US20170204015A9 - Alkali metal ion source with moderate rate of ion release and methods of forming - Google Patents
Alkali metal ion source with moderate rate of ion release and methods of forming Download PDFInfo
- Publication number
- US20170204015A9 US20170204015A9 US15/139,456 US201615139456A US2017204015A9 US 20170204015 A9 US20170204015 A9 US 20170204015A9 US 201615139456 A US201615139456 A US 201615139456A US 2017204015 A9 US2017204015 A9 US 2017204015A9
- Authority
- US
- United States
- Prior art keywords
- alkali metal
- metal ion
- silicate
- potassium
- bearing
- 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.)
- Granted
Links
- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 38
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011591 potassium Substances 0.000 claims abstract description 37
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 31
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 31
- 239000010435 syenite Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 16
- 239000002245 particle Substances 0.000 claims description 14
- 229910052664 nepheline Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052651 microcline Inorganic materials 0.000 claims description 11
- 229910052652 orthoclase Inorganic materials 0.000 claims description 11
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 10
- 239000010434 nepheline Substances 0.000 claims description 8
- 229910052654 sanidine Inorganic materials 0.000 claims description 7
- 229910001462 kalsilite Inorganic materials 0.000 claims description 6
- 229910052907 leucite Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000010438 granite Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000007415 particle size distribution analysis Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 25
- 238000003801 milling Methods 0.000 abstract description 14
- 239000008247 solid mixture Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000000920 calcium hydroxide Substances 0.000 abstract description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 47
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 26
- 239000007788 liquid Substances 0.000 description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 description 15
- 235000010755 mineral Nutrition 0.000 description 15
- 239000011707 mineral Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- 239000002689 soil Substances 0.000 description 14
- 239000011575 calcium Substances 0.000 description 13
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000010433 feldspar Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000013068 control sample Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052656 albite Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- -1 but not limited to Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910052670 petalite Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000005029 sieve analysis Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000021073 macronutrients Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052645 tectosilicate Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/04—Fertilisers containing potassium from minerals or volcanic rocks
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D13/00—Compounds of sodium or potassium not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
Definitions
- Potassium chloride traditional potassium fertilizing agent
- a limited number of geographical locations remote from the southern hemisphere where the transportation costs contribute to the market price significantly, making local manufacturing of potassium fertilizer increasingly attractive.
- modern agriculture development in those regions requires growing crops on soils that are often fully depleted of macronutrients, structural elements, e.g. silicon in a form available for plants (monosilicic acid) or calcium, and structure-developing minerals, such as clay minerals (phylosilicates).
- these soils are not optimal for growing crops due to the lack of proper structure and essential elements resources.
- traditional fertilizing agents such as potassium nitrate and potassium chloride
- potassium nitrate and potassium chloride are not optimal due to their excessive leaching, the lack of retention of their corresponding ions, and their inability to provide a proper structure to the soil.
- Potassium and other nutrition elements introduced into the soil in the form of these highly soluble salts are thus wasted, having potential negative effects on the environment, e.g., chloride contamination. Therefore, new potassium sources and a better means of nutrient delivery are needed to allow high agricultural productivity and expansion in the available regions of the southern hemisphere.
- these sources can simultaneously provide essential elements, such as calcium and plant-available silicon, and promote formation of structural minerals.
- Rock-forming minerals such as potassium feldspars (KAlSi 3 O 8 ) may therefore be considered as earth-abundant alternatives to traditional sources based on their relatively high content of K 2 O (more than 15 wt % of K 2 O in pure KAlSi 3 O 8 ).
- K + potassium ion
- this source be produced from the earth abundant K-bearing silicate rocks, can provide structural components (such as silicon in the form of monosilicic acid and/or calcium), and can promote the formation of clay minerals (phylosilicates). Also, a need exists for a method to produce source of such materials that minimizes the above-mentioned problems.
- the invention generally relates to a method for forming an alkali metal ion source and an alkali metal ion source formed by the method.
- a method of the invention for forming an alkali metal ion source includes combining a first component that includes a particulate alkali metal ion-bearing framework silicate with a second component that includes at least one of an oxide and a hydroxide of at least one of an alkaline earth metal and an alkali metal to form a solid mixture.
- the molar ratio of the silicon of the first component to the at least one of the alkaline earth and alkali metal and alkali metal of the second component is in a range of between about 1.0:0.1 and about 1.0:0.3.
- the mixture is optionally joint wet milled or dry joint milled, or separately milled and blended after the milling.
- the total amount of liquid presents is in a ratio by weight of liquid-to-solid in a range of between about 0.05:1 and about 5:1.
- the mixture is then exposed to elevated temperature and pressure for a period of time sufficient to form a gel that includes the silicon and the alkali metal of the first component, thereby forming the source of alkali metal.
- the weight ratio of tobermorite phase to the unreacted alkali metal ion-bearing framework silicate phases of the alkali metal ion source can be between about 1:1 and about 0:1.
- the weight percent of K(Na)-A-S—H gel of the alkali metal ion source can be between about 10% and about 100%.
- the specific surface area of the alkali metal ion source can be between about 8 m 2 /g and 50 m2/g.
- an alkali metal ion source is formed by reducing the size of a particulate alkali metal ion-bearing framework silicate until at least about 50% by weight of the particles have a diameter of equal to or less than 5 ⁇ m as measured by laser diffraction using a laser diffraction particle size analyzer in liquid mode (e.g., in water medium).
- an alkali metal ion source of the invention is formed from a particulate alkali metal ion-bearing framework silicate by a method of the invention, to thereby form the source of alkali metal that contains not less than 10 wt. % of the alkali ion-bearing silicate gel, has a specific surface area (BET) between about 8 m 2 /g and about 50 m 2 /g, and releases not less than 1 g of potassium per 1 kg of the alkali metal ion source and not less than 1 wt. % of silica acid within 24 hours upon exposure to aqueous solution that is undersaturated with respect to potassium and silica.
- BET specific surface area
- an alkali metal ion source of the invention is formed from a particulate alkali metal ion-bearing framework silicate by a method of the invention, to thereby form the source of alkali metal having Brunauer-Emmett-Teller (BET) specific surface area between about 3 m 2 /g and about 10 m 2 /g.
- BET Brunauer-Emmett-Teller
- the method of the invention of forming an alkali metal ion source from a potassium-bearing rock does not require strong acids or an excessive amount of liquid and can be performed at relatively moderate temperatures ( ⁇ 350° C.).
- the method of the invention also enables control over the rate of release of the alkali metal from the final product without requiring sophisticated intermediate steps by tailoring the amount of gel formed relative to other components bearing the alkali metal ion of the particulate alkali metal ion-bearing framework silicate.
- the release of potassium from the product is accompanied by the introduction to the soil of the entities that constitute the gel (siliceous acid and aluminum hydroxide) and precipitation of them in a secondary phase beneficial for soil (mainly, phylosilicates).
- the method of the invention avoids the formation of solid and liquid wastes that would otherwise need to be separated, recycled, and stockpiled before use of the product, such as where the product is used as a fertilizer.
- composition and structure of the material of the invention permits the tuning of the soil composition by the controllable release of the essential elements.
- pH can be safely raised by calcium ions released from the product.
- tobermorite phase prevents complete release of calcium ions, which can thereby prevent the soil pH from rising above 7.
- Silicate gel provides plant-available silicon, which is a structural and defensive element for many plants, in a form of monomers and low-weight oligomers of silicic acid, which also participates in phylosilicate phase precipitation in-situ.
- the moderate rate of potassium release prevents potassium from being immediately drained away with irrigation.
