WO2024059123A1 - Fertiliser product - Google Patents
Fertiliser product Download PDFInfo
- Publication number
- WO2024059123A1 WO2024059123A1 PCT/US2023/032618 US2023032618W WO2024059123A1 WO 2024059123 A1 WO2024059123 A1 WO 2024059123A1 US 2023032618 W US2023032618 W US 2023032618W WO 2024059123 A1 WO2024059123 A1 WO 2024059123A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- boron
- source
- granules
- release
- product
- Prior art date
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 72
- 229910052796 boron Inorganic materials 0.000 claims abstract description 117
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910021539 ulexite Inorganic materials 0.000 claims abstract description 39
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008187 granular material Substances 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000011785 micronutrient Substances 0.000 claims description 19
- 235000013369 micronutrients Nutrition 0.000 claims description 19
- 235000021073 macronutrients Nutrition 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 15
- 230000003050 macronutrient Effects 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000002689 soil Substances 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 229910021537 Kernite Inorganic materials 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 5
- RDMZIKMKSGCBKK-UHFFFAOYSA-N disodium;(9,11-dioxido-5-oxoboranyloxy-2,4,6,8,10,12,13-heptaoxa-1,3,5,7,9,11-hexaborabicyclo[5.5.1]tridecan-3-yl)oxy-oxoborane;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].O1B(OB=O)OB(OB=O)OB2OB([O-])OB([O-])OB1O2 RDMZIKMKSGCBKK-UHFFFAOYSA-N 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000007580 dry-mixing Methods 0.000 claims description 5
- STNGULMWFPMOCE-UHFFFAOYSA-N ethyl 4-butyl-3,5-dimethyl-1h-pyrrole-2-carboxylate Chemical compound CCCCC1=C(C)NC(C(=O)OCC)=C1C STNGULMWFPMOCE-UHFFFAOYSA-N 0.000 claims description 5
- 238000013268 sustained release Methods 0.000 claims description 3
- 239000012730 sustained-release form Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 description 64
- 241000196324 Embryophyta Species 0.000 description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- -1 cobalt (II) fluorosilicate Chemical compound 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- XDSVFOKTYBLGNG-UHFFFAOYSA-L magnesium;selenite Chemical compound [Mg+2].[O-][Se]([O-])=O XDSVFOKTYBLGNG-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 239000002426 superphosphate Substances 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 description 1
- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 1
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical class N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000002374 bone meal Substances 0.000 description 1
- 229940036811 bone meal Drugs 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- UWZXJRBXKTZILP-UHFFFAOYSA-L calcium;selenite Chemical compound [Ca+2].[O-][Se]([O-])=O UWZXJRBXKTZILP-UHFFFAOYSA-L 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ZVLZZJUHYPMZAH-UHFFFAOYSA-L cobalt(2+) dinitrite Chemical compound [Co+2].[O-]N=O.[O-]N=O ZVLZZJUHYPMZAH-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 229910021540 colemanite Inorganic materials 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229940079895 copper edta Drugs 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- BDXBEDXBWNPQNP-UHFFFAOYSA-L copper;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron Chemical compound [Cu+2].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O BDXBEDXBWNPQNP-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WHYUWYVXDNNLTR-UHFFFAOYSA-J dizinc;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Zn+2].[Zn+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O WHYUWYVXDNNLTR-UHFFFAOYSA-J 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940062135 magnesium thiosulfate Drugs 0.000 description 1
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 1
- TZKHCTCLSRVZEY-UHFFFAOYSA-L magnesium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Mg+2].[O-]S([O-])(=O)=S TZKHCTCLSRVZEY-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YLMXTGWAYICZRY-UHFFFAOYSA-N methyl 2,5-bis(2,2,2-trifluoroethoxy)benzoate Chemical compound COC(=O)C1=CC(OCC(F)(F)F)=CC=C1OCC(F)(F)F YLMXTGWAYICZRY-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 229940118149 zinc sulfate monohydrate Drugs 0.000 description 1
- VRGNUPCISFMPEM-ZVGUSBNCSA-L zinc;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Zn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VRGNUPCISFMPEM-ZVGUSBNCSA-L 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 1
- HSYFJDYGOJKZCL-UHFFFAOYSA-L zinc;sulfite Chemical compound [Zn+2].[O-]S([O-])=O HSYFJDYGOJKZCL-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
Definitions
- the present disclosure relates to a fertiliser product.
- the present disclosure relates particularly, although by no means exclusively, to a boron-containing, i.e. borate, fertiliser product.
- the present disclosure relates particularly, although by no means exclusively, to a boron-containing fertiliser product comprising a fast release source of boron and a slow release source of boron.
- the present disclosure also relates to a process and a plant for producing a boron- containing fertiliser product.
- Fertilisers are used to supplement the amount of essential macronutrients in soil, for example nitrogen, potassium, phosphorous, sulphur, calcium and magnesium.
- micronutrients such as boron, zinc, manganese, iron, copper, molybdenum and chlorine.
- a borate fertiliser is a fertiliser containing boron in a water soluble form.
- Boron can be applied to plants in several ways.
- One option is as sodium borate (i.e. borax - sodium tetraborate).
- the present disclosure provides a boron-containing fertiliser product.
- the disclosure is a borate fertiliser product comprising a fast release source of boron and a slow release source of boron, with the slow release boron source comprising or consisting of ulexite.
- ulexite is a hydrated borate of sodium and calcium.
- Ulexite (for example having a chemical formula Na2O.2CaO.5B2O3.16H2O) is a major sodium/boron mineral. It is a soft mineral consisting of a hydrous borate of sodium and calcium and usually occurs in loose masses of white fibers.
