JP6339815B2 - Lime nitrogen-containing granular fertilizer - Google Patents
Lime nitrogen-containing granular fertilizer Download PDFInfo
- Publication number
- JP6339815B2 JP6339815B2 JP2014021761A JP2014021761A JP6339815B2 JP 6339815 B2 JP6339815 B2 JP 6339815B2 JP 2014021761 A JP2014021761 A JP 2014021761A JP 2014021761 A JP2014021761 A JP 2014021761A JP 6339815 B2 JP6339815 B2 JP 6339815B2
- Authority
- JP
- Japan
- Prior art keywords
- lime nitrogen
- lime
- granular fertilizer
- mass
- containing granular
- 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.)
- Active
Links
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 title claims description 174
- 239000003337 fertilizer Substances 0.000 title claims description 85
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000000292 calcium oxide Substances 0.000 claims description 54
- 235000012255 calcium oxide Nutrition 0.000 claims description 54
- 238000005469 granulation Methods 0.000 claims description 47
- 230000003179 granulation Effects 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229920000877 Melamine resin Polymers 0.000 claims description 36
- 238000005202 decontamination Methods 0.000 claims description 36
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 36
- 239000006259 organic additive Substances 0.000 claims description 33
- 230000003588 decontaminative effect Effects 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 26
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 24
- 239000000920 calcium hydroxide Substances 0.000 claims description 24
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 24
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 22
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 235000013379 molasses Nutrition 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 235000000346 sugar Nutrition 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000006188 syrup Substances 0.000 claims description 3
- 235000020357 syrup Nutrition 0.000 claims description 3
- 150000008163 sugars Chemical class 0.000 claims description 2
- 241000209149 Zea Species 0.000 claims 2
- 238000001035 drying Methods 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 32
- 150000007974 melamines Chemical class 0.000 description 23
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 18
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- UFONUKZQWFSQLP-UHFFFAOYSA-N [N].NC#N Chemical compound [N].NC#N UFONUKZQWFSQLP-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003905 agrochemical Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229960004793 sucrose Drugs 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001934 delay Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011012 sanitization Methods 0.000 description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HQGPAERHHSSKNE-UHFFFAOYSA-N acetonitrile;n-ethylethanamine;hydrate Chemical compound O.CC#N.CCNCC HQGPAERHHSSKNE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004889 fertilizer analysis Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- MBEGFNBBAVRKLK-UHFFFAOYSA-N sodium;iminomethylideneazanide Chemical compound [Na+].[NH-]C#N MBEGFNBBAVRKLK-UHFFFAOYSA-N 0.000 description 2
- -1 specifically Chemical compound 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- RGHNJXZEOKUKBD-MGCNEYSASA-N D-galactonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-MGCNEYSASA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 238000002013 hydrophilic interaction chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Glanulating (AREA)
- Fertilizers (AREA)
Description
本発明は、石灰窒素含有粒状肥料に関する。 The present invention relates to a lime nitrogen-containing granular fertilizer.
石灰窒素は工業的にはカルシウムカーバイドを窒化して製造されるため、通常約１３重量％〜２０重量％程度のＣａＯを含有している。未消和の粉状の石灰窒素を原料に用いて粒状肥料を製造する場合、造粒後においてもなおＣａＯが残存しており、造粒時に使用するバインダーの水分や石灰窒素以外の肥料が含む水分、長期的には空気中の水分と反応して体積膨張を起こし、最終的には造粒した肥料を崩壊させたり、風化粉が発生したりするという不都合が生じることがある。 Since lime nitrogen is industrially produced by nitriding calcium carbide, it usually contains about 13 to 20% by weight of CaO. When granular fertilizer is produced using raw powdered lime nitrogen as raw material, CaO still remains after granulation, and it contains fertilizers other than moisture and lime nitrogen used in the granulation. It may react with moisture, and in the long term, moisture in the air to cause volume expansion, and eventually the granulated fertilizer may be destroyed or weathered powder may be generated.
このため、賦型時にＣａＯを消和するか、または賦型前の原料の段階で石灰窒素中のＣａＯを消和することが必要であり、粉状石灰窒素のみを原料に用いて粒状石灰窒素を製造する場合では、未消和石灰窒素中のＣａＯ含量を可能な限り低減する必要がある。 For this reason, it is necessary to neutralize CaO at the time of shaping, or to eliminate CaO in lime nitrogen at the stage of the raw material before shaping, and granular lime nitrogen using only powdered lime nitrogen as the raw material In the case of manufacturing the CaO, it is necessary to reduce the CaO content in the unslaked lime nitrogen as much as possible.
ＣａＯを消和するに当たっては、消和反応時の温度条件は高温である方が効率的ではあるが、反面、石灰窒素の主成分であるカルシウムシアナミド自体の加水分解反応も進みアンモニアとして揮散したり、肥料成分として肥料取締法上、含有量に制限のあるジシアンジアミドや不純物のメラミンやメラミン誘導体などの副生物の産生が無視できなくなる。逆に、副生物の生成を抑えることができる低温では、消和反応が進みにくいという問題点を抱えている。 In dehydrating CaO, it is more efficient if the temperature condition during the decontamination reaction is high, but on the other hand, the hydrolysis reaction of calcium cyanamide itself, which is the main component of lime nitrogen, advances and volatilizes as ammonia. As a fertilizer component, production of by-products such as dicyandiamide and impurities such as melamine and melamine derivatives, which are limited in terms of fertilizer control law, cannot be ignored. On the other hand, there is a problem that the soothing reaction is difficult to proceed at a low temperature at which the production of by-products can be suppressed.
上記事情のために、石灰窒素の消和方法に関して、消和温度、水の添加量、水添加のタイミング、及びこれらを組み合わせて各種の提案がなされている。 For the above-described circumstances, various proposals have been made regarding the method for eliminating lime nitrogen, combining the soaking temperature, the amount of water added, the timing of water addition, and combinations thereof.
特許文献１には、石灰窒素中の生石灰を８０℃以上の温度を保ちながら水蒸気で消和する石灰窒素質肥料の製造方法が開示されている。特許文献２には、石灰窒素の加水分解速度を遅延させる物質を含有する石灰窒素用改質剤が開示されている。 Patent Document 1 discloses a method for producing a lime-nitrogenous fertilizer in which quick lime in lime nitrogen is dehydrated with water vapor while maintaining a temperature of 80 ° C. or higher. Patent Document 2 discloses a lime nitrogen modifier containing a substance that delays the hydrolysis rate of lime nitrogen.
しかしながら、上記文献記載の従来技術は、以下の点で改善の余地を有していた。 However, the prior art described in the above literature has room for improvement in the following points.
第一に、特許文献１の方法では、石灰窒素中の生石灰を消和する際に、例えば比較例１に示すように石灰窒素８０ｋｇに水１０ｋｇを添加するような実際のプラントサイズに近い反応では急激に温度が上昇するため、後述するように肥料成分として肥料取締法上、含有量に制限のあるジシアンジアミドや不純物であるメラミンやメラミン誘導体といった副生物の産生が無視できず、シアナミドの含有率が低下する問題がある。 First, in the method of Patent Document 1, when quick lime in lime nitrogen is sublimated, for example, as shown in Comparative Example 1, in a reaction close to an actual plant size in which 10 kg of water is added to 80 kg of lime nitrogen. As the temperature rises rapidly, as described later, the production of by-products such as dicyandiamide, which is limited in content, and impurities such as melamine and melamine derivatives cannot be ignored as a fertilizer component, and the content of cyanamide is There is a problem that decreases.
第二に、特許文献２の方法では、すでに消和処理済みの石灰窒素に対して石灰窒素の加水分解速度を遅延させる物質を添加して粒状肥料を製造している。そのため、未消和の石灰窒素を水で消和処理する時点では発熱が抑制されることがなく、後述するように肥料成分として肥料取締法上、含有量に制限のあるジシアンジアミドや不純物であるメラミンやメラミン誘導体といった副生物の産生が無視できず、シアナミドの含有率が低下する問題がある。また、この石灰窒素の加水分解速度を遅延させる物質を含む粒状肥料は、後述するように圧壊強度が低下するために、取扱性および散布性に問題があった。 Secondly, in the method of Patent Document 2, a granular fertilizer is produced by adding a substance that delays the hydrolysis rate of lime nitrogen to lime nitrogen that has already been subjected to decontamination treatment. Therefore, heat generation is not suppressed at the time when the uncalculated lime nitrogen is treated with water, and as described later, dicyandiamide or melamine which is an impurity in terms of fertilizer control law as a fertilizer component. There is a problem that the production of by-products such as melamine derivatives cannot be ignored and the content of cyanamide is reduced. In addition, the granular fertilizer containing a substance that delays the hydrolysis rate of lime nitrogen has a problem in handling property and dispersibility because the crushing strength decreases as described later.
本発明は上記事情に鑑みてなされたものであり、生石灰の含有率が少なく、ジシアンジアミドやメラミンやアンメリンなどといったメラミン誘導体の産生を抑制した石灰窒素含有粒状肥料を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lime nitrogen-containing granular fertilizer having a low content of quicklime and suppressing production of melamine derivatives such as dicyandiamide, melamine, and ammelin.
＜石灰窒素の消和のメカニズム＞
石灰窒素に含まれる未消和石灰（ＣａＯ）は、下記の化学反応で示すとおり、空気中の水分と反応して加水分解する際、カルシウム化合物の形態変化や発熱を伴うために体積膨張を引き起こし粒状から粉状への崩壊などが起こり、肥料としての保管や取り扱いに注意を要する。このため、あらかじめ生石灰（ＣａＯ）を水で消和した消和処理品が流通している。
<Mechanism of calcification of lime nitrogen>
As shown in the following chemical reaction, unreduced lime (CaO) contained in lime nitrogen causes volume expansion due to a change in the form of calcium compounds and heat generation when it reacts with moisture in the air and hydrolyzes. Disintegration from granular to powder occurs, so care must be taken for storage and handling as fertilizer. For this reason, deodorized processed products in which quick lime (CaO) is preliminarily dehydrated with water are in circulation.
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）２ ΔＨ＝１５．３Ｋｃａｌ
ＣａＣＮ２＋２Ｈ２Ｏ→Ｃａ（ＯＨ）２＋Ｈ２ＣＮ２ ΔＨ＝３．４Ｋｃａｌ
CaO + H 2 O → Ca (OH) 2 ΔH = 15.3 Kcal
CaCN2 + 2H2O → Ca (OH) 2 + H2CN2 ΔH = 3.4 Kcal
上記反応式からわかる様に、水は生石灰および石灰窒素の両方に作用するが、生成熱であるΔＨの大きいＣａＯに優先的に使用される。しかし、一部の水はＣａＣＮ２にも接触するため加水分解がおこり、窒素分がアンモニアとして揮発するなど、以下の反応にまで至って有効な農薬成分や肥料成分が低下する問題がある。
Ｈ２ＣＮ２＋２Ｈ２Ｏ→ＣＯ２＋２ＮＨ３
As can be seen from the above reaction formula, water acts on both quicklime and lime nitrogen, but is preferentially used for CaO having a large ΔH, which is the heat of formation. However, since some of the water also comes into contact with CaCN2, hydrolysis occurs, and the nitrogen content volatilizes as ammonia, leading to the following reactions, resulting in a problem that effective agricultural chemical components and fertilizer components are reduced.
