WO2024059126A1 - Enrichissement d'un matériau contenant du sulfate de sodium - Google Patents
Enrichissement d'un matériau contenant du sulfate de sodium Download PDFInfo
- Publication number
- WO2024059126A1 WO2024059126A1 PCT/US2023/032625 US2023032625W WO2024059126A1 WO 2024059126 A1 WO2024059126 A1 WO 2024059126A1 US 2023032625 W US2023032625 W US 2023032625W WO 2024059126 A1 WO2024059126 A1 WO 2024059126A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sulfate
- sop
- sodium sulfate
- product
- pellets
- Prior art date
Links
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 98
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 96
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 58
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 122
- 238000000034 method Methods 0.000 claims abstract description 82
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 42
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 33
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 30
- 239000001103 potassium chloride Substances 0.000 claims abstract description 21
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000003337 fertilizer Substances 0.000 claims description 63
- 239000008187 granular material Substances 0.000 claims description 55
- 229910052796 boron Inorganic materials 0.000 claims description 52
- 239000008188 pellet Substances 0.000 claims description 45
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 42
- 239000002699 waste material Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 29
- 239000011785 micronutrient Substances 0.000 claims description 26
- 235000013369 micronutrients Nutrition 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005056 compaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 6
- 238000007580 dry-mixing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 description 94
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 35
- 241000196324 Embryophyta Species 0.000 description 19
- 239000011780 sodium chloride Substances 0.000 description 18
- 235000002639 sodium chloride Nutrition 0.000 description 18
- 239000007787 solid Substances 0.000 description 13
- 239000012452 mother liquor Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 235000010338 boric acid Nutrition 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 235000021073 macronutrients Nutrition 0.000 description 8
- 235000015097 nutrients Nutrition 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000012066 reaction slurry Substances 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000003050 macronutrient Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 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 5
- 239000010446 mirabilite Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 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 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000013270 controlled release Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 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
- 239000011572 manganese Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 2
- VUEGYUOUAAVYAS-JGGQBBKZSA-N (6ar,9s,10ar)-9-(dimethylsulfamoylamino)-7-methyl-6,6a,8,9,10,10a-hexahydro-4h-indolo[4,3-fg]quinoline Chemical compound C1=CC([C@H]2C[C@@H](CN(C)[C@@H]2C2)NS(=O)(=O)N(C)C)=C3C2=CNC3=C1 VUEGYUOUAAVYAS-JGGQBBKZSA-N 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 229910021537 Kernite Inorganic materials 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000011021 bench scale process Methods 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
- 238000005119 centrifugation Methods 0.000 description 2
- -1 cobalt (II) fluorosilicate Chemical compound 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
- 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
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 2
- RSCACTKJFSTWPV-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 RSCACTKJFSTWPV-UHFFFAOYSA-N 0.000 description 2
- 238000007908 dry granulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012535 impurity Substances 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 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
- 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 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000001728 nano-filtration Methods 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
- 239000002245 particle Substances 0.000 description 2
- 239000012466 permeate Substances 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
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000002426 superphosphate Substances 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
- 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 2
- 229910021539 ulexite Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005550 wet granulation Methods 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
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 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
- 230000009286 beneficial effect Effects 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
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- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
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- 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
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
Definitions
- the present disclosure relates to beneficiating a sodium sulfate-containing material and producing a marketable product.
- the present disclosure relates particularly, although by no means exclusively, to beneficiating a sodium sulfate-containing waste material and producing a marketable product.
- the present disclosure also relates particularly, although by no means exclusively, to a process for producing potassium sulfate, i.e. sulfate of potash (SOP), from a sodium sulfate- containing material, such as a sodium sulfate-containing waste material.
- SOP potash
- the present disclosure also relates particularly, although by no means exclusively, to beneficiating a sodium sulfate-containing material, such as a sodium sulfate-containing waste material and producing SOP and using the SOP to produce a fertiliser product comprising SOP and boron, referred to herein as a SOP+B fertiliser product.