- the fast release boron source provides boron to plants immediately upon application while the slow release boron source breaks down slowly and provides continued supply of boron during and after the fast release boron source has been consumed. This is a value added product.
- the ratios of the slow release boron source and the fast release boron source may be selected as required having regard to a required boron release profile and total % boron for a targeted application.
- the ulexite:fast boron source ratio may be in a range of 5:95-95:5, typically 10:90- 90: 10, and more typically 20:80-80:20.
- the ulexite may be in any suitable form.
- the fast release boron source may be any suitable fast release boron source or combination of fast release boron sources in any suitable form.
- the fast release boron source may be any one or more than one of boric acid (H3BO3), disodium octaborate tetrahydrate (DOT - Na2BsOi3 AEEO), anhydrous borax (TSfeE ⁇ O?), anhydrous boric acid, kernite (Na2B4O? 4H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O), and potassium borate (B4K2O7) (with the potassium acting as a macronutrient).
- boric acid H3BO3
- DOT - Na2BsOi3 AEEO disodium octaborate tetrahydrate
- TfeE ⁇ O? anhydrous borax
- TfeE ⁇ O? anhydrous boric acid
- kernite Na2B4O? 4H2O
- tincal Na2B4O?.10
- Zinc borate ⁇ CEZm (with the zinc acting as a micronutrient) may be used to modulate the release property of the fertiliser product.
- Zinc borate is typically considered to have low solubility in water and consequently a “slow release” boron source. It follows that applying zinc borate to the fertiliser product for example as a coating agent can slow the release property of a fertiliser product containing a large amount of “fast release” boron source material.
- zinc borate can increase the release property of a fertiliser product containing a large amount of boron source material such as ulexite which have slower release properties.
- the fertiliser product may comprise materials in addition to the fast release source of boron and ulexite.
- the fertiliser product may comprise a micronutrient in addition to boron.
- the additional micronutrient may be any suitable micronutrient such as zinc.
- the zinc may be in a form of zinc acetate, zinc fluoride, zinc bromide, zinc nitrate, zinc chloride, zinc iodide, zinc oxide, zinc permanganate, zinc sulfate heptahydrate, zinc sulfate monohydrate, zinc sulfite, zinc tartrate, zinc oxysulfate, zinc EDTA, and zinc ammonia salts.
- the additional micronutrient may be any one of the following micronutrients in the following forms:
- Micronutrient iron iron (II) carbonate, iron (II) nitrate, iron (II) chloride, iron (II) hydroxide, iron (II) oxalate, iron (II) sulfate, iron (III) chloride, iron (III) fluoride, iron (III) hydroxide, iron (III) nitrate, iron (III) sulfate, iron EDTA.
- Micronutrient manganese manganese (II) bromide, manganese (II) carbonate, manganese (II) chloride, manganese (II) hydroxide, manganese (II) nitrate, manganese (II) fluoride, manganese (II) oxalate, manganese (II) sulfate, manganese oxy-sulfate, manganese EDTA.
- Micronutrient copper (not commonly needed): copper (I) chloride, copper (I) hydroxide, copper (I) iodide, copper (I) sulfide, copper (I) oxide, copper (II) fluoride, copper (II) bromide, copper (II) carbonate, copper (II) chloride, copper (II) hydroxide, copper (II) nitrate, copper (II) oxide, copper oxalate, copper (II) sulfate, copper (II) sulfide, copper EDTA.
- Micronutrient molybdenum ammonium molybdate, molybdenum tri oxide, molybdenum disulfide, calcium molybdate, magnesium molybdate.
- Micronutrient nickel nickel sulfate, nickel bromide, nickel carbonate, nickel chloride, nickel fluoride, nickel formate, nickel hydroxide, nickel iodide, nickel nitrate, nickel oxalate, nickel sulfate.
- Micronutrient cobalt (not commonly needed): cobalt (II) fluorosilicate, cobalt (II) iodide, cobalt (II) nitrate, cobalt (II) nitrite, cobalt (II) oxalate, cobalt (II) sulfate, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) fluoride.
- the fertiliser product may comprise a macronutrient.
- the macronutrient may be any suitable macronutrient such as potassium.
- the additional macronutrient may be any one of the following macronutrients in the following forms:
- boron is the main active fertiliser component of the fertiliser product.
- the amount of boron in the fertiliser product may be any suitable percentage of the active fertiliser components of the fertiliser product.
- boron is at least 90 wt.%, and more typically at least 95 wt.%, of the active fertiliser components of the fertiliser product. In one example, boron ranges from 10-20 wt.%, preferably 15 wt.%. In this example, the B2O3 content ranges from 40-50 wt.%, preferably 47 wt.%.
- the fertiliser product may comprise an organic acid, such as a citric acid or an oxalic acid, for improving the release of boron from the slow release boron source such as ulexite in the fertiliser product by slow acidic hydrolysis.
- the organic acid may act as a pH modifying agent or a chelating agent.
- fertiliser products contain minimum amounts of materials that provide no fertiliser benefit (e.g. starch binders). Therefore, typically, the formulated fertiliser product contains minimal amounts of such other materials.
- the borate fertiliser product may be in any suitable form.
- the borate fertiliser product may be in the form of granules.
- granules is understood herein to mean medium-sized particles, for example having have an irregular shape, formed by compacting together or agglomerating together or otherwise forming together smaller-sized particles.
- the granules may be crushed.
- the granules may be any suitable size.
- the granules are 1-5 mm in size, more typically 2-4 mm in size.