H2CN2 + 2H2O → CO2 + 2NH3
また、生石灰を水で消和させるときに、その反応温度が８０℃以上の温度を保つ場合には、後述する実施例で示すようにメラミンやメラミン誘導体やジシアンジアミドなどを副生し、有効な成分であるシアナミドが失われ易いという問題がある。 In addition, when the quick lime is hydrated with water, if the reaction temperature is kept at 80 ° C. or higher, as shown in the examples described later, melamine, melamine derivatives, dicyandiamide, etc. are by-produced and effective ingredients There is a problem that cyanamide is easily lost.
本発明者らは、上記事情に鑑みて、後述する実施例に示すように、いろいろ実験を重ねた結果、消和工程で生成される水酸化カルシウムに着目し、水酸化カルシウムの結晶構造、具体的には［１００］面の結晶子サイズをある範囲に制御することにより、生石灰の含有率が少なく、シアナミドの含有率が保たれ、シアナミドからの誘導体、たとえばジシアンジアミド、メラミンやメラミン誘導体の含有率が抑制された石灰窒素含有粒状肥料が得られることを見いだした。 In view of the above circumstances, the inventors of the present invention, as shown in the examples described later, as a result of various experiments, paying attention to calcium hydroxide produced in the decontamination process, Specifically, by controlling the crystallite size of the [100] plane within a certain range, the content of quick lime is small, the content of cyanamide is maintained, and the content of derivatives from cyanamide, such as dicyandiamide, melamine and melamine derivatives It has been found that a lime nitrogen-containing granular fertilizer is obtained in which is suppressed.
すなわち本発明は、生石灰の消和反応を抑制する有機添加剤および造粒助材として硝酸塩又は塩酸塩と、消和処理済みの石灰窒素と、を含み、
前記消和処理済みの石灰窒素のうち、水酸化カルシウム結晶の［１００］面の結晶子サイズを４００オングストローム以下、
好ましくは３００オングストローム以下
とした石灰窒素含有粒状肥料である。
That is, the present invention includes nitrate or hydrochloride as an organic additive and a granulating aid for suppressing the decalcification reaction of quick lime, and decalcified lime nitrogen,
Of the lime nitrogen that has been subjected to the decontamination treatment, the crystallite size of the [100] plane of the calcium hydroxide crystal is 400 angstroms or less,
The lime nitrogen-containing granular fertilizer is preferably 300 angstroms or less.
または、生石灰の消和反応を抑制する有機添加剤を含まない水のみによる消和処理済みの石灰窒素のうち、水酸化カルシウムの結晶構造において、
［１００］面の結晶子サイズを７００オングストローム以上、１２００オングストローム以下、
好ましくは８００オングストローム以上、１０００オングストローム以下
とした石灰窒素含有粒状肥料である。
Or in the crystal structure of calcium hydroxide among the lime nitrogen that has been dehydrated only with water that does not contain organic additives that suppress the decalcification reaction of quicklime,
The crystallite size of the [100] plane is 700 angstroms or more and 1200 angstroms or less,
The lime nitrogen-containing granular fertilizer is preferably 800 angstrom or more and 1000 angstrom or less.
粉末Ｘ線回折法による結晶子サイズの算出は、日本工業規格 JIS K0131-1996および「Ｘ線回折ハンドブック」（株式会社リガク 2006年発行 第５版）に記載のScherrerの式に基づき行った。本測定及び結果の算出は迅速に行うことができるため、必要に応じて製造工程から測定試料を抜き出して本測定を行うことにより、製造プロセスの制御に速やかにフィードバックすることができる。 The calculation of the crystallite size by the powder X-ray diffraction method was performed based on the Scherrer formula described in Japanese Industrial Standard JIS K0131-1996 and “X-ray diffraction handbook” (Rigaku Corporation, 2006, 5th edition). Since the main measurement and the calculation of the result can be performed quickly, the measurement sample can be extracted from the manufacturing process as necessary, and the main measurement can be performed to promptly feed back to the control of the manufacturing process.
本発明によれば、粉末Ｘ線回折測定により水酸化カルシウム結晶の［１００］面の結晶子サイズを計測することで、未消和石灰窒素中の生石灰を様々な手法により消和するに際し、目的とする消和反応に制御されているか否かの判断を正確に行うことが可能になると共に、それらの消和反応が均一に行われているか否かの判断も正確に行うことができる。 According to the present invention, by measuring the crystallite size of the [100] plane of the calcium hydroxide crystal by powder X-ray diffraction measurement, the purpose of reducing the quicklime in the uncalculated lime nitrogen by various methods is Thus, it is possible to accurately determine whether or not the reaction is controlled by the above-described decontamination reaction, and it is also possible to accurately determine whether or not the decontamination reaction is performed uniformly.
本発明によれば、生石灰の含有率が少なく、シアナミドの含有率が保たれ、シアナミドからの誘導体、具体的にはジシアンジアミドおよびメラミン、アンメリンといったメラミン誘導体の含有率が抑制された石灰窒素含有粒状肥料が得られる。 According to the present invention, a lime nitrogen-containing granular fertilizer in which the content of quick lime is low, the content of cyanamide is maintained, and the content of derivatives from cyanamide, specifically melamine derivatives such as dicyandiamide, melamine, and ammelin is suppressed. Is obtained.
また、本発明によれば、４０℃、４週間貯蔵後の圧壊強度が１．５Ｋｇｆ以上である、貯蔵後の強度低下が抑制された石灰窒素含有粒状肥料が得られる。 Further, according to the present invention, a lime nitrogen-containing granular fertilizer having a crushing strength after storage at 40 ° C. for 4 weeks of 1.5 kgf or more and suppressed in strength reduction after storage is obtained.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜有機添加剤を添加した石灰窒素含有粒状肥料＞
本実施形態の石灰窒素含有粒状肥料は、未消和石灰窒素中の生石灰の消和反応を抑制する有機添加剤および又は造粒助材である硝酸塩又は塩酸塩と、消和処理済みの石灰窒素と、を含む。
<Lime nitrogen-containing granular fertilizer with organic additives added>
The lime nitrogen-containing granular fertilizer according to the present embodiment is composed of an organic additive and / or a granulation aid that suppresses the decontamination reaction of quick lime in undehydrated lime nitrogen, and decontaminated lime nitrogen. And including.
本実施形態に用いる消和処理済みの石灰窒素には、未消和の石灰窒素を水または水蒸気などで消和して得られる石灰窒素が含まれる。本実施形態に用いる消和処理済みの石灰窒素においては、
ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）２
の化学反応によって大部分の生石灰（未消和生石灰（ＣａＯ））が消石灰（水酸化カルシウム（Ｃａ（ＯＨ）２））に変化してしまっていることが好ましい。
The lime nitrogen that has been subjected to the decontamination treatment used in the present embodiment includes lime nitrogen that is obtained by decontamination of uncalculated lime nitrogen with water or steam. In the lime nitrogen that has been dehydrated for use in this embodiment,
CaO + H2O → Ca (OH) 2
It is preferable that most of the quicklime (unsettled quicklime (CaO)) has been changed to slaked lime (calcium hydroxide (Ca (OH) 2)) by the chemical reaction.
本実施形態に用いる消和処理済みの石灰窒素は、例えば生石灰の含有率が２質量％以下であることが好ましい。石灰窒素に含まれる生石灰が主に空気中の水分と反応して加水分解する際に、カルシウム化合物に形態変化を起こし、発熱と体積膨張を伴うため粒状から粉状への崩壊などが起こることを抑制できるからである。あるいは、本実施形態に用いる消和処理済みの石灰窒素に含まれる生石灰の含有率は、２．０質量％、１．５質量％、１．０質量％、０．５質量％、０．１質量％のいずれかの値以下、またはこれらの任意の２つの値の範囲内であってもよい。
For the lime nitrogen that has been subjected to the decontamination treatment used in the present embodiment, for example, the content of quick lime is preferably 2% by mass or less. When quick lime contained in lime nitrogen mainly reacts with moisture in the air and hydrolyzes, it causes a change in the form of calcium compounds, and it causes heat generation and volume expansion, causing collapse from granular to powder. This is because it can be suppressed. Or the content rate of the quick lime contained in the lime nitrogen after the decontamination process used for this embodiment is 2.0 mass%, 1.5 mass%, 1.0 mass%, 0.5 mass%, 0.1 It may be less than or equal to any value of mass%, or within the range of any two of these values.
本実施形態に用いる消和処理済みの石灰窒素は、シアナミド性窒素の含有率が１０質量％以上であることが好ましい。有効な農薬成分や肥料成分であるシアナミドが多いほど土壌に対する肥料効果が高くなるためである。あるいは、本実施形態に用いる消和処理済みの石灰窒素に含まれるシアナミド性窒素の含有率は１０質量％、１２質量％、１４質量％、１６質量％、１８質量％、２０質量％、２２質量％、２４質量％、２６質量％、２８質量％のいずれかの値以上、またはこれらの任意の２つの値の範囲内であってもよい。 The lime nitrogen that has been subjected to the decontamination treatment used in the present embodiment preferably has a cyanamide nitrogen content of 10% by mass or more. It is because the fertilizer effect with respect to soil becomes high, so that there are many cyanamide which is an effective agricultural chemical component and a fertilizer component. Alternatively, the content of cyanamide nitrogen contained in the lime nitrogen that has been subjected to decontamination treatment used in the present embodiment is 10% by mass, 12% by mass, 14% by mass, 16% by mass, 18% by mass, 20% by mass, and 22% by mass. %, 24 mass%, 26 mass%, 28 mass% or more, or any two of these values.
本実施形態に用いる消和処理済みの石灰窒素は、不純物としてのメラミンの含有率が０．４質量％以下であることが好ましく、更に０．２質量％以下であることが好ましい。メラミンの含有率が増えると、その分だけシアナミドの含有率が少なくなるためである。あるいは、本実施形態に用いる消和処理済みの石灰窒素に含まれるメラミンの含有率は０．４質量％、０．３５質量％、０．３０質量％、０．２５質量％、０．２０質量％、０．１５質量％、０．１０質量％、０．０５質量％、０．０２５質量％、０．０２０質量％、０．０１５質量％、０．０１０質量％のいずれかの値以下、またはこれらの任意の２つの値の範囲内であってもよい。 The lime nitrogen that has undergone decontamination treatment used in the present embodiment preferably has a content of melamine as an impurity of 0.4% by mass or less, and more preferably 0.2% by mass or less. This is because as the content of melamine increases, the content of cyanamide decreases accordingly. Or the content rate of the melamine contained in the lime nitrogen after the decontamination process used for this embodiment is 0.4 mass%, 0.35 mass%, 0.30 mass%, 0.25 mass%, 0.20 mass. %, 0.15% by mass, 0.10% by mass, 0.05% by mass, 0.025% by mass, 0.020% by mass, 0.015% by mass, 0.010% by mass or less, Or it may be in the range of these arbitrary two values.
本実施形態に用いる消和処理済みの石灰窒素は、不純物としてのアンメリンの含有率が０．２質量％以下であることが好ましく、更に０．１質量％以下であることが好ましい。
あるいは、本実施形態に用いる消和処理済みの石灰窒素に含まれるアンメリンの含有率は０．２質量％、０．１５質量％、０．１０質量％、０．０５質量％、０．０２５質量％、０．０２０質量％、０．０１５質量％、０．０１０質量％のいずれかの値以下、またはこれらの任意の２つの値の範囲内であってもよい。
The lime nitrogen that has been subjected to the decontamination treatment used in the present embodiment preferably has a content of ammeline as an impurity of 0.2% by mass or less, and more preferably 0.1% by mass or less.
