EP3142990A1 - Sulfur fertilizer - Google Patents
Sulfur fertilizerInfo
- Publication number
- EP3142990A1 EP3142990A1 EP15725542.3A EP15725542A EP3142990A1 EP 3142990 A1 EP3142990 A1 EP 3142990A1 EP 15725542 A EP15725542 A EP 15725542A EP 3142990 A1 EP3142990 A1 EP 3142990A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- fertilizer composition
- sulfur
- fertilizer
- manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003337 fertilizer Substances 0.000 title claims abstract description 81
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 74
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011593 sulfur Substances 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 claims abstract description 35
- 239000002689 soil Substances 0.000 claims description 49
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 44
- 239000011777 magnesium Substances 0.000 claims description 42
- 235000019738 Limestone Nutrition 0.000 claims description 37
- 239000008187 granular material Substances 0.000 claims description 37
- 239000006028 limestone Substances 0.000 claims description 37
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 25
- 239000000292 calcium oxide Substances 0.000 claims description 25
- 235000012255 calcium oxide Nutrition 0.000 claims description 25
- 241000196324 Embryophyta Species 0.000 claims description 23
- 238000005469 granulation Methods 0.000 claims description 21
- 230000003179 granulation Effects 0.000 claims description 21
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 17
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 17
- 235000006008 Brassica napus var napus Nutrition 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 235000004977 Brassica sinapistrum Nutrition 0.000 claims description 15
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 15
- 150000004679 hydroxides Chemical class 0.000 claims description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 14
- 239000000920 calcium hydroxide Substances 0.000 claims description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 14
- 230000004720 fertilization Effects 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000010459 dolomite Substances 0.000 claims description 13
- 229910000514 dolomite Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 241000234282 Allium Species 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 9
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 claims description 8
- 240000002791 Brassica napus Species 0.000 claims description 8
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 235000010216 calcium carbonate Nutrition 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 240000006108 Allium ampeloprasum Species 0.000 claims description 6
- 235000005254 Allium ampeloprasum Nutrition 0.000 claims description 6
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 6
- 240000002234 Allium sativum Species 0.000 claims description 6
- 235000007319 Avena orientalis Nutrition 0.000 claims description 6
- 244000075850 Avena orientalis Species 0.000 claims description 6
- 235000011331 Brassica Nutrition 0.000 claims description 6
- 241000219198 Brassica Species 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 6
- 244000068988 Glycine max Species 0.000 claims description 6
- 235000010469 Glycine max Nutrition 0.000 claims description 6
- 244000299507 Gossypium hirsutum Species 0.000 claims description 6
- 241000208818 Helianthus Species 0.000 claims description 6
- 235000003222 Helianthus annuus Nutrition 0.000 claims description 6
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 6
- 240000005979 Hordeum vulgare Species 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 241000219828 Medicago truncatula Species 0.000 claims description 6
- 241000745991 Phalaris Species 0.000 claims description 6
- 244000088415 Raphanus sativus Species 0.000 claims description 6
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 claims description 6
- 240000006394 Sorghum bicolor Species 0.000 claims description 6
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 241000219793 Trifolium Species 0.000 claims description 6
- 235000019714 Triticale Nutrition 0.000 claims description 6
- 235000021307 Triticum Nutrition 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000002950 deficient Effects 0.000 claims description 6
- 244000013123 dwarf bean Species 0.000 claims description 6
- 235000004611 garlic Nutrition 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 235000009973 maize Nutrition 0.000 claims description 6
- 235000021278 navy bean Nutrition 0.000 claims description 6
- 241000228158 x Triticosecale Species 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011785 micronutrient Substances 0.000 claims description 5
- 235000013369 micronutrients Nutrition 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- -1 preferably diluted Chemical compound 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 229910052925 anhydrite Inorganic materials 0.000 claims description 4
- 150000004688 heptahydrates Chemical class 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 235000012245 magnesium oxide Nutrition 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 235000012216 bentonite Nutrition 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000005056 compaction Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 235000013379 molasses Nutrition 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 239000006072 paste Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 244000188595 Brassica sinapistrum Species 0.000 claims 2
- 241000219823 Medicago Species 0.000 claims 2
- 244000098338 Triticum aestivum Species 0.000 claims 2
- 238000001228 spectrum Methods 0.000 claims 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims 1
- 239000011575 calcium Substances 0.000 description 36
- 240000004658 Medicago sativa Species 0.000 description 20
- 240000000385 Brassica napus var. napus Species 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 206010039509 Scab Diseases 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 11
- 235000011941 Tilia x europaea Nutrition 0.000 description 11
- 239000004571 lime Substances 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000007812 deficiency Effects 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 235000014413 iron hydroxide Nutrition 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000005662 Paraffin oil Substances 0.000 description 4
- 241000209140 Triticum Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000011573 trace mineral Substances 0.000 description 4
- 235000013619 trace mineral Nutrition 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000010624 Medicago sativa Nutrition 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000001863 plant nutrition Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 244000016163 Allium sibiricum Species 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000589180 Rhizobium Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000009088 enzymatic function Effects 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 235000021374 legumes Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C05D3/00—Calcareous fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
-
- 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
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
- C05F7/005—Waste water from industrial processing material neither of agricultural nor of animal origin
-
- 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
- C05G3/80—Soil conditioners
Definitions
- the present invention refers to a sulfur fertilizer composition, the process for preparing the same and its use.
- S Sulfur
- N nitrogen
- K potassium
- P P
- Sulfur is an important component of several essential amino acids and thus, sulfur is important for both protein quality and quantity. It is also involved in nitrogen metabolism, photosynthesis, synthesis of oils in oilseed crops such as canola, and in synthesis and function of enzymes, amino acids and other organic compounds.
- Sulfur deficiencies can have a major impact on crop yield and quality. Sulfur deficiencies mainly arise on acid sandy soils where sulfate has been leached, especially in such areas with high winter rainfall. Naturally, deficiencies of sulfur mainly occur for cultures with high demand for sulfur, like alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale, furthermore cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic.
- Fertilizing with sulfur may overcome those problems. Fertilizing with sulfur may not only affect sulfur content of plants but also positively affect the storability of the products (e.g. garlic).
- sulfur fertilizers are: Ammonium sulfate, potassium sulfate, magnesium sulfate, gypsum or elemental sulfur.
- Elemental sulfur and ammonium sulfate result in acidification of soil and therefore, they can be used without negative impact on soils with high pH only.
- NH 3 volatilization can be a problem with ammonium sulfate in case of high pH of soil.
- Ammonium sulfate, potassium sulfate, magnesium sulfate have very high solubilities and sulfate may be washed out in case of strong rainfall. Elemental sulfur has a very low solubility. Elemental sulfur applied during winter is ineffective for overcoming sulfur deficiency because the S is oxidized too slowly by soil microorganisms. Gypsum exhibits a useful solubility, but usually is not available in form of stable granulates and does not raise soil pH.
- ferrous sulfate obtained as by-product from ⁇ 2 production. So far, the use of ferrous sulfate is known for waste water treatment, for iron oxide pigments, or as chromate reducing agent.
- iron sulfate has not been mentioned or suggested as sulfur fertilizer. Some applications mention iron sulfate as moss killer or as Fe source in case of Fe deficiency (chlorosis) or as phosphorus and heavy metal absorber in polluted soils. However, the use of iron sulfate results in acidification of soil.
- GB 1 473 403 discloses a method for preparing compositions useful as soil modifiers or fertilizers by thoroughly mixing ferrous sulfate heptahydrate
- DE 42 19 351 discloses an additive for agriculture obtained from ferrous sulfate (not ferrous sulfate heptahydrate!) obtained as by-product from titanium dioxide manufacture optionally blended with earth alkaline compounds and an organic material. Use of this material is for treating Fe, Mn and Zn deficiencies. No application as sulfur fertilizer is disclosed in DE 42 19 351 .
- EP 0 093 204 discloses a process for granulating Fe containing fertilizing mixtures comprising ferrous sulfate and fertilizing agents by use of hydrophilic additives. Also admixing of other fertilizing agents like ammonium sulfate, NPK compounds, micronutrients or natural fertilizers is disclosed. No application as sulfur fertilizer is disclosed in EP 0 093 204.