- the borate fertiliser product typically being in the form of compacted granules of 2 to 4 mm in granule size or granules of 1-5 mm in granule size, is suitable for use as a controlled release fertilizer, general fertilizer, or crops nutrient, in soil applications.
- the granules may be formed by agglomeration or compaction.
- the granules are formed by agglomeration including a mixing step that involves mixing material having a total moisture content of greater than 20 wt.%, suitably greater than 30 wt.%.
- the granules are formed by agglomeration including a mixing step that involves mixing material having a total moisture content of less than 30 wt.%, suitably less than 20 wt.%.
- the granules may have any suitable physical and chemical properties (hardness, solubility, particle size distribution).
- the physical and chemical properties are similar to known ulexite granular fertiliser products.
- the fertiliser product may comprise granules and a coating of a control release agent to control release of boron to plants.
- the coating may be made from any suitable material.
- the coating may be made from a sulphur-containing material.
- the coating may be made from a sulphur-containing polymeric material.
- the coating may include any one of the following materials: Inorganic materials: bentonite, phosphogypsum, gypsum, hydroxy apatite, zeolites, sepiolite.
- Synthetic polymers polyurethane, polyethylene, polyacrylamide, polycaprolactone, polystyrene, polysulfone, aliphatic polyester, polyvinyl alcohol, bio-based epoxy.
- Natural polymers starch, cellulose, chitosan, ethyl cellulose, carboxymethyl cellulose, hydroxy methyl cellulose, hydroxypropyl methylcellulose, bio-based polyurethane, polysulfone, latex, natural rubber, lignin, alginate.
- the coating may be formed by any one of the following coating techniques: rotary drum, pan, fluidized bed, melting and extrusion, solution polymerization and crosslinking, inverse suspension polymerization, and microwave irradiation.
- the sulfur-containing coating on borate fertiliser product granules may assist sustained release of boron to plants due to the low water/soil dissolution of sulfur.
- sulfur-coated borate granules may also assist in lowering the pH of acidic soils.
- the fertiliser product may comprise a binder.
- the binder may be any suitable material.
- the binder may be a starch.
- the binder may be water.
- the fertiliser product may comprise a slow release boron source in addition to ulexite.
- a process for producing a fertiliser product comprising:
- blending step (a) comprises wet mixing the fast release source of boron and the slow release source of boron
- the process may include agglomerating the blend to form granules.
- blending step (a) includes drying the agglomerated granules.
- step (a) comprises dry mixing the fast release source of boron and the slow release source of boron
- the process may include compacting the blend to form granules.
- the fast release boron source may be any one or more than one of boric acid (H3BO3), disodium octaborate tetrahydrate (DOT - Na2BsOi3 4H2O), anhydrous borax (TSfeB ⁇ ?), anhydrous boric acid, kernite (Na2B4O? 4H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O), and potassium borate (B4K2O7) (with the potassium being a macronutrient).
- boric acid H3BO3
- TSfeB ⁇ ? disodium octaborate tetrahydrate
- TSfeB ⁇ ? anhydrous boric acid
- kernite Na2B4O? 4H2O
- tincal Na2B4O?.10H2O
- Blending step (a) may comprise mixing an organic acid, such as a citric acid or an oxalic acid with the other components of the blend.
- organic acid such as a citric acid or an oxalic acid
- Blending step (a) may comprise mixing a binder with the other components of the blend.
- the binder may be a starch.
- the binder may be water.
- Blending step (a) may be a bulk blending step in which the ulexite and the fast release source of boron and any other components of the blend are added together at the same time and then mixed together.
- Blending step (a) may comprise any suitable sequence of adding and mixing the ulexite and the fast release source of boron and any other components of the blend.
- the process may comprise forming coatings of a control release agent to control release of boron to plants on the granules.
- the process may comprise crushing the granules.
- the process may comprise classifying, for example screening, the granules and separating the granules on the basis of size and producing a product fraction.
- the process may comprise classifying, for example by screening, the granules into an oversize fraction, a product fraction, and an undersize fraction.
- the product fraction may be any suitable size fraction.
- the product fraction may be at least 1 mm.
- the product fraction may be at least 2 mm.
- the product fraction may be no more than 6 mm.
- the product fraction may be no more than 5 mm.
- the product fraction may be no more than 4 mm.
- the product fraction may be a 1-4 mm size fraction.
- the product fraction may be a 1-6 mm size fraction.
- the process may comprise a crushing step for the oversize fraction.
- the process comprises returning crushed oversize fraction to the blending step (a).
- the process comprises returning crushed oversize fraction and undersize fraction to the blending step (a).
- the process may comprise returning the undersize fraction to the blending step (a).
- the process may comprise drying the product fraction to form the fertiliser product.
- the present disclosure also provides a plant for producing a fertiliser product that comprises a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite, the plant comprising:
- the plant may comprise a coating unit for forming coatings of a control release agent to control release of boron to plants on the granules.
- the screening unit may be configured for screening the granules and producing an oversize fraction, the product fraction, and an undersize fraction.
- the plant may comprise a crushing unit for crushing the oversize fraction.
- the plant may be configured for returning the crushed oversize fraction to the blending unit.
- the plant may be configured for returning the undersize fraction to the blending unit.
- the applicant has developed a borate fertiliser product comprising a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite.
- the fast release boron source may be any one or more than one of boric acid (H3BO3), disodium octaborate tetrahydrate (DOT - Na2BsOi3 4H2O), anhydrous borax (Na2B4O?), anhydrous boric acid, kernite (Na2B4O? 4H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O, and potassium borate (B4K2O7) (with the potassium being a macronutrient).