Alternatively, the content of ammelin contained in the lime nitrogen that has been subjected to decontamination treatment used in the present embodiment is 0.2% by mass, 0.15% by mass, 0.10% by mass, 0.05% by mass, and 0.025% by mass. %, 0.020 mass%, 0.015 mass%, 0.010 mass% or less, or within the range of any two of these values.
本実施形態で用いる生石灰の消和反応を抑制する有機添加剤は、未消和石灰窒素中の生石灰の消和反応に影響を与え、水酸化カルシウムの結晶構造において［１００］面の結晶子サイズを４００オングストローム以下、好ましくは３００オングストローム以下とすることによって、メラミンやアンメリンなどといったメラミン誘導体の副生物の産生を抑制した石灰窒素含有粒状肥料が得られる。 The organic additive that suppresses the decalcification reaction of quicklime used in this embodiment affects the decontamination reaction of quicklime in uncalculated lime nitrogen, and the crystallite size of the [100] plane in the crystal structure of calcium hydroxide By setting the value to 400 angstroms or less, preferably 300 angstroms or less, a lime nitrogen-containing granular fertilizer that suppresses the production of by-products of melamine derivatives such as melamine and ammelin can be obtained.
実施例５から実施例１３に示すように有機添加剤を使用して未消和石灰窒素中の生石灰を消和する場合、消和時のピーク温度を１００℃から１３０℃と、比較的低く抑えることにより、メラミンやアンメリンなどといったメラミン誘導体の生成を低く抑えることができる。これは水に溶けた有機添加剤が分子レベルで生石灰を取り囲み生石灰と水との反応を制御することにより消和反応熱の発生を抑制するからと思われる。また、一方で、消和反応の結果として生成する水酸化カルシウムは周りを取り囲む分子レベルの有機分子により、互いに合体して結晶化する挙動が抑えられるため、結晶成長が抑えられ結晶のサイズが小さくなる傾向にあると推定される。 As shown in Example 5 to Example 13, when the quick lime in unsettled lime nitrogen is sanitized using an organic additive, the peak temperature at the time of sacrificing is kept relatively low from 100 ° C to 130 ° C. Thus, the production of melamine derivatives such as melamine and ammelin can be kept low. This is thought to be because the organic additive dissolved in water surrounds quicklime at the molecular level and controls the reaction between quicklime and water, thereby suppressing the generation of heat of reaction. On the other hand, the calcium hydroxide produced as a result of the reconciliation reaction is restrained by the molecular level organic molecules that surround it, causing it to coalesce and crystallize, so that crystal growth is suppressed and the crystal size is reduced. It is estimated that
本実施形態で用いる生石灰の水和反応を抑制する有機添加剤は、例えば、グルコヘプトン酸、グルコン酸、ガラクトン酸、クエン酸、酒石酸、リンゴ酸などのオキシカルボン酸類又はその塩、ピルビン酸などのケトカルボン酸類又はその塩、イタコン酸又はその塩、ソルビトール、マンニトールなどの糖アルコール類、グルコース、マンノース、ガラクトース、フラクトース、アラビノース、スクロース（サッカロース）、ラクトース、マルトース、ラフィノース、デキストリン、キシロースなどの糖類、でんぷん、芳香族スルホン酸又はその塩、リグニンスルホン酸又はその塩、イノシトールからなる群から選ばれる１種以上の有機物を含むことが好ましいが、中でもグルコン酸、およびその塩、グルコース、スクロースなどから選ばれる１種以上が、作用効果などの観点から更に好ましい。これらの有機物は、後述する実施例で示すように、実際に生石灰の消和反応を抑制する機能を有することを本発明者らは確認しているからである。また、これらの有機物は農薬または肥料の原料として用いる場合に安全性が確認されている面でも好ましい。これらの有機物は、後述する実施例で示すように、実際に生石灰の水和反応を抑制する機能を有することを本発明者らは確認しているからである。 Examples of the organic additive that suppresses the hydration reaction of quicklime used in the present embodiment include oxycarboxylic acids such as glucoheptonic acid, gluconic acid, galactonic acid, citric acid, tartaric acid, malic acid, and salts thereof, and ketocarbon such as pyruvic acid. Acids or salts thereof, Itaconic acid or salts thereof, sugar alcohols such as sorbitol and mannitol, glucose, mannose, galactose, fructose, arabinose, sucrose (saccharose), lactose, maltose, raffinose, dextrin, xylose and other sugars, starch, It is preferable to include one or more organic substances selected from the group consisting of aromatic sulfonic acid or a salt thereof, lignin sulfonic acid or a salt thereof, and inositol, among which gluconic acid and a salt thereof, glucose, sucrose, and the like are selected. More species, more preferred from the viewpoint of working effect. This is because the present inventors have confirmed that these organic substances actually have a function of suppressing the quick-lime decontamination reaction, as shown in Examples described later. Moreover, these organic substances are also preferable in terms of safety when used as raw materials for agricultural chemicals or fertilizers. This is because the present inventors have confirmed that these organic substances actually have a function of suppressing the hydration reaction of quicklime, as shown in the examples described later.
これらの分子レベルの有機化合物の作用は、水に均質に溶解した水溶液中の有機分子が未消和の生石灰（ＣａＯ）分子に均質に作用することにより効果を発揮し、結果として水酸化カルシウムの結晶のサイズを小さくならしめる。具体的には水酸化カルシウム結晶の［１００］面の結晶子サイズが４００オングストローム以下、好ましくは３００オングストローム以下になるときに、有機分子が均質に作用し、より大きな効果を生むと推定される。 The action of these organic compounds at the molecular level is exerted by the fact that the organic molecules in the aqueous solution homogeneously dissolved in water act uniformly on the uncalculated quicklime (CaO) molecules. Reduce the size of the crystals. Specifically, when the crystallite size of the [100] plane of the calcium hydroxide crystal is 400 angstroms or less, preferably 300 angstroms or less, it is estimated that the organic molecules act homogeneously and produce a greater effect.
また、本実施形態で用いる生石灰の消和反応を抑制する有機添加剤は、廃糖蜜、コーンシロップ、パルプ廃液からなる群から選ばれる１種であってもよい。これらの有機物は、後述する実施例で示すように、実際に生石灰の消和反応を抑制する機能を有することを本発明者らは確認しているからである。また、これらの有機物は農薬または肥料の原料として用いる場合に安全性が確認されており、さらに入手が容易で購入コストが低い面でも好ましい。なお、本明細書において、「廃糖蜜」とは、砂糖を精製する時に発生する、糖分以外の成分も含んだ粘状で黒褐色の液体を含む。すなわち、廃糖蜜には、モラセス（Ｍｏｌａｓｓｅｓ）が含まれる。 In addition, the organic additive that suppresses the soaking reaction of quicklime used in the present embodiment may be one selected from the group consisting of molasses, corn syrup, and pulp waste liquid. This is because the present inventors have confirmed that these organic substances actually have a function of suppressing the quick-lime decontamination reaction, as shown in Examples described later. These organic substances have been confirmed to be safe when used as raw materials for agricultural chemicals or fertilizers, and are also preferable in terms of easy availability and low purchase costs. In the present specification, “waste molasses” includes a viscous black-brown liquid containing components other than sugar, which are generated when sugar is refined. That is, molasses is contained in molasses.
また、本実施形態で用いる生石灰の消和反応を抑制する造粒助材は、硝酸カルシウム、塩化カルシウム、塩化マグネシウムなどの無機塩類であることが好ましい。なお、これらの中でも、硝酸カルシウムが好ましい。 Moreover, it is preferable that the granulation aid for suppressing the soaking reaction of quicklime used in the present embodiment is an inorganic salt such as calcium nitrate, calcium chloride, or magnesium chloride. Of these, calcium nitrate is preferred.
有機添加剤の石灰窒素に対する配合量の下限については、用いる有機添加剤又は造粒助材の種類、組み合わせにより異なるが、消和時に石灰窒素１００質量部に対して０．１質量部以上の適当量を配合することで、未消和石灰窒素中の生石灰の消和反応を抑制することができ、上記の要請に対応することができる。 About the minimum of the compounding quantity with respect to the lime nitrogen of an organic additive, although it changes with kinds and combination of the organic additive or granulation auxiliary agent to be used, 0.1 mass part or more suitable with respect to 100 mass parts of lime nitrogen at the time of soaking By blending the amount, it is possible to suppress the quickening reaction of quick lime in unsettled lime nitrogen, and to meet the above requirements.
また、有機添加剤の石灰窒素に対する配合量の上限については、特に定める必要はないが、有機添加剤の多量の添加は、結果的に窒素含有率の低下をもたらす。また、有機添加剤の多量の添加は副次的な効果として、石灰窒素の加水分解速度の遅延効果が現れるため、肥料等に用いた時に、石灰窒素の加水分解速度が予想よりも遅くなり、通常の石灰窒素として用いる場合は具合が悪い。そのため、有機添加剤による分解遅延効果が肥料として不都合なまでには現れない範囲、すなわち消和処理済みの石灰窒素１００質量部に対して０．１〜５質量部の範囲で添加するのが望ましい。あるいは、本実施形態に用いる消和処理済みの石灰窒素に対する有機添加剤の配合量は、石灰窒素１００質量部に対して０．１質量部、０．２質量部、０．３質量部、０．４質量部、０．５質量部、１．０質量部、１．５質量部、２．０質量部、２．５質量部、３．０質量部、３．５質量部、４．０質量部、４．５質量部、５．０質量部の任意の２つの値の範囲内であってもよい。 In addition, the upper limit of the blending amount of the organic additive with respect to lime nitrogen is not particularly required, but a large amount of the organic additive results in a decrease in nitrogen content. In addition, the addition of a large amount of organic additive has a secondary effect of delaying the hydrolysis rate of lime nitrogen, so when used in fertilizers, the hydrolysis rate of lime nitrogen is slower than expected, When used as normal lime nitrogen, the condition is poor. Therefore, it is desirable to add in a range where the decomposition delay effect due to the organic additive does not appear to be inconvenient as a fertilizer, that is, in a range of 0.1 to 5 parts by mass with respect to 100 parts by mass of lime nitrogen that has been dehydrated. . Or the compounding quantity of the organic additive with respect to the lime nitrogen after the decontamination process used for this embodiment is 0.1 mass part, 0.2 mass part, 0.3 mass part, 0 with respect to 100 mass parts of lime nitrogen. .4 parts by mass, 0.5 parts by mass, 1.0 part by mass, 1.5 parts by mass, 2.0 parts by mass, 2.5 parts by mass, 3.0 parts by mass, 3.5 parts by mass, 4.0 parts by mass It may be within the range of any two values of mass parts, 4.5 mass parts, and 5.0 mass parts.
本実施形態で用いる造粒助材である硝酸あるいはその塩又は塩酸あるいはその塩は、後述する実施例で示すように石灰窒素含有粒状肥料の圧壊強度を向上させる。そのため、硝酸あるいはその塩又は塩酸あるいはその塩を用いることによって、上述する有機添加剤の石灰窒素含有粒状肥料の圧壊強度を低下させやすいという弱点を補って、取扱性および散布性に優れた石灰窒素含有粒状肥料を得ることができる。さらに、本発明者らはメラミンおよびアンメリンなどといったメラミン誘導体の生成抑制にも効果があることを見いだしている。 Nitric acid or a salt thereof or hydrochloric acid or a salt thereof, which is a granulation aid used in the present embodiment, improves the crushing strength of the lime nitrogen-containing granular fertilizer as shown in the examples described later. Therefore, the use of nitric acid or its salt or hydrochloric acid or its salt compensates for the weak point that the crushing strength of the lime nitrogen-containing granular fertilizer of the organic additive mentioned above is easily reduced, and lime nitrogen that is excellent in handleability and sprayability A contained granular fertilizer can be obtained. Furthermore, the present inventors have found that the production of melamine derivatives such as melamine and ammelin is also effective in suppressing the production.