- the present disclosure also relates particularly, although by no means exclusively, to a plant for producing a fertiliser product that comprises potassium sulfate (sulfate of potash or “SOP”) and boron, with the potassium sulfate being produced by beneficiating a sodium sulfate- containing material, such as a sodium sulfate-containing waste material.
- a fertiliser product that comprises potassium sulfate (sulfate of potash or “SOP”) and boron
- the invention is not confined to sodium sulfate-containing waste material and extends to any sodium sulfate-containing material.
- Sodium sulfate is produced as a part of by-products of a number of industrial processes, including processes for producing borates and/or lithium from borate-containing minerals, lithium-containing minerals, and borate/lithium-containing minerals and processes for producing boric acid from borate-containing minerals.
- Sodium sulfate can be a part of bleed or tailings streams from industrial processes and, typically, is contained in storage ponds and tailings dams of those operations. Sodium sulfate can be a part of any other suitable sodium sulfate-containing waste material streams from industrial processes.
- the applicant has developed a process for beneficiating sodium sulfate-containing waste material streams from sodium sulfate-containing waste material sources and producing marketable potassium sulfate, i.e. sulfate of potash (SOP).
- SOP potash
- the present disclosure provides a process for beneficiating a sodium sulfate-containing material that comprises processing a sodium sulfate-containing material and potassium chloride and forming potassium sulfate, i.e. sulfate of potash (SOP), as a marketable product.
- SOP potash
- marketable product is understood herein to mean a product that can be sold to the market.
- marketable product is understood herein to include SOP that can be sold to the market as a fertiliser or as a feed material for the production of a fertiliser product.
- the present disclosure also provides a process for producing potassium sulfate, i.e. sulfate of potash (SOP), that comprises processing a sodium sulfate-containing material and potassium chloride and forming SOP.
- SOP potash
- the sodium sulfate-containing material may be a sodium sulfate-containing material that is regarded as a waste material.
- the sodium sulfate-containing material may be obtained from any suitable sodium sulfate-containing material, including any suitable source of sodium sulfate-containing waste material.
- the waste material source may be mineral processing operations such as borates production processes, lithium production processes, borates/lithium production processes, and boric acid production processes.
- the waste material source may be existing storage ponds and tailings dams of the operations described above.
- the process may comprise processing the sodium sulfate-containing material, such as a sodium sulfate-containing waste material, and potassium chloride in a Glaserite process and forming SOP.
- sodium sulfate-containing material such as a sodium sulfate-containing waste material
- potassium chloride in a Glaserite process
- the Glaserite process is a two-stage process for converting sodium sulfate into potassium sulfate, with the following reactions (1) and (2) in each respective stage 1 and 2:
- stage 1 sodium sulfate reacts with KC1 at near ambient temperature in accordance with reaction (1) and produces a reaction slurry comprising Glaserite solids (K 3 Na(SO 4 ) 2 ) and a soluble sodium chloride solution.
- stage 2 the Glaserite solids and a KC1 solution are mixed together and allowed to react at near ambient temperature in accordance with reaction (2) and produce a reaction slurry containing potassium sulfate (SOP) solids.
- SOP potassium sulfate
- the SOP solids are separated from the slurry and are dried to produce a dry powdered product.
- the present disclosure also provides a SOP+B fertiliser product which provides a macronutrient and a micronutrient.
- the SOP+B fertiliser product of the disclosure allows farmers to use a single fertiliser product to correct potassium and sulphur deficiencies in soils while providing boron in sufficient quantities for plant growth in crops.
- the exact quantity of boron in the fertiliser product can be selected based on the boron demand of the plant in crops.
- a fertiliser product comprising (a) potassium sulfate (sulfate of potash or “SOP”) produced from a sodium sulfate- containing material source and potassium chloride and (b) boron, wherein the amount of boron is equivalent to 0.2 to 3.0 wt.% B.
