EP3523246A1 - Method for manufacturing crystals of aluminate of at least one metal and/or one metalloid and/or one lanthanide, and applications of same - Google Patents
Method for manufacturing crystals of aluminate of at least one metal and/or one metalloid and/or one lanthanide, and applications of sameInfo
- Publication number
- EP3523246A1 EP3523246A1 EP17786983.1A EP17786983A EP3523246A1 EP 3523246 A1 EP3523246 A1 EP 3523246A1 EP 17786983 A EP17786983 A EP 17786983A EP 3523246 A1 EP3523246 A1 EP 3523246A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- precursor
- aluminate
- crystals
- suspension
- starting
- 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.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 145
- 238000000034 method Methods 0.000 title claims abstract description 97
- 150000004645 aluminates Chemical class 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- 229910052747 lanthanoid Inorganic materials 0.000 title claims abstract description 12
- 150000002602 lanthanoids Chemical class 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 title claims abstract description 12
- 229910052752 metalloid Inorganic materials 0.000 title claims abstract description 12
- 150000002738 metalloids Chemical class 0.000 title claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 100
- 238000001354 calcination Methods 0.000 claims abstract description 88
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 58
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 70
- 239000011325 microbead Substances 0.000 claims description 64
- 230000008569 process Effects 0.000 claims description 58
- 238000000227 grinding Methods 0.000 claims description 44
- -1 manganese aluminate Chemical class 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 239000012141 concentrate Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910001679 gibbsite Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 2
- 229910016583 MnAl Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910004116 SrO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract 2
- 238000003801 milling Methods 0.000 abstract 1
- 239000002609 medium Substances 0.000 description 28
- 238000001228 spectrum Methods 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 15
- 239000005084 Strontium aluminate Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 13
- 239000011324 bead Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 7
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 229910052729 chemical element Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000010669 acid-base reaction Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910020068 MgAl Inorganic materials 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 229910015999 BaAl Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910003668 SrAl Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 239000011872 intimate mixture Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000000133 mechanosynthesis reaction Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- CBVWMGCJNPPAAR-HJWRWDBZSA-N (nz)-n-(5-methylheptan-3-ylidene)hydroxylamine Chemical compound CCC(C)C\C(CC)=N/O CBVWMGCJNPPAAR-HJWRWDBZSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910017414 LaAl Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229940104825 bismuth aluminate Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PDSAKIXGSONUIX-UHFFFAOYSA-N hexaaluminum;dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Bi+3].[Bi+3] PDSAKIXGSONUIX-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/162—Magnesium aluminates
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/31—Density
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/51—Spheres
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/164—Calcium aluminates
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/166—Strontium aluminates
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/168—Barium aluminates
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- C09K11/0838—Aluminates; Silicates
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- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Definitions
- the present invention relates to a method for producing aluminate crystals of at least one metal and / or one metalloid and / or one lanthanide.
- the present invention relates to a process for manufacturing crystals of these various aluminates, in particular implementing a micromilling step in a three-dimensional microbead mill in a liquid medium (generally water) produced in a very short time and without heating.
- This micromilling step also makes it possible to facilitate a possible calcination step that can be performed later.
- the crystals obtained by the abovementioned process can be used to manufacture: luminescent materials in the ultraviolet range, catalysts, in particular for the synthesis of biofuels, photocatalytic materials, photoluminescent materials, dielectric ceramics, or even materials. transparent resistant.
- the preparation of aluminate crystals by chemical means consists first of all in preparing the starting reagents, in mixing them as homogeneously as possible and in calcining the mixture thus obtained so as to carry out the combination reaction.
- the mixture of the raw materials can be carried out dry.
- the imperfect homogeneity of the mixture is compensated by long-term calcination, of the order of several hours and at high temperature (often exceeding 1200 ° C.) in order to give the time necessary to carry out the reaction by solid diffusion.
- the end product is usually not completely transformed. It is then necessary to carry out one or more additional calcination cycles before arriving at a sufficiently pure final product.
- the mixture of the raw materials can also be carried out in liquid medium (aqueous solution), in order to give, after drying, a more homogeneous powder which will then be heated several times at high temperature, and for very long periods of time (sometimes requiring three stages of heating, for a total heating time of more than 200 ° C up to 13h).
- liquid medium aqueous solution
- Sol-Gel In order to further improve the homogeneity of the mixture comprising the starting reagents, many authors use the "Sol-Gel” method. This method consists in preparing an alcoholic solution, for example in isopropanol, aluminum isopropoxide and the salt of the other chemical element, and in gelling it before calcining it.
- J. Kanakova describes in his publication “Preparation and structural investigations of sol-gel derived Eu3 + -doped CaAI204" published in the Journal of Physics and Chemistry of Solids 65 (2007), the preparation of aluminum aluminate crystals. calcium.
- Another approach is thus to prepare the aluminate crystals of another element and in particular the mixing step mentioned above, by mechano-synthesis.
- This method consists of generally dry milling (non-liquid medium) starting reagents in the form of powder in a bowl, steel or agate, with balls whose diameter is generally of the order of 10 mm and at then carry out a calcination step.
- the object of the present invention is, therefore, to provide a new aluminate manufacturing process of at least one other element avoiding, at least in part, the aforementioned drawbacks.
- the object of the present invention is to propose a new process for manufacturing crystals of different aluminates that is simple to implement and industrially exploitable (that is, does not require a number of high stages), while decreasing the time requiring special heating, and not requiring special pressurization.