本実施形態で用いる硝酸塩又は塩酸塩は、例えば、硝酸カルシウム、塩化カルシウム、塩化マグネシウムからなる群から選ばれる１種以上の塩を含むことが好ましい。これらの硝酸塩又は塩酸塩は、後述する実施例で示すように、実際に石灰窒素含有粒状肥料の圧壊強度を向上させること、さらには特に、造粒工程で添加することによって、その後の乾燥工程におけるメラミンやアンメリンなどのメラミン誘導体の生成抑制にも効果があることを本発明者らは確認しているからである。 The nitrate or hydrochloride used in the present embodiment preferably contains one or more salts selected from the group consisting of calcium nitrate, calcium chloride, and magnesium chloride, for example. These nitrates or hydrochlorides actually improve the crushing strength of the lime nitrogen-containing granular fertilizer, and more particularly by adding them in the granulation step, as shown in the examples described later, in the subsequent drying step This is because the present inventors have confirmed that the production of melamine derivatives such as melamine and ammelin is effective.
硝酸塩又は塩酸塩の石灰窒素に対する配合量の下限については、用いる硝酸塩又は塩酸塩の種類、組み合わせにより異なるが、造粒時に石灰窒素１００質量部に対して３質量部以上の適当量を配合することで、石灰窒素含有粒状肥料の圧壊強度を向上させることができ、上記の要請に対応することができる。また、硝酸塩又は塩酸塩の石灰窒素に対する配合量の上限については、特に定める必要はないが、硝酸塩又は塩酸塩の多量の添加は、結果的にシアナミド含有率の低下をもたらす。そのため、硝酸塩又は塩酸塩は、消和処理済みの石灰窒素１００質量部に対して３〜２０質量部の範囲で添加するのが望ましい。あるいは、本実施形態に用いる消和処理済みの石灰窒素に対する硝酸塩又は塩酸塩の配合量は、石灰窒素１００質量部に対して３質量部、４質量部、５質量部、６質量部、７質量部、８質量部、９質量部、１０質量部、１２質量部、１４質量部、１６質量部、１８質量部、２０質量部の任意の２つの値の範囲内であってもよい。 About the minimum of the compounding quantity with respect to the lime nitrogen of nitrate or hydrochloride, although it changes with kinds and combinations of nitrate or hydrochloride to be used, it mix | blends an appropriate quantity of 3 mass parts or more with respect to 100 mass parts of lime nitrogen at the time of granulation. Thus, the crushing strength of the lime nitrogen-containing granular fertilizer can be improved, and the above request can be met. In addition, the upper limit of the blending amount of nitrate or hydrochloride with respect to lime nitrogen is not particularly required, but addition of a large amount of nitrate or hydrochloride results in a decrease in cyanamide content. Therefore, it is desirable to add nitrate or hydrochloride in the range of 3 to 20 parts by mass with respect to 100 parts by mass of the lime nitrogen that has been subjected to decontamination treatment. Or the compounding quantity of the nitrate or hydrochloride with respect to the lime nitrogen after the decontamination process used for this embodiment is 3 mass parts, 4 mass parts, 5 mass parts, 6 mass parts, 7 mass with respect to 100 mass parts of lime nitrogen. Part, 8 parts by mass, 9 parts by mass, 10 parts by mass, 12 parts by mass, 14 parts by mass, 16 parts by mass, 18 parts by mass, and 20 parts by mass.
＜有機添加剤を含まない水のみにより消和される石灰窒素含有粒状肥料＞
前記有機添加剤を含まない水のみによる消和処理済みの石灰窒素のうち、水酸化カルシウムの結晶構造において［１００］面の結晶子サイズを７００オングストローム以上、１２００オングストローム以下、好ましくは８００オングストローム以上、１０００オングストローム以下とすることによって消和反応が制御され、シアナミド性窒素の含有率が多く、メラミンおよびアンメリンなどのメラミン誘導体の含有率が少ない石灰窒素含有粒状肥料が得られる。
<Lime nitrogen-containing granular fertilizer that can be reconstituted only with water that does not contain organic additives>
Of the lime nitrogen that has been dehydrated only with water that does not contain the organic additive, the crystallite size of the [100] plane in the crystal structure of calcium hydroxide is 700 angstroms or more and 1200 angstroms or less, preferably 800 angstroms or more, By adjusting to 1000 angstroms or less, the soothing reaction is controlled, and a lime nitrogen-containing granular fertilizer with a high content of cyanamide nitrogen and a low content of melamine derivatives such as melamine and ammelin is obtained.
本実施形態で用いる未消和石灰窒素中の消和反応時に、有機添加剤を含まない水のみにより生石灰を消和する際、消和反応に用いる水を複数回に分けて添加する、あるいは水を1回で添加したのち攪拌あるいは転動を続け、蓄熱防止、放熱促進、急激な発熱を抑制しつつ消和するなど、消和反応熱による高温化を制御しながら消和する場合、生成する水酸化カルシウム結晶の［１００］面の結晶子サイズが７００オングストローム以上となる様に制御することができる。 At the time of the decontamination reaction in the uncalculated lime nitrogen used in the present embodiment, when the quick lime is decontaminated only with water that does not contain an organic additive, the water used for the decontamination reaction is added in several portions, or water Is generated when adding heat at one time and then continuing stirring or rolling to prevent heat storage, promote heat dissipation, and reduce heat while suppressing sudden heat generation, etc. The crystallite size of the [100] plane of the calcium hydroxide crystal can be controlled to be 700 angstroms or more.
実施例１から実施例３および実施例４に示す様に、水のみを使用して未消和石灰窒素中の生石灰を消和する場合、消和時のピーク温度を６０℃から９０℃と、比較的低く抑えている。消和反応が穏やかに進行するために、生成する水酸化カルシウムの生成は急激な生成を伴う高温時の消和反応に比較して緩やかとなり、結果として、生成する水酸化カルシウムの結晶のサイズは大きくなる傾向にある。具体的には水酸化カルシウム結晶の［１００］面の結晶子サイズが７００オングストローム以上、１２００オングストローム以下、好ましくは８００オングストローム以上、１０００オングストローム以下になる場合に特に消和反応が効果的に制御される。 As shown in Example 1 to Example 3 and Example 4, when using only water to slake quicklime in unslaked lime nitrogen, the peak temperature during squeezing is 60 ° C to 90 ° C, Relatively low. Since the soothing reaction proceeds moderately, the formation of calcium hydroxide produced is slow compared with that at high temperatures accompanied by abrupt formation, and as a result, the crystal size of the produced calcium hydroxide is It tends to grow. Specifically, when the crystallite size of the [100] plane of the calcium hydroxide crystal is 700 angstroms or more and 1200 angstroms or less, preferably 800 angstroms or more and 1000 angstroms or less, the soothing reaction is effectively controlled. .
これによってもたらされる不純物濃度の低減効果、また消和後の造粒助材の使用による粒の圧壊強度の向上や乾燥工程におけるメラミンやメラミン誘導体の生成抑制、および長期にわたる貯蔵安定性にも効果があることは、有機添加剤系と同様である。 This has the effect of reducing the impurity concentration, improving the crushing strength of the grains by using the granulation aid after decontamination, suppressing the formation of melamine and melamine derivatives in the drying process, and effective for long-term storage stability. It is similar to the organic additive system.
＜造粒効果＞
石灰窒素含有肥料は、粉末の場合には作業時に飛散しやすいという理由から、粒状であることが望まれている。本実施形態の方法の一つは、消和工程において、生石灰の消和反応を抑制する有機添加剤を含有する水溶液を用い、その後の造粒工程において、石灰窒素含有粒状肥料の圧壊強度を高める硝酸塩又は塩酸塩を含有する水溶液状の造粒助材を用いる。特に造粒工程で添加することによって、その後の乾燥工程におけるシアナミドの変性抑制にも効果がある。そのために、本実施形態の方法の一つによれば、生石灰の含有率が少なく圧壊強度に優れ、メラミンやアンメリンなどのメラミン誘導体などの副生物の産生を抑制した石灰窒素含有粒状肥料が得られる。
<Granulation effect>
Lime nitrogen-containing fertilizer is desired to be granular in the case of powder because it is easily scattered during work. One of the methods of the present embodiment uses an aqueous solution containing an organic additive that suppresses the quickening reaction of quick lime in the dehydration step, and increases the crushing strength of the lime nitrogen-containing granular fertilizer in the subsequent granulation step. An aqueous granulation aid containing nitrate or hydrochloride is used. In particular, the addition in the granulation step is also effective in suppressing cyanamide modification in the subsequent drying step. Therefore, according to one of the methods of the present embodiment, a lime nitrogen-containing granular fertilizer is obtained that has a low content of quick lime, excellent crushing strength, and suppresses the production of by-products such as melamine derivatives such as melamine and ammelin. .
造粒品を得ようとする場合、未消和の石灰窒素含有肥料粉体に、有機添加剤を含有する水溶液を加えて消和反応を行った後、消和処理済みの石灰窒素含有肥料粉体に硝酸塩又は塩酸塩を含有する造粒に用いる水溶液を加えて、一般に混練して均一度を高めた後、押し出し、型押し等の造粒方法で、或いはパン型造粒機、キルン型造粒機、ドラム型造粒機等を用いて粉末から造粒するなどの従来公知の方法で造粒することができる。 When trying to obtain a granulated product, an aqueous solution containing an organic additive is added to an unsatisfied lime nitrogen-containing fertilizer powder, and after performing a soothing reaction, the lime nitrogen-containing fertilizer powder that has been sanitized After adding an aqueous solution used for granulation containing nitrate or hydrochloride to the body and generally kneading to increase the uniformity, the granulation method such as extrusion, embossing, bread type granulator, kiln type granulation Granulation can be performed by a conventionally known method such as granulation from powder using a granulator, a drum type granulator or the like.
使用する造粒機は、対象物質にせん断、圧密、転動作用を加えることで造粒を進行させる形式であることが好ましい。例えば、攪拌造粒機を挙げることができる。攪拌造粒機には、攪拌羽根が槽内を自転しながら遊星運動するプラネタリー型、攪拌羽根を持つ軸が容器中心にあり、それとは別に解砕羽根を持つ副軸が設置される高速型などがあるが、型による制限はない。 The granulator to be used is preferably of a type in which granulation proceeds by adding shearing, compaction, and rolling operations to the target substance. For example, a stirring granulator can be mentioned. The agitation granulator has a planetary type in which the agitating blades rotate in a tank while moving in a planetary manner, and a high-speed type in which a shaft with the agitating blades is at the center of the container and a secondary shaft with crushing blades is installed separately. However, there is no restriction by type.
造粒工程の後、乾燥工程において、加熱、送風などの手段で乾燥することにより、容易に製品を得ることができる。又、粉状のリン酸肥料や加里肥料との混合物、粉状のリン酸肥料や加里肥料との混合後造粒物についても、本実施形態を利用して石灰窒素中の生石灰を消和して、その後造粒することができる。 After the granulation step, the product can be easily obtained by drying by means such as heating and blowing in the drying step. In addition, for the mixture with powdered phosphate fertilizer and potato fertilizer, and the granulated product after mixing with powdered phosphate fertilizer and kari fertilizer, this embodiment is used to relieve the quick lime in lime nitrogen. And can then be granulated.