- boric acid H3BO3
- Na2B4O? disodium octaborate tetrahydrate
- Na2B4O? anhydrous borax
- anhydrous boric acid kernite
- Na2B4O? tincal
- Na2B4O?.5H2O sodium
- the ratios of the different boron sources can be selected appropriately to suit boron release profile and total % boron as required for the targeted application.
- the fertiliser product may also comprise other components, such as any one or more than one of:
- micronutrient(s) in addition to boron, with the other micronutrient(s) being selected by way of example from zinc and the above list of micronutrients,
- a macronutrient such as potassium or any other macronutrient selected by way of example from the above list of macronutrients,
- an organic acid such as a citric acid or an oxalic acid, as a pH modifying agent for improving the release of boron from ulexite in the fertiliser product by slow acidic hydrolysis, and
- boron is the main active fertiliser component of the fertiliser product.
- the above fertiliser product formulation provides continued sustained release of borates to plants depending on the demand of boron.
- the formulation typically is in a granular form to help optimize boron availability to plants.
- the amounts of the water soluble fast release boron source(s) may be equivalent to up to 10 mol, typically equivalent to up to 5 mol.
- the fast release boron source(s) provide an initial supply of boron due to the quicker dissolution in water/soil, while ulexite would ensure continued sustained supply of boron to plants owing to its slower release profile.
- the release profile of ulexite can also be modified to ensure continued availability of boron to plants by mixing ulexite with an appropriate amount of acid.
- the acid could be an organic acid such as citric or oxalic acid that slowly hydrolyse ulexite owing to their low pH thus modifying their release kinetics.
- the release profile of ulexite can also be modified to ensure continued availability of boron to plants by mixing ulexite with an appropriate amount of inorganic acids like hydrochloric, nitric, sulfuric or phosphoric acids that slowly hydrolyze ulexite owing to their low pH thus modifying their release kinetics.
- inorganic acids like hydrochloric, nitric, sulfuric or phosphoric acids that slowly hydrolyze ulexite owing to their low pH thus modifying their release kinetics.
- the fertiliser product is in the form of granules of 2 to 4 mm in size with a coating of a sulphur-containing material as a release control agent to control release of boron to plants.
- sulfur-coated borate granules may also assist in lowering the pH of acidic soils.
- the fertiliser product may be manufactured by:
- step (a) comprises wet mixing the fast release source of boron, the slow release source of boron, and any other components mentioned above
- the process may include agglomerating the blend to form granules.
- step (a) includes drying the agglomerated granules.
- step (a) comprises dry mixing the fast release source of boron and the slow release source of boron
- the process may include compacting the blend to form granules.
- the ulexite may be obtained from any suitable source.
- ulexite may be mined and then upgraded to separate clays and other gangue by any one or more of mechanical dispersion, ultrasonic wave treatment, water absorption, and magnetic separation options.
- the blend is compacted and dried in a compaction unit, thereby forming granules.
- the blend is agglomerated in an agglomeration unit and forms granules and the granules are dried or allowed to dry.
- the target size of the granules in the final fertiliser product is 2-4mm.
- the granules are transferred to a screen unit and separated in an oversize fraction, and undersize fraction, and a product fraction.
- the undersize fraction is returned to the compaction unit and re-processed.
- the oversize fraction is returned to the crusher unit and re-crushed.
- the product fraction which are target size granules, is transferred to a dryer unit and dried to form the final fertiliser product.
- the applicant has conducted bench scale trials with a laboratory scale magnetic separator (1-3 kg) and operating with prototype batch production using a pilot scale magnetic separator to produce an ulexite fraction containing -7.8% B.
- the ulexite fraction was combined with 5 mol. of a fast release boron source(s), namely boric acid, DOT, anhydrous borax, anhydrous boric acid, kernite, potassium borate or any combination of the above thereof at appropriate ratios and compacted to form granules at an external toll site.
- a fast release boron source(s) namely boric acid, DOT, anhydrous borax, anhydrous boric acid, kernite, potassium borate or any combination of the above thereof at appropriate ratios and compacted to form granules at an external toll site.
- the disclosure extends to fertiliser products that comprise other slow release boron sources in addition to ulexite.
Abstract
A borate fertiliser product comprising a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite.
Description
FERTILISER PRODUCT
CROSS REFERENCE TO RELATED APPLICATION
This Application claims priority to United States Provisional Patent Application No. 63/406,698 filed on September 14, 2022.
TECHNICAL FIELD
The present disclosure relates to a fertiliser product.
The present disclosure relates particularly, although by no means exclusively, to a boron-containing, i.e. borate, fertiliser product.
The present disclosure relates particularly, although by no means exclusively, to a boron-containing fertiliser product comprising a fast release source of boron and a slow release source of boron.
The present disclosure also relates to a process and a plant for producing a boron- containing fertiliser product.
BACKGROUND
Fertilisers are used to supplement the amount of essential macronutrients in soil, for example nitrogen, potassium, phosphorous, sulphur, calcium and magnesium.
Other elements that are needed in much smaller amounts for plant growth are called micronutrients, such as boron, zinc, manganese, iron, copper, molybdenum and chlorine.
A borate fertiliser is a fertiliser containing boron in a water soluble form.
Boron can be applied to plants in several ways. One option is as sodium borate (i.e. borax - sodium tetraborate).
Borate fertiliser products that are currently available can be divided into two types, namely:
1) Fast release: refined borate fertilizers that have higher solubility in water, are released immediately on application, and are readily available for plant uptake.