- Original phases when contained in the product, allows colonization of plant roots and long term slow release of all its entities.
- FIG. 1 is a schematic representation of the sequence of steps of certain embodiments of the method of the invention to produce embodiments of products of the invention.
- FIGS. 2A through 2D are transmission electron microscopy (TEM) images showing an amorphous component (gel) co-formed and stabilized along with a tobermorite phase in one embodiment of a product of the invention, referenced as Material #1.
- TEM transmission electron microscopy
- FIGS. 3A through 3D are secondary electron images of one embodiment of an embodiment of the invention.
- FIG. 4A is a backscattering electron image of one embodiment of the invention
- FIG. 4B is an energy-dispersive X-ray spectroscopy compositional map of one embodiment of the invention showing distribution of potassium (light grey color) along the bulk material.
- FIGS. 5A-5B are representations of the dynamic of cumulative release rates of potassium (K) from embodiments of the invention described below, and a comparison of those rates to control samples, also described below.
- FIGS. 6A and 6B represent instant rates of release of potassium from embodiments of the invention described below, and a comparison of those rates to control samples, also discussed below.
- the invention generally is directed to a method for forming an alkali metal ion source and a metal ion source formed by the method of the invention.
- the alkali metal ion source of the invention has many uses, such as where the alkali metal is potassium, a fertilizer for growing crops.
- FIG. 1 is a schematic 10 representing certain embodiments of the method of the invention. The steps of three possible embodiments of the method of the invention are represented in FIG. 1 as “ 1 ” for “Process 1 ,” “ 1 I ” for “Process 1 I ” and “ 2 ” for “Process 2 .”
- First component 12 shown in FIG. 1 is a particulate alkali metal ion-bearing framework silicate. It is to be understood that “silicate” in the phrase “particulate alkali metal ion-bearing framework silicate” includes aluminosilicates.
- first component 12 is formed from a suitable ore containing the alkali metal that is reduced in size by a suitable method known to those skilled in the art, such as crushing.
- a suitable ore can be reduced in particle size to a mean particle size of equal to or less than about 5 mm, as measured by, for example, sieve analysis. (ASTM C136-06 Standard Test Method for Sieve Analysis of Fine and Coarse Aggregates, the teachings of which are incorporated herein by reference in their entirety).
- suitable alkali metals for use in the method of the invention to produce the alkali metal ion source include, for example, at least one member of the group consisting of lithium (Li), sodium (Na) and potassium (K).
- An example of a suitable source of lithium includes petalite (LiAlSi 4 O 10 ).
- suitable sources of sodium include albite (NaAlSi 3 O 8 ) and nepheline (Na 3 KAl 4 Si 4 O 16 ).
- suitable sources of potassium include potassium feldspar (KAlSi 3 O 8 ), leucite (KAlSi 2 O 6 ), kalsilite (KAlSiO 4 ), and nepheline (Na 3 KAl 4 Si 4 O 16 ).
- suitable sources of the potassium include ores, such as syenite, nepheline syenite, and granite.
- the alkali metal is potassium
- the preferred alkali metal ion-bearing framework silicate is potassium feldspar (KAlSi 3 O 8 ) wherein the suitable ore contains at least about 5% by weight of an equivalent amount of potassium oxide (K 2 O).
- the second component includes at least one of an alkali metal and an alkaline earth metal.
- the alkaline earth metals of second component 14 includes at least one member of the group consisting of beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (Sr).
- the alkaline earth metal of the second component includes calcium.
- the alkaline earth metal of the second component is combined with the first component when the alkaline earth metal is in the form of calcium oxide (CaO) or calcium hydroxide (Ca(OH) 2 ).
- the second component includes an alkali metal.
- the alkali metal of the second component includes at least one member of the group consisting of lithium (Li), sodium (Na), and potassium (K).
- the molar ratio of the silicon of first component 12 to the at least one of an alkaline earth metal and an alkali metal of second component 14 is in a range of between about 1.0:0.1 and about 1.0:0.3.
- second component 14 includes calcium as an alkaline earth metal element of second component 14 in the form of calcium oxide or calcium hydroxide. Based on the amount of calcium oxide present in the solid mixture of first component 12 and second component 14 , the concentration of calcium oxide preferably is in a range of between about 5% and about 30% by weight of the combined first and second components.
- first component 12 is combined with second component 14 and liquid water 18 to form a mixture of liquid and solid.
- the amount of liquid water present is in a ratio by weight of liquid-to-solid of the liquid-and-solid mixture in a range of between about 0.05:1 and about 5:1, preferably, in a range of between about 2:1 and about 3:1.
- the combined liquid and solid mixture is wet joint milled 20 to thereby reduce the mean particle size of the particulate alkali metal ion-bearing framework silicate until the weight percent of the particles of the particulate alkali metal ion-bearing framework silicate having a diameter of 5 ⁇ m or less is at least about 50%. Milling of the liquid and solid mixture is preferred, but optional. Alternatively, the solid and liquid mixture can be treated hydrothermally as described below, with first conducting a wet joint milling step.
- the liquid-and-solid mixture is hydrothermally treated 22 by exposure to an elevated temperature and pressure to thereby form an alkali metal ion-bearing silicate gel, a key component of “Material #1” 24 .
- the gel includes the alkali metal of the first component, thereby forming the alkali metal ion source.
- the liquid-and-solid mixture is exposed to both a temperature in the range of between about 100° C. and about 350° C., and a pressure of between about 100 PSIG (pound force per square inch gage) and about 500 PSIG to thereby form the alkali ion-bearing silicate gel.
- the liquid-and-solid mixture is exposed to the elevated temperature and pressure until essentially all of the alkali metal of the first component is present as a component of the silicate gel.
- first component 12 is combined with second component 14 to form a solid mixture and optionally dry milled 16 .
- second component 14 includes at least one of an oxide and a hydroxide of at least one of an alkali metal and an alkaline earth metal.
- the alkali metal of second component 14 can be the same as the alkali metal of first component 12 .
- Process 1 I The solid mixture of Process 1 I is then hydrothermally treated as in Process 1 , but with additional water 18 , as necessary, to thereby obtain the same ratio by weight of liquid-to-solid as in Process 1 .
- hydrothermal treatment 22 causes formation of an alkali ion-bearing silicate gel, a key component of Material #1 (24).
- the Material #1 formed by the method of Process 1 or Process 1 I of the invention is combined with soil to form a mixture.
- the weight ratio of silicate gel-to-soil is in a range of between about 0.0001:1 and about 0.01:1.
- a method of the invention represented in FIG. 1 as “Process 2 ,” includes forming an alkali metal ion source by reducing the size of a particulate alkali metal ion-bearing framework silicate by dry milling 28 until at least about 50% by weight of the particles have a diameter of equal to or less than about 5 ⁇ m, as measured by laser diffraction using a Laser Diffraction Particle Size Analyzer in liquid mode (water), to thereby form “Material #2” 30 .
- suitable methods of reducing the size of the particulate alkali metal-ion bearing silicate framework include ball milling and micronizing.
- the particulate alkali metal ion-bearing framework silicate is an ore, such as syenite including, for example, nepheline syenite, and granite, and a preferred method of reducing the size of the syenite includes wet ball milling.
- the invention is an alkali metal ion source formed from a particulate alkali metal ion-bearing framework silicate by a method of the invention.
- suitable particulate alkali metal ion-bearing framework silicates from which the alkali metal ion source with moderate rate of ion release of the invention is derived are as listed above.