- the subject of the present invention is a process for producing aluminate crystals (hydrated or otherwise) of one or more element (s) other than aluminum (Al), noted " A "independently selected from a metal, a metalloid or a lanthanide, said method comprising at least the following steps:
- starting reagents comprising at least: a source of the aluminum element and a source of said element or elements A which has a degree of oxidation ranging from 1 to 6, in a liquid medium, such as water, so as to form a suspension called "starting suspension", the mass concentration of starting reagents being between 10 g / l and 1000 g / l, preferably between 50 g / l and 800 g / l, and especially between 100g / L and 600g / L;
- step (3) optionally, drying or concentrating the final suspension obtained at the end of step (3), so as to obtain a powder or a concentrate comprising, respectively, said starting reagents in the form of activated or said crystals, generally in hydrated form, of aluminate of said element (s)
- a powder or a concentrate comprising, respectively, said starting reagents in the form of activated or said crystals, generally in hydrated form, of aluminate of said element (s)
- the starting suspension comprises at least two starting reagents. Therefore, the source of the aluminum element and the source of said element or elements A are distinct.
- these starting reagents for obtaining aluminate crystals (hydrated or not) of one or more element (s) A are non-nanometric and non-heat-sensitive.
- an ambient temperature of less than or equal to 50 ° C comprises the following values: 50; 49; 48; 47; 46; 45; 44; 43; 42; 41; 40; 39; 38; 37; 36; 35; 34; 33; 32; 31; 30 ; 29; 28; 27; 26; 25; 24; 23; 22; 21; 20; 1 9; 18; 17; 16; 15; 14; 13; 12; 1 1; 10; etc. or any intervals between these values.
- a residence time less than or equal to 5 min comprises the following values: 5 min; 4 min; 3 min; 2 min ; 1 min; 55 sec; 50 sec; 45 sec; 40 sec; 35 sec; 30 sec; 25 sec; 20 sec; 15 sec; 10 sec; 5 sec; etc. or any intervals between these values.
- the calcination step (5) is carried out at a temperature of between 400 ° C. and 1700 ° C., preferably between 500 ° and 1500 ° C., and in particular between 700 ° C. and 1200 ° C. for a period of time ranging from preferably from 15 minutes to 3 hours, in particular from 30 minutes to 1 hour 30 minutes and typically from 30 minutes to 1 hour.
- the temperatures between 400 and 1700 ° C includes, according to the invention, the following temperatures and any interval between these values: 400, 450, 500, 550, 600, 650, 700, 750, 800, 850 , 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700 ° C.
- the mass concentration of the starting reagents corresponds to the mass of the source of the aluminum element + the mass of the source of said chemical element (s) A on the volume of the liquid medium.
- the final suspension comprises starting reagents in activated form when these are insoluble in the liquid medium.
- the final suspension preferably comprises said aluminate crystals of said element (s) A being generally in hydrated form when the starting reagents are at least partially soluble in water.
- the source of the aluminum element has a +3 oxidation state.
- the indication of a range of values "from X to Y" or “between X and Y” in the present invention means as also including the X and Y values.
- the sign " ⁇ ” means strictly inferior and the sign ">” means strictly superior, while the sign " ⁇ " and “>” respectively means “less than or equal to” and " greater than or equal to ".
- the aluminate crystals of one or more element (s) A obtained, preferably after calcination of the aforementioned process, can be used to manufacture luminescent materials in the range of ultraviolet, catalysts, in particular for the synthesis of biofuels photocalytic materials, photoluminescent materials, dielectric ceramics, or resistant transparent materials.
- FIG. 1 represents a sectional view along the longitudinal axis XX of a three-dimensional microbead mill in a liquid phase, according to an alternative embodiment suitable for implementing the method according to the invention
- FIG. 2 represents sectional views along the axis XX and the axis AA, of liquid-phase three-dimensional microbead grinder variants according to FIG. 1 in which: (a) the agitator is in disks, (b) agitator has fingers and (c) the grinding chamber is annular;
- FIG. 3 is an X-ray diffractometry (XRD) spectrum of zinc aluminate crystals obtained according to the method of the invention, using the following parameters: starting suspension comprising 150 g / l of raw materials Al (OH) 3 Sigma Aldrich + ZnO, a flow rate of the feed suspension in the mill of 30L / h, a bead diameter of 500 ⁇ and a calcination temperature of 650 ° C for 1 hour; FIG.
- XRD X-ray diffractometry
- XRD X-ray diffractometry
- FIG. 5 is an X-ray diffractometry (XRD) spectrum of calcium aluminate crystals obtained according to the method of the invention, using the following parameters: starting slurry comprising 150 g / l of raw materials Al (OH) 3 Sigma Aldrich + CaC0 3 , a flow rate of the feed suspension in the mill of 30L / h, a bead diameter of 500 ⁇ and a calcination temperature is 1050 ° C for 1 hour;
- FIG. 6 is an X-ray diffractometry (XRD) spectrum of barium aluminate crystals obtained according to the process of the invention, using the following parameters: starting suspension comprising 300 g / l of raw materials Al (OH) 3 Sigma Aldrich + BaO 2 , a flow rate of the starting slurry in the mill of 30L / h, a bead diameter of 500 ⁇ and a calcination temperature is 1050 ° C. for 1 hour;
- FIG. 7 is an X-ray diffractometry (XRD) spectrum of strontium aluminate crystals obtained according to the process of the invention, using the following parameters: starting slurry comprising 300 g / l of raw materials AI (OH) 3 SH300 + Sr (OH) 2 -8H 2 0, a flow rate of the starting suspension in the mill of 30L / h and a bead diameter of 500 ⁇ . ;
- FIG. 8 is an X-ray diffractometry (XRD) spectrum of strontium aluminate crystals obtained according to the method of the invention, using the following parameters: starting suspension comprising 300 g / l of raw materials Al (OH) 3 SH300 + Sr (OH) 2 -8H 2 0, a flow rate of the starting slurry in the mill of 30L / h, a bead diameter of 500 ⁇ and a calcination temperature of 950 ° C for 1 hour.
- XRD X-ray diffractometry
- the Applicant has focused on the development of a new process for the production of aluminate crystals of one or more chemical element (s) other than aluminum (Al), noted “A” adapted to be implemented on an industrial scale and simple to implement.