- EP 2 165 976 discloses a method for pressure compacting of compositions based on ferrous sulfate heptahydrate. Use of this material is as Fe source for
- the inventors have considered the disadvantages of the prior art compositions and came to the inventive solution by providing a sulfur fertilizer without detrimental impact on soil pH and plant nutrition, preferably in form of stable granulates, without expensive additives or processes for granulation, and a process for preparing the same as well as its use as fertilizer.
- the present invention is directed to a process for manufacturing a fertilizer composition comprising S, Fe and one or more earth alkaline elements, including Ca and/or Mg, being suitable for administration onto a sulfur deficient soil wherein a material, comprising Fe and sulfate ions, in form of a solid salt, filter cake, paste, slurry, or solution, is blended with at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements including at least one of Ca and Mg, preferably CaCO3, MgCO3, dolomite (Ca,Mg)CO 3 , MgO, burnt dolomite (Ca,Mg)O, CaO, semi-hydrated dolomite
- Blending and converting into an administration form may be carried out
- the inventive process can be carried out in an apparatus which can also serve for compaction, granulation and/or pelletizing the reaction product
- Blending and/or converting may be carried out in the presence of any of water, dilute sulfuric acid, preferably diluted, CaSO 4 , elemental sulfur or other S
- micronutrients preferably a boron compound, binder or granulation aids, or mixtures thereof, also assisting in obtaining the required form of the product.
- the material comprising Fe and sulfate ions may preferably be FeSO 4 which may contain crystal water, such as Fe(ll)SO 4
- heptahydrate preferably obtained from the titanium dioxide production process.
- the at least one component comprising oxides, hydroxides or carbonates of earth alkaline elements which is generally used for neutralizing any acid such as any adhering sulfuric acid and also for increasing the pH-value may preferably be limestone, limestone, which is a natural material without critical contents of harmful substances with respect to agricultural applications.
- the limestone may consist of fine particles 95 % ⁇ 0,09 mm, and comprise >95 % CaCO 3 .
- the component comprising oxides, hydroxides or carbonates of earth alkaline elements can also be a slag from steel manufacturing or a reaction product from such a slag.
- the slag has a high basicity and is more reactive than CaCO3.
- the component comprising oxides, hydroxides or carbonates of earth alkaline elements can be burnt lime or burnt dolomite or hydrated lime, providing a higher neutralization potential and higher reactivity than CaCO3 and slag.
- the neutralizing value of said at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements according to DIN EN 12945:2014-07 standard may be 1 to 55% (as CaO), preferably 20 to 55%, most preferably 33 to 48%.
- At least one of starch, magnesium sulfates, citric acid, clay, mortar binder, cellulose glue, glucosidic binder such as starch, molasses, lignosulfonate, water, hydrated lime, water glass, bentonite, cellulose fibres, stearates, urea or combinations of these materials may be used as binder or granulation aid in a weight ratio of 0.1 to 10 weight-%, preferably 0.3 to 5 weight-%, most preferably 0.8 to 3 weight-%, related to the total mass of the composition comprising Fe and sulfate ions and the at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements Ca and Mg.
- the inventive process is carried out by blending:
- a material comprising carbonates of the earth alkaline elements Ca and/or Mg, preferably CaCO3, MgCO3, or dolomite, and
- the present invention is also directed to a fertilizer composition
- a fertilizer composition comprising S, Fe and at least one earth alkaline element including at least one of Ca and/or Mg, wherein the molar ratio of (Ca+Mg)/Fe is in the range of 2 to 200, preferably 2.5 to 25, most preferably 10 to 25.
- the molar ratio of Fe to S in the inventive fertilizer composition may be 0.3 to 6, preferably 0.5 to 2, most preferably 0.8 to 1 .2.
- compositions are calcium sulfate, iron hydroxide and unreacted earth alkaline compounds.
- the iron hydroxide obtained has two important functions: The first function is an effective and efficient binder for granulates; and the second function is partial retention of sulfate and trace element ions by adsorption. Therefore, a sulfur fertilizer comprising iron hydroxide (or reaction products of iron sulfate with alkaline compounds) has improved properties compared to a material without iron hydroxide as the sulfate is not washed out of the soil so easily.
- calcium sulfate may also be added additionally.
- iron sulfate has been converted mainly or completely into earth alkaline sulfates in the composition.
- crystal structures generally are determined by x-ray diffraction (XRD) and quantitative relation of XRD peaks with actual relation of crystal structures can be somewhat ambiguous, the ratio of XRD signals are compared rather than ratio of crystal structures for analyzing and defining the inventive fertilizer composition.
- XRD x-ray diffraction
- the invention also concerns a process for fertilizing S and one or more earth alkaline elements, preferably Ca and/or Mg wherein the above inventive fertilizer composition is applied, preferably in form of granulates, onto a sulfur deficient soil used for agriculture, preferably for fertilizing sulfur to plants supplying amino acids, proteins and/or oil, in particular cultures of alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats, triticale, cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic.
- Advantage of this process is that fertilizing S and fertilizing Ca (and optionally Mg), and raising the soil pH is achieved at the same time with one single step.
- Another advantage is that part of Ca (and optionally Mg) is available in soluble form (as CaSO4), whereas Ca (and optionally Mg) from conventional limestone or dolomite fertilizers is not soluble but has to get leached by contact with an acidic environment.
- a fertilizer composition offering both Ca (and optionally Mg) solubility and at the same time considerable alkaline character has a clear advantage over conventional fertilizer types. Even more, the content of soluble sulfur (as sulfate), valuable trace elements like Mn and Zn (and optionally B) and the low content of unwanted elements (e.g. As, Hg, Cd, Pb) and toxic organic compounds results in a highly valuable fertilizer type.
- said application on fields used for agriculture is made for base fertilization between summer and winter time, i.e. between August and December for areas north of the equator or between February and June for areas south of the equator, respectively, before the growth phase of the plants start.
- the ratio of the (acidic) Fe(ll)sulfate and the (alkaline) Ca and/or Mg compound may vary depending on soil pH:
- a molar ratio (Ca+Mg)/S of >2 may be appropriate, whereas for more acidic soils a molar ratio (Ca+Mg)/S of »2 may be appropriate.
- Ca/S 7.5 - 15.
- the pH of the soil may be raised to above 5.8, preferably above >6.0, most preferably >6.2.
- sulfur in the inventive fertilizer is available in the form of sulfate, but for calculation purpose sulfur virtually is expressed as S.
- the present invention also provides the use of a solution comprising iron sulfate or the use of crystalline iron sulfate with more than 3 molecules of crystal water, preferably iron(ll)sulfate heptahydrate, more preferably copperas as obtained as by-product from titanium dioxide manufacturing, for preparing a sulfur fertilizing composition and/or for moistening and/or granulating of powderous fertilizer materials.
- - Preferred is a granular free flowing and dust free form of the fertilizer.
- iron hydroxide due to its high capability for absorption of trace elements is able to avoid the micronut ents present in the inventive fertilizer (Mn, Zn) to be washed out.
- the inventive fertilizer additionally comprises valuable plant nutrients and
- micronutrients e.g. Mg, Mn, Zn.
- the product is free of Hg, Cd, As, Pb, Cr.
- the inventive composition can be used for all cultures, preferably those with high sulfur demand, e.g. alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, lucerne, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale; furthermore cruciferous plants like Brassicas, radish, rocket and allium crops like onion, leek and garlic, especially suitable for canola and rapeseed and most preferably during winter time.
- canola canola
- cotton clovers, phalaris, barrel medic, lucerne, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale
- cruciferous plants like Brassicas, radish, rocket and allium crops like
- the pH of the fertilizer can be 5.5 to 13, for most applications preferably 6.0 to 1 1 , most preferably 6.5 to 8.5.
- the pH of the fertilizer is preferably 8.5 to 13.
- the present invention also concerns:
- An inventive composition wherein it contains Zn with mass ratio of Zn/Fe 0.0001 to 0.003, preferably 0.0002 to 0.0015, and/or Mn with the mass ratio of Mn/Fe 0.00001 to 0.01 , preferably 0.00001 to 0.001 ; these elements are valuable micronutrients and therefore no separate application of Zn and Mn is necessary.
- Said inventive composition wherein the pH according to ISO standard is 5.5 to 13, for most application preferably 6.0 to 1 1 , most preferably 6.5 to 8.5, but preferably 8.5 to 13 for compositions comprising calcium oxide or calcium dihydroxide.