2) Slow release: mostly unrefined or minimally refined borate ores with low water solubility like ulexite and colemanite which break down slowly in soil and are not released immediately after application. They release boron over longer period after application.
The disclosure is concerned with providing a borate fertiliser product comprising a fast release source of boron and a slow release source of boron.
It is understood that the above description is not to be taken as an admission of the common general knowledge anywhere.
SUMMARY OF THE DISCLOSURE
The present disclosure provides a boron-containing fertiliser product.
The disclosure is a borate fertiliser product comprising a fast release source of boron and a slow release source of boron, with the slow release boron source comprising or consisting of ulexite.
In general terms, ulexite is a hydrated borate of sodium and calcium.
Ulexite (for example having a chemical formula Na2O.2CaO.5B2O3.16H2O) is a major sodium/boron mineral. It is a soft mineral consisting of a hydrous borate of sodium and calcium and usually occurs in loose masses of white fibers.
The applicant has found that the combination of ulexite (as a slow release boron source) and a fast release boron source ensures effective, sustained continued release of boron to plants over an extended period.
The fast release boron source provides boron to plants immediately upon application while the slow release boron source breaks down slowly and provides continued supply of boron during and after the fast release boron source has been consumed. This is a value added product.
The ratios of the slow release boron source and the fast release boron source may be selected as required having regard to a required boron release profile and total % boron for a targeted application.
The ulexite:fast boron source ratio may be in a range of 5:95-95:5, typically 10:90- 90: 10, and more typically 20:80-80:20.
The ulexite may be in any suitable form.
The fast release boron source may be any suitable fast release boron source or combination of fast release boron sources in any suitable form.
The fast release boron source may be any one or more than one of boric acid (H3BO3),
disodium octaborate tetrahydrate (DOT - Na2BsOi3 AEEO), anhydrous borax (TSfeE^O?), anhydrous boric acid, kernite (Na2B4O? 4H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O), and potassium borate (B4K2O7) (with the potassium acting as a macronutrient).
Zinc borate ^CEZm) (with the zinc acting as a micronutrient) may be used to modulate the release property of the fertiliser product. Zinc borate is typically considered to have low solubility in water and consequently a “slow release” boron source. It follows that applying zinc borate to the fertiliser product for example as a coating agent can slow the release property of a fertiliser product containing a large amount of “fast release” boron source material. Corresponding, zinc borate can increase the release property of a fertiliser product containing a large amount of boron source material such as ulexite which have slower release properties.
The fertiliser product may comprise materials in addition to the fast release source of boron and ulexite.
For example, the fertiliser product may comprise a micronutrient in addition to boron.
The additional micronutrient may be any suitable micronutrient such as zinc.
The zinc may be in a form of zinc acetate, zinc fluoride, zinc bromide, zinc nitrate, zinc chloride, zinc iodide, zinc oxide, zinc permanganate, zinc sulfate heptahydrate, zinc sulfate monohydrate, zinc sulfite, zinc tartrate, zinc oxysulfate, zinc EDTA, and zinc ammonia salts.
The additional micronutrient may be any one of the following micronutrients in the following forms:
1) Micronutrient iron: iron (II) carbonate, iron (II) nitrate, iron (II) chloride, iron (II) hydroxide, iron (II) oxalate, iron (II) sulfate, iron (III) chloride, iron (III) fluoride, iron (III) hydroxide, iron (III) nitrate, iron (III) sulfate, iron EDTA.
2) Micronutrient manganese: manganese (II) bromide, manganese (II) carbonate, manganese (II) chloride, manganese (II) hydroxide, manganese (II) nitrate, manganese (II) fluoride, manganese (II) oxalate, manganese (II) sulfate, manganese oxy-sulfate, manganese EDTA.
3) Micronutrient copper (not commonly needed): copper (I) chloride, copper (I) hydroxide, copper (I) iodide, copper (I) sulfide, copper (I) oxide, copper (II) fluoride, copper (II) bromide, copper (II) carbonate, copper (II) chloride, copper (II) hydroxide, copper (II) nitrate, copper (II) oxide, copper oxalate, copper (II) sulfate, copper (II) sulfide, copper EDTA.
4) Micronutrient molybdenum: ammonium molybdate, molybdenum tri oxide, molybdenum disulfide, calcium molybdate, magnesium molybdate.
5) Micronutrient nickel: nickel sulfate, nickel bromide, nickel carbonate, nickel chloride, nickel fluoride, nickel formate, nickel hydroxide, nickel iodide, nickel nitrate, nickel oxalate, nickel sulfate.
6) Micronutrient cobalt (not commonly needed): cobalt (II) fluorosilicate, cobalt (II) iodide, cobalt (II) nitrate, cobalt (II) nitrite, cobalt (II) oxalate, cobalt (II) sulfate, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) fluoride.
The fertiliser product may comprise a macronutrient.
The macronutrient may be any suitable macronutrient such as potassium.
The additional macronutrient may be any one of the following macronutrients in the following forms:
1) Macronutrient phosphorous: super phosphate, concentrated super phosphate, mono-ammonium phosphate, di-ammonium phosphate, ammonium polyphosphate, phosphoric acid, phosphorous acid, phosphonic acids, bone ash, bone meal, rock phosphates.
2) Macronutrient magnesium: magnesium acetate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium formate, magnesium hydroxide, magnesium fluoride, magnesium iodide, magnesium nitrate, magnesium oxalate, magnesium oxide, magnesium phosphate, magnesium sulfate, magnesium sulfite, magnesium thiosulfate, magnesium selenite, magnesium selenite.