- s chemical element
- Al aluminum
- the other element (s) (noted for example Ai, A 2 , A n ) suitable for the process of the invention are independently selected from a metal, a metalloid or a lanthanide.
- the process according to the invention makes it possible to manufacture aluminate crystals only from an element A.
- the crystals thus obtained (after calcination) can correspond to the following general formula: Al x A y OH z , with 0 ⁇ x ⁇ 1; 0 ⁇ y ⁇ 1 and 0 ⁇ z ⁇ 1 and can correspond to the crystals of formulas: MgAl 2 O 4 , CaAl 4 O 7 , LiAl 2 O 5 , etc.
- the method according to the invention makes it possible to manufacture aluminate crystals of several elements A, denoted "A1", “A2", “An”, etc.
- the crystals thus obtained may for example satisfy the following general formula: A1 V (Al x A2 W ) 0 3 , with 0 ⁇ x ⁇ 1; 0 ⁇ v ⁇ 1 and 0 ⁇ w ⁇ 1.
- crystals can be obtained according to the process of the invention after calcination: Sr (AI1 ⁇ 2Nb1 ⁇ 2) 0 3 , Ca (AI1 ⁇ 2Nb1 ⁇ 2) 0 3 or Sr (Al1 ⁇ 2Ta1 ⁇ 2) 0 3 .
- the method according to the invention makes it possible to manufacture aluminate crystals only of an element A.
- the method for manufacturing the aluminate crystals of said element (s) "A” comprises at least the following steps:
- starting suspension suspending at least one source of the aluminum element which preferably has a +3 oxidation state and at least one source of said element or elements A which has a degree of oxidation ranging from 1 to 6, in a liquid medium, such as water, so as to form a suspension called "starting suspension", the mass concentration of starting reactants being between 10 g / L and 1000 g / L, preferably between 50g / L and 800g / L, and particularly between 100g / L and 600g / L;
- final suspension comprising, depending on the nature of the starting reagents and the liquid medium, said starting reagents in activated form or aluminate crystals of said said A element (s) generally being in hydrated form;
- step (3) optionally, drying or concentrating the final suspension obtained at the end of step (3), so as to obtain a powder or a concentrate comprising, respectively, said starting reagents in activated form, or
- said crystals generally in hydrated form, of aluminate of said element (s) A;
- step (3) the calcination of said final suspension obtained at the end of step (3) when it comprises said starting reagents in activated form, or of the powder or concentrate obtained at the end of step (4) when (it) comprises said starting reagents in activated form, so as to obtain crystals, generally non-hydrated, of aluminate of said element (s) A.
- aluminate crystals of the element A or elements directly at the end of the process.
- grinding step (3) namely in a single step not requiring special heating and in a very short time (in general, a single passage in the grinder is sufficient).
- This first variant is in particular carried out when the starting reagents are at least partially soluble in the liquid medium and they are furthermore capable of performing an acid-base reaction.
- the Applicant has discovered that when an acid-base reaction can take place in the three-dimensional micro-bead mill, then there was formation of crystals from the grinding step (3) and that it was therefore not necessary to carry out a calcination step in order to obtain aluminate crystals.
- this first variant can be implemented when the source of the element A or elements has a basic character and is, for example, in the form of hydroxide and the liquid medium is water.
- the source of the aluminum element such as Al (OH) 3 will react in water with the source of the element A in the form of hydroxide and thus allow a synthesis reaction of the crystals of aluminate during the grinding step.
- the final suspension resulting from step (3) comprises aluminate crystals or elements A, including crystals in hydrated form.
- step (3) of said final suspension obtained at the end of step (3) when it comprises said aluminate crystals of said element (s) A in hydrated form or,
- this calcination step (5) not required to obtain crystals according to this first embodiment, however, allows to obtain aluminate crystals or elements A in non-hydrated form.
- aluminate crystals are not obtained directly after step (3). ); a calcination step is then necessary in order to finish the combination reaction aluminum + element (s) A in the form of crystals.
- the starting reagents have been mixed so intensely that they are said to be "activated", ie the source of the aluminum element is mixed with very homogeneous and intimate way with the source of the element A.
- the grinding in the three-dimensional microbead mill according to the invention would cause a change in the surface of the starting reagents, or even disorders in the crystal lattice or crystal defects.
- the Applicant has discovered that when the starting reagents are in "activated” form, it facilitates the subsequent calcination step. It has indeed been found that the calcination step required to obtain aluminate crystals (for this embodiment) was shorter and did not require as high a temperature as the calcination steps described in the drawings. processes of the prior art.
- the starting reagents are in "activated" form at the end of the step grinding mill (3) according to the invention.
- the calcination step (5) is carried out at a temperature of between 400 ° C. and 1700 ° C., preferably between 500 ° and 1500 ° C., and in particular between 700 ° C. and 1200 ° C. for a period of time ranging from preferably from 15 minutes to 3 hours and in particular from 30 minutes to 1 hour 30 minutes.
- the Applicant has developed a general method which, unexpectedly, makes it possible to manufacture aluminate crystals of one or more elements A (preferably an element A) in a very short time (reaction time inferior or equal to 15 minutes and in general, less than or equal to 1 minute), in only one or two stages (grinding step followed, if necessary a calcination step).
- the first grinding stage is in particular carried out at room temperature (the process does not require a particular heating step before proceeding with the calcination), and this with energy and water (liquid medium) consumptions minimum (non-polluting), with excellent performance.
- the process of the invention also makes it possible to obtain, surprisingly, aluminate crystals of excellent quality, namely very pure and of fine and well-controlled particle size.
- the method according to the invention also has the advantages of having a very low cost (the raw materials used are indeed widely available, non-polluting and inexpensive) and to have excellent reproducibility, which makes it more unique processes described in the prior arts.
- the method according to the invention also has the advantage of being able to be implemented continuously. However, these characteristics are important for an application on an industrial scale.