- the alkali metal ion source is derived from potassium feldspar and has Brunauer-Emmett-Teller (BET) specific surface area in a range of between about 8 m 2 /g and about 50 m 2 /g, and micropore specific surface area (the surface area of pores, cavities, and defects with the width of 4 to 20 ⁇ ) in a range of between about 1 m 2 /g and about 10 m 2 /g.
- BET Brunauer-Emmett-Teller
- Tables I and II The following non-limiting examples of two embodiments of products of the invention (Material #1 and Material #2), and of industrially ball-milled mineral powders are presented in Tables I and II.
- Table I reports examples of mixtures of chemical (in oxides) and mineral (phase) compositions of the initial mineral (syenite ore), and the compositions of products ultimately formed.
- Table II reports some of the physical properties of products of the invention formed from the mixtures described in Table I.
- the suspension was transferred to a batch pressure vessel commercially available from Parr Instrument Co., of Moline, Ill. and maintained at a temperature of about 200° C. and pressure of about 225 PSIG for about 24 hours without stirring. After the reaction, a resulting solid phase containing residual liquid was dried overnight at about 110° C.
- the ultimate compositions of the material are listed as Examples 1, 2 and, 3 in Table I. Examples 4, 5 and 6 of Table I, were obtained by sole dry milling. Milling was performed in the McCrone Micronizing Mill; the weight ratio between milling elements and mineral sample was about 67.
- Example 7 control samples in the experiment was prepared by sole industrial ball milling from the same syenite ore as Examples 1, 2, and 3.
- Example 8 control sample in the experiment was prepared by sole industrial ball milling from the same syenite ore as the examples the Examples 4, 5, and 6. The milling parameters are listed in Table I, and the properties of the materials obtained are listed in Table II. The following analytical techniques were used to characterize key material properties and the performance:
- the Specific Surface Area according to Brunauer-Emmett-Teller (SSA-BET) was determined for each of the synthesized samples. The analysis was performed with a surface area and porosity analyzer using nitrogen as the adsorbing gas. In this study, nitrogen sorption isotherms were collected at a Micrometric ASAP 2020 Surface area and Porosity Analyzer, available from Micrometrics Co., Norcross, Ga., at 77 K. Samples were degassed under low vacuum at 110° C. for ⁇ 24 hours. The SSA calculation under the Brunauer-Emmett-Teller (BET) model was applied to the absorption branch of the isotherm. For the estimation of the area of micropores (area of pores and surface roughness with the width of 4-20 ⁇ ), a T-Plot model was applied.
- SSA-BET Brunauer-Emmett-Teller
- Particle Size Distribution (PSD) analysis was performed for powder samples by the laser diffraction method using a Laser Diffraction Particle Size Analyzer LS 13 320 (Beckman Coulter, Inc.) in liquid mode (in water medium). The diffraction pattern was obtained after preliminary sonication of the suspension aimed at avoiding random error caused by aggregation.
- Phase composition by powder X-Ray diffraction Powder X-ray diffraction patterns of the samples before and after leaching experiments were obtained using PANalytical X′Pert Pro Diffractometer, available from PANalytical, Co. A scan rate 150 sec/step and incident/diffracted beam optics recommended for a slow scans of complex poorly crystallized samples was used.
- the phase composition of crystalline part and the amount of amorphous part (K(Na)-A-S—H gel) in the Material #1 were determined by quantitate line-profile analysis of XRD-patterns performed using High-Score plus software available from PANalytical, Co.
- the microstructure of the materials was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).
- SEM scanning electron microscopy
- TEM transmission electron microscopy
- a Scanning Electron Microscopy (SEM) investigation was carried out using a JEOL 6610LV microscope available from JEOL USA, Inc. both in low-vacuum (30 Pa) and high-vacuum ( ⁇ 10 ⁇ 3 Pa) modes.
- a 15-20 kV accelerating voltage, 40-50 spot size, and 1015 mm working distance were used for imaging Secondary Electrons imaging (SE) to study the microtexture of the grains, and to observe surface roughness, topography, inclusions, and porosity at the micron-/submicron-scale. Natural defects and “man-made” defects caused by commination were best distinguished in this mode.
- BSE Back-Scattered Electrons imaging
- EDX Energy dispersive X-ray analysis
- Nutrition elements release was studied as following.
- the concentration of elements in the effluent was measured by use of an inductively-coupled plasma mass spectrometer provided by Agilent Technologies, Inc., USA. Release of such elements as calcium Ca and Si was analyzed by the same method employed to measure the rate of release of K.
- a “gel” is defined as a non-fluid colloidal network or polymer network that is expanded throughout its whole volume by a fluid.
- An aluminosilicate gel contains an inorganic colloidal or polymer network of [SiO 4 ] 4 ⁇ and [AlO 4 ] 5 ⁇ clusters. Charge-balancing ions of alkali metals are distributed along the random framework.
- Cumulative release of potassium for the Material #1 and Material #2 described above is illustrated by histograms and FIGS. 5 a - 5 b.
- the dynamic of instant release of potassium is plotted in FIG. 6 .
- SSA-BET Available specific surface area
- concentration of the amorphous part the parameter is relevant to Material #1 only and expressed as wt. % of K(Na)-A-S—H gel, see Table II
- surface concentration of imperfections at sub-nanometer scale the parameter is relevant both to Material #1 and Material #2 and estimated by micropore T-Plot Area, see Table II
- FIG. 5 a the higher the SSA, concentration of the amorphous part (gel), and the area of micropores (T-plot area), the higher the rate of release of K + .
- Material #1 of the Example 1 is characterized by the highest gel content, SSA-BET, and T-Plot area; therefore, it demonstrates the highest (24-fold increase in respect to control sample 7).
- Example 2 is in the middle both in terms of the material properties described above and K-release (13-fold increase in respect to control sample 7).
- Material #1 of the Example 3 also follows this trend and has the lowest (5-fold) increase.
- the weight ratio between Tobermorite/(Microcline+Orthoclase) contributes to the amount of Ca, rapidly available: the higher this ratio, the lower the availability of Ca due to its fixation within the crystalline structure of tobermorite.
- the SSA-BET, micropore area and the volume concentration of micron-sized particles contribute to the dynamics of ions release.
- Other parameters being the same, the materials of Examples 4, 5, and 6 show 2-fold, 3-fold and 4-fold increase in K-release with respect to control sample 8, respectively. Comparing the K-release performance of Material #1 and Material #2, it is reasonable to conclude that, in general, the effect of sole mechanical treatment is significantly lower than that of mechano-chemical one.
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Abstract
Description
- This application is a divisional of U.S. application Ser. No. 14/271,042, filed on May 6, 2014, which claims the benefit of U.S. Provisional Application No. 61/819,699, filed on May 6, 2013. The entire teachings of the above applications are incorporated herein by reference.
- There is a growing need for alternative sources of alkali metals, such as, but not limited to, potassium. Potassium chloride (traditional potassium fertilizing agent) is produced in a limited number of geographical locations remote from the southern hemisphere, where the transportation costs contribute to the market price significantly, making local manufacturing of potassium fertilizer increasingly attractive. As human population grows, agriculture also must grow and evolve with it, in particular, in available regions in the southern hemisphere. Among others, modern agriculture development in those regions requires growing crops on soils that are often fully depleted of macronutrients, structural elements, e.g. silicon in a form available for plants (monosilicic acid) or calcium, and structure-developing minerals, such as clay minerals (phylosilicates). In other words, these soils are not optimal for growing crops due to the lack of proper structure and essential elements resources. From the perspective of soil fertilization, traditional fertilizing agents, such as potassium nitrate and potassium chloride, are not optimal due to their excessive leaching, the lack of retention of their corresponding ions, and their inability to provide a proper structure to the soil. Potassium and other nutrition elements introduced into the soil in the form of these highly soluble salts are thus wasted, having potential negative effects on the environment, e.g., chloride contamination. Therefore, new potassium sources and a better means of nutrient delivery are needed to allow high agricultural productivity and expansion in the available regions of the southern hemisphere. Ideally, these sources can simultaneously provide essential elements, such as calcium and plant-available silicon, and promote formation of structural minerals.