3) Macronutrient calcium: calcium acetate, calcium benzoate, calcium bicarbonate, calcium bromide, calcium carbonate, calcium fluoride, calcium chloride, calcium citrate, monocalcium phosphate, calcium formate, di-calcium phosphate, calcium hydroxide, calcium iodide, calcium nitrate, calcium nitrite, calcium oxalate, calcium oxide, calcium phosphate, calcium selenite, calcium sulfate.
While the disclosure extends to the above micronutrient and macronutrient additions, boron is the main active fertiliser component of the fertiliser product.
The amount of boron in the fertiliser product may be any suitable percentage of the active fertiliser components of the fertiliser product.
Typically, boron is at least 90 wt.%, and more typically at least 95 wt.%, of the active fertiliser components of the fertiliser product. In one example, boron ranges from 10-20 wt.%, preferably 15 wt.%. In this example, the B2O3 content ranges from 40-50 wt.%, preferably 47 wt.%.
The fertiliser product may comprise an organic acid, such as a citric acid or an oxalic acid, for improving the release of boron from the slow release boron source such as ulexite in
the fertiliser product by slow acidic hydrolysis. The organic acid may act as a pH modifying agent or a chelating agent.
It is an important consideration in the agricultural fertiliser industry that fertiliser products contain minimum amounts of materials that provide no fertiliser benefit (e.g. starch binders). Therefore, typically, the formulated fertiliser product contains minimal amounts of such other materials.
The borate fertiliser product may be in any suitable form.
Typically, the borate fertiliser product may be in the form of granules.
The term “granules” is understood herein to mean medium-sized particles, for example having have an irregular shape, formed by compacting together or agglomerating together or otherwise forming together smaller-sized particles.
After being formed, the granules may be crushed.
The granules may be any suitable size.
Typically, the granules are 1-5 mm in size, more typically 2-4 mm in size.
The borate fertiliser product, typically being in the form of compacted granules of 2 to 4 mm in granule size or granules of 1-5 mm in granule size, is suitable for use as a controlled release fertilizer, general fertilizer, or crops nutrient, in soil applications.
The granules may be formed by agglomeration or compaction. In one example, the granules are formed by agglomeration including a mixing step that involves mixing material having a total moisture content of greater than 20 wt.%, suitably greater than 30 wt.%. In another example, the granules are formed by agglomeration including a mixing step that involves mixing material having a total moisture content of less than 30 wt.%, suitably less than 20 wt.%.
The granules may have any suitable physical and chemical properties (hardness, solubility, particle size distribution).
Typically, the physical and chemical properties are similar to known ulexite granular fertiliser products.
The fertiliser product may comprise granules and a coating of a control release agent to control release of boron to plants.
The coating may be made from any suitable material.
The coating may be made from a sulphur-containing material.
The coating may be made from a sulphur-containing polymeric material.
The coating may include any one of the following materials:
Inorganic materials: bentonite, phosphogypsum, gypsum, hydroxy apatite, zeolites, sepiolite.
Synthetic polymers: polyurethane, polyethylene, polyacrylamide, polycaprolactone, polystyrene, polysulfone, aliphatic polyester, polyvinyl alcohol, bio-based epoxy.
- Natural polymers: starch, cellulose, chitosan, ethyl cellulose, carboxymethyl cellulose, hydroxy methyl cellulose, hydroxypropyl methylcellulose, bio-based polyurethane, polysulfone, latex, natural rubber, lignin, alginate.
- Hydrophobic sealants: paraffin, polyols.
The coating may be formed by any one of the following coating techniques: rotary drum, pan, fluidized bed, melting and extrusion, solution polymerization and crosslinking, inverse suspension polymerization, and microwave irradiation.
The sulfur-containing coating on borate fertiliser product granules may assist sustained release of boron to plants due to the low water/soil dissolution of sulfur.
In addition, sulfur-coated borate granules may also assist in lowering the pH of acidic soils.
The fertiliser product may comprise a binder.
The binder may be any suitable material.
The binder may be a starch.
The binder may be water.
The fertiliser product may comprise a slow release boron source in addition to ulexite.
According to the present disclosure, there is also provided a process for producing a fertiliser product comprising:
(a) blending together, for example by dry mixing or wet mixing, a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite, and forming a blend; and
(b) compacting or agglomerating or otherwise forming the blend into granules.
When blending step (a) comprises wet mixing the fast release source of boron and the slow release source of boron, the process may include agglomerating the blend to form granules. Suitably, blending step (a) includes drying the agglomerated granules.
When blending step (a) comprises dry mixing the fast release source of boron and the slow release source of boron, the process may include compacting the blend to form granules.
The fast release boron source may be any one or more than one of boric acid (H3BO3), disodium octaborate tetrahydrate (DOT - Na2BsOi3 4H2O), anhydrous borax (TSfeB^?),
anhydrous boric acid, kernite (Na2B4O? 4H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O), and potassium borate (B4K2O7) (with the potassium being a macronutrient).
Blending step (a) may comprise mixing an organic acid, such as a citric acid or an oxalic acid with the other components of the blend.
Blending step (a) may comprise mixing a binder with the other components of the blend.
The binder may be a starch.
The binder may be water.
Blending step (a) may be a bulk blending step in which the ulexite and the fast release source of boron and any other components of the blend are added together at the same time and then mixed together.
Blending step (a) may comprise any suitable sequence of adding and mixing the ulexite and the fast release source of boron and any other components of the blend.
The process may comprise forming coatings of a control release agent to control release of boron to plants on the granules.
The process may comprise crushing the granules.
The process may comprise classifying, for example screening, the granules and separating the granules on the basis of size and producing a product fraction.