- the sodium sulfate-containing material may be a sodium sulfate-containing material that is regarded as a waste material.
- the amount of boron in the fertiliser product may be equivalent to more than 0.5 wt.%
- the amount of boron in the fertiliser product may be equivalent to more than 0.6 wt.%
- the amount of boron in the fertiliser product may be equivalent to more than 0.9 wt.% B.
- the amount of boron in the fertiliser product may be equivalent to no more than 10 wt.% B.
- the amount of boron in the fertiliser product may be equivalent to no more than 7 wt.% B.
- the amount of boron in the fertiliser product may be equivalent to no more than 1.75 wt.% B.
- the amount of boron in the fertiliser product may be equivalent to no more than 1.5 wt.% B.
- the amount of boron in the fertiliser product may range from 5 to 7 wt.% B.
- the fertiliser product may comprise boron in any one or more than one of the boron- containing compounds boric acid, borax pentahydrate, anhydrous borax, boric oxide, kernite, ulexite, borax decahydrate, zinc borate, tincal and disodium octaborate tetrahydrate (DOT) or combinations thereof.
- boron-containing compounds boric acid, borax pentahydrate, anhydrous borax, boric oxide, kernite, ulexite, borax decahydrate, zinc borate, tincal and disodium octaborate tetrahydrate (DOT) or combinations thereof.
- the fertiliser product may comprise a micronutrient in addition to boron.
- the fertiliser product may further comprise an additional micronutrient selected from a group consisting of iron, molybdenum, cobalt, manganese, nickel, copper, zinc or a combination thereof.
- 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 in addition to potassium and sulphur.
- the additional macronutrient may be any one of the following macronutrients in the following forms:
- the fertiliser product may be in a form of granules or pellets.
- granule is understood herein to mean a small compact particle of material, which may have a regular or irregular shape.
- a granule may be formed by agglomeration or compaction or otherwise, which may further be followed by crushing.
- pellet is understood herein to mean a particle of material, which suitably has a regular shape.
- a pellet may be formed by compression or compaction or molding or otherwise.
- the granules or pellets may be formed to provide required mechanical properties for materials handling of the granules or pellets.
- the granules or pellets may be compacted in a compaction or dry granulation process.
- the granules or pellets may be compacted using other granulation processes, such as wet granulation in a disc or other suitable pelletizer or fluidized bed or high energy mixing granulator.
- the granules or pellets may be 1-5 mm in size, typically 2-4 mm in size.
- the fertiliser product may be a slow-release product.
- slow-release is understood herein to mean the release of nutrients in the soil occurs gradually over a period of time because the nutrients are in a form that is not readily available for plant uptake in crops until some time has elapsed after the fertiliser has been applied.
- the fertiliser product may be a controlled-release product.
- controlled-release is understood herein to mean the release of nutrients in the soil is controlled to match the dynamic nutrient requirements in crops.
- Controlled-release fertilisers typically contain water-soluble nutrients that are coated or encapsulated with a material that controls the rate of nutrient release in crops.
- the coating is typically a semi- permeable material that allows the rate, pattern and duration of nutrient release to be controlled.
- the fertiliser product may comprise granules or pellets and a coating to control the release of macronutrients and micronutrients from the granules or pellets.
- the coating may be made from any suitable material.
- the coating may be made from a polymeric material.
- the coating may be made from a sulphur-containing polymer 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 fertiliser product may further comprise a binder.
- the binder may be any suitable material.
- the binder may be a starch.
- the binder may be water.
- a process for producing a fertiliser product comprising:
- Water may be added during the blending step (a).
- the sodium sulfate-containing material may be a sodium sulfate-containing material that is regarded as a waste material.
- the potassium chloride may be obtained from any suitable source.
- the process may comprise adding up to 30 wt.% moisture before forming step (b).
- the process comprises adding up to 20 wt. % moisture before forming step (b). More suitably, the process comprises adding up to 10 wt.% moisture before forming step (b). Even more suitably, the process comprises adding up to 2 wt.% moisture before forming step (b).