- Rock-forming minerals, such as potassium feldspars (KAlSi3O8), may therefore be considered as earth-abundant alternatives to traditional sources based on their relatively high content of K2O (more than 15 wt % of K2O in pure KAlSi3O8). Numerous research efforts dedicated to the extraction of potassium ion (K+) from rock-forming minerals have been conducted in the last decades. Among such proposals are methods for complete disintegration of potassium-bearing silicates and aluminosilicates aimed at extracting K+ in the form of a highly soluble salt, such as, but not limited to KCl. These extraction methods are typically based on the precipitation of a water-soluble potassium salt from an aqueous solution obtained after disintegration of the raw minerals. The methods of disintegration, in turn, typically employ relatively high temperatures (>1000° C.), or/and aggressive acid-basic treatments, inevitably creating large volumes of liquid and/or solid wastes involving sophisticated and expensive separation techniques. (“Processing for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization,” CN 103172074 A; Hao Zhang, et al. (2012). The Extraction of Potassium from Feldspar by Molten Salt Leaching Method with Composite Additives. Advanced Materials Research, 524-527, 1136; and Pedro Lucas Gervasio Ladiera Potash product and method Patent Application WO 2013061092 A1. The teachings of all of which are incorporated herein by reference in their entirety.)
- Attempts to use unaltered stone-meals (crushed rocks) as an alternative source of potassium for fertilizer and a source of plant-available silicon have also been made. (Anne Kjersti Bakken, Harvard Gautneb, Kristen Myhr (1997) Plant available potassium in rocks and mine tailings with biotite, nepheline and K-feldspar as K-bearing minerals. Acta Agriculturae Scandinavica, Section B—Soil & Plant Science. Vol. 47; and Y. Tokunaga, Potassium silicate (1991). A slow-release potassium fertilizer. Fertilizer Research. 30, 55-59. The teachings of all of which are incorporated herein by reference in their entirety.) However, natural chemical weathering of those crushed stone is an extremely slow process, and the benefits such as nutrients release and phylosilicate formation from crushed primary minerals appear only on a timescale that far exceed—several years, potentially decades—the timescale of growth and harvesting of crops of modern agriculture.
- Therefore, a need exists to produce a source of potassium ion that releases the nutrient at a moderate rate, lower than the infinite dissolution rate of a traditional salts, but faster than the rate generally exhibited by naturally-occurring minerals. Ideally, this source be produced from the earth abundant K-bearing silicate rocks, can provide structural components (such as silicon in the form of monosilicic acid and/or calcium), and can promote the formation of clay minerals (phylosilicates). Also, a need exists for a method to produce source of such materials that minimizes the above-mentioned problems.
- The invention generally relates to a method for forming an alkali metal ion source and an alkali metal ion source formed by the method.
- In one embodiment, a method of the invention for forming an alkali metal ion source includes combining a first component that includes a particulate alkali metal ion-bearing framework silicate with a second component that includes at least one of an oxide and a hydroxide of at least one of an alkaline earth metal and an alkali metal to form a solid mixture. The molar ratio of the silicon of the first component to the at least one of the alkaline earth and alkali metal and alkali metal of the second component is in a range of between about 1.0:0.1 and about 1.0:0.3. The mixture is optionally joint wet milled or dry joint milled, or separately milled and blended after the milling. In the event that the solid mixture is wet joint milled, the total amount of liquid presents is in a ratio by weight of liquid-to-solid in a range of between about 0.05:1 and about 5:1. The mixture is then exposed to elevated temperature and pressure for a period of time sufficient to form a gel that includes the silicon and the alkali metal of the first component, thereby forming the source of alkali metal. The weight ratio of tobermorite phase to the unreacted alkali metal ion-bearing framework silicate phases of the alkali metal ion source can be between about 1:1 and about 0:1. The weight percent of K(Na)-A-S—H gel of the alkali metal ion source can be between about 10% and about 100%. The specific surface area of the alkali metal ion source can be between about 8 m2/g and 50 m2/g.
- In another embodiment of a method of the invention, an alkali metal ion source is formed by reducing the size of a particulate alkali metal ion-bearing framework silicate until at least about 50% by weight of the particles have a diameter of equal to or less than 5 μm as measured by laser diffraction using a laser diffraction particle size analyzer in liquid mode (e.g., in water medium).
- In one embodiment, an alkali metal ion source of the invention is formed from a particulate alkali metal ion-bearing framework silicate by a method of the invention, to thereby form the source of alkali metal that contains not less than 10 wt. % of the alkali ion-bearing silicate gel, has a specific surface area (BET) between about 8 m2/g and about 50 m2/g, and releases not less than 1 g of potassium per 1 kg of the alkali metal ion source and not less than 1 wt. % of silica acid within 24 hours upon exposure to aqueous solution that is undersaturated with respect to potassium and silica.
- In one embodiment, an alkali metal ion source of the invention is formed from a particulate alkali metal ion-bearing framework silicate by a method of the invention, to thereby form the source of alkali metal having Brunauer-Emmett-Teller (BET) specific surface area between about 3 m2/g and about 10 m2/g.
- This invention has many advantages. For example, the method of the invention of forming an alkali metal ion source from a potassium-bearing rock does not require strong acids or an excessive amount of liquid and can be performed at relatively moderate temperatures (≦350° C.). The method of the invention also enables control over the rate of release of the alkali metal from the final product without requiring sophisticated intermediate steps by tailoring the amount of gel formed relative to other components bearing the alkali metal ion of the particulate alkali metal ion-bearing framework silicate. Also, the release of potassium from the product is accompanied by the introduction to the soil of the entities that constitute the gel (siliceous acid and aluminum hydroxide) and precipitation of them in a secondary phase beneficial for soil (mainly, phylosilicates). This provides several key elements in a single material and the necessary structural components for the soils in the manner described above. Further, the method of the invention avoids the formation of solid and liquid wastes that would otherwise need to be separated, recycled, and stockpiled before use of the product, such as where the product is used as a fertilizer.
- The composition and structure of the material of the invention permits the tuning of the soil composition by the controllable release of the essential elements. For example, in the case of highly acidic soils (pH<5), pH can be safely raised by calcium ions released from the product. Moreover, the presence of tobermorite phase prevents complete release of calcium ions, which can thereby prevent the soil pH from rising above 7. Silicate gel provides plant-available silicon, which is a structural and defensive element for many plants, in a form of monomers and low-weight oligomers of silicic acid, which also participates in phylosilicate phase precipitation in-situ. The moderate rate of potassium release prevents potassium from being immediately drained away with irrigation. Original phases, when contained in the product, allows colonization of plant roots and long term slow release of all its entities.