- the pH is determined according to DIN EN ISO 787 part 3, whereby the pH measurement is made no earlier than 5 days after preparation of the sample and whereby the sample is ground prior to pH measurement.
- Said inventive composition wherein the neutralizing value according to DIN EN 12945:2014-07 standard is 1 to 55% (as CaO), preferably 20 to 55%, most preferably 33 to 48%.
- Said inventive composition wherein the fertilizer is granulated with volume based average granule size is 1 - 8 mm, preferably 2 - 6, most preferably 2 - 4 mm;
- Said inventive composition wherein it is granulated in a pan granulator, or a granulation drum, or an intensive mixer.
- Said inventive composition wherein it is granulated in a pan granulator, or a granulation drum, or an intensive mixer, without the addition of water to aid granulation.
- Said inventive composition wherein it is granulated in a combination of an intensive mixer and a granulator such as a pan granulator or a granulation drum.
- Ca and/or Mg compound preferably CaCO 3 or dolomite (Ca,Mg)CO 3 o iron sulfate, preferably Fe(ll)SO 4 heptahydrate,
- the fertilizer comprises iron sulfate and/or products obtained from neutralization of iron sulfate and at least one calcium and/or magnesium compound and/or the reaction products of iron sulfate and calcium and/or magnesium compounds; o Use of the composition as a sulfur fertilizer for alfalfa, canola
- composition between summer and winter time, i.e. between
- composition as a calcium-sulfur fertilizer in such way that he pH of the soil is raised to >5.8, preferably >6.0, most preferably >6.2;
- trace element nutrients like boron, copper, molybdenum
- the calcium and/or magnesium compound has a pH >8, e.g. slag from steel manufacturing, burnt or hydrated lime / dolomite
- the present invention is further illustrated by the following Examples.
- Example 1 a - Preparation of compacted Ca-S-fertilizer with 2.4% S and
- the granules had a residual moisture content determined by drying at 105 ° C of 21 .6 wt.%. From this fraction, 10 fresh granules were arbitrarily taken out and crushed by applying a pressing force. The average crushing strength was 0.3 kg. Granules with a high residual moisture exhibit low crushing strength.
- Example 2d Preparation of granulated Ca-S-fertilizer with 2% S and
- the alkaline content of the inventive fertilizer is determined by an acid-base titration.
- an acid-base titration For this analytical method, about 1 g of a representative sample of the product is reacted in a beaker with 25 ml of a hydrochloric acid solution of a concentration of 1 mol per liter. The reaction of the calcium carbonate and hydrochloric acid produces carbon dioxide. The sample is left overnight in order for the reaction to complete and the bulk of the carbon dioxide to be emitted from the beaker. The next day, the beaker is briefly heated to just below the boiling point of water to emit any remaining carbon dioxide. Subsequently, the excess
- hydrochloric acid is back-titrated with a solution of sodium hydroxide of a concentration of 1 mol per liter. The extent of the titration is monitored by measuring the pH of the liquid, for example potentiometrically, and determining the consumption of sodium hydroxide solution at the equivalence point. The amount of alkaline substance is then expressed as equivalent percentage of CaCO3. 1 .501 g of a fertilizer sample is reacted with 25 ml of 1 M hydrochloric acid with a titer of 0.9921 in a beaker.
- the soil pH was measured in a suspension of 1 part soil with 2.5 parts of a solution of 0.01 M CaCI 2
- the effect of the limestone / FeSO4 preparations on pH is stronger than the effect of pure limestone!
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Abstract
The present invention refers to a sulfur fertilizer composition, the process for preparing the same and its use.
Description
SULFUR FERTILIZER
The present invention refers to a sulfur fertilizer composition, the process for preparing the same and its use.
Sulfur (S) is an important plant nutrient. It is required by plants in amounts similar to phosphorus (P), thus it is grouped with nitrogen (N), potassium (K) and P as the fourth major plant nutrient. Sulfur is an important component of several essential amino acids and thus, sulfur is important for both protein quality and quantity. It is also involved in nitrogen metabolism, photosynthesis, synthesis of oils in oilseed crops such as canola, and in synthesis and function of enzymes, amino acids and other organic compounds.
Due to increasing removal of sulfur compounds from flue gas, especially of power plants, waste and biomass incineration plants, in the last three decades the intake of sulfur compounds into soil has decreased significantly in many regions. In Germany for example the SO2 emissions have come down from ca. 5 million tons per year to ca. 0.5 million tons per year. Accordingly, the average intake of S into the soil has changed from ca. 500 kg S / (ha * a) to less than 50 kg S / (ha * a).
Sulfur deficiencies can have a major impact on crop yield and quality. Sulfur deficiencies mainly arise on acid sandy soils where sulfate has been leached, especially in such areas with high winter rainfall. Naturally, deficiencies of sulfur mainly occur for cultures with high demand for sulfur, like alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale, furthermore cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic.
Deficiencies of sulfur result in lower yield and worse quality of cultures. Fertilizing with sulfur may overcome those problems. Fertilizing with sulfur may not only
affect sulfur content of plants but also positively affect the storability of the products (e.g. garlic).
In the state of art commonly used sulfur fertilizers are: Ammonium sulfate, potassium sulfate, magnesium sulfate, gypsum or elemental sulfur.
Elemental sulfur and ammonium sulfate result in acidification of soil and therefore, they can be used without negative impact on soils with high pH only. On the other hand, NH3 volatilization can be a problem with ammonium sulfate in case of high pH of soil.
Ammonium sulfate, potassium sulfate, magnesium sulfate have very high solubilities and sulfate may be washed out in case of strong rainfall. Elemental sulfur has a very low solubility. Elemental sulfur applied during winter is ineffective for overcoming sulfur deficiency because the S is oxidized too slowly by soil microorganisms. Gypsum exhibits a useful solubility, but usually is not available in form of stable granulates and does not raise soil pH.
Other source of sulfur might be ferrous sulfate obtained as by-product from ΤΊΟ2 production. So far, the use of ferrous sulfate is known for waste water treatment, for iron oxide pigments, or as chromate reducing agent.
In the state of art, iron sulfate has not been mentioned or suggested as sulfur fertilizer. Some applications mention iron sulfate as moss killer or as Fe source in case of Fe deficiency (chlorosis) or as phosphorus and heavy metal absorber in polluted soils. However, the use of iron sulfate results in acidification of soil.
In several patent applications, agricultural uses of iron sulfate are described.
GB 1 473 403 discloses a method for preparing compositions useful as soil modifiers or fertilizers by thoroughly mixing ferrous sulfate heptahydrate
(copperas) with compounds chosen from oxides, hydroxides or carbonates of alkaline or earth alkaline elements thereby obtaining reaction products consisting of alkaline or earth alkaline sulfates and ferrous hydroxide. Subsequently, the
ferrous hydroxide is converted into ferric hydroxide by oxidation with oxygen or air. No application as sulfur fertilizer is disclosed in GB 1 473 403.
DE 42 19 351 discloses an additive for agriculture obtained from ferrous sulfate (not ferrous sulfate heptahydrate!) obtained as by-product from titanium dioxide manufacture optionally blended with earth alkaline compounds and an organic material. Use of this material is for treating Fe, Mn and Zn deficiencies. No application as sulfur fertilizer is disclosed in DE 42 19 351 . EP 0 093 204 discloses a process for granulating Fe containing fertilizing mixtures comprising ferrous sulfate and fertilizing agents by use of hydrophilic additives. Also admixing of other fertilizing agents like ammonium sulfate, NPK compounds, micronutrients or natural fertilizers is disclosed. No application as sulfur fertilizer is disclosed in EP 0 093 204.
EP 2 165 976 discloses a method for pressure compacting of compositions based on ferrous sulfate heptahydrate. Use of this material is as Fe source for
agriculture. No application as sulfur fertilizer is disclosed in EP 2 165 976. In the state of art, there is still the need for an improved sulfur fertilizer composition which provides sufficient sulfur to the soil upon application of the composition to the soil.
For solving the problem of the invention, the inventors have considered the disadvantages of the prior art compositions and came to the inventive solution by providing a sulfur fertilizer without detrimental impact on soil pH and plant nutrition, preferably in form of stable granulates, without expensive additives or processes for granulation, and a process for preparing the same as well as its use as fertilizer.