- a degree of oxidation ranging from 1 to 6 comprises the following values: 1; 2; 3; 4; 5; 6 and any intervals between these values.
- obtaining aluminate has many industrial applications.
- the use of zinc aluminate is at the origin of many applications in the field of catalysis, particularly as a catalyst for the synthesis of biodiesel, but also photocatalysis (to degrade some organic pollutants such as toluene), or as a semiconductor material.
- photocatalysis to degrade some organic pollutants such as toluene
- a three-dimensional microbead mill capable of obtaining an intimate mixture and A homogeneous suspension of aluminate crystals of said element (s) A will firstly be described below with reference to FIGS. 1 and 2.
- a three-dimensional micro-bead mill 1 comprises at least:
- a stationary grinding chamber 2 of generally cylindrical shape extending along a longitudinal axis XX, said chamber 2 being at least partially filled with said microbeads (not shown) and comprises: at a first end 3 at least one inlet 5 for introducing said starting suspension, and at a second end 4, an outlet 6 having a separating means 7 adapted to evacuate the suspension formed in said chamber 2; and
- an agitator 8 disposed in the stationary grinding chamber 2, in the form of an elongated rod along the longitudinal axis XX, said stirrer 8 being able to set in motion the microbeads / starting suspension assembly.
- the inlet 5 is generally connected to a peristaltic pump (not shown).
- This pump makes it possible to bring the initial suspension, for example contained in a container, such as a tank, inside the grinding chamber 2 via the inlet 5.
- the pump also allows, during the operation of the three-dimensional crusher, to bring this starting suspension according to a certain flow rate that is adjustable, hereinafter called "flow rate”.
- flow rate further forms a current in the grinding chamber 2 for driving the starting suspension from the inlet 5 to the outlet 6.
- the outlet 6 of the grinding chamber 2 comprises in particular the separation system 7 of the microspheres of the final suspension comprising an intimate and homogeneous mixture of the raw materials.
- This separation means 7 may be a sieve whose orifices have a smaller dimension than that of the microbeads or a separation slot whose width is also adapted to retain the microbeads within the chamber 2.
- the inner wall 9 of the grinding chamber 2 comprises, according to a first embodiment, a smooth internal surface. However, according to an alternative embodiment that will be described below, it can be arranged on the inner surface 9 fingers 1 1.
- stirrer 8 which, in addition to the flow rate, also allows the start of movement of the suspension.
- the agitator 8 is able to rotate about the X axis via a rotary shaft (14, FIG. 2) to impart a vortex movement to the starting suspension within the grinding chamber 2 and thereby perform a stirring intense between this starting suspension and the microbeads present in the chamber 2 along the inner wall 9 of this chamber 2.
- the mill via its rotary shaft 14 has a rotation speed greater than or equal to 100 revolutions per minute, advantageously greater than or equal to 1000 revolutions per minute (rpm), preferably greater than or equal to 2000 revolutions per minute and typically greater than or equal to 2500 rpm.
- 100 “includes the following values: 100; 150; 200; 250; 300; 350; 400; 450, 500; 550; 600; 650, 700; 750; 800; 850; 900, 950, 1000 rpm) includes the following values: 1000; 1,100; 1200; 1300; 1400; 1500; 1600; 1700; 1800; 1900; 2000; 2100; 2200; 2300; 2400; 2500; 2600; 2700; 2800; 2900; 3000; 3100; 3200; 3300; 3400; 3500; 3600; 3700; 3800; 3900; 4000, 4500; 5000; 5500; 6000; etc., or any intervals between these values.
- the mill has a rotation speed ranging from 1000 rpm to 5000 rpm, in particular from 1500 rpm to 4500 rpm, preferably from 2000 rpm to 4000 rpm and typically from 2800 to 3200 rpm.
- stirrer 8 just like the internal wall 9 of the chamber 2, can have various possible configurations represented for example in FIG. 2.
- the stirrer 8 comprises, along its elongated rod, disks 10, arranged perpendicular thereto. Their number can vary from 2 to 8, preferably from 2 to 5. These discs 10 allow on the one hand, to improve the grinding of the starting suspension by stirring the microbeads further and on the other hand, to accelerate the reaction time.
- the stirrer 8 may also comprise along its stem one or more perpendicularly arranged disks 10 which are furthermore capable of cooperating with fingers 1 1 arranged perpendicularly with respect to the internal wall 9 of the chamber 2.
- a finger is in particular in the form of a ring which extends perpendicularly from the wall 9.
- the disks 10 and the fingers 1 1 are arranged in staggered rows, namely the disks 10 and the fingers 1 1 are alternately arranged in the chamber 2.
- the thickness of the rod 8 is increased relative to the previous configuration ( Figure 2a) so that the periphery of the disks 10 is close to the inner wall 9 and that the fingers 1 1 is close to the periphery of the rod of the agitator 8.
- the volume of the chamber is reduced compared to the configuration therefore, a better mixing between the starting suspension, the microbeads and the inner wall 9 of the chamber 2.
- the volume of the chamber 2 can be further reduced as shown in FIG. 2c.
- the agitator 8 has an external diameter slightly smaller than the internal diameter of the chamber 2, thus forming an annular chamber 12 of small volume disposed between the outer wall of the stirrer 8 and the inner wall 9 of the chamber 2.
- the microbeads (not shown) are arranged in this annular chamber 12.
- the starting suspension is introduced by the inlet 5 with a certain flow, which will then go through the annular chamber 12 to the outlet 6 while being brewed by the microbeads.
- the mill suitable for carrying out the process according to the invention comprises a grinding chamber having a diameter of 75 mm to 300 mm for a length of 80 mm to 900 mm and an agitator having a size ranging from 65 mm to 260 mm.
- the volume of the grinding chamber varies from 0.35 L to 600 L, preferably from 0.35 L to 400 L, and typically from 0.35 L to 62 L.