The process may comprise classifying, for example by screening, the granules into an oversize fraction, a product fraction, and an undersize fraction.
The product fraction may be any suitable size fraction.
The product fraction may be at least 1 mm.
The product fraction may be at least 2 mm.
The product fraction may be no more than 6 mm.
The product fraction may be no more than 5 mm.
The product fraction may be no more than 4 mm.
The product fraction may be a 1-4 mm size fraction.
The product fraction may be a 1-6 mm size fraction.
The process may comprise a crushing step for the oversize fraction.
Suitably, the process comprises returning crushed oversize fraction to the blending step (a).
Suitably, the process comprises returning crushed oversize fraction and undersize fraction to the blending step (a).
The process may comprise returning the undersize fraction to the blending step (a).
The process may comprise drying the product fraction to form the fertiliser product.
The present disclosure also provides a plant for producing a fertiliser product that comprises a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite, the plant comprising:
(a) a blending unit for blending together a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite, and forming a blend,
(b) a compaction unit or an agglomeration unit or other unit for forming the blend into granules,
(c) a screening unit for screening the granules and producing a product fraction; and
(d) drying the granules in the product fraction and forming the fertiliser product.
The plant may comprise a coating unit for forming coatings of a control release agent to control release of boron to plants on the granules.
The screening unit may be configured for screening the granules and producing an oversize fraction, the product fraction, and an undersize fraction.
The plant may comprise a crushing unit for crushing the oversize fraction.
The plant may be configured for returning the crushed oversize fraction to the blending unit.
The plant may be configured for returning the undersize fraction to the blending unit.
DESCRIPTION OF EMBODIMENT
The applicant has developed a borate fertiliser product comprising a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite.
The fast release boron source may be any one or more than one of boric acid (H3BO3), disodium octaborate tetrahydrate (DOT - Na2BsOi3 4H2O), anhydrous borax (Na2B4O?), anhydrous boric acid, kernite (Na2B4O? 4H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O, and potassium borate (B4K2O7) (with the potassium being a macronutrient).
The ratios of the different boron sources can be selected appropriately to suit boron release profile and total % boron as required for the targeted application.
The fertiliser product may also comprise other components, such as any one or more than one of:
(a) another micronutrient(s) in addition to boron, with the other micronutrient(s) being selected by way of example from zinc and the above list of micronutrients,
(b) a macronutrient such as potassium or any other macronutrient selected by way of example from the above list of macronutrients,
(c) an organic acid, such as a citric acid or an oxalic acid, as a pH modifying agent for improving the release of boron from ulexite in the fertiliser product by slow acidic hydrolysis, and
(d) a binder.
While the disclosure extends to the above micronutrient and macronutrient additions, boron is the main active fertiliser component of the fertiliser product.
The above fertiliser product formulation provides continued sustained release of borates to plants depending on the demand of boron.
The formulation typically is in a granular form to help optimize boron availability to plants.
The amounts of the water soluble fast release boron source(s) may be equivalent to up to 10 mol, typically equivalent to up to 5 mol.
The fast release boron source(s) provide an initial supply of boron due to the quicker dissolution in water/soil, while ulexite would ensure continued sustained supply of boron to plants owing to its slower release profile.
The release profile of ulexite can also be modified to ensure continued availability of boron to plants by mixing ulexite with an appropriate amount of acid.
The acid could be an organic acid such as citric or oxalic acid that slowly hydrolyse ulexite owing to their low pH thus modifying their release kinetics.
The release profile of ulexite can also be modified to ensure continued availability of boron to plants by mixing ulexite with an appropriate amount of inorganic acids like hydrochloric, nitric, sulfuric or phosphoric acids that slowly hydrolyze ulexite owing to their low pH thus modifying their release kinetics.
Typically, the fertiliser product is in the form of granules of 2 to 4 mm in size with a coating of a sulphur-containing material as a release control agent to control release of boron to plants.
Sulfur, owing to its lower solubility in water would prevent complete dissolution of
water soluble borates immediately in soil. The release of boron would be possible only with slow break down of the sulfur coating and subsequent controlled dissolution of water soluble borates. This would ensure continued release of boron to plants in crops over longer periods of time. In addition, sulfur-coated borate granules may also assist in lowering the pH of acidic soils.
The fertiliser product may be manufactured by:
(a) bulk blending together, for example by dry mixing or wet mixing, a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite, and any other components mentioned above as may be required, in appropriate ratios; and
(b) compacting or agglomerating or otherwise forming the blend into granules.
When blending step (a) comprises wet mixing the fast release source of boron, the slow release source of boron, and any other components mentioned above, the process may include agglomerating the blend to form granules. Suitably, step (a) includes drying the agglomerated granules.
When blending step (a) comprises dry mixing the fast release source of boron and the slow release source of boron, the process may include compacting the blend to form granules. The ulexite may be obtained from any suitable source.
By way of example, ulexite may be mined and then upgraded to separate clays and other gangue by any one or more of mechanical dispersion, ultrasonic wave treatment, water absorption, and magnetic separation options.
Typically, the blend is compacted and dried in a compaction unit, thereby forming granules.
Typically, the blend is agglomerated in an agglomeration unit and forms granules and the granules are dried or allowed to dry.
The target size of the granules in the final fertiliser product is 2-4mm.
Typically the granules are transferred to a screen unit and separated in an oversize fraction, and undersize fraction, and a product fraction.
The undersize fraction is returned to the compaction unit and re-processed.
The oversize fraction is returned to the crusher unit and re-crushed.
The product fraction, which are target size granules, is transferred to a dryer unit and dried to form the final fertiliser product.