Therefore, the present invention is directed to a process for manufacturing a fertilizer composition comprising S, Fe and one or more earth alkaline elements, including Ca and/or Mg, being suitable for administration onto a sulfur deficient soil
wherein a material, comprising Fe and sulfate ions, in form of a solid salt, filter cake, paste, slurry, or solution, is blended with at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements including at least one of Ca and Mg, preferably CaCO3, MgCO3, dolomite (Ca,Mg)CO3, MgO, burnt dolomite (Ca,Mg)O, CaO, semi-hydrated dolomite
Ca(OH)2MgO, or Ca(OH)2 or mixtures thereof in molar ratio of (Ca+Mg)/Fe = 2 to 200, preferably 2.5 to 25, more preferably 10 to 25, and the blend is converted into an administration form. Blending and converting into an administration form may be carried out
simultaneously or subsequently, leading to a reaction mixture in a granulated, pelletized or powderous form depending on the ratio of the used components. Thus, the inventive process can be carried out in an apparatus which can also serve for compaction, granulation and/or pelletizing the reaction product
Blending and/or converting may be carried out in the presence of any of water, dilute sulfuric acid, preferably diluted, CaSO4, elemental sulfur or other S
containing compounds, other compounds useful for a fertilizer, such as
micronutrients, preferably a boron compound, binder or granulation aids, or mixtures thereof, also assisting in obtaining the required form of the product.
In the inventive process, the material comprising Fe and sulfate ions may preferably be FeSO4 which may contain crystal water, such as Fe(ll)SO4
heptahydrate, preferably obtained from the titanium dioxide production process.
The at least one component comprising oxides, hydroxides or carbonates of earth alkaline elements which is generally used for neutralizing any acid such as any adhering sulfuric acid and also for increasing the pH-value may preferably be limestone, limestone, which is a natural material without critical contents of harmful substances with respect to agricultural applications. To provide suitable reactivity against FeSO4 in blending process as well as suitable reactivity and effect in soil, the limestone may consist of fine particles 95 % < 0,09 mm, and comprise >95 % CaCO3.
The component comprising oxides, hydroxides or carbonates of earth alkaline elements can also be a slag from steel manufacturing or a reaction product from such a slag. The slag has a high basicity and is more reactive than CaCO3.
For application on more acidic soils or if faster effects are required, the component comprising oxides, hydroxides or carbonates of earth alkaline elements can be burnt lime or burnt dolomite or hydrated lime, providing a higher neutralization potential and higher reactivity than CaCO3 and slag.
The neutralizing value of said at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements according to DIN EN 12945:2014-07 standard may be 1 to 55% (as CaO), preferably 20 to 55%, most preferably 33 to 48%.
In addition, at least one of starch, magnesium sulfates, citric acid, clay, mortar binder, cellulose glue, glucosidic binder such as starch, molasses, lignosulfonate, water, hydrated lime, water glass, bentonite, cellulose fibres, stearates, urea or combinations of these materials may be used as binder or granulation aid in a weight ratio of 0.1 to 10 weight-%, preferably 0.3 to 5 weight-%, most preferably 0.8 to 3 weight-%, related to the total mass of the composition comprising Fe and sulfate ions and the at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements Ca and Mg. In an embodiment, the inventive process is carried out by blending:
- a material comprising Fe and sulfate ions,
- a material comprising carbonates of the earth alkaline elements Ca and/or Mg, preferably CaCO3, MgCO3, or dolomite, and
- a material comprising oxides or hydroxides of earth alkaline elements,
preferably MgO, CaO, Mg(OH)2, or Ca(OH)2,
in the form of powder without any addition of water, with the reaction of these materials while being mixed and granulated in the same apparatus, thus leading to a granulated composition.
The present invention is also directed to a fertilizer composition comprising S, Fe and at least one earth alkaline element including at least one of Ca and/or Mg, wherein the molar ratio of (Ca+Mg)/Fe is in the range of 2 to 200, preferably 2.5 to 25, most preferably 10 to 25.
In the inventive fertilizer composition, the molar ratio of Fe to S in the inventive fertilizer composition may be 0.3 to 6, preferably 0.5 to 2, most preferably 0.8 to 1 .2.
The main reaction products of the inventive process or in the inventive
composition are calcium sulfate, iron hydroxide and unreacted earth alkaline compounds. The iron hydroxide obtained has two important functions: The first function is an effective and efficient binder for granulates; and the second function is partial retention of sulfate and trace element ions by adsorption. Therefore, a sulfur fertilizer comprising iron hydroxide (or reaction products of iron sulfate with alkaline compounds) has improved properties compared to a material without iron hydroxide as the sulfate is not washed out of the soil so easily. Besides of calcium sulfate being a reaction product during mixing, calcium sulfate may also be added additionally.
As stated, iron sulfate has been converted mainly or completely into earth alkaline sulfates in the composition. As crystal structures generally are determined by x-ray diffraction (XRD) and quantitative relation of XRD peaks with actual relation of crystal structures can be somewhat ambiguous, the ratio of XRD signals are compared rather than ratio of crystal structures for analyzing and defining the inventive fertilizer composition. Therefore, the ratio of (P*Q) / (PJ) > 8, preferably more than 5, most preferred more than 2, with P being the integral area of the x- ray diffraction peaks between 2 Θ = 20.0 and 21 .5°, Q the integral area of the XRD peaks between 2 Θ = 29.0 and 30.5°, I the integral area of the XRD peaks between 2 Θ = 16.0, and 20.0° and J the integral area of the XRD peaks between 2 Θ = 23.4 and 28.0 (measured using Cu-Ka-radiation diffraction peaks).
Alternatively, the inventive fertilizer composition may have the ratio A B > 1 , preferably >5, most preferably >10, with A being the integral area of the x-ray diffraction peaks between 2 Θ = 20.2 and 21 .5° and B being the integral area of the x-ray diffraction peaks between 2 Θ = 25.0 and 28.0.
The invention also concerns a process for fertilizing S and one or more earth alkaline elements, preferably Ca and/or Mg wherein the above inventive fertilizer composition is applied, preferably in form of granulates, onto a sulfur deficient soil used for agriculture, preferably for fertilizing sulfur to plants supplying amino acids, proteins and/or oil, in particular cultures of alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats, triticale, cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic. Advantage of this process is that fertilizing S and fertilizing Ca (and optionally Mg), and raising the soil pH is achieved at the same time with one single step.
Therefore, costs and efforts for separate fertilizing steps can be avoided.
Another advantage is that part of Ca (and optionally Mg) is available in soluble form (as CaSO4), whereas Ca (and optionally Mg) from conventional limestone or dolomite fertilizers is not soluble but has to get leached by contact with an acidic environment. A fertilizer composition offering both Ca (and optionally Mg) solubility and at the same time considerable alkaline character has a clear advantage over conventional fertilizer types. Even more, the content of soluble sulfur (as sulfate), valuable trace elements like Mn and Zn (and optionally B) and the low content of unwanted elements (e.g. As, Hg, Cd, Pb) and toxic organic compounds results in a highly valuable fertilizer type.
Preferably, said application on fields used for agriculture is made for base fertilization between summer and winter time, i.e. between August and December for areas north of the equator or between February and June for areas south of the equator, respectively, before the growth phase of the plants start.
Generally; the ratio of the (acidic) Fe(ll)sulfate and the (alkaline) Ca and/or Mg compound may vary depending on soil pH:
For slightly acidic soils, a molar ratio (Ca+Mg)/S of >2 may be appropriate, whereas for more acidic soils a molar ratio (Ca+Mg)/S of »2 may be appropriate. With typical data of 300 - 600 kg Ca / (ha * a) for refreshing fertilizing with Ca and 30 kg S / (ha * a) => molar ratio Ca/S = 7.5 - 15.
By applying the inventive fertilizer composition, the pH of the soil may be raised to above 5.8, preferably above >6.0, most preferably >6.2.
Generally, sulfur in the inventive fertilizer is available in the form of sulfate, but for calculation purpose sulfur virtually is expressed as S. The present invention also provides the use of a solution comprising iron sulfate or the use of crystalline iron sulfate with more than 3 molecules of crystal water, preferably iron(ll)sulfate heptahydrate, more preferably copperas as obtained as by-product from titanium dioxide manufacturing, for preparing a sulfur fertilizing composition and/or for moistening and/or granulating of powderous fertilizer materials.