- a volume of the grinding chamber ranging from 0.35 L to 600 L comprises the following values: 0.35; 0.5; 0.8; 1; 2; 3; 4; 5; 6; 7; 8; 9; 10; 15; 20; 25; 30 ; 35; 40; 45; 50; 55; 60; 65; 70; 80; 85; 90, 100; 1 10; 120; 130; 140; 150; 160; 170; 180; 190; 200; 210; 220; 230; 240; 250; 260; 270; 280; 290; 300; 350; 400; 450; 500; 550; 600, etc., or any interval between these values.
- the geometry of the grinding chamber and the stirrer may be adjusted by those skilled in the art depending on the amount of reactants initially introduced, as well as the desired reaction time.
- the grinding chamber 2 comprises an accelerator to improve the grinding of the starting suspension.
- the microbeads housed in the grinding chamber 2 and suitable for the process according to the invention are substantially spherical in shape and have an average diameter of less than or equal to 5 mm, generally ranging from 0.05 mm to 4 mm, of preferably from 0.2 to 3 mm, in particular from 0.3 to 2 mm, and typically of the order of 0.5 to 1 mm.
- the diameter of the microbeads is less than or equal to 1 mm and is typically of the order of 0.05 mm to 1 mm.
- microbeads having a high hardness and relatively resistant to abrasion.
- the microbeads have a Vickers hardness measured according to the EN ISO 6507-1 standard greater than or equal to 900 HV1, preferably ranging from 900 HV1 to 1600 HV1, typically ranging from 1000 to 1400 HV1 and especially from the order of 0.05 mm to 1 mm.
- a Vickers hardness greater than or equal to 900 HV1 comprises the following values: 900; 910; 920; 930; 940; 950; 960; 970; 980; 990; 1000; 1010; 1020; 1030; 1040; 1050; 1060; 1070; 1080; 1090; 1000; 1 1 10; 1120; 1,130; 1,140; 1,150; 1,160; 1,170; 1,180; 1,190; 1200; 1300; 1400; 1500; 1600; 1700; etc., or any intervals between these values.
- they have a high real density.
- the microbeads according to the invention have a real density greater than or equal to 2 g / cm 3 , in particular ranging from 2 to 15 g / cm 3 , preferably from 3 to 12 g / cm 3 , and typically from 4 to at 10 g / cm 3 .
- the microbeads according to the invention may be ceramic microspheres, (zirconium oxide Zr0 2 , zirconium silicate ZrSiO 4 ); steel microbeads, tungsten carbide microbeads, glass microbeads or a combination thereof.
- the microbeads are ceramic because they do not generate pollution by their wear.
- the microbeads are made of zirconium oxide.
- the zirconium oxide microbeads may be stabilized by another oxide, such as cerium oxide, yttrium oxide and / or silicon.
- compositions are suitable for forming the microbeads according to the invention:
- microbeads suitable for the process of the invention are not glass or exclusively glass.
- the microbeads represent, in volume, relative to the total volume of the stationary chamber 2 from 50% to 85%, preferably from 55% to 70%.
- a volume of 50 to 85% comprises the following values: 50; 55; 60; 65; 70; 75; 80; 85; etc., or any intervals between these values.
- the three-dimensional wet-phase microbead mill suitable for carrying out the process according to the invention may correspond to grinders marketed by the WAB companies, Dyno-Mill range: Multi Lab, ECM and KD, NETZCH Company, by example LABSTAR LS1, or Alpine Hosokawa, for example, Agitated Media Mill AHM.
- Dyno-Mill range Multi Lab
- ECM and KD NETZCH Company
- LABSTAR LS1 LABSTAR LS1
- Alpine Hosokawa for example, Agitated Media Mill AHM.
- the manufacture of aluminate crystals of one or more element (s) A comprises firstly (1) a step of suspending starting reagents.
- the latter comprise at least: an aluminum source typically having a +3 oxidation state and at least one source of said element or elements A, preferably of said element A, having an oxidation degree ranging from +1 to +6 .
- the suspension obtained is hereinafter referred to as "suspension of departure".
- the starting suspension is conventionally prepared by mixing the starting reagents with the liquid medium in a suitable device, such as a vessel or tank, equipped with a stirring system (such as a magnetic stirrer, stirring blades). agitation, etc.).
- a suitable device such as a vessel or tank, equipped with a stirring system (such as a magnetic stirrer, stirring blades). agitation, etc.).
- the device and the stirring system may be adapted by the skilled person depending on the amount of different aluminate crystals or elements A to be manufactured.
- the liquid medium may be chemically inert or not.
- the liquid medium such as water (H 2 0) may react with the starting reagents and in particular the source of the element A or elements having a basic character (if it is for example in the form of a hydroxide) and form an acid-base reaction with the source of the aluminum element (such as Al 2 O 3 or AI (OH) 3 ).
- the liquid medium is chemically inert, ie it does not react with the aluminum source and the source of the element (s) A.
- the liquid medium will generally be water (H 2 0).
- the liquid medium may also correspond to an organic solvent, such as methanol or isopropanol.
- this step (1) is carried out in a large excess of liquid medium (water).
- the mass concentration of starting reagents is between 10 g / l and 1000 g / l, preferably between 50 g / l and 800 g / l, and particularly between 100g / L and 600g / L.
- This excess of liquid medium makes it possible in particular to improve the synthesis of the aluminate crystals of the element (s) A (first variant) or to improve the activation of the starting reagents within the mill by allowing an intense mixing (second variant of production). Indeed, an excess of liquid medium promotes the movement of the microspheres of the mill for better grinding of the starting slurry and therefore a better synthesis of aluminate crystals or elements A or a better mixture.
- the source of the aluminum element and the source of the element (s) A are mixed in the starting slurry in stoichiometric proportion. It is of course possible to deviate substantially from this stoichiometric proportion if, for example, a composition containing an excess of one of the reactants is desired and come within the scope of the process of the invention.