- the process may include drying the blended potassium sulfate and boron-containing compound(s) to form a mixture having a moisture content of not more than 30 wt.% before forming step (b).
- the process comprises drying the blended potassium sulfate and boron-containing compound(s) to form a mixture having a moisture content of not more than 20 wt.% before forming step (b).
- the process comprises drying the blended potassium sulfate and boron-containing compound(s) to form a mixture having a moisture content of not more than 10 wt.% before forming step (b).
- the process comprises drying the blended potassium sulfate and boron- containing compound(s) to form a mixture having a moisture content of not more than 2 wt.% before forming step (b).
- the process may include drying the granules or pellets.
- the SOP and the boron-containing compound(s) may be dry powders.
- the process may comprise producing SOP from a sodium sulfate-containing material, such as a sodium sulfate-containing waste material, by the above-described process.
- the SOP may be produced by a Glaserite process.
- the process may comprise supplying a sodium sulfate waste material and potassium chloride as feed materials for the Glaserite process and forming SOP.
- the boron-containing compound(s) may be selected from any one or more than one of boric acid, borax pentahydrate, anhydrous borax, boric oxide, kernite, ulexite, borax decahydrate, zinc borate, tincal and disodium octaborate tetrahydrate (DOT) or a combination thereof.
- Blending step (a) may comprise mixing a binder with potassium sulfate and the boron- containing compound(s).
- the binder may be a starch.
- the binder may be water.
- Blending step (a) may be a bulk blending step in which the compounds are added together at the same time and then mixed together.
- Blending step (a) may comprise any suitable sequence of adding and mixing the compounds.
- the process may comprise crushing the granules or pellets produced in the granule/pellet-forming step (b).
- the process may comprise classifying, for example screening, the crushed granules or pellets and separating the classified granules or pellets on the basis of size and producing a product fraction.
- the process may comprise classifying, for example by screening, the crushed granules or pellets 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 1-5 mm size fraction.
- the product fraction may be a 1-6 mm size fraction.
- the process may comprise returning the oversize fraction to the crushing step.
- the process may comprise returning the undersize fraction to the granule/pellet-forming step (b).
- the process may comprise drying the product fraction to form the fertiliser product.
- the present disclosure also provides a process for producing a fertiliser product that comprises potassium sulfate (sulfate of potash or “SOP”) and boron, the process comprising:
- Water may be added during the blending step (a).
- the process may comprise crushing the granules or pellets produced in the granule/pellet-forming step.
- the classifying step (c) may comprise producing an oversize fraction, an undersize fraction, and a product fraction.
- the process may comprise a crushing step after classifying step (c).
- the process comprises returning the crushed material after the screening step to the blending step.
- the crushed material may comprise either or a mixture of crushed oversize material and undersized material.
- the process may comprise returning the oversize fraction to the granule/pellet-forming step (b).
- the process may comprise returning the undersize fraction to the compaction step.
- the present disclosure also provides a plant for producing a fertiliser product that comprises potassium sulfate (sulfate of potash or “SOP”) and boron, the plant comprising:
- a unit for producing SOP from a sodium sulfate material source such as a sodium sulfate waste material source, and potassium chloride
- the SOP production unit (a) may be a Glaserite process unit.
- the plant may comprise a crushing unit for crushing the granules or pellets produced in the compaction unit or other suitable granule/pellet-forming unit.
- the crushing unit may be used to crush the compacted material from the compaction unit or other suitable granule/pellet-forming unit (c).
- Figure l is a flowsheet illustrating one embodiment of a process and a plant for producing a SOP+B fertiliser product according to the present disclosure
- Figure 2 is a flowsheet illustrating another embodiment of a process and a plant for producing a SOP+B fertiliser product according to the present disclosure
- Figure 3 is a flowsheet illustrating another, but not the only other, embodiment of a process and a plant for producing a SOP+B fertiliser product according to the present disclosure.