-
FIG. 1 is a schematic representation of the sequence of steps of certain embodiments of the method of the invention to produce embodiments of products of the invention. -
FIGS. 2A through 2D are transmission electron microscopy (TEM) images showing an amorphous component (gel) co-formed and stabilized along with a tobermorite phase in one embodiment of a product of the invention, referenced asMaterial # 1. -
FIGS. 3A through 3D are secondary electron images of one embodiment of an embodiment of the invention. -
FIG. 4A is a backscattering electron image of one embodiment of the invention;FIG. 4B is an energy-dispersive X-ray spectroscopy compositional map of one embodiment of the invention showing distribution of potassium (light grey color) along the bulk material. -
FIGS. 5A-5B are representations of the dynamic of cumulative release rates of potassium (K) from embodiments of the invention described below, and a comparison of those rates to control samples, also described below. -
FIGS. 6A and 6B represent instant rates of release of potassium from embodiments of the invention described below, and a comparison of those rates to control samples, also discussed below. - The foregoing will be apparent from the following more particular description of example embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating embodiments of the present invention.
- The invention generally is directed to a method for forming an alkali metal ion source and a metal ion source formed by the method of the invention. The alkali metal ion source of the invention has many uses, such as where the alkali metal is potassium, a fertilizer for growing crops.
FIG. 1 is a schematic 10 representing certain embodiments of the method of the invention. The steps of three possible embodiments of the method of the invention are represented inFIG. 1 as “1” for “Process 1,” “1 I” for “Process 1 I” and “2” for “Process 2.”First component 12 shown inFIG. 1 is a particulate alkali metal ion-bearing framework silicate. It is to be understood that “silicate” in the phrase “particulate alkali metal ion-bearing framework silicate” includes aluminosilicates. - In one embodiment of the method of the invention represented in
FIG. 1 ,first component 12 is formed from a suitable ore containing the alkali metal that is reduced in size by a suitable method known to those skilled in the art, such as crushing. For example, a suitable ore can be reduced in particle size to a mean particle size of equal to or less than about 5 mm, as measured by, for example, sieve analysis. (ASTM C136-06 Standard Test Method for Sieve Analysis of Fine and Coarse Aggregates, the teachings of which are incorporated herein by reference in their entirety). Examples of suitable alkali metals for use in the method of the invention to produce the alkali metal ion source include, for example, at least one member of the group consisting of lithium (Li), sodium (Na) and potassium (K). An example of a suitable source of lithium includes petalite (LiAlSi4O10). Examples of suitable sources of sodium include albite (NaAlSi3O8) and nepheline (Na3KAl4Si4O16). Examples of suitable sources of potassium include potassium feldspar (KAlSi3O8), leucite (KAlSi2O6), kalsilite (KAlSiO4), and nepheline (Na3KAl4Si4O16). Examples of suitable sources of the potassium include ores, such as syenite, nepheline syenite, and granite. - In a particularly preferred embodiment, the alkali metal is potassium, and the preferred alkali metal ion-bearing framework silicate is potassium feldspar (KAlSi3O8) wherein the suitable ore contains at least about 5% by weight of an equivalent amount of potassium oxide (K2O).
- In one embodiment, the second component includes at least one of an alkali metal and an alkaline earth metal. Preferably, the alkaline earth metals of
second component 14 includes at least one member of the group consisting of beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (Sr). Preferably, the alkaline earth metal of the second component includes calcium. Most preferably, the alkaline earth metal of the second component is combined with the first component when the alkaline earth metal is in the form of calcium oxide (CaO) or calcium hydroxide (Ca(OH)2). - In another embodiment, the second component includes an alkali metal. Preferably, the alkali metal of the second component includes at least one member of the group consisting of lithium (Li), sodium (Na), and potassium (K).
- In one embodiment, the molar ratio of the silicon of
first component 12 to the at least one of an alkaline earth metal and an alkali metal ofsecond component 14 is in a range of between about 1.0:0.1 and about 1.0:0.3. In a preferred embodiment,second component 14 includes calcium as an alkaline earth metal element ofsecond component 14 in the form of calcium oxide or calcium hydroxide. Based on the amount of calcium oxide present in the solid mixture offirst component 12 andsecond component 14, the concentration of calcium oxide preferably is in a range of between about 5% and about 30% by weight of the combined first and second components. - In
Process 1,first component 12 is combined withsecond component 14 andliquid water 18 to form a mixture of liquid and solid. In one embodiment, the amount of liquid water present is in a ratio by weight of liquid-to-solid of the liquid-and-solid mixture in a range of between about 0.05:1 and about 5:1, preferably, in a range of between about 2:1 and about 3:1. - In a preferred embodiment, the combined liquid and solid mixture is wet joint milled 20 to thereby reduce the mean particle size of the particulate alkali metal ion-bearing framework silicate until the weight percent of the particles of the particulate alkali metal ion-bearing framework silicate having a diameter of 5 μm or less is at least about 50%. Milling of the liquid and solid mixture is preferred, but optional. Alternatively, the solid and liquid mixture can be treated hydrothermally as described below, with first conducting a wet joint milling step.
- The liquid-and-solid mixture is hydrothermally treated 22 by exposure to an elevated temperature and pressure to thereby form an alkali metal ion-bearing silicate gel, a key component of “
Material # 1” 24. The gel includes the alkali metal of the first component, thereby forming the alkali metal ion source. In a preferred embodiment, the liquid-and-solid mixture is exposed to both a temperature in the range of between about 100° C. and about 350° C., and a pressure of between about 100 PSIG (pound force per square inch gage) and about 500 PSIG to thereby form the alkali ion-bearing silicate gel. In a specific embodiment, the liquid-and-solid mixture is exposed to the elevated temperature and pressure until essentially all of the alkali metal of the first component is present as a component of the silicate gel. - In
Process 1 I, also represented inFIG. 1 ,first component 12 is combined withsecond component 14 to form a solid mixture and optionally dry milled 16. InProcess 1 I,second component 14 includes at least one of an oxide and a hydroxide of at least one of an alkali metal and an alkaline earth metal. Optionally, the alkali metal ofsecond component 14 can be the same as the alkali metal offirst component 12. - The solid mixture of
Process 1 I is then hydrothermally treated as inProcess 1, but withadditional water 18, as necessary, to thereby obtain the same ratio by weight of liquid-to-solid as inProcess 1. As inProcess 1,hydrothermal treatment 22 causes formation of an alkali ion-bearing silicate gel, a key component of Material #1 (24). - In one embodiment, the
Material # 1 formed by the method ofProcess 1 orProcess 1 I of the invention is combined with soil to form a mixture. Preferably, the weight ratio of silicate gel-to-soil is in a range of between about 0.0001:1 and about 0.01:1. - In another embodiment, a method of the invention represented in
FIG. 1 as “Process 2,” includes forming an alkali metal ion source by reducing the size of a particulate alkali metal ion-bearing framework silicate bydry milling 28 until at least about 50% by weight of the particles have a diameter of equal to or less than about 5 μm, as measured by laser diffraction using a Laser Diffraction Particle Size Analyzer in liquid mode (water), to thereby form “Material # 2” 30. Examples of suitable methods of reducing the size of the particulate alkali metal-ion bearing silicate framework include ball milling and micronizing. Examples of suitable sources of particulate alkali metal ion-bearing framework silicate for use with this embodiment of the method are as described above. In a preferred embodiment, the particulate alkali metal ion-bearing framework silicate is an ore, such as syenite including, for example, nepheline syenite, and granite, and a preferred method of reducing the size of the syenite includes wet ball milling. - In one embodiment, the invention is an alkali metal ion source formed from a particulate alkali metal ion-bearing framework silicate by a method of the invention. Examples of suitable particulate alkali metal ion-bearing framework silicates from which the alkali metal ion source with moderate rate of ion release of the invention is derived are as listed above. In one embodiment, the alkali metal ion source is derived from potassium feldspar and has Brunauer-Emmett-Teller (BET) specific surface area in a range of between about 8 m2/g and about 50 m2/g, and micropore specific surface area (the surface area of pores, cavities, and defects with the width of 4 to 20 Å) in a range of between about 1 m2/g and about 10 m2/g.