Advantages of the inventive products and processes are:
- Supply of bio-available soluble sulfur in large quantities and for low cost.
- The inventive compounds or the products of the inventive process exhibit
optimum solubility of sulfur: Not too high and not too low.
=> long-term supply of sulfur and calcium / magnesium improves soil structure and porosity.
- High alkalinity => useful also for neutralization of acidic soils. This leads to
improved bio-availability of other applied fertilizing substances.
- Preferred is a granular free flowing and dust free form of the fertilizer.
- Iron hydroxide exhibits excellent stabilizing properties for the granules
obtained. Also iron hydroxide due to its high capability for absorption of trace
elements is able to avoid the micronut ents present in the inventive fertilizer (Mn, Zn) to be washed out.
If the iron sulfate is taken from the by-product of the titanium dioxide process, the inventive fertilizer additionally comprises valuable plant nutrients and
micronutrients, e.g. Mg, Mn, Zn. At the same time the product is free of Hg, Cd, As, Pb, Cr. The inventive composition can be used for all cultures, preferably those with high sulfur demand, e.g. alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, lucerne, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale; furthermore cruciferous plants like Brassicas, radish, rocket and allium crops like onion, leek and garlic, especially suitable for canola and rapeseed and most preferably during winter time.
The pH of the fertilizer can be 5.5 to 13, for most applications preferably 6.0 to 1 1 , most preferably 6.5 to 8.5. When comprising calcium oxide or calcium dihydroxide for stronger and faster neutralizing effects, the pH of the fertilizer is preferably 8.5 to 13. As a consequence, no acidification of soil can be observed; jointly fertilizing with both S and Ca; iron sulfate is completely or nearly completely reacted and good stability of granulates is given.
The present invention also concerns:
An inventive composition , wherein it contains Zn with mass ratio of Zn/Fe 0.0001 to 0.003, preferably 0.0002 to 0.0015, and/or Mn with the mass ratio of Mn/Fe 0.00001 to 0.01 , preferably 0.00001 to 0.001 ; these elements are valuable micronutrients and therefore no separate application of Zn and Mn is necessary.
Said inventive composition, wherein the mass ratio of Cr/Fe is 0.0000001 - 0.0001 , preferably 0.0000001 - 0.00005, most preferably 0.1 - 0.00002; this concentration of Cr is sufficiently low to avoid detrimental effects.
- Said inventive composition, wherein mass ratio of Ti/Fe is 0.001 - 0.03,
preferably 0.002 - 0.02, most preferably 0.003 - 0.015;
Said inventive composition, wherein the pH according to ISO standard is 5.5 to 13, for most application preferably 6.0 to 1 1 , most preferably 6.5 to 8.5, but
preferably 8.5 to 13 for compositions comprising calcium oxide or calcium dihydroxide. Hereby the pH is determined according to DIN EN ISO 787 part 3, whereby the pH measurement is made no earlier than 5 days after preparation of the sample and whereby the sample is ground prior to pH measurement.
Said inventive composition, wherein the neutralizing value according to DIN EN 12945:2014-07 standard is 1 to 55% (as CaO), preferably 20 to 55%, most preferably 33 to 48%.
Said inventive composition, wherein the fertilizer is granulated with volume based average granule size is 1 - 8 mm, preferably 2 - 6, most preferably 2 - 4 mm;
Said inventive composition, wherein it is granulated in a pan granulator, or a granulation drum, or an intensive mixer.
Said inventive composition, wherein it is granulated in a pan granulator, or a granulation drum, or an intensive mixer, without the addition of water to aid granulation.
Said inventive composition, wherein it is granulated in a combination of an intensive mixer and a granulator such as a pan granulator or a granulation drum.
Said inventive composition, wherein the fertilizer composition is obtainable by blending
o Ca and/or Mg compound, preferably CaCO3 or dolomite (Ca,Mg)CO3 o iron sulfate, preferably Fe(ll)SO4 heptahydrate,
o optionally CaSO4;
o optionally CaO, (Ca,Mg)O or Ca(OH)2
o optionally an iron sulfate monohydrate,
o optionally an iron sulfate monohydrate obtained from ΤΊΟ2
manufacturing, which has been reacted beforehand with lime or limestone or slaked lime or burnt lime to yield a reaction product with a typical pH of about 4;
o Said inventive composition, wherein the fertilizer comprises iron sulfate and/or products obtained from neutralization of iron sulfate and at least
one calcium and/or magnesium compound and/or the reaction products of iron sulfate and calcium and/or magnesium compounds; o Use of the composition as a sulfur fertilizer for alfalfa, canola
(rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale; furthermore cruciferous plants like Brassicas, radish, rocket and allium crops like onion, leek and garlic,
o Use of the composition between summer and winter time, i.e. between
August and December for areas north of the equator or between February and June for areas south of the equator, respectively;
o Use of the composition as a calcium-sulfur fertilizer in such way that he pH of the soil is raised to >5.8, preferably >6.0, most preferably >6.2;
Further modifications of the invention can include:
- Adding other elements suitable for fertilizing purposes, e.g. trace element nutrients like boron, copper, molybdenum
- Additional elemental sulfur may be used; the presence of alkaline compounds can avoid acidification of soil.
- Preferably the calcium and/or magnesium compound has a pH >8, e.g. slag from steel manufacturing, burnt or hydrated lime / dolomite
- Low content of Sr or As.
- Passivation of the granule surface during granulation with limestone.
- Passivation of the granule surface during granulation with an iron sulfate
monohydrate which has been reacted beforehand with limestone, or lime, or slaked lime or burnt lime
- Thermal treatment / drying.
- Compacting with roller mill or pelletizer.
The present invention is further illustrated by the following Examples.
Example 1 a - Preparation of compacted Ca-S-fertilizer with 2.4% S and
neutralization value of 45% CaO equivalents and with low crushing strength
Two batches, each consisting of 2 kg copperas from the titanium dioxide production by the sulfate process, and 8 kg of powdered limestone were brought together and mixed in a ploughshare mixer for about 2 minutes. The molar ratio (Ca+Mg)/Fe was 12. These mixtures were fed at room temperature over a hopper with a screw conveyor onto a pair of rollers of a roller compactor and compressed into scabs. The contact pressure during densification was about 9.5 N/mm2. The scabs attained a density of about 2070 kg / m3, measured in paraffin oil, according to the Archimedes principle. The scabs were crushed, and of the resulting pellets a sieve fraction between 2 to 5 mm was collected. The granules had a residual moisture content determined by drying at 105 °C of 8.2 wt.%.
From this fraction, 10 fresh granules were arbitrarily taken out and crushed by applying a pressing force. The average crushing strength was 1 .6 kg. The test was repeated in exactly the same way with fresh batches of copperas and limestone flour. The crushing strength of the fresh granules was 1 .3 kg. After drying 10 granules at 105 °C overnight, the crushing strength was found to be 1 .5 kg.
Example 1 b - Preparation of compacted Ca-S-fertilizer with 2.4% S and
neutralization value of 45% CaO equivalents and with low crushing strength
Two batches, each consisting of 2 kg copperas from the titanium dioxide production by the sulfate process, and 8 kg of powdered limestone, which had been mixed by hand and aged for 1 week by occasional mixing by hand and with a molar ratio (Ca+Mg)/Fe of 12 were fed at room temperature over a hopper with a screw conveyor onto a pair of rollers of a roller compactor and compressed into scabs. The contact pressure during densification was about 8.0 N/mm2. The scabs attained a density of about 2320 kg / m3, measured in paraffin oil, according to the Archimedes principle. The scabs were crushed, and of the resulting pellets a sieve fraction between 2 to 5 mm was collected. The granules had a residual moisture content determined by drying at 105 ° C of 8.5 wt.%.
From this fraction, 10 fresh granules were arbitrarily taken out and crushed by applying a pressing force. The average crushing strength was 2.2 kg. Ageing of the mixture prior to compacting results in moderate improved crushing strength.