- Figure 4 is a flowsheet illustrating one embodiment of the steps in the granulation process and a plant of Figure 1 according to the present disclosure. DESCRIPTION OF EMBODIMENTS
- Figure l is a process flowsheet of one, but not the only, embodiment of a process and a plant of the present disclosure.
- (b) produces a fertiliser product for use as a micronutrient enriched fertiliser, general fertiliser, or crops nutrient in soil applications from the SOP produced in the above stage (a).
- a feed material for the process is a mother liquor slip stream 3 sourced from a boric acid plant (BAP) - not shown.
- the BAP mother liquor slip stream 3 contains sodium sulphate, sodium sulfate, boric acid and other impurities, and boric acid in concentrations depending on the composition of the borate ore and the temperature at which the boric acid is recovered.
- the disclosure extends to the use of sodium sulfate-containing waste streams that are sourced from any suitable sodium sulfate-containing waste material sources.
- the disclosure also extends to the use of sodium sulfate-containing streams that are sourced from any suitable sodium sulfate-containing material sources that are not necessarily sodium sulfate-containing waste streams.
- the feed material 3 is transferred to a sodium sulfate recovery unit 7 and formed into a sodium sulfate concentrate liquor 5 and a boric acid (BA) liquor 9.
- the sodium sulfate recovery unit 7 may be any suitable unit.
- suitable units include a reverse osmosis (RO) and/or a nanofiltration membrane unit, an evaporator and a crystalliser.
- RO reverse osmosis
- nanofiltration membrane unit an evaporator and a crystalliser.
- the boric acid (BA) liquor 9 is recycled to the BAP.
- the sodium sulfate concentrate liquor 5 is transferred to a sulfate mother liquor preparation unit 15.
- the sodium sulfate concentrate 5, water 11, Glauber’s salt (sodium sulfate decahydrate or Na2SO 4 - IOH2O) 13, and a sodium sulfate solution 45 are mixed together in the unit 15 and produce a sodium sulfate mother liquor (ML) 17.
- the sulfate mother liquor preparation unit 15 is a mixing tank.
- the Glauber’s salt stream is sourced from a lithium plant (not shown).
- the Glauber’s salt stream would otherwise be disposed of in ponds.
- the disclosure is not confined to this source of Glauber’s salt.
- the sodium sulfate solution 45 is sourced from a downstream step in the process.
- the disclosure is not confined to this source of sodium sulfate.
- the sodium sulfate ML 17 is transferred to a polishing filtration unit 19 or any other suitable unit that removes solid impurities and produces a product stream 21 comprising sodium sulfate in solution and a solid filter cake 23.
- the filter cake 23 is a waste product.
- the sodium sulfate product stream 21 is converted into potassium sulfate in a two-stage Glaserite reaction with the following reactions (1) and (2) in each respective stage 1 and 2:
- stage 1 the sodium sulfate stream 21 reacts with potash (KC1) 27, water 29, and a concentrated potassium liquor 87 at near ambient temperature in reactor 25 in accordance with reaction (1) and produces a reaction slurry (SI) 31 comprising Glaserite solids (K 3 Na(SO 4 )2) and a soluble sodium chloride solution.
- the reaction slurry 31 from stage 1 is transferred to a solid-liquid separation unit 33 that recovers the Glaserite solids as a Glaserite cake 37 and produces a Glaserite solution 39.
- the solid-liquid separation unit 33 may be by way of example a centrifugation step that uses wash water 35 to separate a Glaserite cake 37 from the slurry 31.
- the Glaserite solution 39 contains soluble sodium chloride and is treated in a NaCl recovery unit 41 and sodium chloride separation unit 43 that produces a solid sodium chloride cake 91 and the above-described sodium sulfate solution 45.
- the sodium sulfate solution 45 is transferred to the sulfate mother liquor preparation unit 15 or disposed of in ponds or other disposal options.