- the molar ratio (Al): (the element or elements A) ranges from 0.001 to 10, in particular it varies from 0.01 to 5.
- the source of the aluminum element generally having a +3 oxidation state may be chosen from one or more of the following compounds: gibbsite (AI ((OH) 3 ), boehmite AIO (OH) alumina (Al 2 O 3 ), such as ⁇ - ⁇ 2 0 3 (corundum), a precursor thereof or a mixture thereof.
- the source of the aluminum element is chosen from: AI (OH) 3 or ⁇ - ⁇ 2 0 3 or a mixture thereof.
- the source of said element (s) A is in the form of an oxide, a dioxide, a peroxide, a hydroxide, a di- or trihydroxide, a hydroxide oxide, carbonate, or a precursor thereof.
- the element or elements A are independently selected from a metal, a metalloid or a lanthanide, "A" being however different from aluminum.
- Said element (s) A may be chosen in particular from:
- alkali metals lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs);
- alkaline earth metals beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba); the following transition metals: titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), cadmium (Cd), hafnium (Hf), tantalum (Ta);
- Be beryllium
- Mg magnesium
- Ca calcium
- Ba barium
- transition metals titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo),
- metalloids boron (B), silicon (Si);
- lanthanum lanthanum
- the element (s) A are chosen independently from: Ba, Ca,
- Fe Li, Mg, Zn, Zr.
- Ba, Ca, Li, Mg, Zn are preferred.
- the source of the element (s) A may be chosen from:
- LiOH, U2CO 3 or one of their precursors so in particular to obtain, after calcination, lithium aluminate crystals, for example of formulas:
- magnesium aluminate crystals for example formulas: MgAl 2 O 4 ;
- ZnO, ZnO 2 , Zn (OH) 2 , ZnCO 3 or one of their precursors so as to obtain, in particular after calcination, zinc aluminate crystals corresponding, for example, to the formula ZnAl 2 O 4 ;
- Y 2 0 3 or one of their precursors so as to obtain, in particular after calcination, yttrium aluminate crystals corresponding, for example, to the formula Y 3 Al 5 O 12 ;
- TaAI 2 0 4 a precursor thereof, so in particular to obtain after calcination of tantalum aluminate crystals, for example of formula TaAI 2 0 4 ;
- Ga (OH) 3 Ga 2 0 3 or a precursor thereof, so in particular to obtain after calcination of gallium aluminate crystals, for example of formula GaAl 2 0 4 ;
- Si0 2 , H 2 SiO 3 or one of their precursors so in particular to obtain, after calcination, silicon aluminate crystals, for example of formula:
- precursor means any chemical compound, which in contact with water, moisture and / or air (C0 2 , etc.) can synthesize the aforementioned compounds.
- Li 2 O 2 peroxide
- the precursors thus include, for example, the following compounds: Li 2 O / Li 2 O 2 / Na 2 O 2 MgO 2 , CaO 2 , etc.
- the sources of aluminum and element A or elements are in the form of powder.
- the alpha aluminum oxide suitable for the present invention is also in powder form and generally has a particle size of less than or equal to 100 ⁇ and preferably less than or equal to 10 ⁇ , and in particular the particle size ranges from 0.01 ⁇ to 1 ⁇ .
- the aluminum oxide of CAS number: 1344-28-1 and marketed for example by the company Baikowski under the reference BA15, having a purity of 100% in the alpha phase, is suitable for carrying out the process of the invention.
- the source of the element A or elements is also in the form of powder.
- the particle size is less than or equal to 100 ⁇ , preferably less than or equal to 50 ⁇ and advantageously less than or equal to 20 ⁇ as ranging from 0.01 ⁇ to 20 ⁇ .
- the source of element A it is not necessary for the source of element A to be at the nanoscale.
- the magnesium hydroxide that is suitable for the present invention preferably has a particle size of less than or equal to 100 ⁇ and preferably less than or equal to 50 ⁇ , such as less than or equal to 30 ⁇ , and in particular the size of the particles. particles can range from 0.01 ⁇ to 20 ⁇ .
- Toplus Inc. of purity greater than or equal to 99%, is suitable for carrying out the process of the invention.
- the aluminum source and the source of the element (s) A have a high purity, in general greater than or equal to 90%, in particular greater than or equal to 95% and typically greater than or equal to 99%, or even greater than or equal to equal to 99.9%.
- the initial suspension is prepared, it is brought to the three-dimensional micro-bead mill 1 generally via the adjustable-rate peristaltic pump via the inlet 5.
- the peristaltic pump makes it possible to continue the mixing of the suspension before entering the chamber 2.
- this pump allows to introduce the starting suspension into the chamber
- the starting suspension is introduced at a flow rate greater than or equal to 10 L / h.
- a flow rate greater than or equal to 10 L / h comprises the following values: 10 L / h; L / h; 20 L / h; L / h; L / hr; L / h; 40 L / h;
- the starting suspension is introduced at a flow rate ranging from 10 to 130 L / h, preferably from 20 to 100 L / h and typically from 30 to 90 L / h.
- the flow rates may vary depending on the size of the three-dimensional micro-bead mill used to carry out the process.
- the flow rate may be of the order of 40 to 150L / h, such as about 45 L / h; while for larger mills having in particular a stationary chamber 2 of 60L, the flow rate may be of the order of 2 to 15 m 3 / h, such as about 4 m 3 / h.
- the grinding step (2) begins.
- the starting suspension traverses the stationary chamber 2 of the inlet 5 to the outlet 6, while being set in motion by the stirrer 8 which allows intense mixing of this suspension with the microbeads and, if necessary, with the disks 10, the fingers 1 1, etc., along the inner wall 9 of the chamber 2.
- the rotational speed of the stirrer may for example vary from 4 to 20 pi rad / s, preferably from 4 to 8 pi rad / s.