Example 1 c - Preparation of compacted Ca-S-fertilizer with 6% S and
neutralization value of 22% CaO equivalents and with low crushing strength
Two batches, each consisting of 5 kg copperas from the titanium dioxide production by the sulfate process, and 5 kg of powdered limestone were brought together and mixed in a ploughshare mixer for about 2 minutes. The molar ratio (Ca+Mg)/Fe was 3. These mixtures were fed at room temperature over a hopper with a screw conveyor onto a pair of rollers of a roller compactor and compressed into scabs. The specific force during densification was about 9.0 N/mm2. The scabs attained a density of about 1840 kg / m3, measured in paraffin oil, according to the Archimedes principle. The scabs were crushed, and of the resulting pellets a sieve fraction between 2 to 5 mm was collected. The granules had a residual moisture content determined by drying at 105 ° C of 21 .6 wt.%. From this fraction, 10 fresh granules were arbitrarily taken out and crushed by applying a pressing force. The average crushing strength was 0.3 kg. Granules with a high residual moisture exhibit low crushing strength.
Example 1 d - Preparation of compacted Ca-S-fertilizer with 6% S and
neutralization value of 22% CaO equivalents and with high crushing strength
Two batches, each consisting of 5 kg copperas from the titanium dioxide production by the sulfate process, and 5 kg of powdered limestone, which had been mixed by hand and aged for 1 week by occasional mixing by hand and with a molar ratio (Ca+Mg)/Fe of 3 were fed at room temperature over a hopper with a screw conveyor onto a pair of rollers of a roller compactor and compressed into scabs. The contact pressure during densification was about 8.0 N/mm2. The scabs attained a density of about 2220 kg / m3, measured in paraffin oil, according to the Archimedes principle. The scabs were crushed, and of the resulting pellets a sieve fraction between 2 to 5 mm was collected. The granules had a residual moisture content determined by drying at 105 ° C of 7.9 wt.%.
From this fraction, 10 fresh granules were arbitrarily taken out and crushed by applying a pressing force. The average crushing strength was 3.5 kg. After drying
10 granules at 105 °C overnight, the crushing strength was found to be 8.9 kg. Ageing of the mixture prior to compacting results in improved crushing strength.
Example 2a - Preparation of granulated Ca-S-fertilizer with 5% S and
neutralization value of 28% CaO equivalents and with high crushing strength
In a rotating and inclined (30°) mixing tank with a capacity of 150 liters and with eccentrically arranged, high-speed mixing tool and fixed wall scraper, 50 kg limestone powder, 50 kg copperas from the titanium dioxide production by the sulphate process and 6 kg of water were thoroughly mixed for 2 minutes in the co- current mode. The rotational speed of the mixing tool was 16.5 m/s, and the container was rotating at 1 m / s. This mixing process resulted in micro-granules that were granulated on a rotating and inclined pan granulator (diameter 1 m) with fixed deflector and rotating scraper. During granulation, about about 20 kg of limestone was added for drying purposes. The final composition had a molar ratio (Ca+Mg)/Fe of 4. The resulting granules were round. Of the granules about 80% by volume were between 2-6 mm.
From the volume fraction from 3.15 to 5 mm, 10 granules were arbitrarily taken out, dried overnight at 40 °C and crushed by applying a pressing force. The average crushing strength was 7.4 kg. Granulation with subsequent slow drying results in good crushing strength.
Example 2b - Preparation of granulated Ca-S-fertilizer with 5% S and
neutralization value of 28% CaO equivalents and with high crushing strength
In a rotating and inclined (30°) mixing tank with a capacity of 150 liters and with eccentrically arranged, high-speed mixing tool and fixed wall scraper, 50 kg limestone powder, 50 kg copperas from the titanium dioxide production by the sulphate process, 1 kg of lignosulfonate and 4.5 kg of water were thoroughly mixed for 1 .5 minutes in the co-current mode. The rotational speed of the mixing tool was 16.5 m/s, and the container was rotating at 1 m / s. This mixing process resulted in micro-granules that were granulated on a rotating and inclined pan granulator (diameter 1 m) with fixed deflector and rotating scraper. During granulation, about about 17.5 kg of lime was added for drying purposes. The final
composition had a molar ratio (Ca+Mg)/Fe of 4. The resulting granules were round. Of the granules about 90% by volume were between 2-6 mm.
From the volume fraction from 3.15 to 5 mm, 10 granules were arbitrarily taken out, dried overnight at 40 °C and crushed by applying a pressing force. The average crushing strength was 3.0 kg.
Use of lignosulfonate resulted in lower water demand for granulation.
Example 2c
With the same setup as in example 2b 50 kg limestone powder, 50 kg copperas from the titanium dioxide production by the sulphate process and 5 kg of water were thoroughly mixed.
It was not possible to granulate this mixture on the pan granulator of example 2b as the water content was too low for generation of a granulation effect. Example 2d - Preparation of granulated Ca-S-fertilizer with 2% S and
neutralization value of 46% CaO equivalents
In a rotating and inclined (30°) mixing tank with a capacity of 150 liters and with eccentrically arranged, high-speed mixing tool and fixed wall scraper, 80 kg limestone powder, 20 kg copperas from the titanium dioxide production by the sulphate process and 8 kg of water were thoroughly mixed for 2 minutes in the co- current mode. The rotational speed of the mixing tool was 16.5 m/s, and the container was rotating at 1 m / s. This mixing process resulted in micro-granules that were granulated on a rotating and inclined pan granulator (diameter 1 m) with fixed deflector and rotating scraper. During granulation, about about 20 kg of lime was added for drying purposes. The final composition had a molar ratio
(Ca+Mg)/Fe of 15. The resulting granules were round. Of the granules about 80% by volume were between 2-6 mm.
From the volume fraction from 3.15 to 5 mm, 10 granules were arbitrarily taken out, dried overnight at 40 °C and crushed by applying a pressing force. The average crushing strength was 5.3 kg. Granulation with subsequent slow drying results in good crushing strength.
Example 2e - Preparation of granulated Ca-S-fertilizer with 6% S and neutralization value of 22% CaO equivalents
In a rotating and inclined (30°) mixing tank with a capacity of 150 liters and with eccentrically arranged, high-speed mixing tool and fixed wall scraper, 45 kg limestone powder, 5 kg burnt lime and 50 kg copperas from the titanium dioxide production by the sulphate process were thoroughly mixed for 30 minutes in the co-current flow mode. The molar ratio (Ca+Mg)/Fe was 3. The rotational speed of the mixing tool was 4 m/s, and the container was rotating at 1 m / s. During the mixing process the chemical reaction of the components resulted in a temperature increase to about 50°C.
This mixing process resulted in a black granular product with good handling properties. The resulting granules were round. Example 3 - Determination of the alkaline content of a fertilizer
The alkaline content of the inventive fertilizer is determined by an acid-base titration. For this analytical method, about 1 g of a representative sample of the product is reacted in a beaker with 25 ml of a hydrochloric acid solution of a concentration of 1 mol per liter. The reaction of the calcium carbonate and hydrochloric acid produces carbon dioxide. The sample is left overnight in order for the reaction to complete and the bulk of the carbon dioxide to be emitted from the beaker. The next day, the beaker is briefly heated to just below the boiling point of water to emit any remaining carbon dioxide. Subsequently, the excess
hydrochloric acid is back-titrated with a solution of sodium hydroxide of a concentration of 1 mol per liter. The extent of the titration is monitored by measuring the pH of the liquid, for example potentiometrically, and determining the consumption of sodium hydroxide solution at the equivalence point. The amount of alkaline substance is then expressed as equivalent percentage of CaCO3. 1 .501 g of a fertilizer sample is reacted with 25 ml of 1 M hydrochloric acid with a titer of 0.9921 in a beaker. The reaction mixture is left overnight, after which the excess hydrochloric acid is titrated with 12.8726 ml of 1 M NaOH with a titer of 1 .0031 until a pH of 7.454. This sample contained 39.6 wt.-% CaCO3.
Calculated is as follows: 100%*{[(25 ml HCI * 0.9921 )-(12.8726 ml NaOH *
1 .0031 )] * 0.001 L/ml * 100.087 g/mol CaCO3 * 0.5 mol H+/mol CaCO3 }/[1 .501 g]
= 39.6 wt.-% CaCO3.
39.6 wt.-% of CaCO3 corresponds to 22.2 wt.-% of CaO.