- the NaCl recovery unit 41 may include but is not limited to, an evaporative crystallization step to precipitate a NaCl solute in combination with or without a prior sulfate separation step by membrane, producing a sodium sulfate concentrate which can be used in the sulfate mother liquor preparation unit or elsewhere in the process.
- Other suitable technologies to replace the crystallization step may include reverse osmosis and/or nanofiltration step.
- the Glaserite cake 37 produced in the solid-liquid separation unit 33 is transferred to a SOP reactor 51.
- the Glaserite cake 37 and a KC1 solution 53 are mixed together and allowed to react in the SOP reactor 51 at near ambient temperature in accordance with reaction (2) and produce a reaction slurry (S2) 55 containing potassium sulfate (SOP) solids and a solution containing mainly potassium chloride (from excess KC1 added in stage 2), sulfates, and traces of NaCl from the reaction.
- S2 reaction slurry
- SOP potassium sulfate
- the KC1 solution 53 is prepared in this embodiment by mixing potash 57 in the form of dry solids and water 59 in a mixing tank 61.
- the SOP solids are separated from the reaction slurry 55 in a solid-liquid separation unit 63.
- the solid-liquid separation unit 63 is a centrifugation step.
- a wash water 99 is provided and this separates the solids from the reaction slurry 55 and produces an output SOP cake 65 and a centrate 81.
- the centrate 81 contains a high concentration of potassium and a significant but much lower amount of NaCl .
- the centrate 81 is transferred to a potassium solution concentration unit 85 and is concentrated for example by evaporation and produces the concentrated potassium liquor 87 that is supplied to the reactor 25 to contribute to the Glaserite reaction to maximize the yield of potassium.
- Steam 91 produced in the concentration unit 85 can be used in various units of the SOP production process or elsewhere.
- Suitable technologies to replace the evaporation step may include reverse osmosis that could concentrate our potassium stream enough to recycle back to stage 1.
- the SOP cake 65 produced in the solid-liquid separation unit 63 is dried in a dryer 67, such as a rotary dryer, forming a dry SOP powdered product 69 and steam 97.
- a dryer 67 such as a rotary dryer
- the sodium sulfate waste material sources are readily available on site - either as waste material streams produced as part of continuing process operations or as stored waste material in ponds and tailings dams.
- sodium sulfate waste material is an opportunity to reduce production costs of SOP as compared to other options, such as using a Manheim process (i.e. H2SO4 + KC1) to produce sodium sulfate, or buying sodium sulfate from other sources.
- a Manheim process i.e. H2SO4 + KC1
- Figure 2 is a flowsheet illustrating another embodiment of a process and a plant for producing a SOP+B fertiliser product.
- Figure 3 is a flowsheet illustrating another, but not the only other, embodiment of a process and a plant for producing a SOP+B fertiliser product.
- the sodium sulfate recovery unit 7 is shown as a membrane unit.
- the Glaserite solution 39 produced in the solid-liquid separation unit 33 is treated in a sodium sulfate separation unit 85 in the form of a membrane unit and produces a sodium sulfate concentrate 47 and a chloride containing permeate 49.
- the sodium sulfate concentrate 47 is transferred to and becomes part of the sodium sulfate solution 45 that is transferred to the sulfate mother liquor preparation unit 15.
- the permeate 49 is transferred to the NaCl recovery unit 41, in this embodiment in the form of a membrane unit, and the sodium chloride separation unit 43 and processed as described in relation to Figure 1.
- the Figure 3 flowsheet is the same as the Figure 2 flowsheet, save that the NaCl recovery unit 41 is in the form of an evaporative crystalliser rather than the membrane unit of the Figure 2 flowsheet.
- the dry SOP powdered product 69 is a marketable product.
- the dry SOP powdered product 69 is used in the production of a fertiliser product, as described below.
- the dry SOP powdered product 69 can also be used as a soluble fertilizer, a potassium sulfate fine powder, and/or used in the production of a granular fertilizer product.