本実施形態の石灰窒素含有粒状肥料は、このようにして消和および造粒して得られるため圧壊強度に優れているが、例えば、木屋式硬度計（Ｍｏｄｅｌ Ｎｕｍｂｅｒ ０２０４０００１）による圧壊強度（造粒物直径２〜４ｍｍを２０個測定した平均値）は１．５Ｋｇｆ以上であることが好ましい。石灰窒素含有粒状肥料の圧壊強度が高いほど取扱性および散布性に優れるからである。あるいは、本実施形態の石灰窒素含有粒状肥料の圧壊強度は、１．５Ｋｇｆ、２．０Ｋｇｆ、２．５Ｋｇｆ、３．０Ｋｇf、３．５Ｋｇｆ、４．０Ｋｇｆのいずれかの値以上、又は任意の２つの値の範囲内であってもよい。 The lime nitrogen-containing granular fertilizer of this embodiment is excellent in crushing strength because it is obtained by soaking and granulating in this way. For example, the crushing strength (granulation by a Kiyama-type hardness meter (Model Number 02040001) is used. The average value obtained by measuring 20 object diameters of 2 to 4 mm is preferably 1.5 kgf or more. This is because the higher the crushing strength of the lime nitrogen-containing granular fertilizer, the better the handleability and sprayability. Alternatively, the crushing strength of the lime nitrogen-containing granular fertilizer of the present embodiment is 1.5 Kgf, 2.0 Kgf, 2.5 Kgf, 3.0 Kgf, 3.5 Kgf, 4.0 Kgf or more, or any 2 It may be within a range of two values.
本実施形態の石灰窒素含有粒状肥料は、防湿性能を有する合成樹脂製の袋に所定の量が密閉包装され最終製品となる。その後、包装袋が開封され肥料として使用されるまでには、様々な貯蔵環境に置かれる。貯蔵中の製品としての粒状肥料の貯蔵安定性を調べた。条件は、「農薬の登録申請書等に添付する資料について」（平成１４年１月１０日付け１３生産第３９８７号農林水産省生産局長通知）記載（経時安定性に関する検査では４０℃１ヶ月の苛酷試験は室温での１か年の試験と同等として取り扱う）に準拠した。貯蔵安定性能は粒の圧壊強度により評価した。 A predetermined amount of the lime nitrogen-containing granular fertilizer of this embodiment is hermetically packaged in a synthetic resin bag having moisture-proof performance to become a final product. Then, until the packaging bag is opened and used as fertilizer, it is placed in various storage environments. The storage stability of granular fertilizer as a product during storage was investigated. Conditions are described in “Documents to be attached to registration application forms for agricultural chemicals” (Notice of the Director of Production, Ministry of Agriculture, Forestry and Fisheries, No. 13 Production No. 3987 dated 10 January 2002). The stress test is treated as equivalent to a one-year test at room temperature). The storage stability performance was evaluated by the crushing strength of the grains.
本実施形態の石灰窒素含有粒状肥料は、このようにして４０℃、４週間貯蔵後に測定した圧壊強度が１．５Ｋｇｆ以上であることが好ましい。この圧壊強度が高いほど貯蔵安定性に優れるからである。あるいは、この圧壊強度は、１．０Ｋｇｆ、１．５Ｋｇｆ、２．０Ｋｇｆ、２．５Ｋｇｆ、３．０Ｋｇf、３．５Ｋｇｆ、４．０Ｋｇｆのいずれかの値以上、又は任意の２つの値の範囲内であってもよい。 The lime nitrogen-containing granular fertilizer of this embodiment preferably has a crushing strength of 1.5 kgf or more measured after storage at 40 ° C. for 4 weeks. This is because the higher the crushing strength, the better the storage stability. Alternatively, the crushing strength is 1.0 Kgf, 1.5 Kgf, 2.0 Kgf, 2.5 Kgf, 3.0 Kgf, 3.5 Kgf, 4.0 Kgf or more, or within the range of any two values. It may be.
＜石灰窒素含有粒状肥料の生産方法＞
本実施形態の石灰窒素含有粒状肥料の生産方法は、未消和処理の石灰窒素含有組成物に消和に用いる有機添加剤を含んだ水溶液を添加し、石灰窒素を消和処理する工程と、消和処理済みの前記石灰窒素含有組成物を造粒する工程と、を含む。なお、本実施形態の石灰窒素含有粒状肥料の生産方法は、造粒した石灰窒素含有粒状肥料を乾燥する工程をさらに含んでもよい。本実施形態の生産方法によれば、後述する実施例で示すように、生石灰の含有率が少なく、シアナミド性窒素の含有率が多くメラミンおよびアンメリンといったメラミン誘導体の含有率が少ない石灰窒素含有粒状肥料が得られる。
<Production method of lime nitrogen-containing granular fertilizer>
The production method of the lime nitrogen-containing granular fertilizer of the present embodiment is a process of adding an aqueous solution containing an organic additive used for soaking to an unsettled lime nitrogen-containing composition, and sacrificing lime nitrogen, And granulating the lime nitrogen-containing composition that has been subjected to the decontamination treatment. In addition, the production method of the lime nitrogen containing granular fertilizer of this embodiment may further include the process of drying the granulated lime nitrogen containing granular fertilizer. According to the production method of this embodiment, as shown in the examples described later, lime nitrogen-containing granular fertilizer with a low content of quicklime, a high content of cyanamide nitrogen, and a low content of melamine derivatives such as melamine and ammelin Is obtained.
本発明者らは、生石灰の消和反応を抑制する有機添加剤を添加し消和反応を行った水酸化カルシウムの結晶構造において、［１００］面の結晶子サイズを４００オングストローム以下とすることによって、シアナミド性窒素の含有率が多くジシアンジアミドおよびメラミン、アンメリンなどのメラミン誘導体の含有率が少ない石灰窒素含有粒状肥料が得られることを見出した。 In the crystal structure of calcium hydroxide in which an organic additive that suppresses the decalcification reaction of quicklime is added, the present inventors have made the crystallite size of the [100] plane to be 400 angstroms or less. The present inventors have found that a lime nitrogen-containing granular fertilizer having a high content of cyanamide nitrogen and a low content of melamine derivatives such as dicyandiamide, melamine, and ammelin can be obtained.
本発明者らは、単純に消和に用いる水に各種有機添加剤を添加して水溶液とした場合には、消和時の発熱ピーク温度自体は低下させることができるが、その代わりに石灰窒素含有粒状肥料の圧壊強度が低下しやすいことに気づいた。そこで、本発明者らは、いろいろ実験を重ねた結果、石灰窒素含有粒状肥料の造粒時に硝酸塩又は塩酸塩のいずれかの造粒助材を添加する場合には、石灰窒素含有粒状肥料の圧壊強度が向上するためにこの弱点を克服できることに気づいた。さらには特に、造粒工程で添加することによって、その後の乾燥工程におけるジシアンジアミドおよびメラミン、アンメリンなどのメラミン誘導体の生成抑制にも効果があることを見出した。 In the case where the present inventors simply add various organic additives to the water used for soaking to obtain an aqueous solution, the exothermic peak temperature itself at the time of soaking can be lowered. It was noticed that the crushing strength of the contained granular fertilizer tends to decrease. Therefore, as a result of repeated experiments, the present inventors have crushed the lime nitrogen-containing granular fertilizer when adding a granulation aid of either nitrate or hydrochloride during granulation of the lime nitrogen-containing granular fertilizer. I realized that this weakness could be overcome because of the increased strength. Furthermore, in particular, it has been found that the addition in the granulation step is effective in suppressing the formation of dicyandiamide and melamine derivatives such as melamine and ammelin in the subsequent drying step.
また、本発明者らは、造粒した石灰窒素含有粒状肥料を乾燥する際に、乾燥温度が高すぎると、後述する実施例で示すように、乾燥工程においてもメラミンやメラミン誘導体などが副生され、有効な肥料成分であるシアナミドが失われ易いという問題も見出した。 In addition, when drying the granulated lime nitrogen-containing granular fertilizer, the present inventors, if the drying temperature is too high, melamine, melamine derivatives and the like are by-produced in the drying process as shown in Examples described later. The present inventors also found a problem that cyanamide, which is an effective fertilizer component, is easily lost.
そこで、本発明者らは、本実施形態の石灰窒素含有粒状肥料の生産方法に、造粒した石灰窒素含有粒状肥料を１００℃以下の条件で流動乾燥機を用いて乾燥する工程をさらに加えることが好ましいことを見出した。１００℃以下の条件で流動乾燥機を用いて乾燥すれば、低温かつ短時間で効率良く乾燥ができるために、乾燥工程でメラミンやアンメリンなどのメラミン誘導体などの副生を抑制することができる。あるいは、この乾燥工程の温度は、１００℃、９５℃、９０℃、８５℃、８０℃、７５℃、６５℃、６０℃、５５℃、５０℃、４５℃、４０℃のいずれかの値以下又は任意の２つの値の範囲内であってもよい。 Therefore, the inventors further add a step of drying the granulated lime nitrogen-containing granular fertilizer using a fluidized dryer under a condition of 100 ° C. or less to the method for producing the lime nitrogen-containing granular fertilizer of the present embodiment. Has been found to be preferable. If drying is performed using a fluidized dryer under conditions of 100 ° C. or lower, drying can be efficiently performed at a low temperature and in a short time, so that by-products such as melamine derivatives such as melamine and ammelin can be suppressed in the drying step. Alternatively, the temperature of this drying step is 100 ° C, 95 ° C, 90 ° C, 85 ° C, 80 ° C, 75 ° C, 65 ° C, 60 ° C, 55 ° C, 50 ° C, 45 ° C, 40 ° C or less. Or it may be in the range of any two values.
乾燥工程における水分率は３．０質量％以下であることが好ましく、更には、２．０質量％以下であることが好ましい。後に示す実施例のように、乾燥工程で水分を３．０質量％よりも高くなった場合、貯蔵後のメラミン濃度が上昇するためである。水分率を２質量％以下とした場合には、貯蔵後でもメラミン濃度の大幅な上昇は認められない。水分率の測定は、加熱減量法（農林水産省農業環境技術研究所、肥料分析法（１９９２年版））によった。 The moisture content in the drying step is preferably 3.0% by mass or less, and more preferably 2.0% by mass or less. This is because the melamine concentration after storage increases when the water content is higher than 3.0% by mass in the drying step as in the examples shown later. When the water content is 2% by mass or less, no significant increase in melamine concentration is observed even after storage. The moisture content was measured by a heat loss method (Ministry of Agriculture, Forestry and Fisheries, Agricultural Environment Technology Laboratory, Fertilizer Analysis Method (1992)).
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
また、上記実施の形態では乾燥工程を流動乾燥機で行うこととしたが、特に限定する趣旨ではなく、低温かつ短時間で乾燥できるのであれば他の乾燥機を用いても良い。例えば、振動乾燥機、キルン式乾燥機、送風乾燥機、減圧乾燥機などを好適に用いることができる。 Moreover, in the said embodiment, although the drying process was performed with the fluid dryer, it is not the meaning to limit in particular, As long as it can dry at low temperature and for a short time, you may use another dryer. For example, a vibration dryer, a kiln dryer, a blower dryer, a vacuum dryer, or the like can be suitably used.
以下、本発明を実施例によりさらに説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these.