Example 4 - Elution tests of soil samples impregnated with sulfur fertilizer
In two soil incubation experiments the effect of limestone/FeSO4 mixtures on the pH of two soils was analyzed. Application of limestone and of limestone/ FeSO4 preparations result in an increase of pH in both soils one week after fertilization, see table 1 with pH data.
Table 1 - Effect of a fertilization of limestone and limestone/FeSO4 mixtures on the pH of two soils
The soil pH was measured in a suspension of 1 part soil with 2.5 parts of a solution of 0.01 M CaCI2 The effect of the limestone / FeSO4 preparations on pH is stronger than the effect of pure limestone!
Example 5 - Plant nutrition tests using sulfur fertilizer (pot experiments)
The effects of limestone/FeSO mixtures on the growth of plants was investigated with summer rape and alfalfa under natural conditions in pot experiments in small Mitscherlich pots with 6 kg soil per pot. The experimental soil was a subsoil (0.4 - 0.8 m depth) from a luvisol derived from loess with a total S concentration of 0.027%. Summer rape (Brassica napus L, cv. Belinda) and alfalfa (Medicago sativa L, ) were cultivated in a treatment without lime and sulfur fertilization
(control), in a treatment with lime and without sulfur application and in treatments
with various limestone/FeSO mixture applications with 50 mg S kg"1 soil (= 0.3 g S / pot). Each treatment contained four replications for rape and alfalfa each. The soil in the pots was treated with nitrogen (1 g N / pot as NH NOs), phosphorus and potassium (0.6 g P and 1 .6 g K / pot as K2HPO4 & KCI), magnesium (0.3 g Mg / pot as Mg(NO3)2, boron (3 mg B / pot as H3BO3), copper (30 mg Cu / pot as
CuCI2), manganese (120 mg Mn / pot as MnCI2), molybdenum (0.6 mg Mo / pot as NH molybdate) and zinc (60 mg Zn / pot as ZnCI2). After mixing the fertilizers with the soil and an incubation period of one week at 60% of the water holding capacity, rape and alfalfa were sown. The seeds of alfalfa were inoculated with Rhizobium melilotii. After germination rape plants were thinned on three plants / pot and alfalfa on 20 plants / pot. Then rape plants were fertilized with 0.5 g / pot in liquid form as NH NO3. In contrast to summer rape, alfalfa was not further applied with mineral nitrogen in order to analyze effect of a S fertilization in form of the new products on the N2 fixation.
Three months after sowing, summer rape plants were harvested and alfalfa was cut three times during the vegetation period. After the 1 st and 2nd harvest alfalfa was fertilized with 0.5 g K / pot in liquid form as K2HPO . In the following tables, the effects of sulfur fertilization in form of gypsum and various limestone/FeSO4 mixtures on the yields of summer rape are presented.
Application of sulfur in form of limestone/FeSO mixtures resulted in an increase of the growth of summer rape. In the treatments without S fertilization rape plants showed the typical S deficiency symptoms at the older leaves. Such symptoms were not visible at the leaves in the treatments with sulfur fertilization with lime/FeSO fertilization. The sulfur deficiency was so strong that summer rape did not produce any seeds in the control without sulfur treatment, as it can be seen from Table 2 and Figure 1 .
Table 2 - Effect of a sulfur fertilization (0.3 g S / pot) in form of various
limestone/FeSO4 mixtures on the seed and straw yield of summer rape
The here presented results of the effect of lime/FeSO4 mixtures show that the inventive products are suitable as mineral sulfur and lime fertilizers for agricultural plants.
In a further experiment we have tested the effects of S fertilization in form of the various limestone/FeSO4 mixtures on the yield of alfalfa. In contrast to summer rape S fertilization did not result to an initial significant yield increase. The soil had enough sulfur for a first growth of alfalfa. However, an increasing part of CaCO3 resulted to a decrease of the shoot biomass at the first harvest, s. Table 3.
This is due to the sensitivity of alfalfa to "free lime" in the soil solution which may have result to a OH" ion toxicity. At the 2nd and 3rd harvest, however, there was found a clear positive effect for the limestone/FeSO mixtures. The highest cumulative shoots biomass was produced in the treatment with basic slag lime /FeSO4 mixture.
Table 3: Effect of a sulfur fertilization (0.3 g S / pot) in form of various limestone/FeSO mixtures on the soil pH before sowing of alfalfa and on the shoot yields of alfalfa
Conclusion: The here presented results of the effect of limestone/FeSO4 mixtures show that the products are suitable as mineral sulfur and limestone fertilizers for agricultural plants. Limestone/FeSO4 mixtures should not applied to legumes in a ratio greater than 1 :1 .
Claims
1 . Process for manufacturing a fertilizer composition comprising S, Fe and one or more earth alkaline elements, including Ca and/or Mg, being suitable for administration onto a sulfur deficient soil wherein a material, comprising Fe and sulfate ions, in form of a solid salt, filter cake, paste, slurry, or solution, is blended with at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements including at least one of Ca and Mg, preferably CaCO3, MgCO3, dolomite (Ca,Mg)CO3, MgO, burnt dolomite (Ca,Mg)O, CaO, semi-hydrated dolomite Ca(OH)2MgO, or Ca(OH)2 or mixtures thereof in molar ratio of (Ca+Mg)/Fe = 2 to 200, preferably 2.5 to 25, more preferably 10 to 25, and the blend is converted into an administration form.
2. Process for manufacturing a fertilizer composition according to claim 1
wherein blending and converting is carried out simultaneously.
3. Process for manufacturing a fertilizer composition according to any of claims 1 or 2 wherein blending and/or converting is carried out in the presence of any of water, dilute sulfuric acid, preferably diluted, CaSO4, elemental sulfur or other S containing compounds, other compounds useful for a fertilizer, such as micronutrients, preferably a boron compound, binder or granulation aids, or mixtures thereof.
4. Process for manufacturing a fertilizer composition according to any of claims 1 to 3, wherein the material comprising Fe and sulfate ions is FeSO which may contain crystal water.
5. Process for manufacturing a fertilizer composition according to claim 4,
wherein FeSO is Fe(ll)SO heptahydrate, preferably obtained from the titanium dioxide production process.
6. Process for manufacturing a fertilizer composition according to any of claims 1 to 5, wherein the at least one component comprising oxides, hydroxides or carbonates of earth alkaline elements is limestone, consisting of fine particles 95 % < 0,09 mm and comprising >95 % CaCO3.
7. Process for manufacturing a fertilizer composition according to any of claims 1 to 5, wherein the at least one component comprising oxides, hydroxides or carbonates of earth alkaline elements is burnt lime, burnt dolomite or hydrated lime.
8. Process for manufacturing a fertilizer composition according to any of claims 1 to 5, wherein the at least one component comprising oxides, hydroxides or carbonates of earth alkaline elements is a slag from steel manufacturing or a reaction product from such a slag.
9. Process for manufacturing a fertilizer composition according to any of claims 1 to 8, wherein at least one of starch, magnesium sulfates, citric acid, clay, mortar binder, cellulose glue, glucosidic binder such as starch, molasses, lignosulfonate, water, hydrated lime, water glass, bentonite, cellulose fibres, stearates, urea or combinations of these materials is used as binder or granulation aid in a weight ratio of 0.1 to 10 weight-%, preferably 0.3 to 5 weight-%, most preferably 0.8 to 3 weight-%, related to the total mass of the composition comprising Fe and sulfate ions and the at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements Ca and Mg.
10. Process for manufacturing a fertilizer composition according to any of claims 1 to 9, wherein the process is carried out in an apparatus which can also serve for compaction, granulation and/or pelletizing the reaction product.
1 1 . Process for manufacturing a fertilizer composition according to claim 10, wherein the granulation is carried out by blending:
a. a material comprising Fe and sulfate ions,
b. a material comprising carbonates of the earth alkaline elements Ca and/or Mg, preferably CaCO3, MgCO3, or dolomite, and
c. a material comprising oxides or hydroxides of earth alkaline elements, preferably MgO, CaO, Mg(OH)2, or Ca(OH)2,
in the form of powder without any addition of water, with the reaction of these materials while being mixed and granulated in the same apparatus.
12. Process according to any of claims 1 to 1 1 , wherein the neutralizing value of the at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements according to DIN EN 12945:2014-07 standard is 1 to 55% (as CaO), preferably 20 to 55%, most preferably 33 to 48%.