- the fertiliser product produced in the Figures 1-3 embodiments comprises SOP and boron, wherein the amount of boron is equivalent to 0.2 to 3.0 wt.% B.
- the formulated fertiliser product produced in the Figures 1-3 embodiments comprises SOP and boron, with the amount of B equivalent to 0.2 to 3.0 wt.% B being selected based on the B demand of targeted crops.
- the formulated fertiliser product produced in the Figures 1-3 embodiments may also contain other materials, including other micronutrients and a binder.
- 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 fertiliser production section of the process shown in Figures 1-3 comprises:
- the product formulation produced in the Figure 1 process flowsheet is in the form of compacted granules of 1-5 mm, typically 2-4 mm granule size.
- the dry SOP powdered product 69 is combined with a boron- containing compound 71, water 73, and optionally a binder 75 and optionally other additional micronutrients in a granulation plant 77 and forms granules of the SOP+B final product 79.
- the steam 97 produced in the rotary dryer 67 can be used in various units of the SOP production process or elsewhere.
- Figure 4 is a process flowsheet illustrating steps in an embodiment, although not the only embodiment, of a granulation plant 77 according to the present disclosure.
- a key feature of the embodiment of the process for producing the fertiliser product shown in Figure 4 is the formulation and compaction of the SOP+B product.
- the granulation plant 77 includes a bulk blending unit 103 which mixes together the dry SOP powdered product 69, boron-containing compound 71, water 75, optionally a binder 75 and optionally other micronutrients selected from the above list, in targeted proportions depending on the B nutrient crop demands and produces a blended product 105.
- the blended product 105 is compacted and dried in a compaction unit 107, thereby forming granules or pellets 109.
- the target size of the granules or pellets 109 in the final fertiliser product is 1-5 mm, typically 2-4 mm.
- the granules or pellets 109 are crushed in a crusher unit 111 and produce crushed granules or pellets 113.
- crushed granules or pellets 113 are transferred to a screen unit 115 and separated in an oversize fraction 119, and undersize fraction 117, and a product fraction 121.
- the undersize fraction 117 are returned to the compaction unit 107 and re-processed.
- the oversize fraction 119 are returned to the crusher unit 111 and re-crushed.
- the product fraction 121 which a target size granules or pellets, are transferred to a dryer unit 123 and dried to form the final fertiliser product 125.
- the disclosure is not so limited and extends to other additional micronutrients.
- the micronutrient may be selected from a group consisting of iron, molybdenum, cobalt, manganese, copper, nickel, zinc or a combination thereof.
- the disclosure is not so limited and extends to other granulation processes.
- the process may include wet granulation in a disc or other suitable pelletizer or fluidized bed or high energy mixing granulator.
- the granules or pellets may be slow-release granules.
- the embodiment of the process shown in Figure 2 may include coating the granules or pellets with a quick-release coating.
- the applicant has conducted bench scale (IL) trials and batch pilot scale trials (30L batch) to produce the SOP from sodium waste (Glauber’s salt) produced on site at a lithium production plant.
- the trials demonstrate that it is feasible to produce a product with greater than 95% K2SO4 using the two-stage Glaserite process at near ambient temperatures and minimum KC1 addition ratios of 0.79 g KCl/g Na2SO4 in stage 1 and 0.70 g KCl/g Glaserite in stage 2.
- the best reaction times and reagent concentrations in the reaction slurry were also determined by testing different parameters in bench scale trials. It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
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Abstract
Processus d'enrichissement d'un matériau contenant du sulfate de sodium qui comprend le traitement d'un matériau contenant du sulfate de sodium et du chlorure de potassium et la formation de sulfate de potassium, c'est-à-dire de sulfate de potasse (SOP) en tant que produit commercialisable.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20100266482A1 (en) * | 2005-11-10 | 2010-10-21 | Parimal Paul | Process for the Time Recovery of Sulphate of Potash (SOP) From Sulphate Rich Bittern |
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