- a rotation speed ranging from 4 to 20 pi rad / s comprises the following values: 20; 19; 18; 17; 16; 15; 14; 13; 12; 1 1; 10; 9; 8; 7; 6; 5; 4 and any intervals between these values.
- the residence time of the starting suspension is less than or equal to 5 min, preferably less than or equal to 1 minute, and in particular in the mill from 1 to 25 seconds and in particular from 5 to 20 seconds, such as from 5 to 20 seconds. at 15 seconds. It is in fact inherent to the apparent volume of the balls and the flow of passage.
- the residence time of the suspension in the chamber 2 is estimated at about 1 1 seconds. Therefore, the residence time can be advantageously adjusted, for example by controlling the apparent density of the microbeads, as well as the flow rate.
- Appendix volume is meant the volume of microbeads including interstitial air between the beads. Bulk density is the ratio of microbead mass to apparent volume.
- more or less fine crystals can be obtained. For example, a finer grinding can be obtained if the flow rate of the starting suspension is slowed down.
- the grinding step can be carried out in continuous mode or discontinuous mode in one or more passes (pendulum or recirculation mode).
- the number of passages of the so-called initial suspension may be from 1 to 10, preferably from 1 to 5 (ie, after a first pass, the suspension is recovered at the outlet 6 and reinjects it again, thanks to the pump, into the chamber 2 via the inlet 5 to allow a second passage).
- the number of passages of the starting suspension is 1.
- this grinding step will preferably be performed in continuous mode.
- this grinding step takes place at an ambient temperature of less than or equal to 50 ° C., that is to say, most often at an ambient temperature ranging from 15 ° C. to 45 ° C., in particular from 18 ° C. to 35 ° C., and in general is of the order of 20 ° C to 25 ° C.
- the starting / starting suspension reagents are introduced into the mill at room temperature (generally around 20-25 ° C.).
- room temperature generally around 20-25 ° C.
- an exothermic reaction may take place during this grinding stage and the temperature rises slightly (generally the outlet temperature of the mill is less than or equal to 50 ° C. VS).
- this step according to the invention does not require any particular heating in order to obtain, either at the end of the recovery step (3), or at the end of the calcination step (5), aluminate crystals.
- step 2 either the starting reagents in activated form (second variant embodiment).
- the micro grinding performed in step 2 allows the starting reagents to be activated, which will allow subsequently to facilitate the calcination step (5) and thus the synthesis of the crystals during this last step.
- said final suspension described above is concentrated or dried (4), so as to respectively obtain a powder or a concentrate of (usually hydrated) crystals of aluminate of said one or more element (s) A or a powder or a concentrate of starting reagents in activated form.
- the final suspension can be dried in the open air.
- the final suspension may be dried by steaming or by calcination, such as at a temperature of 100 to 400 ° C for 1 to 4 hours.
- the dried or concentrated product is generally stored until used as an aqueous paste or mixed with a solvent. It can also be dried and stored in a sealed container.
- the final suspension recovered after step (3) or the powder or concentrate recovered after step (4) is placed in crucibles, which may be porcelain or alumina, and then calcined (5) in an oven, for example a stationary oven or a passage oven.
- This calcination step generally takes place at a temperature of between 400 ° C. and 1700 ° C., preferably between 500 ° C. and 1500 ° C., and particularly between 600 ° C. and 1250 ° C .; for a period of time for example between 30 minutes and 4 hours, preferably between 30 minutes and 1 hour 30 minutes.
- calcination temperatures for the elements A below may be as follows (indicative data):
- the calcination temperature according to the nature of the element A and the crystals which it wishes to manufacture. Also, the minimum temperature is given as an indication, and will depend on the type of calcination furnace, or the presence of moisture during calcination.
- the calcination of said final suspension obtained at the end of step (3) when this latter comprises said aluminate crystals of said element (s) in hydrated form or the powder or concentrate obtained at the end of step (4) when it comprises said aluminate crystals of said one or more (S) elements in hydrated form allows to form non-hydrated crystals of aluminate of said element (s) A.
- the calcination of said final suspension obtained at the end of step (3) when it comprises said starting reagents in activated form, or of the powder or concentrate obtained (e.g. ) at the end of step (4) when it comprises said starting reagents in activated form makes it possible to form crystals, generally non-hydrated, of aluminate of said element (s) A.
- the present invention also relates to the use of aluminate crystals of said element or elements A obtained according to the process for producing luminescent materials in the ultraviolet range, catalysts, in particular for the synthesis of biofuels, photocatalytic materials, photoluminescent materials, dielectric ceramics, or resistant transparent materials.
- X-ray diffractometry (XRD) spectra were collected with a D8 ADVANCE Series II diffractometer sold by Bruker using CuKal radiation (0.15406 nm) according to the Bragg-Brentano configuration.
- the detector used is a LynxEye 1 D detector from Bruker.
- the opening angle of the detector is 3 ° (150 bands).
- the XRD measurements were performed between 10 ° and 140 ° (at 2 ° scale) with a step of 0.008 ° (1 s / step).
- microbeads are made of zirconium oxide and have a diameter of 0.5 mm.
- the characteristics of the microbeads used for the tests are summarized in Table 3 below: 500 ⁇ beads
- Microbeads of 500 ⁇ are marketed under the brand name Zirmil® Y Ceramic Beads by Saint-Gobain.
- the crushing chamber of the mill has a capacity of 309 ml and is filled, by volume, relative to its total volume and depending on the tests, 80% of the microbeads described above.
- the microbeads are agitated by an agitator at a rotation speed of 2890 rpm.
- the agitator further comprises two polyurethane mixing discs of 64mm diameter.
