[0041]
【The invention's effect】
As described above, according to the present invention, by adding a predetermined amount of a potassium component and a predetermined amount of a phosphoric acid component to a fertilizer containing ammonium nitrate as a main component, even if an organic substance such as an organic fertilizer is mixed, there is a risk of mixing. It is possible to provide a granular nitrate fertilizer which has little storage stability and is excellent in storage stability even when stored outdoors with a large temperature change. Similarly, by coating a granular nitric acid fertilizer to which a potassium component and a phosphoric acid component are added with a resin-containing coating, it is possible to provide a coated granular nitric acid fertilizer which is less dangerous and has excellent storage stability.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003152128A JP2004352558A (en) | 2003-05-29 | 2003-05-29 | Ammonium nitrate fertilizer excellent in preservation stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003152128A JP2004352558A (en) | 2003-05-29 | 2003-05-29 | Ammonium nitrate fertilizer excellent in preservation stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004352558A true JP2004352558A (en) | 2004-12-16 |
Family
ID=34047421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003152128A Pending JP2004352558A (en) | 2003-05-29 | 2003-05-29 | Ammonium nitrate fertilizer excellent in preservation stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004352558A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100891198B1 (en) * | 2007-11-15 | 2009-04-06 | 대한민국 | Slow release fertilizer for broad-lefved tree and preparation method thereof |
-
2003
- 2003-05-29 JP JP2003152128A patent/JP2004352558A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100891198B1 (en) * | 2007-11-15 | 2009-04-06 | 대한민국 | Slow release fertilizer for broad-lefved tree and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3148685B1 (en) | Pelletising a polyhalite mineral | |
| WO2017013573A1 (en) | Fertilizer composition and methods of making and using same | |
| AU2016265900B2 (en) | Fertilizer pellets with micronized sulphur | |
| CN110770194A (en) | Synergistic fertilizer with urease inhibitor and nitrification inhibitor in separate granules | |
| AU2018255908A1 (en) | Enhanced efficiency fertilizer with embedded powder composition | |
| BR112019017664A2 (en) | GRANULAR FERTILIZERS THAT UNDERSTAND MACRONUTRIENTS AND MICRONUTRIENTS, AND PROCESSES FOR THE MANUFACTURE OF THE SAME | |
| JPH01190691A (en) | Production of granule of sucrose fatty acid ester | |
| IL110241A (en) | Controlled release fertilizers | |
| JP5753019B2 (en) | Slow-acting fertilizer and method for producing the same | |
| JP2004352558A (en) | Ammonium nitrate fertilizer excellent in preservation stability | |
| Paré et al. | Physical properties of organo-mineral fertilizers--Short Communication. | |
| JP2000053481A (en) | Mixed fertilizer containing coated nitrification suppressor | |
| US10561118B1 (en) | Method of forming a non-dispersible granular substrate and the granular substrates formed thereby | |
| JP6671327B2 (en) | Method for producing granular oxamide | |
| GB2571914A (en) | A process for producing a fertiliser containing boron | |
| JP4097302B2 (en) | Coated granular fertilizer | |
| JP3454298B2 (en) | Coated granular fertilizer with degradable coating | |
| CN107935703A (en) | Urinate base nitro binary compound fertilizer containing nitrogen and potassium production method | |
| JP4302217B2 (en) | Coated granular fertilizer | |
| JP5057541B2 (en) | Production method of granular salt | |
| JPS59182287A (en) | Manufacture of granular fertilizer | |
| PL183939B1 (en) | Method of obtaining granules of ammonium nitrate, potassium and/or magnesium containing artificial fertiliser as well artificial fertiliser obtained thereby | |
| CN116964023A (en) | Sulfur-coated fertilizer with polymer coating | |
| JPH11228273A (en) | Coated granular fertilizer | |
| JP2004217434A (en) | Sigmoid elution type coated granular potassic fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060420 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20070330 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090428 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090512 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090713 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20090713 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090811 |