＜比較例１＞
消和工程として、直径１ｍ深さ６０ｃｍの混合機に石灰窒素８０ｋｇを入れた。石灰窒素は粉状で、生石灰１３．２％、全窒素２４．５％、シアナミド性窒素２３．７％のものを用意した。次に水１０ｋｇ（石灰窒素１００質量部に対して１２．５質量部）をジョウロで一括添加し、蒸気抜きとして頂部に直径５ｃｍの穴を穿った円錐形の蓋をし、直ちに５分間攪拌を行い、そのまま放置した。頂部穴より温度計を差し込み品温を計測した結果、表１に示すように消和反応ピーク温度は１５５℃に達した。消和反応終了後に消和済みの石灰窒素を採取し、次の造粒工程に用いた。
<Comparative Example 1>
As a soothing process, 80 kg of lime nitrogen was put into a mixer having a diameter of 1 m and a depth of 60 cm. The lime nitrogen was powdery and prepared with 13.2% quick lime, 24.5% total nitrogen, and 23.7% cyanamide nitrogen. Next, 10 kg of water (12.5 parts by mass with respect to 100 parts by mass of lime nitrogen) is added all at once with a water heater, and a conical lid with a hole with a diameter of 5 cm is made at the top for steam removal, and immediately stirred for 5 minutes. Done and left alone. As a result of inserting a thermometer from the top hole and measuring the product temperature, as shown in Table 1, the soaking reaction peak temperature reached 155 ° C. After completion of the soaking reaction, the lime nitrogen that had been sanitized was collected and used for the next granulation step.
消和処理済みの石灰窒素に水を造粒水量が約１５（ｖ／ｗ）％となるように添加して、攪拌造粒機（ハイスピードミキサー：株式会社アーステクニカ製）を用いて造粒時間約１０分間かけて造粒を行った。得られた粒状肥料のうち篩を用いて所望の直径２〜４ｍｍのものだけを篩別したところ、所望の直径の造粒率は８３％（ｗ／ｗ）であった。これらの所望の直径の粒状肥料だけを選び出して、次の乾燥工程に用いた。 Water is added to the lime nitrogen that has been subjected to decontamination treatment so that the amount of granulated water is about 15 (v / w)%, and granulated using a stirring granulator (high speed mixer: manufactured by Earth Technica Co., Ltd.). Granulation was performed for about 10 minutes. Among the obtained granular fertilizers, only those having a desired diameter of 2 to 4 mm were sieved using a sieve. As a result, the granulation rate of the desired diameter was 83% (w / w). Only these granular fertilizers with the desired diameter were selected and used in the next drying step.
次の乾燥工程では、サンプルを流動乾燥機を用いて乾燥温度１００℃、乾燥時間１０分の処理を行った。仕上げ水分２質量％以下を目標とした。その結果、水分１．６質量％（ｗ／ｗ）である乾燥処理済みの石灰窒素が得られた。 In the next drying step, the sample was treated using a fluid dryer at a drying temperature of 100 ° C. and a drying time of 10 minutes. The target was a finish moisture of 2% by mass or less. As a result, dried lime nitrogen having a moisture content of 1.6% by mass (w / w) was obtained.
＜粉末Ｘ線回折法による結晶子サイズ測定＞
消和処理済みの石灰窒素、あるいは造粒、乾燥工程を経た石灰窒素をメノウ乳鉢にて粒度を調製し、ガラス試料板に詰めた。粉末Ｘ線回折測定は以下の条件、すなわち装置：Ｘ線回折装置 ＲＩＮＴ２５００Ｖ〔（株）リガク製〕、出力：Ｘ線源は銅（Ｃｕ）、加速電圧は４０ｋＶ、励起電子線電流は３００ｍＡ、モノクロメーターによる単色化、スリット：ＤＳ、ＳＳ：１／２°、ＲＳ：０．１５ｍｍ、走査条件：ＦＴ法 ０．０２°／ｓｔｅｐ、２ｓ／ｓｔｅｐにて測定を行った。測定後、半値幅を下記に示すScherrerの式に代入して結晶子サイズ求めた。測定した結果を表１に示す。
Scherrerの式
：結晶子の大きさ（ｈｋｌに垂直な方向の結晶子の大きさ）（Å）
hkl ：面指数
：測定Ｘ線波長（１．５４０５Å）
：結晶子の大きさによる回折線の拡がり
: Scherrer定数（０．９０を採用）
：回折線のブラッグ角(水酸化カルシウム結晶［１００］面 ２８．７０°）
<Measurement of crystallite size by powder X-ray diffraction method>
The particle size of lime nitrogen that has been subjected to decontamination treatment or lime nitrogen that has undergone granulation and drying steps was adjusted in an agate mortar and packed into a glass sample plate. The powder X-ray diffraction measurement is performed under the following conditions, that is, an apparatus: X-ray diffraction apparatus RINT2500V [manufactured by Rigaku Corporation], output: X-ray source is copper (Cu), acceleration voltage is 40 kV, excitation electron beam current is 300 mA, monochrome Monochromatic measurement with a meter, slit: DS, SS: 1/2 °, RS: 0.15 mm, scanning condition: FT method 0.02 ° / step, 2 s / step. After the measurement, the crystallite size was determined by substituting the half width into the Scherrer equation shown below. The measured results are shown in Table 1.
Scherrer's formula
: Crystallite size (crystallite size in the direction perpendicular to hkl) (Å)
hkl: Plane index: Measurement X-ray wavelength (1.5405 mm)
: Broadening of diffraction lines due to crystallite size
: Scherrer constant (0.90 adopted)
: Bragg angle of diffraction line (calcium hydroxide crystal [100] plane 28.70 °)
Ｘ線回折による水酸化カルシウムの結晶構造解析から、［１００］面の結晶子サイズに対する［０１１］面の結晶子サイズの比、および［１００］面の結晶子サイズに対する［１０２］面の結晶子サイズの比は０．５〜１．０、同じく［１００］面の結晶子サイズに対する［１１０］面の結晶子サイズの比は、０．８〜１．４であった。 From the crystal structure analysis of calcium hydroxide by X-ray diffraction, the ratio of the crystallite size of the [011] plane to the crystallite size of the [100] plane and the crystallite of the [102] plane to the crystallite size of the [100] plane The size ratio was 0.5 to 1.0, and the ratio of the [110] face crystallite size to the [100] face crystallite size was 0.8 to 1.4.
また、乾燥処理済みの石灰窒素を分析したところ、表１に示すように、石灰窒素のうち生石灰の含有率は、０．１２質量％であった。この生石灰の含有率は、Ｘ線回折装置を用い、試薬のＣａＯにて作成した検量線と試料のピーク強度から算出した。 Moreover, when the lime nitrogen after dry processing was analyzed, as shown in Table 1, the content rate of quick lime among lime nitrogen was 0.12 mass%. The content rate of this quicklime was computed from the analytical curve created with the reagent CaO, and the peak intensity of the sample using the X-ray-diffraction apparatus.
また、乾燥処理済みの石灰窒素を分析したところ、石灰窒素のうちシアナミド性窒素の含有率は、１７．７質量％であった。このシアナミド性窒素の含有率は、農林水産省農業環境技術研究所「肥料分析法」１９９２年版、シアナミド性窒素、硝酸銀法により測定した。また、石灰窒素のうちジシアンジアミドの含有率は、３．５質量％であった。このジシアンジアミドの含有率は、高速液体クロマトグラフ法、農林水産消費安全技術センター 肥料研究報告（２）、２５−３１、２００９年により測定した。 Moreover, when the dried lime nitrogen was analyzed, the content of cyanamide nitrogen in the lime nitrogen was 17.7% by mass. The content of cyanamide nitrogen was measured by the Ministry of Agriculture, Forestry and Fisheries, National Institute for Agro-Environmental Technology, “Fertilizer Analysis”, 1992, cyanamide nitrogen and silver nitrate method. Moreover, the content rate of dicyandiamide in lime nitrogen was 3.5 mass%. The dicyandiamide content was measured by high performance liquid chromatography, Fertilizer Research Report (2), 25-31, 2009, Agriculture, Forestry and Fisheries Consumption Safety Technology Center.
消和処理済みの石灰窒素、あるいは造粒、乾燥工程を経た石灰窒素を分析したところ、メラミンの含有率は、消和工程後０．８８質量％、乾燥工程後１．１９質量％であった。このメラミンの含有率は、アセトニトリル−水−ジエチルアミン（５＋４＋１）を分析試料に加えてメラミンを抽出し、高速液体クロマトグラフに導入し、カルバモイル基を化学結合したシリカゲルカラムで分離し、波長２１４ｎｍで測定することにより算出した。 As a result of analysis of lime nitrogen that had been subjected to decontamination treatment or lime nitrogen that had undergone granulation and drying, the content of melamine was 0.88% by mass after the decontamination step and 1.19% by mass after the drying step. . The content of melamine is measured at a wavelength of 214 nm by adding acetonitrile-water-diethylamine (5 + 4 + 1) to the analytical sample, extracting the melamine, introducing it into a high performance liquid chromatograph, separating it with a silica gel column chemically bonded to the carbamoyl group. It was calculated by doing.
アンメリンの含有率は、アセトニトリル−水−ジエチルアミン（５＋４＋１）を分析試料に加えてメラミンを抽出し、液体クロマトグラフィー質量分析／質量分析法、移動相：１０ｍＭ 酢酸アンモニウム／アセトニトリル＝１５／８５、カラム：Ｗａｔｅｒｓ Ａｃｑｕｉｔｙ ＵＰＬＣ ＢＥＨ ＨＩＬＩＣ２．１×１００ｍｍ、カラム温度４０℃、流速０．５ｍＬ／分、イオン化モード：ＥＳＩポジティブ、定量イオン１２８→８６（ｍ／Ｚ）、ソース温度１５０℃、キャピラリー電圧０．５（ｋＶ）、デソルベーション温度４５０℃により測定した。 The content of ammelin is acetonitrile-water-diethylamine (5 + 4 + 1) added to the analysis sample to extract melamine, liquid chromatography mass spectrometry / mass spectrometry, mobile phase: 10 mM ammonium acetate / acetonitrile = 15/85, column: Waters Acquity UPLC BEH HILIC 2.1 × 100 mm, column temperature 40 ° C., flow rate 0.5 mL / min, ionization mode: ESI positive, quantitative ion 128 → 86 (m / Z), source temperature 150 ° C., capillary voltage 0.5 ( kV) and a desolvation temperature of 450 ° C.
造粒、乾燥工程を経た石灰窒素を分析したところ、アンメリンの含有率は、０．８３質量％であった。 When the lime nitrogen which passed through granulation and a drying process was analyzed, the content rate of ammeline was 0.83 mass%.
また、造粒、乾燥工程を経た石灰窒素の圧壊強度は３．５Ｋｇｆ／ｍｍ２であった。なお、圧壊強度は、篩わけにより得た直径２〜４ｍｍの造粒物について任意の２０個を選び、木屋式硬度計（Ｍｏｄｅｌ Ｎｕｍｂｅｒ ０２０４０００１）により測定した。 Moreover, the crushing strength of the lime nitrogen which passed through the granulation and drying process was 3.5 kgf / mm 2. The crushing strength was measured by selecting 20 arbitrary granulated products having a diameter of 2 to 4 mm obtained by sieving and using a Kiyama-type hardness meter (Model Number 02040001).