- The following examples are provided as embodiments of the present invention and are not necessarily limiting.
- The following non-limiting examples of two embodiments of products of the invention (
Material # 1 and Material #2), and of industrially ball-milled mineral powders are presented in Tables I and II. In accordance with the present invention, Table I reports examples of mixtures of chemical (in oxides) and mineral (phase) compositions of the initial mineral (syenite ore), and the compositions of products ultimately formed. Table II reports some of the physical properties of products of the invention formed from the mixtures described in Table I. - 10 g of roughly ground raw material (ground syenite ore with rough irregular crystalline particles with the size <5 mm) and the composition listed in table I was mixed with dry powdered Ca(OH)2 (Sigma-Aldrich, grade: ≧96.0%≦3.0% calcium carbonate) for 5-10 minutes before addition of water. Distilled water was added to the mixture according to the proportion listed in Table I. The suspension was placed into the chamber of a McCrone Micronising Mill by McCrone Microscope & Accessories of Westmount, Ill., and milled for 30 minutes (weight ratio between the milling elements (agate spheres) and the sample was about 4). After milling, the suspension was transferred to a batch pressure vessel commercially available from Parr Instrument Co., of Moline, Ill. and maintained at a temperature of about 200° C. and pressure of about 225 PSIG for about 24 hours without stirring. After the reaction, a resulting solid phase containing residual liquid was dried overnight at about 110° C. The ultimate compositions of the material are listed as Examples 1, 2 and, 3 in Table I. Examples 4, 5 and 6 of Table I, were obtained by sole dry milling. Milling was performed in the McCrone Micronizing Mill; the weight ratio between milling elements and mineral sample was about 67. This milling did not have a noticeable effect on the phase composition, but provided beneficial effects favoring increased rates of potassium release, including an increase in available surface area, volume of ultra-fine particles and introduction of crystal lattice disturbances. Example 7 (control samples in the experiment) was prepared by sole industrial ball milling from the same syenite ore as Examples 1, 2, and 3. Example 8 (control sample in the experiment) was prepared by sole industrial ball milling from the same syenite ore as the examples the Examples 4, 5, and 6. The milling parameters are listed in Table I, and the properties of the materials obtained are listed in Table II. The following analytical techniques were used to characterize key material properties and the performance:
- The Specific Surface Area according to Brunauer-Emmett-Teller (SSA-BET) was determined for each of the synthesized samples. The analysis was performed with a surface area and porosity analyzer using nitrogen as the adsorbing gas. In this study, nitrogen sorption isotherms were collected at a Micrometric ASAP 2020 Surface area and Porosity Analyzer, available from Micrometrics Co., Norcross, Ga., at 77 K. Samples were degassed under low vacuum at 110° C. for ˜24 hours. The SSA calculation under the Brunauer-Emmett-Teller (BET) model was applied to the absorption branch of the isotherm. For the estimation of the area of micropores (area of pores and surface roughness with the width of 4-20 Å), a T-Plot model was applied.
- Particle Size Distribution (PSD) analysis was performed for powder samples by the laser diffraction method using a Laser Diffraction Particle Size Analyzer LS 13 320 (Beckman Coulter, Inc.) in liquid mode (in water medium). The diffraction pattern was obtained after preliminary sonication of the suspension aimed at avoiding random error caused by aggregation.
- Phase composition by powder X-Ray diffraction: Powder X-ray diffraction patterns of the samples before and after leaching experiments were obtained using PANalytical X′Pert Pro Diffractometer, available from PANalytical, Co. A scan rate 150 sec/step and incident/diffracted beam optics recommended for a slow scans of complex poorly crystallized samples was used. The phase composition of crystalline part and the amount of amorphous part (K(Na)-A-S—H gel) in the
Material # 1 were determined by quantitate line-profile analysis of XRD-patterns performed using High-Score plus software available from PANalytical, Co. - The microstructure of the materials was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A Scanning Electron Microscopy (SEM) investigation was carried out using a JEOL 6610LV microscope available from JEOL USA, Inc. both in low-vacuum (30 Pa) and high-vacuum (<10−3 Pa) modes. In the high-vacuum mode, a 15-20 kV accelerating voltage, 40-50 spot size, and 1015 mm working distance were used for imaging Secondary Electrons imaging (SE) to study the microtexture of the grains, and to observe surface roughness, topography, inclusions, and porosity at the micron-/submicron-scale. Natural defects and “man-made” defects caused by commination were best distinguished in this mode. A Back-Scattered Electrons imaging (BSE) was used to observe various phases based on atomic number in order to correlate grain size, shape and their mineralogy (if possible). Energy dispersive X-ray analysis (EDX) was used for compositional mapping.
- Nutrition elements release (materials performance) was studied as following. “Short term K-release cumulative value” of Table II corresponds to the sum of grams (g) of potassium (K) released in 3 batches from
Material # 1,Material # 2 and the two controls—Examples 7 and 8 with fresh solution of pH=5 performed within 24 hours (solid-to-liquid weight ratio=1:10, pH of influent=5, t=22° C.). “Mid-term K-release cumulative value” of Table II corresponds to the sum of grams of potassium released in 10 batches (each batch is replacing of old influent by fresh influent keeping the same solid-to-liquid ratio) performed within 10 days (solid to liquid weight ratio=1:10, pH of influent=5, t=22° C.). The concentration of elements in the effluent was measured by use of an inductively-coupled plasma mass spectrometer provided by Agilent Technologies, Inc., USA. Release of such elements as calcium Ca and Si was analyzed by the same method employed to measure the rate of release of K. -
TABLE I Industrially ball-milled Material # 1Material # 2powders Example Number 1 2 3 4 5 6 7 8 Initial mineral (Syenite ores) Chemical Composition, wt. % SiO2 62.4 62.9 62.4 62.9 Al2O3 17 17.3 17 17.3 Fe2O3 2.18 1.9 2.18 1.9 CaO 1.31 1.13 1.31 1.13 MgO 0.65 0.39 0.65 0.39 TiO2 0.16 0.19 0.16 0.19 P2O5 0.17 0.123 0.17 0.123 Na2O 0.7 1.85 0.7 1.85 K2O 14.3 12.6 14.3 12.6 MnO <0.1 <0.1 <0.1 <0.1 BaO 0.72 1.17 0.72 1.17 LOI 0.11 0.19 0.11 0.19 Phase composition Microcline + Orthoclase 94.5 80 94.5 80 Albite 1.5 11 1.5 11 Pyroxene 4 9 4 9 Chemical composition of ultimate material produced SiO2 52.0 54.7 57.7 The same as the chemical composition of Al2O3 14.2 14.9 15.7 the initial mineral described in the upper Fe2O3 1.81 1.91 2.0 rows of this table - no chemical CaO 15.3 11.14 6.5 modification applied MgO 0.54 0.57 0.60 TiO2 0.13 0.14 0.15 P2O5 0.14 0.15 0.16 Na2O 0.58 0.61 0.65 K2O 11.9 12.53 13.2 MnO <0.1 <0.1 <0.1 BaO 0.60 0.63 0.67 LOI 2.8 2.73 2.64 Liquid/Solid ratio 3 n/a Milling time, min 30 10 30 60 37 55 Stirring no n/a Max T, ° C.; P, psig 200; 225 Hold time, hours 24 -