The applicant has conducted bench scale trials with a laboratory scale magnetic
separator (1-3 kg) and operating with prototype batch production using a pilot scale magnetic separator to produce an ulexite fraction containing -7.8% B.
The ulexite fraction was combined with 5 mol. of a fast release boron source(s), namely boric acid, DOT, anhydrous borax, anhydrous boric acid, kernite, potassium borate or any combination of the above thereof at appropriate ratios and compacted to form granules at an external toll site.
The test work indicated that, for a given setting of the magnetic separator, the efficiency of separation is independent of the feed quality. The feed quality affects only the yield.
Many modifications may be made to the embodiments described above without departing from the spirit and scope of the invention.
By way of example, whilst the above described fertiliser product comprises ulexite as the slow release boron source, the disclosure extends to fertiliser products that comprise other slow release boron sources in addition to ulexite.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
Claims
1. A borate fertiliser product comprising a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite.
2. The fertiliser product defined in claim 1 wherein the fast release boron source comprises any one or more than one of boric acid (H3BO3), disodium octaborate tetrahydrate (DOT - Na2BsO 13 AH2O), anhydrous borax (Na2B4O?), anhydrous boric acid, kernite
H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O), and potassium borate (B4K2O7).
3. The fertiliser product defined in claim 1 or claim 2 comprises a micronutrient in addition to boron.
4. The fertiliser product defined in any one of the preceding claims comprises a macronutrient.
5. The fertiliser product defined in any one of the preceding claims comprises an organic acid for improving the release of boron from ulexite in the fertiliser product.
6. The fertiliser product defined in any one of the preceding claims being in the form of granules.
7. The fertiliser product defined in any one of the preceding claims being in the form of granules with a coating to control release of boron to plants.
8. The fertiliser product defined in claim 7 wherein the coating comprises a sulphur- containing material for assisting sustained release of boron to plants due to the low water/soil dissolution of sulfur.
9. A process for producing a fertiliser product comprising:
(a) blending together, for example by dry mixing, a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite,
and forming a blend; and
(b) compacting or agglomerating or otherwise forming the blend into granules.
10. The process defined in claim 9 wherein the fast release boron source comprises any one or more than one of boric acid (H3BO3), disodium octaborate tetrahydrate (DOT -
Na2BsO 13 4H2O), anhydrous borax (Na2B4O?), anhydrous boric acid, kernite (Na2B4O? 4H2O), tincal (Na2B4O?.10H2O), sodium tetraborate pentahydrate (Na2B4O?.5H2O), and potassium borate (B4K2O7).
11. The process defined in claim 9 or claim 10 comprises classifying the granules and separating the granules on the basis of size and producing an oversize fraction, a product fraction, and an undersize fraction.
12. The process defined in claim 10 comprise crushing the oversize fraction and returning the crushed oversize fraction to the blending step.
13. The process defined in claim 11 comprises returning the undersize fraction to the blending step (a).
14. A plant for producing a fertiliser product that comprises a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite, the plant comprising:
(a) a blending unit for blending together a fast release source of boron and a slow release source of boron, with the slow release boron source comprising ulexite, and forming a blend,
(b) a compaction unit or an agglomeration unit or any other unit for forming the blend into granules,
(c) a screening unit for screening the granules and producing a product fraction; and
(d) a drying unit for drying the granules in the product fraction and forming the fertiliser product.
Applications Claiming Priority (2)
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US202263406698P | 2022-09-14 | 2022-09-14 | |
US63/406,698 | 2022-09-14 |
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WO2024059123A1 true WO2024059123A1 (en) | 2024-03-21 |
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ID=90275609
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PCT/US2023/032618 WO2024059123A1 (en) | 2022-09-14 | 2023-09-13 | Fertiliser product |
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CA2798880A1 (en) * | 2009-05-08 | 2010-11-11 | Joao Calderon | Method for producing organic and organo-mineral fertilisers with high carbon concentration using physical and biological process |
US20110302975A1 (en) * | 2009-01-29 | 2011-12-15 | Jany Birgitta Maria Antens | Sulphur-containing fertilizers and process for the preparation thereof |
US20120088666A1 (en) * | 2009-06-16 | 2012-04-12 | Lin Gan | Method for preparing boron fertilizer |
US20190225556A1 (en) * | 2018-01-19 | 2019-07-25 | Compass Minerals Usa Inc. | Multi-source micronutrient composition and methods of treating soil with the same |
US20210253488A1 (en) * | 2018-05-10 | 2021-08-19 | Sawant Arun Vitthal | Novel crop nutrition and fortification composition |
US20210347704A1 (en) * | 2017-03-31 | 2021-11-11 | The Mosaic Company | Fertilizers containing slow and fast release sources of boron |
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US20110302975A1 (en) * | 2009-01-29 | 2011-12-15 | Jany Birgitta Maria Antens | Sulphur-containing fertilizers and process for the preparation thereof |
CA2798880A1 (en) * | 2009-05-08 | 2010-11-11 | Joao Calderon | Method for producing organic and organo-mineral fertilisers with high carbon concentration using physical and biological process |
US20120088666A1 (en) * | 2009-06-16 | 2012-04-12 | Lin Gan | Method for preparing boron fertilizer |
US20210347704A1 (en) * | 2017-03-31 | 2021-11-11 | The Mosaic Company | Fertilizers containing slow and fast release sources of boron |
US20190225556A1 (en) * | 2018-01-19 | 2019-07-25 | Compass Minerals Usa Inc. | Multi-source micronutrient composition and methods of treating soil with the same |
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