＜４０℃、４週間貯蔵後の圧壊強度＞
さらに、造粒、乾燥工程を経た石灰窒素を、「農薬の登録申請書等に添付する資料について」（平成１４年１月１０日付け１３生産第３９８７号農林水産省生産局長通知）記載（経時安定性に関する検査では４０℃１ヶ月の苛酷試験は室温での１か年の試験と同等として取り扱う）の条件に準拠させ、恒温槽４０℃、４週間後の貯蔵安定性の尺度である圧壊強度を測定した。これらの評価結果を表１に示す。４０℃、４週間貯蔵後の圧壊強度の測定方法および表記は、上記の測定方法および表記と同様である。なお、後述する表２についても同様である。
<Crushing strength after storage at 40 ° C for 4 weeks>
In addition, lime nitrogen that has undergone granulation and drying processes is described in “Regarding materials to be attached to application forms for registration of agricultural chemicals” (Notice of Director of Production, Ministry of Agriculture, Forestry and Fisheries, No. 13 Production No. 3987 dated January 10, 2002) In the inspection for stability, the severe test at 40 ° C for one month is treated as equivalent to the one-year test at room temperature), and the crushing strength is a measure of storage stability at 40 ° C for 4 weeks. Was measured. These evaluation results are shown in Table 1. The measuring method and notation of the crushing strength after storage at 40 ° C. for 4 weeks are the same as the above measuring method and notation. The same applies to Table 2 described later.
＜比較例２＞
粒状肥料の乾燥工程で、サンプルを流動乾燥機にて、乾燥温度８０℃で乾燥処理を行った以外は、基本的には比較例１と同様にして石灰窒素含有粒状肥料を作製した。条件および評価結果を表１に示す。
<Comparative example 2>
A lime nitrogen-containing granular fertilizer was produced basically in the same manner as in Comparative Example 1 except that the sample was subjected to a drying process at a drying temperature of 80 ° C. in the drying step of the granular fertilizer. Table 1 shows the conditions and the evaluation results.
＜比較例３＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、水２ｋｇ（石灰窒素１００質量部に対して２．５質量部）を添加した。水を添加した後、直ちに５分間攪拌し、その後静置した。水の添加を６０分間隔で行い合計５回で１０ｋｇ（石灰窒素１００質量部に対して１２．５質量部）の水を添加した。乾燥温度８０℃で乾燥処理を行い粉状石灰窒素を得た。条件および評価結果を表１に示す。
<Comparative Example 3>
In the same manner as in Comparative Example 1, the conditions such as the container and the amount of lime nitrogen were aligned, and 2 kg of water (2.5 parts by mass with respect to 100 parts by mass of lime nitrogen) was added. After adding water, the mixture was immediately stirred for 5 minutes and then allowed to stand. Water was added at intervals of 60 minutes, and 10 kg of water (12.5 parts by mass with respect to 100 parts by mass of lime nitrogen) was added 5 times in total. Drying was performed at a drying temperature of 80 ° C. to obtain powdered lime nitrogen. Table 1 shows the conditions and the evaluation results.
＜実施例１＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、水１０ｋｇを添加した。水を添加した後、直ちに３時間攪拌し続けた。乾燥温度８０℃で乾燥処理を行い粉状石灰窒素を得た。条件および評価結果を表１に示す。
<Example 1>
As in Comparative Example 1, conditions such as the container and the amount of lime nitrogen were aligned, and 10 kg of water was added. Stirring was continued for 3 hours immediately after the addition of water. Drying was performed at a drying temperature of 80 ° C. to obtain powdered lime nitrogen. Table 1 shows the conditions and the evaluation results.
＜実施例２＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、水２ｋｇを添加した。水を添加した後、直ちに攪拌した。水を添加する操作の時以外は攪拌を続けた。水の添加を６０分間隔で行い合計５回で１０ｋｇの水を添加した。造粒工程は比較例１と同様に行った。乾燥工程は比較例２と同様、乾燥温度８０℃で行った。条件および評価結果を表１に示す。
<Example 2>
In the same manner as in Comparative Example 1, the container and the amount of lime nitrogen were aligned, and 2 kg of water was added. Stir immediately after adding water. Stirring was continued except during the operation of adding water. Water was added at intervals of 60 minutes, and 10 kg of water was added in total 5 times. The granulation step was performed in the same manner as in Comparative Example 1. The drying process was performed at a drying temperature of 80 ° C. as in Comparative Example 2. Table 1 shows the conditions and the evaluation results.
＜実施例３＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、水１．２５ｋｇ（石灰窒素１００質量部に対して１．５６質量部）を添加した。水を添加した後、直ちに攪拌した。水を添加する操作以外は攪拌を続けた。水の添加を６０分間隔で行い合計８回で１０ｋｇの水を添加した。造粒工程は比較例１と同様に行った。乾燥工程は比較例２と同様、乾燥温度８０℃で行った。条件および評価結果を表１に示す。
<Example 3>
As in Comparative Example 1, the container and the amount of lime nitrogen were aligned, and 1.25 kg of water (1.56 parts by mass with respect to 100 parts by mass of lime nitrogen) was added. Stir immediately after adding water. Stirring was continued except for the operation of adding water. Water was added at intervals of 60 minutes, and 10 kg of water was added a total of 8 times. The granulation step was performed in the same manner as in Comparative Example 1. The drying process was performed at a drying temperature of 80 ° C. as in Comparative Example 2. Table 1 shows the conditions and the evaluation results.
＜比較例４＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、スクロース１．６ｋｇ（石灰窒素１００質量部に対して２質量部）を含み水１０ｋｇとなるように溶解した液を石灰窒素へ添加した。造粒工程は比較例１と同様に行った。乾燥工程は比較例２と同様、乾燥温度８０℃で行った。このとき仕上げ水分を４．７質量％とした。条件および評価結果を表２に示す。
<Comparative Example 4>
As in Comparative Example 1, the container, the amount of lime nitrogen, etc. are aligned, and the liquid dissolved in lime nitrogen containing 1.6 kg of sucrose (2 parts by mass with respect to 100 parts by mass of lime nitrogen) to become 10 kg of water. Added. The granulation step was performed in the same manner as in Comparative Example 1. The drying process was performed at a drying temperature of 80 ° C. as in Comparative Example 2. At this time, the finishing moisture was 4.7 mass%. Table 2 shows the conditions and evaluation results.
＜実施例４＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、水２ｋｇを添加した。水を添加した後、直ちに攪拌した。水を添加する操作以外は攪拌を続けた。水の添加を６０分間隔で行い合計５回で１０ｋｇの水を添加した。造粒工程は硝酸カルシウム４水和物３．４５ｋｇ（石灰窒素１００質量部に対して硝酸カルシウムとして３質量部）を添加した以外は比較例１と同様に行った。乾燥工程は比較例２と同様、乾燥温度８０℃で行った。条件および評価結果を表２に示す。
<Example 4>
In the same manner as in Comparative Example 1, the container and the amount of lime nitrogen were aligned, and 2 kg of water was added. Stir immediately after adding water. Stirring was continued except for the operation of adding water. Water was added at intervals of 60 minutes, and 10 kg of water was added in total 5 times. The granulation step was performed in the same manner as in Comparative Example 1 except that 3.45 kg of calcium nitrate tetrahydrate (3 parts by mass as calcium nitrate with respect to 100 parts by mass of lime nitrogen) was added. The drying process was performed at a drying temperature of 80 ° C. as in Comparative Example 2. Table 2 shows the conditions and evaluation results.
＜実施例５＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、スクロースを固形分で１．６ｋｇ（石灰窒素１００質量部に対して２質量部）を含み水１０ｋｇとなるように溶解した液を石灰窒素へ添加した。造粒工程は比較例１と同様に行った。乾燥工程は比較例２と同様、乾燥温度８０℃で行った。条件および評価結果を表２に示す。
<Example 5>
The liquid which melt | dissolved so that the conditions, such as a container and the quantity of lime nitrogen, may be prepared similarly to the comparative example 1, and 1.6 kg (2 mass parts with respect to 100 mass parts of lime nitrogen) of sucrose may be contained to 10 kg of water. Was added to lime nitrogen. The granulation step was performed in the same manner as in Comparative Example 1. The drying process was performed at a drying temperature of 80 ° C. as in Comparative Example 2. Table 2 shows the conditions and evaluation results.
＜実施例６＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、廃糖蜜を固形分で１ｋｇ（石灰窒素１００質量部に対して固形分として１．２５質量部）を含み水１０ｋｇとなるように溶解した液を石灰窒素へ添加した。造粒工程は比較例１と同様に行った。乾燥工程は比較例２と同様、乾燥温度８０℃で行った。条件および評価結果を表２に示す。
<Example 6>
As in Comparative Example 1, the container, the amount of lime nitrogen, etc. are aligned, and the molasses is contained in a solid content of 1 kg (1.25 parts by mass as a solid content with respect to 100 parts by mass of lime nitrogen) to be 10 kg of water. The solution dissolved in was added to lime nitrogen. The granulation step was performed in the same manner as in Comparative Example 1. The drying process was performed at a drying temperature of 80 ° C. as in Comparative Example 2. Table 2 shows the conditions and evaluation results.
＜実施例７＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、廃糖蜜を固形分で１ｋｇ（石灰窒素１００質量部に対して固形分として１．２５質量部）、また硝酸カルシウム４水和物５．７５ｋｇ（石灰窒素１００質量部に対して硝酸カルシウムとして５質量部）を含み水１０ｋｇとなるように溶解した液を石灰窒素へ添加した。造粒工程は比較例１と同様に行った。乾燥工程は比較例２と同様、乾燥温度８０℃で行った。条件および評価結果を表２に示す。
<Example 7>
As in Comparative Example 1, the container, the amount of lime nitrogen, etc. were prepared, the molasses of waste molasses was 1 kg in solid content (1.25 mass parts as solid content with respect to 100 mass parts of lime nitrogen), and calcium nitrate tetrahydrate The liquid which dissolved 5.75 kg (5 mass parts as calcium nitrate with respect to 100 mass parts of lime nitrogen) so that it might become 10 kg of water was added to lime nitrogen. The granulation step was performed in the same manner as in Comparative Example 1. The drying process was performed at a drying temperature of 80 ° C. as in Comparative Example 2. Table 2 shows the conditions and evaluation results.
＜実施例８〜実施例１３＞
比較例１と同様に容器、石灰窒素の量などの条件をそろえ、表２記載の条件にて、消和、造粒、乾燥工程を行った。評価結果を表２に示す。
<Example 8 to Example 13>
In the same manner as in Comparative Example 1, the conditions such as the container and the amount of lime nitrogen were aligned, and the soaking, granulation, and drying steps were performed under the conditions shown in Table 2. The evaluation results are shown in Table 2.
比較例１、２、３と実施例１、２との対比により、水酸化カルシウム結晶の［１００］面の結晶子サイズを７００オングストローム以上となるように消和、造粒、乾燥工程条件を制御することで、生石灰の含有率が少なく、シアナミドの含有率が保たれ、シアナミドからの誘導体、具体的にはジシアンジアミドおよびメラミン、アンメリンなどのメラミン誘導体の含有率が抑制された石灰窒素含有粒状肥料が得られることがわかる。 By comparing Comparative Examples 1, 2 and 3 with Examples 1 and 2, the conditions of soaking, granulating and drying are controlled so that the crystallite size of the [100] plane of the calcium hydroxide crystal is 700 angstroms or more. Thus, a lime nitrogen-containing granular fertilizer in which the content of quick lime is low, the content of cyanamide is maintained, and the content of derivatives from cyanamide, specifically, dicyandiamide and melamine derivatives such as melamine and ammelin is suppressed. It turns out that it is obtained.
また実施例３において、生石灰の含有率が少なく、シアナミドの含有率が保たれ、メラミンやアンメリンなどのメラミン誘導体の含有率が抑制されているなど効果は十分であることがわかる。ただし、水を８回に分けて添加することにより消和工程には長時間を要す。 Moreover, in Example 3, the content rate of quick lime is small, the content rate of cyanamide is maintained, and it turns out that the effects, such as the content rate of melamine derivatives, such as melamine and ammelin being suppressed, are enough. However, a long time is required for the decontamination step by adding water in 8 portions.