TABLE II Industrially ball-milled Material #1 Material #2 powders Example Number 1 2 3 4 5 6 7 8 Phase composition of final material Weight ratio between 0.125:1 0.09:1 0.05:1 0:1 Tobermorite/(Microcline + Orthoclase)** K(Na)—A—S—H gel, wt. %*** 20-25 15-20 10-15 0 Surface Specific Area (SSA-BET) 12 9 8 4.4 8 8 1.4 2.7 Micropores T-Plot Area 2.6 4.2 3.1 0.3 0.4 0.5 0.1 0.1 90 volume % below the size (μm) 500 18 12 12 30 56 Volume % of particles below 5 μm 30 56 70 72 23 30 Cumulative release of nutrition elements (g of element/kg of dry sample) Short Term K-release (24 hours) 10 5.6 2.0 0.4 0.6 0.8 0.2 0.2 Mid Term K-release (30 days) 12 6.5 2.5 0.7 1.0 1.3 0.5 0.3 Mid Term Ca-release (30 days) 0.48 0.53 0.75 <0.1 Mid Term Si-release (30 days) 1.23 1.03 0.77 0.38 0.40 0.50 0.31 0.23 *X-Ray diffraction analysis revealed that all examples of the material #1, both before and after batch leaching experiments shows the presence of Tobermorite-11 Å, a crystalline compound with general formula Ca5Si6O16(OH)2•nH2O* where n ~4. **Two phases that represent K-Feldspar that initially contained in the syenite ore. The general formula both for microcline and orthoclase is KAlSi3O8. ***Following the IUPAC, a “gel” is defined as a non-fluid colloidal network or polymer network that is expanded throughout its whole volume by a fluid. An aluminosilicate gel contains an inorganic colloidal or polymer network of [SiO4]4− and [AlO4]5− clusters. Charge-balancing ions of alkali metals are distributed along the random framework. - In addition to X-Ray diffraction data, formation of amorphous K(Na)-A-S—H gel in the
Material # 1 due to the hydrothermal treatment was confirmed by transmission-electron microscopy, and the images are shown inFIG. 2 . Scanning electron microscopy reveals the microstructure ofMaterial # 1 at submicron-/micron scale (Example 1, depicted inFIGS. 3a-3d ). The coexistence of amorphous gel along with tiny crystals of tobermorite and residual crystalline K-feldspar inMaterial # 1 is illustrated by secondary electron images of high resolution (FIGS. 2a-2d ). Compositional EDX mapping of Material #1 (Example 1) shows the distribution of potassium (K shown with light grey color) in the bulk material (FIG. 4 ). - Cumulative release of potassium for the
Material # 1 andMaterial # 2 described above is illustrated by histograms andFIGS. 5a -5 b. The dynamic of instant release of potassium is plotted inFIG. 6 . - At pH ≦5 and ambient temperatures and pressure, both
Material # 1 andMaterial # 2 release K+ and other ions by two major chemical mechanisms: ion-exchange onto the material-fluid interface and hydrolysis of Al—O—Si and Si—O—Si bonds. As can be seen inFIGS. 5 and 6 , initial dissolution is highly undersaturated in respect to K+ influent results in fast and substantial release within 24 hours both for theMaterial # 1 andMaterial # 2. Subsequent release is limited by the rate of hydrolysis, which is substantially slower than initial ion-exchange. - Available specific surface area (SSA-BET), concentration of the amorphous part (the parameter is relevant to
Material # 1 only and expressed as wt. % of K(Na)-A-S—H gel, see Table II) and surface concentration of imperfections at sub-nanometer scale (the parameter is relevant both toMaterial # 1 andMaterial # 2 and estimated by micropore T-Plot Area, see Table II) contribute to the control of the dynamics of K-release. As can be seen fromFIG. 5a for theMaterial # 1, the higher the SSA, concentration of the amorphous part (gel), and the area of micropores (T-plot area), the higher the rate of release of K+. For instance:Material # 1 of the Example 1 is characterized by the highest gel content, SSA-BET, and T-Plot area; therefore, it demonstrates the highest (24-fold increase in respect to control sample 7). Example 2 is in the middle both in terms of the material properties described above and K-release (13-fold increase in respect to control sample 7).Material # 1 of the Example 3 also follows this trend and has the lowest (5-fold) increase. The weight ratio between Tobermorite/(Microcline+Orthoclase), in turn, contributes to the amount of Ca, rapidly available: the higher this ratio, the lower the availability of Ca due to its fixation within the crystalline structure of tobermorite. - For the
Material # 2, the SSA-BET, micropore area and the volume concentration of micron-sized particles contribute to the dynamics of ions release. Other parameters being the same, the materials of Examples 4, 5, and 6 show 2-fold, 3-fold and 4-fold increase in K-release with respect to controlsample 8, respectively. Comparing the K-release performance ofMaterial # 1 andMaterial # 2, it is reasonable to conclude that, in general, the effect of sole mechanical treatment is significantly lower than that of mechano-chemical one. - The teachings of all patents, published applications and references cited herein are incorporated by reference in their entirety.
- While this invention has been particularly shown and described with references to example embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
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US9684097B2 (en) | 2013-05-07 | 2017-06-20 | Corning Incorporated | Scratch-resistant articles with retained optical properties |
US9366784B2 (en) | 2013-05-07 | 2016-06-14 | Corning Incorporated | Low-color scratch-resistant articles with a multilayer optical film |
US9110230B2 (en) | 2013-05-07 | 2015-08-18 | Corning Incorporated | Scratch-resistant articles with retained optical properties |
US11267973B2 (en) | 2014-05-12 | 2022-03-08 | Corning Incorporated | Durable anti-reflective articles |
US9790593B2 (en) | 2014-08-01 | 2017-10-17 | Corning Incorporated | Scratch-resistant materials and articles including the same |
WO2017048700A1 (en) | 2015-09-14 | 2017-03-23 | Corning Incorporated | High light transmission and scratch-resistant anti-reflective articles |
WO2018136667A1 (en) * | 2017-01-18 | 2018-07-26 | Massachusetts Institute Of Technology | Potassium-releasing material |
EA039758B1 (en) * | 2017-06-16 | 2022-03-10 | Массачусетс Инститьют Оф Текнолоджи | Potassium-releasing material |
WO2020037042A1 (en) | 2018-08-17 | 2020-02-20 | Corning Incorporated | Inorganic oxide articles with thin, durable anti-reflective structures |
CN116589325A (en) * | 2023-05-29 | 2023-08-15 | 瓮福(集团)有限责任公司 | Preparation method of slow-release silicon fertilizer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1357480A (en) * | 1918-03-06 | 1920-11-02 | Seattle Asbestomine Co | Method of grinding diatomaceous earth |
US3383056A (en) * | 1966-02-07 | 1968-05-14 | Mobil Oil Corp | Method for disintegrating porous solids |