13. Fertilizer composition comprising S, Fe and at least one earth alkaline
element including at least one of Ca and/or Mg, wherein the molar ratio of (Ca+Mg)/Fe is in the range of 2 to 200, preferably 2.5 to 25, most preferably 10 to 25.
14. Fertilizer composition according to claim 13, wherein the molar ratio of Fe to S is 0.3 to 6, preferably 0.5 to 2, most preferably 0.8 to 1 .2.
15. Fertilizer composition according to any of claims 13 and 14, wherein the ratio of the peak areas P, Q, I and J in the XRD spectrum (P*Q) / (l*J) is more than 8, preferably more than 5, more preferably more than 2, with P being the integral area of the x-ray diffraction peaks between 2 Θ =20.0 and 21 .5°, with Q being the integral area of the XRD peaks between 2 Θ =29.0 and 30.5°, with I being the integral area of the XRD peaks between 2 Θ =16.0, and 20.0° and with J being the integral area of the XRD peaks between 2 Θ =23.4 and 28.0.
16. Fertilizer composition according to any of claims 13 to 15, wherein the ratio of the peak areas A/B is more than 1 , preferably more than 5, more preferably more than 10, with A being the integral area of the x-ray diffraction peaks
between 2 Θ =20.2 and 21 .5° and with B being the integral area of the x-ray diffraction peaks between 2 Θ =25.0 and 28.0.
17. Fertilizer composition according to any of claims 13 to 16, wherein it contains Zn with mass ratio of Zn/Fe from 0.0001 to 0.003, preferably from 0.0002 to 0.0015, and/or Mn with the mass ratio of Mn/Fe from 0.00001 to 0.01 , preferably from 0.00001 to 0.001 .
18. Fertilizer composition according to any of claims 13 to 17, wherein the
fertilizer is in a granulated form with volume based average granule size in the range from 1 to 8 mm, preferably 2 to 7, most preferably 3 to 6 mm.
19. Fertilizer composition, in particular according to any of claims 13 to 18, which is obtainable according to the process of any of claims 1 to 12.
20. Process for fertilizing S and one or more earth alkaline elements, preferably Ca and/or Mg wherein a fertilizer composition according to claim 19 is applied, preferably in form of granulates, onto a sulfur deficient soil used for agriculture, preferably for fertilizing sulfur to plants supplying amino acids, proteins and/or oil, in particular cultures of alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats, triticale, cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic.
21 . Process according to claim 20, wherein the application onto a sulfur deficient soil is made for base fertilization between summer and winter time.
22. Process according to claim 20 or 21 , wherein the fertilizer composition
according to claim 19 is applied onto the sulfur deficient soil in an amount that the pH of the soil is raised to above 5.8, preferably above >6.0, most preferably >6.2.
23. Use of a composition according to claim 19 as a sulfur fertilizer for fertilizing sulfur to plants supplying amino acids, proteins and/or oil, in particular to alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale, cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic.
24. Use of iron sulfate, preferably iron(ll)sulfate heptahydrate, more preferably copperas as obtained as by-product from titanium dioxide manufacturing, for preparing a sulfur fertilizing composition.
25. Use of a solution comprising iron sulfate or use of crystalline iron sulfate with more than 3 molecules of crystal water, preferably iron(ll)sulfate
heptahydrate, more preferably copperas as obtained as by-product from titanium dioxide manufacturing, as aid for moistening and/or granulating powderous fertilizer materials.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102014106980 | 2014-05-16 | ||
| PCT/EP2015/060769 WO2015173396A1 (en) | 2014-05-16 | 2015-05-15 | Sulfur fertilizer |
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| EP3142990A1 true EP3142990A1 (en) | 2017-03-22 |
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ID=53274507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15725542.3A Withdrawn EP3142990A1 (en) | 2014-05-16 | 2015-05-15 | Sulfur fertilizer |
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| EP (1) | EP3142990A1 (en) |
| CN (1) | CN106536453A (en) |
| BR (1) | BR112016026684A2 (en) |
| TW (1) | TWI555721B (en) |
| WO (1) | WO2015173396A1 (en) |
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| DE102015119480A1 (en) | 2015-11-11 | 2017-05-11 | Fels-Werke Gmbh | Fertilizer mixture and process for its preparation |
| CN108440185A (en) * | 2018-04-20 | 2018-08-24 | 浙江省农业科学院 | A kind of biological nutrition type water-retaining agent and preparation method thereof |
| TWI783312B (en) * | 2020-12-01 | 2022-11-11 | 國立屏東科技大學 | Sulfide-contained organic fertilizer material and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB356195A (en) * | 1929-06-01 | 1931-08-31 | Eduard Dedolph | Composition serving as a fertilizer and agricultural pest destroyer |
| IT995512B (en) * | 1973-09-26 | 1975-11-20 | Sir Soc Italiana Resine Spa | COMPOSITIONS SUITABLE FOR THEM USED IN AGRICULTURE AS SOIL MODIFIERS AND AS FERTILIZERS |
| US4264570A (en) * | 1979-02-27 | 1981-04-28 | Sokolov Igor D | Method of producing magnesium sulphate |
| EP0093204B1 (en) | 1982-04-29 | 1985-08-21 | Norddeutsche Affinerie Ag | Process for granulating mixtures of fertilizers containing iron (ii) sulfate |
| US4455161A (en) * | 1982-09-13 | 1984-06-19 | The O.M. Scott & Sons Company | Trace element fertilizer composition |
| ES2049127B1 (en) | 1991-06-13 | 1994-10-01 | Tioxide Espa A S A | CORRECTOR OF MICROELEMENTS LAWS FOR AGRICULTURAL SOILS AND PROCEDURE FOR ITS PREPARATION. |
| ES2036949B1 (en) * | 1991-11-21 | 1994-02-01 | Tioxide Europ | MAGNESIUM SULPHATE AND IRON MICRO-ELEMENTS DEFICIENCY CORRECTOR FOR AGRICULTURAL SOILS AND PROCEDURE FOR ITS PREPARATION. |
| ES2111458B1 (en) * | 1995-05-22 | 1999-07-01 | Turol Trading S L | PHOSPHATE FERTILIZER WITH SULFUR AND TRACE ELEMENTS FOR ITS AGRICULTURAL AND INDUSTRIAL USE AND PROCEDURE FOR ITS PREPARATION. |
| CN1434004A (en) * | 2003-03-11 | 2003-08-06 | 赵鹏 | Biological organic-inorganic compound fertilizer and productive method thereof |
| EP1892219B1 (en) * | 2006-06-28 | 2008-03-12 | Kemira Pigments Oy | Method of treating a precipitate comprising iron(II)sulphate monohydrate, a plant, granular material and its uses |
| WO2008000887A1 (en) * | 2006-06-28 | 2008-01-03 | Sachtleben Pigments Oy | Method of treating a precipitate comprising iron (ii) sulphate monohydrate, a plant, granular material and its uses |
| EP2165976B8 (en) * | 2007-07-02 | 2018-02-14 | Fertinagro Biotech, S.L. | Method of compactation of compositions based on ferrous sulphate heptahydrate and product obtained therefrom |
| WO2010058425A2 (en) * | 2008-11-20 | 2010-05-27 | Chetan Navnithlal Shah | Soil conditioner |
| CA2806253C (en) * | 2010-08-10 | 2018-09-11 | Chandrika Varadachari | Polyphosphate fertilizer combinations |
-
2015
- 2015-05-15 TW TW104115570A patent/TWI555721B/en not_active IP Right Cessation
- 2015-05-15 BR BR112016026684A patent/BR112016026684A2/en not_active Application Discontinuation
- 2015-05-15 EP EP15725542.3A patent/EP3142990A1/en not_active Withdrawn
- 2015-05-15 CN CN201580037581.9A patent/CN106536453A/en active Pending
- 2015-05-15 WO PCT/EP2015/060769 patent/WO2015173396A1/en active Application Filing
Non-Patent Citations (2)
| Title |
|---|
| None * |
| See also references of WO2015173396A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015173396A1 (en) | 2015-11-19 |
| BR112016026684A2 (en) | 2017-08-15 |
| TW201609609A (en) | 2016-03-16 |
| CN106536453A (en) | 2017-03-22 |
| TWI555721B (en) | 2016-11-01 |
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