- o gibbsite AI (OH) 3 produced on an industrial scale, purity> 99.7%, marketed under the reference SH300 by Alteo;
- the mineral source of the metallic element may be:
- a starting suspension is prepared in a beaker from the source of the aluminum element and the source of the element A, in stoichiometric proportion, in a liquid phase (water), and then the starting suspension is put under stirring with a magnetic stirrer;
- the throughput rate in the mill can reach 60 l / h;
- the starting suspension is then milled (2) in the three-dimensional mill comprising microbeads of 0.5 mm in diameter for a certain time (which depends on the flow rate of the starting suspension) at room temperature (20-25 °). C), thus making it possible, at the outlet of the mill, to obtain an intimate and homogeneous mixture of the initial reactants (namely the aluminum source and the source of the element A);
- the final suspension comprising either the starting reagents in activated form, or aluminate crystals of the element A or elements (generally in hydrated form) is recovered (3);
- this final suspension is dried (4) in an oven at 80 ° C for 1 hour;
- the final dried suspension thus obtained is calcined (5) at a temperature between 400 ° C and 1500 ° C, preferably 700 ° to 1200 ° C, in a stationary oven.
- the duration of the calcination is between 30 minutes and 4 hours, preferably 30 minutes to 1 hour 30 minutes.
- the zinc aluminate crystals ZnAl 2 O 4 were synthesized according to the general procedure mentioned above, with an initial suspension containing 150 g of reagents (ZnO + Al (OH) 3 Sigma Aldrich) per liter of solvent (water). , with a single passage in the mill at a rate of 30L / h. The calcination was carried out at 650 ° C for 1 h.
- the XRD spectrum also shows that the sample analyzed has excellent purity. Indeed, no contamination is listed:
- the process of the invention makes it possible to easily obtain pure zinc aluminate ZnAl 2 0 4 crystals, in particular from gibbsite Al (OH) 3 and ZnO.
- the general procedure mentioned above was used to obtain magnesium aluminate crystals MgAl 2 O 4 .
- the initial suspension contains 150 g of reagents (MgO + Al 2 O 3 ) per liter of solvent (water).
- a single passage in the mill at a rate of 30L / ha was performed.
- the calcination was carried out at 1200 ° C for 1 h.
- the XRD spectrum also shows that the sample analyzed has excellent purity. Indeed, no contamination is listed:
- the process of the invention makes it possible to easily obtain magnesium aluminate crystals of very good purity, in particular from alpha alumina and MgO.
- the Applicant has also carried out this test with a temperature of lower calcination (of the order of 1050 ° C) which led to the obtaining of magnesium aluminate of a slightly lower purity for the same calcination time.
- Calcium aluminate crystals were synthesized according to the general procedure mentioned above, with initial suspensions containing 150 g reagents (CaCO 3 + Al (OH) 3 Sigma Aldrich) per liter of solvent (water).
- the molar ratio (Al): (Ca) was set at 4.
- a single passage in the mill at a rate of 30 L / ha was made.
- the calcination was carried out at 1050 ° C for 1 hour.
- the XRD spectrum also shows that the sample analyzed has excellent purity. Indeed :
- the process of the invention makes it possible easily to obtain pure calcium aluminate CaAl 4 0 7 crystals, in particular from a carbonate as a source of the calcium element.
- the barium aluminate crystals BaAl 2 O 4 were synthesized according to the general procedure mentioned above, with an initial suspension containing 300 g of reagents (BaO 2 + Al (OH) 3 SH300) per liter of solvent (water). . Two passages in the mill, at a rate of 30L / h, were carried out. The calcination was carried out at 1050 ° C for 1 hour. Referring to FIG. 6, it can be seen that the lines of the DRX spectrum obtained for the barium aluminate are in accordance with those of the BaAI 2 0 4 reference spectrum, known to those skilled in the art (according to JCPDS 04 -010-3758), both for their angular positions and for their relative intensities.
- the XRD spectrum also shows that the sample analyzed has excellent purity. Indeed, no contamination is listed:
- the process of the invention makes it possible to easily obtain pure barium aluminate BaAl 2 0 4 crystals, by using gibbsite AI (OH) 3 SH 300, produced on an industrial scale, as well as peroxide as the source of the barium element.
- the XRD spectrum also shows that the sample analyzed has good purity. Indeed :
- the XRD spectrum also shows that the sample analyzed has good purity. Indeed :
- the laboratory mill makes it possible, for example, to produce 54 kg / h of crystals of the various aluminates. This figure could be multiplied by 10 with the addition of an accelerator accessory. Also, there are industrial versions of the mill using for example up to 100 kg of beads. With this type of mill, it would therefore be possible to manufacture several tons per hour of different aluminates.
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FR1659627A FR3056979B1 (en) | 2016-10-05 | 2016-10-05 | METHOD FOR MANUFACTURING ALUMINATE CRYSTALS OF AT LEAST ONE METAL AND/OR ONE METALLOID AND/OR ONE LANTHANIDE, AS WELL AS THEIR APPLICATIONS |
PCT/FR2017/052737 WO2018065736A1 (en) | 2016-10-05 | 2017-10-05 | Method for manufacturing crystals of aluminate of at least one metal and/or one metalloid and/or one lanthanide, and applications of same |
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US (1) | US11235979B2 (en) |
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FR (1) | FR3056979B1 (en) |
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CN111196737A (en) * | 2020-03-24 | 2020-05-26 | 辽宁科技学院 | Technological method for preparing compact calcium dialuminate refractory clinker by one-step method |
CN111834668B (en) * | 2020-06-30 | 2021-11-02 | 华中科技大学 | γ-LiAlO2With gamma-Al2O3Composite nanosheet and application in preparation of alkali metal ion electrolyte |
CN111889104B (en) * | 2020-09-03 | 2021-06-01 | 福州大学 | Preparation method and application of 0D/2D composite calcium oxide metal oxide nano catalytic material |
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US11235979B2 (en) | 2022-02-01 |
FR3056979A1 (en) | 2018-04-06 |
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CA3038371A1 (en) | 2018-04-12 |
MA46457A (en) | 2019-08-14 |
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