US20110143941A1 (en) * | 2008-10-08 | 2011-06-16 | Advanced Plant Nutrition Pty Ltd | Silicon-containing glass powder particles to improve plant growth |
US20120160944A1 (en) * | 2009-04-24 | 2012-06-28 | Aaron Dodd | Method for the production of commercial nanoparticle and micro particle powders |
Family Cites Families (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR527066A (en) | 1920-10-19 | 1921-10-20 | Felix Jourdan | Process for the manufacture of potassium carbonate |
GB195084A (en) | 1922-03-16 | 1923-05-10 | Felix Jourdan | Improved method of treating leucite or other sodium-potassium silicates, for recovering potassium, sodium and aluminium compounds |
FR556994A (en) | 1922-03-16 | 1923-08-01 | Utilisation Des Leucites Soc P | Method of treating leucite with lime to obtain caustic potash and a residue suitable for making cement |
FR693074A (en) | 1930-02-07 | 1930-11-14 | Improvements in processes for extracting potash and alumina from leucite | |
BE376589A (en) | 1930-02-07 | |||
US3137564A (en) * | 1959-09-04 | 1964-06-16 | Phillips Petroleum Co | Process for producing a silica gel fertilizer and the product thereof |
US3838192A (en) * | 1971-10-28 | 1974-09-24 | Huber Corp J M | Production of alkali metal polysilicates |
CA1004655A (en) * | 1973-03-05 | 1977-02-01 | Yoshiharu Nomura | Preparation of zeolites |
US3956467A (en) * | 1974-06-07 | 1976-05-11 | Bertorelli Orlando L | Process for producing alkali metal polysilicates |
DD142802A3 (en) * | 1977-03-10 | 1980-07-16 | Anton Kullmann | METHOD FOR PRODUCING A NUTRITATED GROUND-IMPROVING ORGANIC SUBSTANCE |
DD140802A1 (en) * | 1977-11-03 | 1980-03-26 | Walter Dressler | ARRANGEMENT FOR CONTINUOUS ARC DETECTION IN SECONDARY SWITCHGEAR |
IT1194749B (en) | 1981-02-23 | 1988-09-28 | Italia Alluminio | METALLURGIC PROCESS FOR THE TREATMENT OF SILICO-ALUMINUM-ALKALINE MINERALS, LEUCYTIC MINERALS |
SU986852A1 (en) * | 1981-03-24 | 1983-01-07 | Институт общей и неорганической химии АН АрмССР | Method of producing calcum metasilicate |
US4493725A (en) | 1983-05-17 | 1985-01-15 | Korea Advanced Institute Of Science And Technology | Fertilizer product with sustained action and process therefor |
US4810280A (en) * | 1987-05-08 | 1989-03-07 | Raymond Le Van Mao | Method for enhancing water retention in soil |
JP2564581B2 (en) * | 1987-12-28 | 1996-12-18 | 水澤化学工業株式会社 | Manufacturing method of high silica content zeolite |
SU1640129A1 (en) * | 1988-05-26 | 1991-04-07 | Научно-производственное объединение "Камень и силикаты" | Method of producing porous granules |
DE3938729A1 (en) * | 1989-11-23 | 1991-05-29 | Henkel Kgaa | METHOD FOR THE HYDROTHERMAL PRODUCTION OF SODIUM POLYSILICATE |
CN1064262A (en) | 1992-03-26 | 1992-09-09 | 李勇金 | Processing method with producing potassium fertilizer from potash feldspar |
US5433766A (en) | 1992-10-16 | 1995-07-18 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Slow-release fertilizer |
CN1098398A (en) | 1994-04-29 | 1995-02-08 | 刘金荣 | A kind of method of producing potash fertilizer by potassium felspar sand |
AUPN012194A0 (en) * | 1994-12-16 | 1995-01-19 | University Of Queensland, The | Alumino-silicate derivatives |
US5695542A (en) | 1995-11-14 | 1997-12-09 | Chang; Hsin-Jen | Method of preparing a slow release fertilizer |
KR100225565B1 (en) * | 1996-12-12 | 1999-10-15 | 유규재 | Process for preparing ultrafine particles of a calcium and magnesium salt of aluminium silicate |
CN1207250C (en) | 2001-01-15 | 2005-06-22 | 中国科学院地质与地球物理研究所 | Process for preparing K fertilizer or K salt from K-enriched rock and lime by hydrothermal method |
CN1209323C (en) | 2001-01-15 | 2005-07-06 | 中国科学院地质与地球物理研究所 | Process for preparing K fertilizer (K salt) from K-enriched rock and lime by hydrothermal method |
US6887828B2 (en) | 2001-12-21 | 2005-05-03 | A. John Allen | Phillipsitic zeolite soil amendments |
CN1246262C (en) | 2002-07-05 | 2006-03-22 | 华南农业大学 | Process for preparing efficient ammonium phosphate |
CN1308265C (en) | 2002-12-19 | 2007-04-04 | 中国科学院地质与地球物理研究所 | Method for preparing potash manure (kali salt) from potassium-rich rock using hydrothermal chemical reaction |
CN101054313B (en) | 2007-04-26 | 2012-01-18 | 中科建成矿物技术(北京)有限公司 | Method for producing micro-pore silicon-potassium-calcium mineral fertilizer |
CN101450875A (en) | 2007-12-05 | 2009-06-10 | 中国科学院地质与地球物理研究所 | Method for preparing multielement micropore mineral fertilizer from silicate rock through hydrothermal chemical reaction |
ES2324972B1 (en) * | 2008-02-19 | 2010-03-22 | Bionatur Biotechnologies, S.L. | MATERIALS IN THE FORM OF HOLLOW CYLINDERS CONTAINING BENTONITE AND ITS USE IN ADSORTION / DESORTION PROCESSES. |
CN101921141B (en) * | 2010-08-31 | 2012-01-11 | 王月明 | Method for preparing mineral potassic fertilizer from potassium-enriched rock |
CN102030338B (en) | 2010-11-11 | 2013-04-10 | 中国地质大学(北京) | Method for hydrothermally synthesizing kalsilite by using potassium feldspar powder |
CN102408256A (en) * | 2011-08-24 | 2012-04-11 | 烟台大学 | Method for quickly extracting soluble potassium at low temperature |
KR102060844B1 (en) | 2011-09-21 | 2019-12-30 | 아리조나 보드 오브 리전트스, 아리조나주의 아리조나 주립대 대행법인 | Geopolymer resin materials, geopolymer materials, and materials produced thereby |
WO2013061092A1 (en) | 2011-10-27 | 2013-05-02 | Verde Potash Plc | Potash product and method |
CN102583429A (en) * | 2012-02-17 | 2012-07-18 | 中国地质大学(北京) | Method for synthesizing 4A-type molecular sieve by utilizing aluminum-silicon tailings obtained in process of carrying out potassium extraction on potassium feldspar |
CN103172074B (en) | 2013-01-17 | 2014-11-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
WO2014182693A1 (en) | 2013-05-06 | 2014-11-13 | Massachusetts Institute Of Technology | Alkali metal ion source with moderate rate of ion relaease and methods of forming |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1357480A (en) * | 1918-03-06 | 1920-11-02 | Seattle Asbestomine Co | Method of grinding diatomaceous earth |
US3383056A (en) * | 1966-02-07 | 1968-05-14 | Mobil Oil Corp | Method for disintegrating porous solids |
US20110143941A1 (en) * | 2008-10-08 | 2011-06-16 | Advanced Plant Nutrition Pty Ltd | Silicon-containing glass powder particles to improve plant growth |
US20120160944A1 (en) * | 2009-04-24 | 2012-06-28 | Aaron Dodd | Method for the production of commercial nanoparticle and micro particle powders |
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AP2015008831A0 (en) | 2015-10-31 |
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BR112015027969B1 (en) | 2022-05-31 |
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CA2911246C (en) | 2023-01-03 |
CN106866207A (en) | 2017-06-20 |
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US9340465B2 (en) | 2016-05-17 |
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RU2015152085A (en) | 2017-06-14 |
CN104350010B (en) | 2017-03-22 |
US20140345348A1 (en) | 2014-11-27 |
WO2014182693A1 (en) | 2014-11-13 |
ZA201508100B (en) | 2017-05-31 |
CN104350010A (en) | 2015-02-11 |
CA2911246A1 (en) | 2014-11-13 |
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