また実施例４において、造粒工程で硝酸カルシウムを添加することで、硬度に優れ、シアナミドの含有率が保たれ、シアナミドからの誘導体、具体的にはジシアンジアミドおよびメラミン、アンメリンなどのメラミン誘導体の含有率が一層抑制された石灰窒素含有粒状肥料が得られることがわかる。 Further, in Example 4, by adding calcium nitrate in the granulation step, the hardness is excellent and the content of cyanamide is maintained. Derivatives from cyanamide, specifically containing dicyandiamide and melamine derivatives such as melamine and ammelin It turns out that the lime nitrogen containing granular fertilizer in which the rate was further suppressed is obtained.
比較例４と実施例５との対比において、スクロースを添加し水酸化カルシウム結晶の［１００］面の結晶子サイズを４００オングストローム以下に制御しても、乾燥工程で水分を４．７質量％とした場合、貯蔵後のメラミン濃度が上昇することがわかる。一方で水分率を２質量％以下とした場合には、貯蔵後でもメラミン濃度の大幅な上昇は認められない。 In contrast to Comparative Example 4 and Example 5, even when sucrose was added and the crystallite size of the [100] plane of the calcium hydroxide crystal was controlled to 400 angstroms or less, the water content was 4.7% by mass in the drying step. When it does, it turns out that the melamine concentration after storage rises. On the other hand, when the moisture content is 2% by mass or less, no significant increase in melamine concentration is observed even after storage.
実施例６〜１３において、未消和石灰窒素中の生石灰の消和反応を抑制する有機添加剤および造粒助材として硝酸カルシウムと消和処理済みの石灰窒素とを含み、石灰窒素中の水酸化カルシウム結晶の［１００］面の結晶子サイズが４００オングストローム以下になるよう制御された消和、造粒、乾燥工程を組み合わせることで産生した石灰窒素含有粒状肥料において、硬度に優れ、生石灰の含有率が少なく、シアナミドの含有率が保たれ、シアナミドからの誘導体、具体的にはジシアンジアミドおよびメラミン、アンメリンなどのメラミン誘導体の含有率が抑制された石灰窒素含有粒状肥料が得られることがわかる。さらに乾燥温度が１００℃であっても、メラミン含有率を０．２質量％に抑制できることがわかる。
In Examples 6-13, the organic additive which suppresses the decontamination reaction of the quick lime in unsettled lime nitrogen, and calcium nitrate and slaked lime nitrogen as a granulation aid are contained, and the water in lime nitrogen The lime nitrogen-containing granular fertilizer produced by combining the soaking, granulating and drying processes controlled so that the crystallite size of the [100] face of the calcium oxide crystal is 400 angstroms or less, has excellent hardness and contains quick lime It can be seen that a lime nitrogen-containing granular fertilizer in which the content of cyanamide is suppressed and the content of derivatives of cyanamide, specifically dicyandiamide and melamine derivatives such as melamine and ammelin, is suppressed is obtained. Furthermore, even if a drying temperature is 100 degreeC, it turns out that a melamine content rate can be suppressed to 0.2 mass%.
Claims (13)
消和処理済みの石灰窒素と、
を含み、
前記消和処理済みの石灰窒素のうち、水酸化カルシウム結晶の［１００］面の結晶子サイズが４００オングストローム以下である、
石灰窒素含有粒状肥料。 An organic additive that suppresses the decalcification reaction of quicklime in unslaked lime nitrogen;
With lime nitrogen that has been treated
Including
Of the lime nitrogen that has been subjected to the decontamination treatment, the crystallite size of the [100] plane of the calcium hydroxide crystal is 400 angstroms or less.
Lime nitrogen-containing granular fertilizer.
消和処理済みの石灰窒素と、
を含み、
前記消和処理済みの石灰窒素のうち、水酸化カルシウム結晶の［１００］面の結晶子サイズが４００オングストローム以下である、
石灰窒素含有粒状肥料。 An organic additive that suppresses the decalcification reaction of quicklime in unslaked lime nitrogen, and nitrate or hydrochloride as a granulation aid,
With lime nitrogen that has been treated
Including
Of the lime nitrogen that has been subjected to the decontamination treatment, the crystallite size of the [100] plane of the calcium hydroxide crystal is 400 angstroms or less.
Lime nitrogen-containing granular fertilizer.
石灰窒素含有粒状肥料。 The lime nitrogen-containing granular fertilizer in which the crystallite size of the [100] plane of the calcium hydroxide crystal is 700 angstroms or more and 1200 angstroms or less among the lime nitrogen that has been dehydrated only with water.
消和処理済みの石灰窒素と、
を含み、
前記消和処理済みの石灰窒素のうち水酸化カルシウム結晶の［１００］面の結晶子サイズが７００オングストローム以上、１２００オングストローム以下である
石灰窒素含有粒状肥料。 Of the lime nitrogen that has been treated with water only, nitrate or hydrochloride as a granulating aid,
With lime nitrogen that has been treated
Including
The lime nitrogen-containing granular fertilizer in which the crystallite size of the [100] plane of calcium hydroxide crystal is 700 angstroms or more and 1200 angstroms or less among the lime nitrogen that has been subjected to the decontamination treatment.
請求項１、２に記載の石灰窒素含有粒状肥料。 The organic additive includes one or more organic substances selected from the group consisting of gluconic acid or salts thereof, glucose, sucrose,
Lime nitrogen-containing granular fertilizer according to claims 1 and 2.
請求項１、２のいずれかに記載の石灰窒素含有粒状肥料。 The organic additive is one selected from the group consisting of molasses, corn syrup, and pulp waste liquid.
Lime nitrogen-containing granular fertilizer according to any one of claims 1 and 2.
請求項２、４〜６のいずれかに記載の石灰窒素含有粒状肥料。 The granulation aid contains one or more salts selected from the group consisting of calcium nitrate, calcium chloride, and magnesium chloride.
Lime nitrogen-containing granular fertilizer according to any one of claims 2 and 4-6.
４０℃、４週間貯蔵後の圧壊強度が１．５Ｋｇｆ以上である、
請求項２、５、６、１０、１１に記載の消和済石灰窒素含有粒状肥料。 The organic additive is at least one selected from the group consisting of gluconic acid or salts thereof, sugars such as glucose and sucrose or salts thereof, molasses, corn syrup, and pulp waste liquid, and the granulation aid is calcium nitrate Including
The crushing strength after storage at 40 ° C. for 4 weeks is 1.5 kgf or more.
The lime nitrogen-containing granular fertilizer according to claim 2 , 5 , 6 , 10 , 11.
請求項４、１０、１１に記載の消和済石灰窒素含有粒状肥料。
The granulation aid contains calcium nitrate, and the crushing strength after storage at 40 ° C. for 4 weeks is 1.5 kgf or more.
The slaked lime nitrogen-containing granular fertilizer according to claim 4, 10, or 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014021761A JP6339815B2 (en) | 2014-02-06 | 2014-02-06 | Lime nitrogen-containing granular fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014021761A JP6339815B2 (en) | 2014-02-06 | 2014-02-06 | Lime nitrogen-containing granular fertilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015147710A JP2015147710A (en) | 2015-08-20 |
| JP6339815B2 true JP6339815B2 (en) | 2018-06-06 |
Family
ID=53891431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014021761A Active JP6339815B2 (en) | 2014-02-06 | 2014-02-06 | Lime nitrogen-containing granular fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6339815B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848458B (en) * | 2020-08-05 | 2022-04-26 | 原平市同利化工有限责任公司 | Process for extracting dicyandiamide in process of preparing 3-mercaptopropionic acid |
| CN114105827A (en) * | 2022-01-27 | 2022-03-01 | 天津凯莱英医药科技发展有限公司 | System and method for continuously synthesizing dicyandiamide |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3868095B2 (en) * | 1997-02-25 | 2007-01-17 | 電気化学工業株式会社 | Lime nitrogen-containing composition and fertilizer using the same |
| JP3483775B2 (en) * | 1998-08-14 | 2004-01-06 | 電気化学工業株式会社 | Lime nitrogen composition |
| JP4020230B2 (en) * | 1999-07-19 | 2007-12-12 | 電気化学工業株式会社 | Method for producing lime nitrogenous fertilizer |
| JP3461764B2 (en) * | 1999-09-13 | 2003-10-27 | 電気化学工業株式会社 | Lime nitrogen composition |
| JP2002012488A (en) * | 2000-06-22 | 2002-01-15 | Denki Kagaku Kogyo Kk | Method for producing granulated fertilizer |
| JP2003055071A (en) * | 2001-08-23 | 2003-02-26 | Denki Kagaku Kogyo Kk | Mixed granular fertilizer |
| JP2007217231A (en) * | 2006-02-17 | 2007-08-30 | Denki Kagaku Kogyo Kk | Lime nitrogen granular fertilizer and method of manufacturing the same |
| JP4597904B2 (en) * | 2006-04-21 | 2010-12-15 | 電気化学工業株式会社 | Wet granulation method of lime nitrogen powder |
-
2014
- 2014-02-06 JP JP2014021761A patent/JP6339815B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015147710A (en) | 2015-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1595860B1 (en) | Process of preparation of granulated ammonium nitrate-sulphate fertilizer | |
| Al-Rawajfeh et al. | Clean and efficient synthesis using mechanochemistry: Preparation of kaolinite–KH2PO4 and kaolinite–(NH4) 2HPO4 complexes as slow released fertilizer | |
| CA1163417A (en) | Treating calcined gypsum with solubilizing agent | |
| US7691169B2 (en) | Partially chelated carboxylate nutrients and methods for their production and use | |
| US4355014A (en) | Stable calcium hypochlorite composition and method for manufacture thereof | |
| DE69207727T2 (en) | Process for the production of salt granules | |
| WO2007132060A2 (en) | Fertilizer granules and manufacturing process thereof | |
| CS273641B2 (en) | Method of water-soluble fertilizers granulation with high kieserite portion | |
| JP6339815B2 (en) | Lime nitrogen-containing granular fertilizer | |
| CN108356054A (en) | A kind of matrixing gangue and preparation method thereof and a kind of seedling medium | |
| US5676729A (en) | Particulate urea with mineral filler incorporated for hardness | |
| DE60107678T2 (en) | METHOD FOR STABILIZING AMMONIUM NITRATE | |
| EP3016920B2 (en) | Process for preparing a fertiliser | |
| JP6129840B2 (en) | Lime nitrogen-containing granular fertilizer and production method thereof | |
| EP1923376A2 (en) | Process of preparation ammonium nitrate-sulphate | |
| WO2006057573A2 (en) | Method for producing a nitrogen-potassium fertiliser | |
| US4454103A (en) | High acid monocalcium phosphate and process for preparing the same | |
| US1893946A (en) | Production of calcium nitrate | |
| CN105084331B (en) | A kind of production method of no waste residue phosphoric acid by wet process | |
| JPS5918498A (en) | Method of processing radioactive liquid waste | |
| RU2614874C2 (en) | Method of producing lime-ammonium nitrate | |
| RU2225384C1 (en) | Nitrogen-potassium fertilizer production method | |
| JPH03285638A (en) | Permanganate composition for reaction with ethylene and freshness retaining agent using the same | |
| US1690627A (en) | Process of making arsenate of lime | |
| RU1494480C (en) | Method of production unconsolidated potash-cupric fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170118 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180219 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180227 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180327 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180508 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180511 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6339815 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |