OA20565A - Cementitious reagents, method of manufacturing and uses thereof. - Google Patents
Cementitious reagents, method of manufacturing and uses thereof. Download PDFInfo
- Publication number
- OA20565A OA20565A OA1202100601 OA20565A OA 20565 A OA20565 A OA 20565A OA 1202100601 OA1202100601 OA 1202100601 OA 20565 A OA20565 A OA 20565A
- Authority
- OA
- OAPI
- Prior art keywords
- particles
- cementitious
- feedstock
- reagent
- cernent
- Prior art date
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- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 286
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 301
- 239000000463 material Substances 0.000 claims abstract description 223
- 239000007787 solid Substances 0.000 claims abstract description 143
- 238000010791 quenching Methods 0.000 claims abstract description 98
- 238000002844 melting Methods 0.000 claims abstract description 80
- 230000000171 quenching Effects 0.000 claims abstract description 68
- 239000000725 suspension Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims description 240
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 162
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 122
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 122
- 239000000843 powder Substances 0.000 claims description 120
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 81
- 239000011734 sodium Substances 0.000 claims description 57
- 229910052791 calcium Inorganic materials 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000010881 fly ash Substances 0.000 claims description 50
- 229910052904 quartz Inorganic materials 0.000 claims description 47
- 229910052681 coesite Inorganic materials 0.000 claims description 43
- 229910052906 cristobalite Inorganic materials 0.000 claims description 43
- 229910052682 stishovite Inorganic materials 0.000 claims description 43
- 229910052905 tridymite Inorganic materials 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 239000000446 fuel Substances 0.000 claims description 36
- 229910052742 iron Inorganic materials 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 34
- 239000011230 binding agent Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 229910052700 potassium Inorganic materials 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 23
- 239000011435 rock Substances 0.000 claims description 21
- 239000006227 byproduct Substances 0.000 claims description 20
- 239000002699 waste material Substances 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- -1 admixtures Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 230000001590 oxidative Effects 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 10
- 229910052570 clay Inorganic materials 0.000 claims description 10
- 238000003801 milling Methods 0.000 claims description 9
- 239000004848 polyfunctional curative Substances 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L Potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims 2
- 239000012190 activator Substances 0.000 claims 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims 2
- 235000011151 potassium sulphates Nutrition 0.000 claims 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims 2
- 235000011152 sodium sulphate Nutrition 0.000 claims 2
- 239000004568 cement Substances 0.000 abstract description 15
- 239000011575 calcium Substances 0.000 description 81
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 69
- 229920000876 geopolymer Polymers 0.000 description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 56
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 54
- NTGONJLAOZZDJO-UHFFFAOYSA-M disodium;hydroxide Chemical compound [OH-].[Na+].[Na+] NTGONJLAOZZDJO-UHFFFAOYSA-M 0.000 description 53
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 45
- 239000007788 liquid Substances 0.000 description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 36
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 33
- 239000000523 sample Substances 0.000 description 29
- 239000007789 gas Substances 0.000 description 28
- 241000196324 Embryophyta Species 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 239000011521 glass Substances 0.000 description 25
- 239000007791 liquid phase Substances 0.000 description 24
- 239000003245 coal Substances 0.000 description 22
- 238000010586 diagram Methods 0.000 description 22
- 238000002485 combustion reaction Methods 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 230000000576 supplementary Effects 0.000 description 21
- NNHHDJVEYQHLHG-UHFFFAOYSA-N Potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 19
- 239000004111 Potassium silicate Substances 0.000 description 19
- 229910052913 potassium silicate Inorganic materials 0.000 description 19
- 235000019353 potassium silicate Nutrition 0.000 description 19
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- 239000011396 hydraulic cement Substances 0.000 description 13
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000002956 ash Substances 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 11
- 210000002381 Plasma Anatomy 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 235000010599 Verbascum thapsus Nutrition 0.000 description 9
- 238000004017 vitrification Methods 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 8
- 229920003041 Geopolymer cement Polymers 0.000 description 8
- 239000011413 geopolymer cement Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910001950 potassium oxide Inorganic materials 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004642 transportation engineering Methods 0.000 description 6
- 238000003991 Rietveld refinement Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000005335 volcanic glass Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N Iron(II,III) oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 235000015450 Tilia cordata Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- JHLNERQLKQQLRZ-UHFFFAOYSA-N Calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 3
- 210000001847 Jaw Anatomy 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910001678 gehlenite Inorganic materials 0.000 description 3
- 230000001965 increased Effects 0.000 description 3
- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L Calcium fluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- SQVRNKJHWKZAKO-LUWBGTNYSA-M N-acetylneuraminate Chemical compound CC(=O)N[C@@H]1[C@@H](O)CC(O)(C([O-])=O)O[C@H]1[C@H](O)[C@H](O)CO SQVRNKJHWKZAKO-LUWBGTNYSA-M 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
- 241001486234 Sciota Species 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 2
- 229910052891 actinolite Inorganic materials 0.000 description 2
- 101700065596 aho-3 Proteins 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- 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 description 2
- SPPOVYALFLURKN-UHFFFAOYSA-N aluminum;silicic acid;sodium Chemical compound [Na].[Al].O[Si](O)(O)O SPPOVYALFLURKN-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- 229910052862 chloritoid Inorganic materials 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 229910052900 illite Inorganic materials 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001718 melilite group Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052664 nepheline Inorganic materials 0.000 description 2
- 239000010434 nepheline Substances 0.000 description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052652 orthoclase Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- 229910052611 pyroxene Inorganic materials 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 230000001131 transforming Effects 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- FPRULFHDSFKYBV-UHFFFAOYSA-N 3-amino-N-[(4-chlorophenyl)methyl]-4,6-dimethylthieno[2,3-b]pyridine-2-carboxamide Chemical compound S1C2=NC(C)=CC(C)=C2C(N)=C1C(=O)NCC1=CC=C(Cl)C=C1 FPRULFHDSFKYBV-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000872931 Myoporum sandwicense Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N Silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 240000000969 Verbascum thapsus Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052658 andesine Inorganic materials 0.000 description 1
- 229910052639 augite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- KQMBEUPSQAQIKF-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;magnesium Chemical compound [Mg].[Ca].O[Si](O)=O KQMBEUPSQAQIKF-UHFFFAOYSA-N 0.000 description 1
- VTVVPPOHYJJIJR-UHFFFAOYSA-N carbon dioxide;hydrate Chemical compound O.O=C=O VTVVPPOHYJJIJR-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052871 clinozoisite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000005824 corn Nutrition 0.000 description 1
- 230000002596 correlated Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- WMVRXDZNYVJBAH-UHFFFAOYSA-N dioxoiron Chemical compound O=[Fe]=O WMVRXDZNYVJBAH-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 230000004301 light adaptation Effects 0.000 description 1
- 229910052899 lizardite Inorganic materials 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000116 mitigating Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229910052655 plagioclase feldspar Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007637 random forest analysis Methods 0.000 description 1
- 239000003638 reducing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002364 soil amendment Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 229910052854 staurolite Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000161 steel melt Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IBPRKWGSNXMCOI-UHFFFAOYSA-N trimagnesium;disilicate;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IBPRKWGSNXMCOI-UHFFFAOYSA-N 0.000 description 1
- 238000004450 types of analysis Methods 0.000 description 1
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Abstract
Described are cementitious reagent materials produced from globally abundant inorganic feedstocks. Also described are methods for the manufacture of such cementitious reagent materials and forming the reagent materials as microspheroidal glassy particles. Also described are apparatuses, systems and methods for the thermochemical production of glassy cementitious reagents with spheroidal morphology. The apparatuses, systems and methods makes use of an in-flight melting/quenching technology such that solid particles are flown in suspension, melted in suspension, and then quenched in suspension. The cementitious reagents can be used in concrete to substantially reduce the CO2 emission associated with cement production.
Description
CEMENTITIOUS REAGENTS, METHODS OF MANUFACTURING AND USES THEREOF
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application daims the benefit under 35 U.S.C. § 119(e) of United States Provisional Application No. 62/867,480, filed June 27, 2019, and. of United States Provisional Application No. 63/004,673, filed April 3, 2020, and of United States Provisional Application No. 63/025,148, filed on May 14, 2020, the disclosures of which are incorporated, în their entirety, by this reference.
BACKGROUND
[0002] The field of the présent disclosure is related to cementitious reagents, and more particularly, to the création of relatively homogeneous cementitious reagent materials and cementitious materials from abundant heterogeneous feedstocks.
[0003] Concrète has played an important rôle in cîvilizatîon for thousands of years and is still the most commonly used building material. Cernent is the essential binding component of concrète that allows flowable concrète slurrîes to harden into a useful composite material at ambient températures. Many binder chemistries hâve been successfully used to make concrète, but Portland cernent and its variations hâve been the dominant concrète binder for almost 200 years. Despîte advances in production efficiency and material performance, there are significant and întrinsîc problems with Portland cernent chemistry that cannot be solved at any reasonable cost by current methods.
[0004] Portland cernent production is a CO2 intensive process that causes about 8% of global anthropogenic CO2 émissions. Some estimâtes project that cernent demand will increase by 1223% by 2050. However, the growing absolute demand for cernent is at odds with the need for complété decarbonîzation of the economy that is also required by 2050 to avoid catastrophîc effects of climate change, according to the UN IPCC Climate Report 2018. There is therefore an urgent need for drastically lowering the spécifie CO2 émissions of cernent, especially because absolute production volume is increasing.
[0005] One way that the industry has tried to reduce the CO2 émission of cernent is by developing geopolymer cements, which are general ly aluminosîlÎcate inorganic polymer that cures through a geopoiymerization process. Commercially relevant geopolymer cements in use today require access to several spécifie solid reagents (commonly: metakaolin (MK-750), ground
- 1 20565 granulated blast furnace slag (GGBFS), and coal fly ash). However, these reagents cannot satisfy the global transition to low-COz cements because supply is relatively limited in geography and volume compared to the enormous demand for cernent. Also, the cost of shipping these products from production locations is signîficant compared to their market value.
[0006) Cementitious reagents are useful in both hydraulic and geopolymer cements. Geopolymer reagents, and supplementary cementitious materials (SCM)} are typically selected from several common cementitious materials: byproduct ashes from combustion (e.g. coal fly ash), slag byproducts (e.g. ground granulated blast furnace slag), calcined clays (e.g. metakaolin), and natural pozzolans (e.g. volcanic ash). These materials are generally substantially non-crystalline and sometîmes reactive in cementitious Systems such as în geopolymerîc Systems.
[0007] Since the majority of SCMs that are used in blended hydraulic cements are industrial by-products (e.g. coal combustion, or quality iron production), their material properties are a resuit ofthe industrial by-product and are not specifically tailored as a quality cementitious reagent. Accordingly, these materials lack any guarantee of idéal or even consistent composition and quality, and their suitability as cementitious reagents varies from plant to plant, and over time. There is also no control over production location, and the concrète industry lacks control over future availability of these critically important cementitious materials. It would be much more advantageous if the production location could be chosen based on market needs, partïcularly because shipping of cementitious materials is very expensive.
[0008] Fly ash is a partially glassy ahimïnosilicate by-product of coal combustion. It is frequently used as an admixture in hydraulic cernent mixes to improve flowability and create a pozzolanic reaction to improve properties of concrète including strength, résistance to alkalisilica réaction and others. Unfortunately, only certain coal and combustion processes create a consistent supply of fly ash of a quality acceptable for use in concrète (e.g. ASTM Type C and Type F ash, or CSA Type C, CI, and F ashes). Ash is not produced as an optimal SCM; rather, combustion is oplimized for power génération and pollution prévention: there is no guaranteed consistency of by-product ash. Further problems for the future of fly ash in concrète include a significant decrease in régional availability due to transition from coal energy to natural gas in many markets, carbon introduced post-combustion can negatîvely affect aïr entrainment in
-220565 concrète, recovery of ash from impoundments will increase cost, and quality must be verified through testing in each case.
[0009] Ground Granulated BlastFumace Slag (GGBFS) is aglassy CaO-SiOs by- product of iron production in blast furnaces. Concrètes incorporating GGBFS hâve many advantageous properties including improved Chemical durability, whiteness, reduced heat of hydration, mitigation of CO2 footprint, and other bénéficiai properties. Unfortunately, the supply of blast fumace slag is quite limited due to the small number of blast furnaces operating in most markets. As such, GGBFS is in high demand as a quality SCM and prices for this by~product are now similar to the price of cernent itself. Additionally, the limited géographie supply leads to shortages or at least high shipping costs for many local concrète markets. Finally, iron production and resulting blast furnace slag supply are not coupled directly to concrète demand, leaving supply volume, local availability, and market price of these important admixtures largely up to chance.
[0010] Natural pozzolans are silîceous or aluminosiliceous materîals that are able to participate in the pozzolanîc reaction with Ca(OH)2. These include as-mîned or calcined volcanic ash, diatomaceous earth, kaolinite and other clays, MK-750 and other natural minerais and rocks that react with lime to produce a hydrated calcium silicate compound. Natural pozzolans can be very effective SC Ms in concrète, however they require mining of non-renewable resources and pozzolans often require significant shipping distances since deposits are not extremely common. Also, natural materîals often require significant processing such as calcining to enhance reactivity of natural pozzolans.
[0011] Fly ash (usually with low CaO content, as in type F), GGBFS, and certain natural and processed ‘pozzolans” (e.g. volcanic ashes, zeolîtes, and MK-750) are also common geopolymer reagents, and the same unfortunate limitations on supply, géographie availability, price, quality, and consistency apply for their application in geopolymer binders and cements.
[0012] To overcome certain limitations of these existing SCM and geopolymer reagent supplies, several attempts hâve been made to improve on aspects of traditional methods. Despi te some improvements, these man-made products or compositions still possess numerous deficiencies, for instance with respect to reactivity and chemistry of reagents for use in geopolymer chemistry (e.g., optimizîng reagents to later produce high coordination, branched,
-3 20565 and three-dimensional alkali/alkaline earth aluminosilicate polymers). They also require expensive lab-grade reagents and cannot simply use globally abundant feedstocks.
[0013] Also, previously manufactured glassy cementitïous reagents hâve angular or fibrous particle morphology. Thus, cernent pastes made from such reagents require a lot of water and hâve relatively poor workability (e.g., with excessive yield stress or higher than optimal plastic viscosity) which is a barrier to use in practical concrète applications.
[0014] Combustion ashes and silica fume typically do not hâve angular particle morphology. However, these are not available in sufficient quantifies, do not hâve appropriate chemistry, and/or are too expensive to support a large-scale transition to high SCM blend hydraulic or geopolymer cements.
[0015] There is thus a need for cementitïous reagents that solve exîsting workability issues with a similar degree of effectiveness as super plasticizers and water reducers in équivalent Portland cernent mix designs. There is also a need for a method of reducing CO2 émissions in production of Portland cernent, and particularly, a need for an engineered cementitïous reagent with low or zéro process CO2 émissions that can be used as a supplementary cementitïous material in hydraulic cements, and/or as a solid geopolymer reagent.
[0016] There îs also need for a cementitïous reagent that can be produced ubiquitously from globally abundant feedstocks, is reactive in cementitïous Systems, and delivers workable lowyield stress cernent mixes.
[0017] Furthermore, there is a need for production of cementitïous reagents wherein the production location could be chosen based on market needs. There îs particularly a need for non-angular particle or microspheroîdal glassy particles useful in cementitïous reagents, geopolymer reagents, supplementary cementitïous materials (SCM), cernent mixes and concrète. [0018] There is also a need for the economical production of such microspheroîdal glassy particles, e.g. by using globally abundant feedstocks. There is also a need for apparatuses, Systems and methods using in-flight melting/quenching such wherein solid particles are flown în suspension, melted in suspension, and then quenched in suspension.
[0019] The présent invention addresses these needs and other needs as it will be apparent from review of the disclosure and description of the features of the invention hereinafter.
[0020] The dominant cernent used in concrète today is a hydration-curing calcium silicate product known as Portland cernent. Unfortunately, manufacture of Portland cernent clinker
-4 20565 causes CO2 process émissions (from heating limestone) that are globally impactful (about 3-5%, not counting fuel-derived GHG émissions). The process îs carried out in a rotary kiln with raw meal flowing countercurrent to the kiln burner. The process is very energy intensive, consuming ~3-5 GJ/ton, of which about 1.5 GJ/ton is spent simply calcining limestone. Of the few viable strategies to decrease environmental impact of cernent, geopolymer chemistry provides a globally viable alternative cernent with improved environmental and material performance. The inconsîstent supply and limited géographie availabilîty of traditional geopolymer reagents such as fly ash and slags hâve limited standardization and adoption of geopolymer concrètes. On the other hand, an încreasing demand for supplementary cementitious materials (SCM) in hydraulic cements (to enhance material and environmental performance) has further squeezed demand for these materials.
[0021] As mentioned hereinbefore various attempts hâve been made to manufacture cementitious reagents. However, these methods suffer from crucial deficiencies that hâve prevented an économie manufacturing process for glassy cementitious reagents.
[0022] For instance, high-temperature refractory-lined fumaces and crucibles hâve been used to directly contain glass melts in existing academie research on cementitious reagents (a natural extension of traditional glassmaking techniques). However, solid refractory materials in crucibles and surrounding conventional fumaces require low heating and cooling rates (order of 10-50 C/min) to avoid thermal shock breakage. Conventional melting furnaces hâve high thermal mass which makes maintenance difficuit and costly as a resuit of long startup and shutdown cycles. It is préférable to avoid the need for refractories that directly contact the melt, so as to avoid, complexîty, wear. and also considérable start up and shut down times.
[0023] Quenching of molten glass for cementitious reagents (blast furnace slag, for example) has previously required water, which is costly, înhibits heat recovery, could hâve négative environmental conséquences and may require added complication of solid/lîquid séparation. Melt quenching methods were thus either wasteful or slow, diminishîng reactivity. Airquenching methods of cooling melts are either too slow or require very spécifie chemistry to ensure low melt viscosîties of about 1 Pa*s or less, which is not feasible for most desired feedstock materials.
]0024] Previous glass manufacturing methods hâve required costly particle size réduction (milling) of glassy product (typicalîy before and after thermal processing).
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[0025] Accord ingly, there is stîll a need for a convenient and économie method of manufacturing a glassy cementîtîous reagent from globally abundant feedstocks.
[0026] There is also a need to minimize energy consumption and cope with very high and variable melt viscosîty without requiring fluxes.
[0027] There is also a need for methods of producing microspheroîdal glassy particles and for apparatuses and Systems useful for producing such microspheroîdal glassy particles.
[0028] The present invention addresses these needs and other needs as it will be apparent from review ofthe disclosure and description of the features ofthe invention hereinafter.
SUMMARY
[0029] Embodiments relate to, among other things, an alternative cernent material (ACM), which in some embodiments comprises a solid microspheroîdal glassy particles comprising one or more of the following properties: mean roundness (R) > 0.8 ; and less than about 40% particles having angular morphology (R < 0.7).
[0030] In some embodiments, the particles comprise a mean roundness (R) of at least 0.9. In embodiments, less than about 30% particles, or less than about 25% particles, or less than about 20% particles, or less than about 15% particles, or less than about 10% particles hâve an angular morphology (R < 0.7).
[0031] In some embodiments, the particles comprise the mean oxide Formula 1 : (CaO,MgO)a*(Na2O,K2O)b*(A12O3,Fe2O3)c*(SiO2)d [Formula 1]; wherein a is about 0 to about 4, b is about 0.1 to about 1, c is 1, and d is about 1 to about 20.
[0032] In some embodiments, the particles further comprise one or more of the following properties: (i) a content of 45%-100%, and preferably 90-100%, X-ray amorphous solid; and (ii) molar composition ratios of (Ca,Mg)0-l2’(Na,K)0.05-l*(Al, Fe3+)I*Sil-20.
[0033] According to another aspect, some embodiments relate to a cementîtîous reagent comprising a mixture of microspheroîdal glassy particles as defined herein.
[0034] According to another particular aspect, some embodiments the invention relate to a cementitious reagent comprising a mixture of microspheroîdal glassy particles, these particles comprising one or more of the following properties: (i) mean roundness (R) > 0.8; (ii) less than about 20% particles having angular morphology (R < 0.7); (iii) the oxide Formula 1 as defined hereinbefore; (iv) a content of 45%-ΐ00%, and preferably 90-100%, X-ray amorphous solid; and (v) a molar composition ratios of (Ca,Mg)o-i2*(Na,K)o.o5-i’(Al, Fe3+)i*Sii.2o; and (vi) a low
-620565 calcium content of about <10wt% CaO, or an intermediate calcium content of about 10 to about 20% wt% CaO, or a high calcium content of >30wt% CaO.
[0035] In some embodiments, the cementitious reagent is in the form of a non-crystalline solid. In some embodinnents, the cementitious reagent is in the form of a powder. In some embodiments, the particle size distribution with D[3,2] (i.e., surface area mean, or Sauter Mean Diameter) of about 20μπι or less, more preferably lÛpm or less, or most preferably 5pm or less. In one embodiment, the mixture of microspheroidal glassy particles ofthe cementitious reagent comprises the oxide Formula 1 as defined hereinabove. In some embodiments, the cementitious reagent comprises less than about 10 wt.% CaO. In some embodiments, the cementitious reagent comprises more than about 30 wt.% CaO. In some embodiments the cementitious reagent is about 40-100% and preferably about 80% X-ray amorphous, 90% X-ray amorphous, and up to about 100% X-ray amorphous, and in some embodiments, is 100% non-crystalline.
[0036] According to some embodiments, a geopolymer binder comprises a cementitious reagent as defined herein. According to another particular aspect, some embodiments of the invention relate to a supplementary cementitious material (SCM) comprising a cementitious reagent as defined herein, for instance a SCM comprising at least 20 wt.% of the cementitious reagent.
[0037] According to another particular aspect, some embodiments relate to a solid concrète comprising a cementitious reagent as defined herein.
[0038] According to another particular aspect, some embodiments relate to the use of microspheroidal glassy particles as defined herein, and to the use of a cementitious reagent as defined, to manufacture a geopolymer binder or cernent, a hydraulic cernent, a supplementary cementitious material (SCM) and/or solid concrète.
[0039] According to another particular aspect some embodiments relate to a method for producing a cementitious reagent from aluminosilicate materials, comprising the steps of: (i) providing a solid aluminosilicate material; (ii) in-flight melting/quenching said solid aluminosilicate material to melt said material into a liquîd and thereafter to quench said liquid to obtain a molten/quenched powder comprising solid microspheroidal glassy particles; thereby obtaining a cementitious reagent with said powder of microspheroidal glassy particles.
[0040] In some embodiments, the method further comprises step (iii) of grindîng said powder of microspheroidal glassy particles into a fïner powder. In one embodiment, the powder
-7 20565 comprises particle size distribution with D[3,2] of about 20pm or less, more preferably lOpm or less, or most preferably 5pm or less.
[0041] In some embodiments, the cementitious reagent obtained by the method comprises one or more of the following properties: îs reactive in cementitious Systems and/or in geopolymeric Systems; delivers workable low yield stress geopolymer cernent mixes below 25 Pa when a cernent paste has an oxide mole ratio of Η2θ/(Ν»2θ,Κ2θ) < 20 ]; requires water content in cernent paste such that the oxide mole ratio H2O/(Na2O,K2O) < 20; and delivers a cernent paste with higher workability than an équivalent paste with substantially angular morphology, gîven the same water content.
[0042] In some embodiments, the method further comprises the step of adjusting composition of a ηοπ-ideal solid aluminosilicate material to a desired content of the éléments Ca, Na, K, Al, Fe, and Si. In one embodiment the adjusting comprises blending a non-ideal aluminosilicate material with a composition adjustment material in order to reach desired ratio(s) with respect to one or several of the éléments Ca, Na, K, Al, Fe, and Si.
[0043] In some embodiments, the method further comprises the step of sorting the solid aluminosilicate material to obtain a powder of aluminosilicate particies of a desired size. In some embodiments, the method further comprises the step of discardîng undesirable waste material from said solid aluminosilicate material.
[0044] In some embodiments, the in-flight melting comprises heating at a température above a liquid phase température to obtain a liquid. In some embodiments, the température is between about 1000-1600°C, or between about 1300-1550°C.
[0045] In some embodiments, the method further comprises the step of addîng a fluxing material to the solid aluminosilicate material to lower its melting point and/or to induce greater enthalpy, volume, or depolymerîzation ofthe liquid. In some embodiments, the fluxing material is mîxed with the solid aluminosilicate material prior to, or during the melting.
[0046] In some embodiments, the in-flight melting/quenching comprises reducing température of the liquid below température of glass transition to achieve a solid. In some embodiments, the in-flight melting/quenching comprises reducing température of the liquid below about 500°C, or preferably below about 200ûC or lower. In some embodiments, reducing température of the liquid comprises quenching at a rate of about 102 Ks'1 to about 106 Ks'1, preferably at a rate of >103 5 Ks-1. In some embodiments, quenching comprises a stream ofcool
-8 20565 air, steam, or water. In one embodiment, the method further comprises separating quenched solid particles from hot gases in a cyclone separator.
[0047] In some embodiments, the method for producing a cementitious reagent from aluminosilicate materials further comprises reducing partie le size of the powder of solid microspheroidal glassy particles. In some embodiments reducing particle size comprises crushing and/or pulverizing the powder in a bail mi II, a roi 1er mi 11, a vertical roi 1er mill or the like.
[0048] Accordîng to another aspect, some embodiments relate to an apparatus for producing microspheroidal glassy particles, the apparatus comprising a bumer, a melting chamber and a quenching chamber. The melting chamber and the quenching chamber may be completely separate or may be first and second sections of the same chamber, respectîvely.
[0049] The apparatus may be configured such that solid particles are flown in suspension, melted in suspension, and then quenched in suspension in the apparatus.
[0050] In some embodiments, the burner provides a flame heating solid particles in suspension to a heating température sufficient to substantially melt said solid particles into a liquid. In some embodiments, the burner comprises a flame that is fueled with a gas that entrains aluminosilicate feedstock particles towards the melt/quench chamber. The gas may comprise an oxidant gas and a combustible fuel. In some embodiments the burner comprises at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a soiar concentrating fumace.
[0051] In some embodiments, the quenching chamber of the apparatus comprises a cooling system for providing cool air inside the quenching chamber, the cool air quenching molten particles to solid microspheroidal glassy particles. In some embodiments, the cooling system comprises a liquid cooling loop positioned around the quenching chamber.
[0052] In some embodiments, the apparatus further comprises a cyclone separator to collect microspheroidal glassy particles. Accordîng to some embodiments, a method for producing a cementitious reagent from aluminosilicate materials comprises the steps of: (i) providing a solid aluminosilicate material; (ii) in-flight melting/quenching said solid aluminosilicate material to melt said material into a liquid and thereafter to quench said liquid to obtaîn a molten/quenched powder comprising solid microspheroidal glassy particles; thereby obtaining a cementitious reagent wîth said powder of microspheroidal glassy particles.
-920565
[0053] According to some embodiments, a method for producing microspheroidal glassy particles comprises the steps of: providing an in-flight melting/quenching apparatus comprising a bumer, a melting chamber and a quenching chamber; providing solid particles; flowing said solid particles in suspension in a gas to be bumed by said burner; heating said solid particles into said melting chamber to a heating température above liquid phase to obtain liquid particles in suspension; and quenching said liquid particles în suspension to a cooling température below liquid phase to obtain a powder comprising solid microspheroidal glassy particles.
[0054] In some embodiments of these methods, the solid particles comprise aluminosilicate materials. In some embodiments of these methods. the heating température is between about 1000-1600°C, or between about 1300-1550°C. In some embodiments of these methods, the cooling (quench) température is below about 500°C, or below about 200°C.
[0055] In some embodiments of these methods, the quenching comprises providing cool air inside the quenching chamber. In some embodiments, these methods further comprise collecting the powder with a cyclone separator.
[0056] Additional aspects of some embodiments of the invention relate to the use of an apparatus as defined herein, particularly an apparatus comprising at least one of a plasma torch, an oxy-fuel bumer, an air-fuel burner, a biomass burner, and a solar concentrating fumace, for producing microspheroidal glassy particles using in-flight melting/quenching.
[0057] Additional aspects of some embodiments of the invention relate to the use of an apparatus as defined herein, particularly an apparatus comprising at least one of a plasma torch, an oxy-fuel burner, an air-fuel bumer, a biomass burner, and a solar concentrating fumace, for producing a cementitious reagent from aluminosilicate materials using in-flight melting/quenching.
[0058) Additional aspects, advantages and features ofthe présent invention will become more apparent upon reading ofthe following non-restrictive description ofpreferred embodiments which are exemplary and should not be interpreted as limitîng the scope ofthe invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0059] A better understanding of the features, advantages and principles of the présent disclosure will be obtained by reference to the following detaîled description that sets forth illustrative embodiments, and the accompanying drawings of whîch:
- 1020565
[0060] FIG.l is a flow diagram showing production of a cementitious reagent starting from a solid aluminosilicate material, in accordance with some embodiments;
[00611 FIG.2 is a set of four temary CaO, MgO — S1O2 — (NazOXsO) —(AI2O3, FezOa) composition diagrams, in accordance with some embodiments;
[0062] FIG. 3 is a three-dimensional quaternary diagram in (CaO, MgO) — (AI2O3, FeaOj) — (Na^O, K2O) — (S1O2) space using the same material compositional data plotted în Figure 2, in accordance with some embodiments;
[0063] F IGA is a particle size distribution graph comparing angular and spheroidal partiel e size distributions for commercîally avaîlable natural volcanic glass powder (angular morphology) and parti clés produced in accordance with Example 1 (spheroidal morphology). Percentage of particles by volume below a given diameter (y axis) is provided as a function of particle diameter in mîcrometers (x axis). Electron microphotographs demonstrate particle morphology of the samples.
[0064] FIG.5 is a graph provîdîng a comparison of particle roundness (R) distributions of various powders, in accordance with some embodiments; (211-218, 519, 520, as defïned hereinafter) before processing (501) and after (502) processing in accordance with Examples 1-8, in accordance with some embodiments. Image analysis was used to détermine R values from microphotographs of the same powders shown in Figure 6 and Figure 7 following the method of Takashimizu & Liyoshi (Takashimizu, Y,, liyoshi, M. (2016). New parameter of roundness R: circularîty corrected by aspect ratio. Progress in Earth and Planetary Sciences 3,2.
https://doi.org/10.] 186/s40645-015-0078-x). Also see Table 17 for more précisé data. For convenience, two Type F fly ash samples are also included; 519 (B-FA) a beneficiated fly ash sold commercially, and 520 (L FA) an unbeneficiated fly ash direct from a coal power plant.
[0065] FIG.6 is a panel showing a collection of électron microphotograph pairs comparing unprocessed particles (501) and processed particles (502) from various materials (211-218 as defïned hereinafter) as described in Example 1 through Example 8. Field of view width for individual panels is 140 pm.
[0066] FIG.7 is a panel showing pictures of two Type F fly ashes, one directly from a coal power plant in Nova Scotia (L-FA; 520) and another commercially available fly ash that has been beneficiated to remove activated carbon and other contaminants (B-FA; 519). Field of view width for individual panels is 140 μσι.
- 11 20565
[0067] F1G.8 is a schematic process flow diagram of a system to produce a glassy microspheroidal cementitious reagent, in accordance wîth one embodiment of the invention. [0068] FIG. 9A and 9B are a photograph and a corresponding illustration, respectively of a burner flame (bottom) entering a melt/quench chamber (top) with entrained alumînosilicate feedstock particles, in accordance wîth one embodiment of the invention.
[0069] FIG. 10 îs a schematic drawîng of an împroved in-flight melting apparatus that includes heat recovery loops for minimïzing energy input and CO2 émissions, in accordance wîth one embodiment of the invention.
[0070] FIG. 11 illustrâtes the complété set of temary représentations of a Novel Composition closed to Si, Al, Fe, Ca+Mg and Na+K; in accordance with some embodiments;
[0071J FIG. 12 illustrâtes ternary dîagrams for aNovel Composition from the Sî perspective; in accordance with some embodiments;
[0072] FIG. 13 illustrâtes ternary diagrams for aNovel Composition from the Al perspective; in accordance with some embodiments;
[0073] FIG. 14 illustrâtes ternary diagrams for a Novel Composition from the Fe perspective; în accordance with some embodiments;
[0074) FIG. 15 illustrâtes temary diagrams for a Novel Composition from the Ca+Mg perspective; in accordance wîth some embodiments;
[0075] FIG. 16 is a schematic flow diagram descrîbîng the process of making an alternative cernent concrète using a relatively small decentralized in-flight minikiln, în accordance with some embodiments;
[0076] FIG. 17 is a schematic diagram showing conventional cernent and aggregate distribution in a modem centralized Portland cernent kiln supply chain, in accordance with some embodiments;
[0077] FIG. IS is a schematic diagram showing the transportation advantages of collocating alternative cernent material (ACM) minikilns at aggregate quarries in a novel decentralized method, in accordance with some embodiments;
[0078] FIG. 19 ts a schematic diagram showing the transportation advantages of collocating alternative cernent material (ACM) minikilns at concrète batch plants in a novel decentralized method, in accordance with some embodiments; and
- 1220565
[0079] FIG. 20 is a schematic diagram showing the transportation advantages of locating alternative cernent material (ACM) minikilns in a novel décentrai ized manner at independent sites în the vicinity of aggregate quarries and concrète batch plants, in accordance with some embodiments.
[0080] Further details of the invention and its advantages will be apparent froin the detailed description included below. in accordance with some embodiments;
DETAILED DESCRIPTION
[0081] The following detailed description and provides a better understanding of the features and advantages ofthe inventions described in the présent disclosure în accordance with the embodiments disclosed herein. Although the detailed description incîudes many spécifie embodiments, these are provided by way of example only and should not be construed as limiting the scope of the inventions disclosed herein.
[0082] In the following description of the embodiments, references to the accompanying drawings are by way of illustration of an example by which embodiments ofthe invention may be practiced. It will be understood that other embodiments may be made without départing from the scope of the invention disclosed.
[0083[ Microspheroidal glassy particles
[0084[ Some embodiments relate to the production and uses of solid microspheroidal glassy particles. As explaîned with more details hereinafter, a related aspect concerna a cementitious reagent comprising a mixture or pluraiity of such microspheroidal glassy particles.
[0085] In accordance with the invention, the solid microspheroidal glassy particles are appreciably round particles ofhigh spherîcity.
[0086] As used herein, the term “roundness” and correspondîng unît “R” refers to roundness as defined by Takashimizu & ILyoshi (2016). The values required to calculate R can be determined by performing image analysis on appropriate photomicrographs of powders. R (roundness) provides a convenient quantitative measure of roundness that is highly correlated with Krumbein’s “roundness” (Krumbein, W.C. (1941 ) Measurement and geological significance of shape and roundness of sedimentary particles. Journal of Sedimentary Petrology 11:64—72. https://doi.org/10.1306/D42690F3-2B26-l 1D7-8648000102C1865D.)
- 13 20565 ]0087] In some embodiments, the microspheroidal glassy particles hâve mean roundness (R.) of at least 0.9 (Standard déviation <0.15).
£0088] In some embodiments, the microspheroidal glassy particles hâve bulk roundness (R) of at least 0.8 (Standard déviation <0.15).
[0089] In some embodiments, the microspheroidal glassy particles hâve bulk roundness (R) of at least 0.7, or 0.6, or 0.5 (Standard déviation <0.15).
10090] In some embodiments, a mixture of microspheroidal glassy particles comprises less than about 50% particles, or less than about 40% particles, or less than about 30% particles, or less than about 25% particles, or less than about 20% particles, or less than about 15% particles, or less than about 10% particles having angular morphology (e.g., R < 0.7) .
[0091] In some embodiments, a mixture or plurality of microspheroidal glassy particles is provided in a powder form comprising a partie le sîze distribution with D[3,2] of about 20 μ m or less, more preferably about 10pm or less. or most preferably about 5pm or less.
[0092] In some embodiments, microspheroidal glassy particles are a non-crystalline solid.
[0093] in some embodiments, the microspheroidal glassy particles comprise the oxide
Formula 1: (CaOjMgOJa’ÇNaÏO.KsCObftAbOSTejOsIC’iSiChjd [Formula 1] wherein a is about 0 to about 4, b is about 0.1 to about 1, c îs 1, and d is about 1 to about 20.
[0094] In some embodiments, the microspheroidal glassy particles comprise one or more of the following properties: (i) a content of45%-100%, and preferably 90-100%, X-ray amorphous solid; and (H) molar composition ratios of (Ca,Mg)o-i2’(Na,K)o.o5-f(AI, Fe3+)i*Sii-2o.
(0095] In some embodiments, the microspheroidal glassy particles are 40-100% X-ray amorphous, more preferably about 80 to about 100% X-ray amorphous, and in some embodiments is 100% non-crystalline.
[0096] In some embodiments, the particles comprise less than about 10 wt.% CaO.
[0097] In some embodiments, the particles comprise more than about 30 wt.% CaO.
[0098] In some embodiments, the particles comprise a high-calcium content with a molar composition of SÎ/(Fe3+,Al) between 1-20, and CaO content of about 10- about 50 wt.%, preferably about 20-45 wt.%.
[0099] In some embodiments, the particles comprise an intermediate-calcium content with a molar composition of Si/(Fe3+,Al) between 1-20, and CaO content of about 10- about 20 wt.%.
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[0100] As described hereinafter, the microspheroîdal glassy particles may advantageously be produced from globally abondant înorganic feedstocks such as aluminosilicate material. As used herein, the term “aluminosilicate material” refers to a material comprising aluminum or aluminum and iron, and Silicon dioxide selected from natural rocks and minerais, dredged materials, mining waste comprising rocks and minerais, waste glass, aluminosilicate-bearing contaminated materials and aluminosiliceous industrial by-products. An aluminosilicate material according to the présent invention is preferably in the form of a crystalline solid (e.g. at least 50 wt. %, or at least 60 wt. %, or at least 70 wt. %, or at least 80 wt. %, or at least 90 wt. %, or 100 wt. % crystalline solid). In some embodiments, the aluminosilicate material comprises at least 2 wt. % (Na2O,K2Û), or at least 3 wt. % (NasOjKsO), or at least 4 wt. % (NasOjKsO), or at least 5 wt. % (NasOjKsO), at least 6 wt. % (NasOjKsO), or at least 7 wt. % (Na2O,K2O), or at least 8 wt. % (NaiO,K2O), or at least 10 wt. % (Na2ÛfK2O), or at least 12 wt. % (NaaO.KsO), or at least 15 wt. % (NasO.KsO), or at least 20 wt. % (Na2O,K2Û). In some instances, the înorganic feedstocks are heterogeneous, and the glassy particles produced are more homogeneous than the feedstock, as shown during partial homogenization during melting. That is, more than 10% of the particles produced fall with in a new intermediate formulation range.
[0101] In some embodiments the aluminosilicate material is selected from dredged sédiments, demolished concrète, mine wastes, glacial clay, glacial deposits, fluvial deposits, rocks and minerai mixtures, for instance rocks and minerai mixtures composed of some or ail the éléments Ca, Mg, Na, K, Fe, Al and Si. These aluminosilicate materials are widely abundant in many different géographie régions.
[0102] As described hereinafter, the elemental composition of the feedstock may be analyzed and optimized for desired uses. The feedstock may be analyzed by quantitative or semiquantitative methods such as XRF, XRD, LIBS, EDS, wet Chemical analysis, and various other existing methods to détermine the feedstock elemental composition.
[0103] As described hereinafter, the microspheroîdal glassy particles may be produced using a process or method for in-flight thermochemîcal processing such as in-flight melting/quenching and/or suspension melting, for melting into a liquid the starting înorganic materials and thereafter quenching the liquid into solid particles. As used herein, the term “in-flight melting/quenching” or “suspension melting” refers to a process wherein solid particles are flown in suspension, melted in suspension, and then quenched in suspension to obtain a powder.
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[0104] In some embodiments, the term “microspheroidal glassy parti cl es” encompasses particles as defined hereinabove that are found in the powder resulting directly from an în-flîght melting/quenching process. In embodiments, the term “microspheroidal glassy particles” refers to particles obtained after grinding or milling (e.g. jaw crusher, an impact mill, etc.) of the powder obtained after the in-flight melting/quenching process.
[0105] As described hereinafter, the microspheroidal glassy particles find many uses including, but not lirnited to, as or in the préparation of cementitious reagents, as or in the préparation of geopolymer binders or cements, as or in the préparation of hydraulic cements, as or in the préparation of supplementary cementitious materials (SCMs), and in the making of solid concrète,
[0106] One additional use may be as a fertilizer or soil amendment, e.g. as a substitute to “rock dust”.
[0107] Cementitious material
[0108] Some embodiments descri bed herein relate to cementitious reagent powders comprising microspheroidal glassy particles as defined herein.
[0109] Some embodiments also relate to geopolymer binders or cements, hydraulic cements, supplementary cementitious materials (SCMs), hydraulic concrète mixtures, and solid concrète powders comprising microspheroidal glassy particles as defined herein.
[0110] Particie morphology has a considérable impact on physîcal properties and handîing of cernent slurries. Accordingly, the high-roundness morphology of the particles according to the présent invention advantageously provides increased workability, fluidity, and/or decreased water demand for geopolymer cernent mixes. In particular, having hîgh degrees of roundness reduces yield stress and viscosity of cernent mixes by reducing interparticle friction.
Addîtîonally, spheroidal morphology decreases water demand by improving packîng for a given particie size distribution.
[OUI] As illustrated in Figures 2 and 3, the composition of cementitious reagents in accordance with embodiments of the invention is different from existing cementitious materials. Indeed, considering combinations of temary compositions of element groups (CaO, MgO), (AI2O3, Fe2Û3), (Na2Û, K2O), and (SiCh), embodiments of a cementitious reagent 201 occupies a position in these figures that is different and distinct from fly ash (C and F) 202, groundgranulated blast-famace slag (GGBS or GGBFS) 203, metakaolin 204, and Portland cernent 205.
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Examples of spécifie feedstock compositions are shown in Figure 2: volcanic pumice 211 (Example 1), basait 212 (Example 2), a second basait 213 (Example 3), coal tailings samples 214 (Example 4), dredged sédiment 215 (Example 5), copper porphyry dotation tailings 216 (Example 6), demolished concrète 217 (Example 7), dioritic aggregate crusher dust 218 (Example 8).
[0112] Advantageously, the cementitious reagent is formulated from globally abundant rock, minerais and compounds of suitable composition. In this way, the abondant feedstock may not need to be shipped very far to a processing facility, or a cernent plant. In some instances, a cernent plant is built at the feedstock location.
[0113| In some embodiments, a cementitious reagent comprises a mixture of microspheroîdal glassy partie les as defined herein and further comprises one or more of the following properties: (i) is in the form of a non-crystalline solid; (ii) is in the form of a powder; (iii) comprises particle size distribution with D[3,2] of about 20gm or less, more preferably 1 Ogm or less, or most preferably 5pm or less; (iv) comprises the oxide Formula 1, as defined hereinbefore; (v) a content of 45%-100%, and preferably 90-100%, X-ray amorphous solid; (vi) a molar composition ratios of (Ca,Mg)o-i2*(Na,K)o.o5-j*(Als Feî+)i*Sii-2o; (vii) comprises less than about 10 wt.% CaO; (viiî) comprises more than about 30 wt.% Cad; (ix) comprises a molar composition of SÎ/(Fe3+,Al) between 1-20, and CaO content of about 10- about 50 wt,%, preferably about 20-45 wt.%; (x) comprises a molar composition of Si/(Fe3+,Al) between 1-20, and CaO content of about 10- about 20 wt.%; (xi) is 40-100% X-ray amorphous, more preferably above 80%, above 90%, and in some cases, up to about 100% X-ray amorphous, and in some cases, is 100% non-crystalline; (xîî) comprises a particle size distribution with D[3,2] of about 20 pm or less, more preferably about 1 Opm or less, or most preferably about 5pm or less.
[0114] In some cases, the CaO content is lower than about 30 wt.% in order to reduce the CO2 impact of cernent by avoiding a need for décomposition of carbonate-sourced calcium. [0115] In some embodiments, the cementitious reagent comprises less than about 10 wt.% CaO. In some embodiments, ihe cementitious reagent comprises more than about 30 wt.% CaO. In some instances, the composition of cementitious reagent with respect to molar ratio of (Na, K), and Ca may be varied to obtain certain advantages depending on the bînder requirements. For example, a cementitious reagent with less than about 10 wt.% CaO is suitable for use in heatcured geopolymer and as a fl y ash substitute. In the alternative, a cementitious reagent with
- 1720565 greater than about 30 wt.% CaO has hydrauiic properties and may be added to geopolymer resin to allow ambient-température curing of geopolymer cernent, and directly replaces blast furnace slag in blended Portland cernent.
[0116] In some embodiments, the cementitious reagent is a low-calcium containing cementitious reagent with a molar composition of Si/(Fe3+,Al) between 1-20, and with a CaO content of about 10 wt.% or less. Preferably such cementitious reagent is 40-100% X-ray amorphous, more preferably about 80% to about 100% X-ray amorphous, and în some embodiments 100% non-crystalline. Such low-calcium containing cementitious reagent may find numerous commercial applications, for instance, as a pozzolanic admixture in hydrauiic cernent, and/or as a reagent in geopolymer binders and cements.
[0117] In some embodiments, the cementitious reagent is a high-calcium containing cementitious reagent with a molar composition of Si/(Fe3+,Al) between 1-20, and CaO content of about 10- about 50 wt.%, preferably about 20-45 wt.%. Preferably such cementitious reagent is 40-100% X-ray amorphous, more preferably about 80- about 100% X-ray amorphous, even more preferably 100% non-crystalline. Such a high-calcium containing cementitious reagent may find numerous commercial applications, for instance as a hydrauiic admixture in blended hydrauiic cernent, and/or as a reagent in geopolymer binders and cements.
[0118] In some embodiments, the cementitious reagent is an întermediate-calcium containing cementitious reagent with a molar composition of SÎ/(Fe3+,Al) between 1-20, and CaO content of about 10- about 20 wt.%. Preferably such cementitious reagent is about 40-100% and preferably about 80% to about 100% X-ray amorphous, and even more preferably 100% non-crystalline. Such an intermediate-calcium containing cementitious reagent may find numerous commercial applications, for instance as a cementitious reagent with désirable intermedîate hydrauiic and pozzolanic properties, particularly in ambient-curing geopolymer applications.
[0119] In some embodiments, the Na,K content in the cementitious reagent is optimized. This may be advantageous for SCM applications where free lime in hydrauiic cernent will exchange with soluble alkalis and coordinate with sialate molécules derived from cementitious reagent to create some extent of relatively stable alkalî aluminosilicate polymerization that greatly improves Chemical properties of traditional hydrauiic cements. In embodiments, the Na,K content is optimized due to the fact that geopolymer reagents wîth signîficant Na,K contents
- 1820565 requîre less soluble silicate hardener than would otherwise be necessary, thus decreasing the soluble silicate requirement (and cost) of a geopolymer mix design.
[0120] Methods of préparation
[0121] Microspheroidal glassy particles as defined herein, as well as compositions comprising same such as cementitious reagents, geopolymer binders or cements, hydraulîc cements, supplementary cementitious materials (SCMs), and concrète can be prepared using any suitable method or process.
[0122] FIG. 1 shows exemplary steps necessary to produce cementitious reagent from aluminosilicate materials in accordance with some embodiments. Briefly, a finely dîvided aluminosilicate material powder 101 is selected and its Chemical composition is analyzed 102 and evaluated. The feedstock may be analyzed by any suitable quantitative or semi-quantitative methods such as XRF, XRD, LIBS, EDS, wet Chemical analysis, and varions other existing methods to détermine the feedstock elemental composition.
[0123] If the selected composition is not acceptable, the material is optionally amended, blended (e.g. in a vessel prior to thermochemical processing), for example, through addition of a composition adjustment material 104 (see hereinafter) or sorted 103 and any undesirable waste material may be discarded.
[0124] The resulting solid aluminosilicate material comprising a powder of désirable composition is next heated 106 and individual particles or particle agglomérâtes are melted into a liquid in suspension. Next the liquid particles in suspension are quenched 107 to obtain a powder comprising solid microspheroidal glassy particles. Next, the powder is optionally crushed and/or pulverized (partialiy or entirely) 108 if it is desired to reduce particle size and/or to optimize reactivity and obtain the cementitious reagent 109.
[0125] Regarding the addition of a composition adjustment material 104, as used herein the term “composition adjustment material” refers to any solid or liquid material with a composition suitable for preferentially altering the bulk or surface composition of aluminosilicate material with respect to one or several of the éléments Ca, Na, K, Al, Fe, and Si.
[0126] Composition adjustment materials that introduce calcium (Ca) may be comprised of calcium salts including CaCOs, Ca(OFI)2, CaO, CaCl, CaF2, calcium silicate minerais and compounds, calcium aluminum silicate minerais and compounds, waste Portland cernent
- 1920565
Products, waste hydraulic cernent products, wollastonite, gehlenite, and other melilite group minerai compositions.
[0127] Composition adjustment materials that introduce aluminum (Al) may be comprised of alumînous rocks, minerais, soils, sédiments, by-products, and compounds including one or more of kaolinite, halloysite and other aluminum-rïch/alkali-poor clay minerais, AhSiOs polymorphs, chloritoid, stauroiite, garnet, corundum, mullite, gehlenite, dîaspore, boehmite, gibbsite, and nepheline and other feldspathoids. Other materials that may be used include aluminum métal, bauxite, alumina, red mud (alumina refinery residues).
[0128] Composition adjustment materials that introduce iron (Fe) may be comprised of ironrich rocks, minerais, soils, sédiments, by-products, and compounds such as olivine, chlorite minerais (chamosite, clinochlore, etc.), pyroxenes, amphiboles, goethite, hématite, magnetite, ferrihydrite, lepidîcrocite and other iron oxy-hydroxide compositions, iron-rich clay and phyllosiiicate minerais, iron ore taîlings, and elemental iron.
[0129] Regarding the heating 106, the heating is carried out to reach a heating température above a liquid phase température to obtain a liquid, for instance at about 1000-1600°C, or about 1300-1550°C. Any suitable method or apparatus may be used for the heating and for obtaîning the liquid including, but not limited to, in-flight melting (i.e. suspension melting). This may be achieved by using an in-flight melting apparatus equipped with, for instance, one or more plasma torches, oxy-fuel bumers, air-fuel burners, biomass bumers, a solar concentrating furnace.
Typically, a furnace température of 1000-1600°C is needed, and most typîcally i 300-1550°C, to rapidly obtain the desired liquid phase particles in suspension. In embodiments, the device is selected such that melting is as fast as possible. An example of a suitable in-flight melting apparatus and method is described hereînafter.
[0130] Regarding the quenching 107, in some embodiments the quenching step comprises reducing température of the liquid below the glass transition, for instance at about 500°C or lower, or preferably below about 200°C or lower. In embodiments, the quenching is doue rapidly, i.e. the température is reduced at a rate of about 102 Ks'1 - 106 Ks-1 (preferably at a rate of >IO35 Ks'1). Any suitable method may be used for the quenching including, but not limited to, contacting the molten material with a sufficient stream of adequately cool air, with steam, or with water to produce a non-crystalline solid.
-2020565
[0131] If desired, a fluxing material may be added to the solid aluminosilicate material in order to lower its melting point and/or to induce depolymerization of the liquid. The fluxing material may be mixed with the solid aluminosilicate material prior to heating/meiting or during the heating/meiting. Common fluxing materials that may induce depolymerization in melts, and/or lower melting température includes CaFz, CaCCh, waste glass, glass cullet, glass frit, alkalî-bearing minerais (e.g. feldspars, zeolites, clays, and feldspathoid minerais), borate salts, halogen compounds (fluoride and chloride bearing salts) and calcium salts.
[0132] Regardîng the optionally crushing and/or pulverîzation step 108, this may be carried out using any suitable method or apparatus including, but not limited to, a bail mill, a roller mill and a vertical roller mill. Preferably the particle size is reduced to obtain a fine powder useful in cementitious applications. Obtaining a finer powder may be useful for increasîng surface area and providing for faster reaction rates, as described for instance in Example 9. Those skilled în the art will be able to détermine the size of the particles desired for a particular need, taking into considération an économie trade-off between loss of spherîcal morphology/workability, cost of grinding, and final performance requirements. In embodiments, the powder comprises a particle size distribution with D[3,2] of approximately ΙΟμιη or less, or preferably 5pm or less. Such a particle size îs generally désirable to ensure sufficient reactivity and consistent material propertîes.
[0133] Uses of Aluminosilicate materials
[0134] As described herein, some embodiments concern the use of aluminosilicate materials to produce solid microspheroidal glassy particles and non-crystalline cementitious reagents as defîned herein.
[0135] Another aspect is the use of in-flight thermochemical processing of aluminosilicate materials to produce solid microspheroidal glassy particles and/or of solid cementitious reagents. The glassy particles and solid cementitious reagents described herein may advantageously be used as an alternative supplementary cementitious material (SCM) in blended hydraulic cernent and/or as a geopolymer solid reagent in geopolymer binders (thus eliminatîng the need for some or ail of MK-750, fly ash, GGBFS, and other common solid reagents).
[0136] Another related aspect is the use of an aluminosilicate material to produce at least one of a supplementary cementitious material (SCM) and a geopolymer reagent comprising solid microspheroidal glassy particles and/or a non-crystallîne cementitious reagent as defîned herein.
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[0137] Uses ofthe microspheroidal glassy particles and cementitious reagent
[0138] One aspect of described embodiments concerns the broad relevance of the solid microspheroidal glassy particles and cementitious reagent described herein. Appropriate compositions of engineered cementitious reagent may be used interchangeably in significant proportion in both geopolymer cements and hydraulic cements (i.e. cements that react with water).
[0139) Accordingly, some embodiments encompass geopolymer cements and hydraulic cements comprising at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 40 wt.%, or at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wl.%, or more, of solid microspheroidal glassy particles and/or cementitious reagent as defined herein.
[0140) In accordance with some aspects, some embodiments described herein relate to a supplementary cementitious material (SCM) comprising a cementitious reagent as defined herein. In some embodiments, the SCM comprises about 5 wt. % to about 50 wt.% (preferably at least 20 wt. %) of solid microspheroidal glassy particles and/or of the cementitious reagent as defined herein.
[0141] In accordance wîth another aspect, some embodiments described herein relate to a supplementary cementitious material (SCM) comprising one or more ofthe following properties: it comprises less than about 35 wt. % CaO, with appréciable content of Na+K (e.g. at least 2 wt. %, preferably at least 5 wt.%) and Al content (e.g. at least 5 wt.%) and is in the form of a noncrystalline solid.
[0142] In accordance with another aspect, some embodiments relate to a solid concrète, comprising solid microspheroidal glassy particles and/or a cementitious reagent as defined as defined herein, i.e. comprising about 5 wt. % to about 50 wt.% (preferably at least 10 wt. %, or at least 20 wt. %, least 30 wt. %, or least 40 wt. %) of solid microspheroidal glassy particles and/or of the cementitious reagent as defined herein.
[0143] In accordance wîth another aspect, some embodiments relate to solid geopolymer concrète comprising about 5 wt. % to about 50 wt.% (preferably at least 10 wt. %, or at least 20 wt. %, least 30 wt. %, or least 40 wt. %) of solid microspheroidal glassy particles and/or of the cementitious reagent as defined herein.
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[0144| Those ski lied in the art can appreciate that embodiments of the présent invention advantageously provide means to produce versatile low-COs cementitious reagents from abundant, cheap, natural materîals. Another significant advantage is the création of a single reagent that meets today’s spécification standards for alternative SCMs, while also meeting the needs of the growing geopolymer market. Further, the cementitious reagents are formed from diverse, heterogeneous feedstocks, and through the described processes, resuit in a reagent material that is more homogeneous and suitable as a cementitious reagent.
[0145] As can be appreciated, one advantage of the Systems and methods described herein is to provide control over the final composition of the cementitious reagent, thereby producing a reagent with predictable composition, which is very important to the industry. Such taiiored composition is not available in other existing cementitious reagents, because they are typically obtained from industrial by-products. In accordance with embodiments described herein, it is possible to modify local feedstocks where necessary to standardize performance for given applications. For example, in SCM for Portland cernent it may be désirable to 1 imît alkali content, but in geopolymer Systems it may be désirable to hâve high alkali content and lessen the need for alkali silicate hardener. In both scénarios, composition modifications may be désirable to limit compositional varîabîlity of the feedstock.
[0146] Another notable concern for the chemistry of geopolymer reagents îs labile calcium content. Adjustment of calcium content and phase containing the calcium are both important variables for adjusting rate of strength gain under different température conditions and final material properties of geopolymer cernent. The methods described herein make it possible to engîneer certain advantageous compositions of microspheroidal cementitious reagents which is not currently possible for by-product-based cementitious reagents.
[0147] In-flight melting apparatus, method and system
[0148] Embodiments also relate to an apparatus, a System, and related methods for the thermochemical production of glassy cementitious reagents with spheroidai morphology.
[0149] According to some embodiments, an apparatus is configured for in-flight melting/quenching. According to some embodiments, such as those illustrated in Figures 9A and 9B, the apparatus 900 comprises: a bumer 809; and a melting chamber combined with a quenching chamber 902. In some embodiments the melting chamber and the quenching chamber
-2320565 may be first and sections of the same chamber 902, respectîvely. In some embodiments, the melting chamber and the quenchîng chamber are separate consecutive chambers.
[0150] As illustrated, the apparatus 900 is configured for in-flight meltîng/quenchîng. Aluminosilicate feedstock particles 903 enters the melt/quench chamber (top; 902) suspended in a flame 901 combusting an oxidant gas 807 with a combustible fuel 808. The aluminosilicate feedstock particles 903 are entrained by a venturi eductor into the oxidant gas and flow in suspension during combustion towards the melt/quench chamber 902 as they become heated and eventually molten, above liquid phase transition. The gas may include an oxidant gas, including but not limited to oxygen, air mixed with a combustible fuel, including but not limited to propane, methane, liquid hydrocarbon fuels, coai, syngas, biomass, coal-water slurries, and mixtures thereof. Preferably the flame 901 is stabilized by an annular flow of quench air 904 that protects the melt/quench chamber 902 and prevents particles from sticking to inner wall 905 of the melt/quench chamber 902.
[0151] In the apparatus 900, molten particles are next quenched by cooling in air as the suspension becomes turbulent at an end of the melt/quench chamber 902. Cooling/quenching of the molten particles may be provided by cool quench air introduced directly into the melt/quench chamber 902, and/or by an optional cooling system, for instance a liquid cooling loop around a quenchîng section of the melt/quench chamber 902 (not shown). The molten particles may be quenched or cooled to a non-crystalline solid powder, and may resuit in a powder comprising microspheroidal glassy particles. The apparatus may further comprise an optional cyclone separator operated under suction from a centrifugal blower to collect the powder comprising microspheroidal glassy particles (not shown).
[0152] The apparatus 900 or similar can be used in various Systems to produce a glassy microspheroidal cementitious reagent. Figure 8 illustrâtes one embodiment of a schematic process flow diagram of an exemplary system 800 for producing a glassy microspheroidal cementitious reagent, which in some cases, produces a microspheroidal glassy reagent powder 109.
[0153] In the embodiment of Figure 8, the system 800 comprises a milling circuit 801 to obtain an aluminosilicate feedstock powder 101. Coarse aluminosilicate feedstock material 802 is fed to a jaw crusher or impact mill 803 to produce a suitably sîzed feed 804 allowing fine
-2420565 grinding în a bail mill 805. The resulting product is a fïnely divided aluminosilicate feedstock powder 101.
[0154] The flnely divided aluminosilicate feedstock powder 101 is next entrained in an oxidant gas (e.g. oxygen) 807, and mixed with a combustible fuel (e.g. propane) 808 in a burner 809 that is fitted with a liquid cooling loop 810 for long torch life. Ambient température quench air 811 is introduced, preferably near the burner 809, and flows down the outside of the melt/quench chamber 8 ! 2 walls for preventing molten particles from sticking to the walls of the burner 809. Wall cooling may be provided by the quench air, and/or by an optional liquid cooling loop 813. Molten particles are quenched by cool quench air as the suspension becomes turbulent at the end of the melt/quench chamber. A cyclone separator 814, operated under suction from a centrifugal blower 815 may be used to collect the microspheroîdal glassy reagent powder 109.
[0155] The apparatus of Figure 9 and system of Figure 8 were successfully used to produce solid microspheroîdal glassy particles, and cementitïous reagent comprising the same, as defined herein and described in the following examples. The operating parameters involved an approximately stoichiometric combustion of propane and oxygen gases (exact mass ratio not measured). Powdered feedstock 101 entered the burner from a pneumatic disperser fed by a vibratory feeder. The suspension of feedstock and combustion air consisted of approximately an equal mass of oxygen and powdered feedstock; for example, 1 g of aluminosilicate feedstock suspended in 1 g of oxygen.
[0156] Those skilled in the art will appreciate that the illustrated apparatus, system and parameters are ones of many potential useful apparatus and system encompassed by the présent invention. For instance, in altemate embodiments, the solid particles fly in suspension în a carrier gas and are heated by one or more energy sources. The energy for melting may be provided by one or a combination of suitable high-température heat sources such as plasma (arc discharge or ïnductively coupled), electrical induction heating, electrical résistance heating, microwave heating, solar irradiation, or heat from Chemical reactions (e.g. combustion). Several of these energy sources may lower the CO2 footprint of the process, but costs of CO2 émissions must be weighed against the unique costs of each energy source. In many jurisdictions today, the cheapest energy sources are based on combustible hydrocarbon fuels. Therefore, the choice of energy source is mostly dictated by price and cost of CO2 émissions in a given jurisdiction.
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Current économie and politîcal factors dictate that preferably, the solid particles fly in suspension in a gas such that combustion beats the solid particles to a température above the liquid phase transition.
[0157] Although an oxygen-fuel burner was used in the examples provided, those ski lied in the art will appreciate that the choice of burner fuels is of only secondary importance as long as adéquate heating occurs. Any source of heat from combustion, plasma, concentrated solar power, nuclear, and others, are possible.
[0158] In some embodiments, an air-fuel burner is préférable to avoid the cost of oxygen enrîchment. When air, consisting of only about 23 wt% oxygen, is combusted with fuels (propane or methane for example) the air-fuel ratio is much higher (~4-5x) to maintain an approximately stoichiometric combustion. A higher air-fuel ratio results in lower flame températures. Therefore, it is préférable to adjust accordingly the feedstock powder mass flow to ensure the particles are heated beyond their solidus, and preferably near or beyond their liquidus température (1000-1600° C, and commonly greater than 1200° C).
[0159] Figure 10 illustrâtes another embodiment of an apparatus and system for in-flight melting/quenching in accordance with embodiments described herein. Feedstock 101 passes through valve 1002 and enters cyclone 1003 where it is preheated by exchanging heat with hot gases. Valve 1004 meters feedstock powder into hot gas (e.g. combustion air) flowing through pipe 1025. Combustion air and feedstock suspension is conveyed through a burner 1005 wherein combustible gas is introduced through pipe 1006. A cylindrical melting chamber 1007 is configured to receîve a hot stream of gas (e.g. combustion gases) entrained with aluminosilicate particles in various stages of melting 1008. The melting chamber 1007 comprises a cylindrical shell 1009 of suitable material such as Steel, and an inner lining of suitable refractory material 1010. The melting chamber 1007 is also protected internally by a stream of cool air (primary quench air) 1011 injected from an upper distribution ring 1012. Cooling air flows inside the melting chamber 1007 around inner chamber walls in a laminar or swirling flow 1013 without mixîng significantly wîth the central stream ofmolten suspended particles 1008. This airflow also protects the inner refractory lining 1010 and limits heat loss.
[0160] Molten particles 1008 next enter a quenching chamber or quench zone 1014 where particles interact with primary quench air 1013 and optionally secondary cool quench air 1015 that passes through a dîstributor 1016 and is injected 1017 into the quenching chamber 1014.
-2620565
[0161] Quenched, hot solid parti clés 1018 flow suspended through pipe 1019 and are separated from hot gases in a cyclone separator 1020. Hot solid glassy particles pass through valve 1021, exchange heat with cool combustion air 1024, and are separated in combustion air preheat cyclone 1022. Valve 1023 régulâtes pressure and allows collection of mîcrospheroidal glassy product 109. The cyclone separators 1003, 1020,1022 also fonction as solîd/gas heat exchangers for important heat recovery loops that increase energy efficiency of the process. In cyclone 1020, hot gases from the melting chamber 1007 are separated from solids and these gases preheat cooler feedstock powder 101 before séparation in cyclone 1003. The heatexchanged exhaust gas 1027 reports to a suitable exhaust System (for example, a baghouse and blower) or passes on to further stages of heat exchange cyclones. In cyclone 1022, hot quenched particles 1018 exchange heat with cool combustion air 1024 and the preheated combustion air is used to convey preheated feedstock powder into the melting chamber 1007 thereby consîderably reducing the amount of energy that must be added to achieve melting of the suspended particles.
EXAMPLES
[0162] EXAMPLE 1: Yield Stress Réduction with Synthetic Spheroidal Particles
[0163] To demonstrate the improvement to geopolymer cernent mix viscosity, the following procedure was employed. A commercially-availabié pulverized volcanic glass powder of oxide composition SiO2-73.77%; A12O3-11.82%, Fe2O3-1.42%; MgO-0.1%; CaO-O.28%; Na2O4.22%; K2O-4.09% was purchased having a D[3,2] mean particle dîameter of 10 micrometers and angular morphology typical of finely ground powders. The volcanic glass powder sample 402 (FIG. 4) was processed by the presently disclosed method of in-flight melting in order to create an optimally molten/quenched powder 403, having a D[3,2] mean particle size of 11 micrometers, and substantially spheroidal morphology characterized by roundness R >8 (see FIG. 4). More specifically, the natural volcanic glass powder (angular morphology) was processed by the apparatus shown in FIG. 8 and FIG. 9. The bumer was a commercial oxygenpropane burner model QHT-7/hA from Shanghai Welding & Cutting Tool Works with modified powder feeding, the burner fired into a Steel melt chamber with water-cooled walls, and particle températures exceeded the mean liquidas température of the material, about 1300°C as estimated from compositîonal data. It is înterpreted that liquidas temperatare was exceeded based on i) the mîcrospheroidal morphology that results from surface tension in liquid phase, ü) homogeneous
-2720565 composition (under backscattered électron imaging) and iii) the absence of unmolten or partially molten particles în the final reagent. In this experiment, the burner was not sealed tîghtly to the melt chamber, and thereby cool quench air was allowed to rush in along the walls of the melt chamber, only quenching the molten entrained powder after sufficient résidence time to allow melting. Quenched hot powder was separated from hot combustion gases with a cyclone as shown in Figure 8 and glass powder was collected for testing. The resulting product in this example is a highly spherical synthetic glass (D[3,2] = 11 micrometer) of équivalent composition and nearly équivalent particle size distribution (Figure 4) as the raw feedstock.
[0164] The microspheroidal minerai glass powder has a molar Si/(AI, Fe3+) of 19.68, and molar cementitious reagent formula of (Ca,Mg)o i2*(Na,K)o 89*(Al, Fej+)i*Si 19.68 and CaO of 0.28 wt.% (CaO,MgO of 0.38%) .
[0165] The experiment compares two geopolymer reagents with particles of équivalent composition and nearly équivalent particle size distribution (confirmed by laser diffraction particle size analysis, FIG. 4). The only drastically changed variable is particle morphology. [0166} The powders were mixed separately as geopolymer binder pastes using the following mix design optimized for minimal water use for angular volcanîc glass (“Mix A”):
[0167] A 99.5 g mixture is made containing 1.77 moles of water, 0.12 moles NazO + K2O, 0.82 moles S1O2 and 0.08 moles AI2O3 + FeaCh. The source of AI2O3 + Fe20î is the cementitious reagent glass or volcanîc glass. The source of S1O2 is also the cementitious reagent or volcanic glass and potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxi de. The oxide mole ratios of each mix are provided in Table 1, shown below.
[0168] Spheroîdal Mix A was too fluid when mixed at the same mass proportions as Angular Mix A, which had very poor workabîlity even at very high water contents of 40 wt.% H2O. Surprisingly, Spheroîdal Mix B, containing only 15 wt.% I-I2O, had excellent workabîlity as indicated by low yield stress of ~6 Pa.
[0169] The glassy spheroîdal powder was remîxed with an îdentical amount of solid reagent, but lower proportions of silicate hardener and water (“Mix B”):
[0170] A 79 g mixture was made containing 0.73 moles of water, 0.11 moles NaaO + K2O, 0.8 moles S1O2 and 0.08 moles AI2O3 + Fe2Oj. The source of AI2O3 + Fe2Û3 is the spheroîdal cementitious reagent. The source of SiÛ2 is also the spheroîdal cementitious reagent and
-28 20565 potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxide. The oxide mole ratios of each mîx are provided in Table 1, shown below.
[0171] A mini-cone slump test (as described by Tan et al. 2017) was employed to détermine the approximate yield stress for the angular powder Mix A (spread radius 24 mm), and the spheroîdal powder Mix B (spread radius 60 mm). The angular powder produced a non-shearflowing mass with approximate yield stress of 425 Pa or greater (as calculated by slump flow équation 10 elaborated in Pierre et al. 2013 (Pierre, A,, Lanos, C., & Estelle, P. (2013). Extension of spread-slump formulae for yield stress évaluation. Applied Rheology, 23(6), 36-44).
Surprisingly, the spheroîdal mix had only 41% of the molecular water content of the angular mix (including water in soluble silicate hardener) y et produced an easily pourable resinous fluid with yield stress of only approximately 6.5 Pa (as calculated by the spreading flow équation 2 in Tan et al. 2017 (Tan, Z., Bernai, S. A., & Provis, J. L. (2017). Reproducîble mini-slump test procedure formeasuring the yield stress of cementitious pastes. Materials and Structures, 50(6), 235).
[0172] Table 1 : Oxide mole ratios of mixes
| Molar ratio | Angular “Mix A” | Spheroîdal “Mix A” | Spheroîdal “Mix B” |
| (Na2O,K2O)/SiO2 | 0.14 | 0.14 | 0.14 |
| SÎO2/(A12O3, Fe2O3) | 11.72 | 11.72 | 10 |
| H2O/(A12O3, Fe2O3) | 22.125 | 22.125 | 9.125 |
| (Na2O,K2O)/(Al2O3, | 1.63 | 1.63 | 1.375 |
| Fe2O3) | |||
| H2O/(Na2O,K2O) | 15.65 | 15.65 | 7.05 |
| H2O in paste (wt.%) | 40% | 40% | 15% |
| Yield Stress (Pa) | 425 | <1 | 6 |
[0173] Angular Mix A and Spheroîdal Mix B were heated and cured in a sealed container at 80 degrees Celsius for 6 hours. The angular paste hardened poorly, likely due to the hîgh water content, while the spheroîdal paste hardened to a ceramic-like solid with a fine glossy surface.
[0174] EXAMPLE 2: Basait “FC”
[0175j Oligocène basaltic rock was sampled in Vancouver, BC, The mineralogy of the rock is domînated by plagioclase, diopsîde and a clay-like phase that is likely a weathering product (Table 2, determined by XRD with Rietveld refînement). The major element oxide composition is provided in Table 3.
-2920565 ]0176] Table 2. Mineralogy of basait sample
| Phase | Weight % |
| albite-low (calcian) | 56.2 |
| diopside | 13.5 |
| clay (montmoriBonite model) | 12.5 |
| forsterite (ferrian) | 5.0 |
| Illite/muscovite 2M1 | 2.6 |
| lizardite IT | 1.7 |
| ilmenite | 1.7 |
| quartz | 1.6 |
| calcite | 1.5 |
| ulvospinel (ferrian) | 1.4 |
| [0177] | Table 3. Oxide Composition of basait “FC” (XRF) |
| Oxide | Weight % |
| SÎO2 A12O3 Fe2O3 MnO MgO CaO Na2O K2O | 48.13 15.97 11.99 0.16 7.83 9.51 2.77 0.5 |
[0178] The basait was crushed in a jaw crusher, then pulverized in a dise mi 11, and further reduced in a ring mill to a powder with mean particle size of approximately 10 pm. The powder was fed through a vitrification apparatus that heated the material through the liquid transition to approximately 1450°C, followed by a rapid quenching step. The resulting glass was 96.7% X-ray amorphous (Table 4).
[0179] Table 4. XRD-Rietveld analysis of basait glass (corundum spike)
| Phase | Weight % |
| amorphous iron-alpha (from grinding media) quartz | 96.7 1.9 1.4 |
[0180] The microspheroîdal basait glass powder has a molar Si/(Al, Fe3+) of 6.93, and molar cementîtîous reagent formula of (Ca,Mg)î.i5*(Na,K)o.2i*(Al, Fe3+)i*SÎ6.93 and CaO of 9.51 wt.% (CaO,MgO of 17.3%).
-3020565
[0181] Individual particles were observed to be highly spherîcal and mean roundness R is >0.8 (as defined previously), and D[3,2] is 10.5 pm.
[0182] A 131 g mixture is made containing 1.31 moles of water, 0.1 moles Na2O + K2O, 0.88 moles SiO2 and 0.24 moles A12O3 + Fe2O3- The source of AI2O3 + Fe2O3 is the microspheroidal basait powder prepared above. The source of SiO2 is also the basait powder and potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxide. The oxide mole ratios are provided in Table 5, shown below.
[0183] Table 5: Oxide mole ratios
| (Na2O,K2O)/SiO2 SiO2/(Al2O3, Fe2O3) FhO/fAhOs, Fe2O2) (Na2O,K2O)/(Al2O3, Fe2O3) H2O/(Na2O,K2O) | o.n 3.67 5.45 0.42 13.76 |
| Yield Stress (Pa) | 21.7 |
[0184] A mini slump cône test was performed on the geopolymer cernent paste and resulted in a flow diameter of 98.4 mm and a calculated yield stress of21.7 Pa. 110 g ofsand was added to the paste, foilowed by 6 hours of sealed curing at 80 degrees Celsius. The compressive strength of a mortar sample cube was determined to be 19 MPa.
[0185] EXAMPLE 3: Basait “BD”
[0186] A commercially available powdered basait “BD” has the oxide composition provided în Table 6, shown below.
[0187] Table 6. Oxide Composition of basait “BD” (XRF)
| Oxide | Weight % |
| SiO2 A12O3 Fe2O MgO CaO Na2O K2O | 49.77 14.42 11.18 4.38 9.66 2.62 0.63 |
| [0188] The powder was fed through | a vitrification apparatus that heated the material through |
a liquid phase change to approximately 1450°C, foilowed by a rapid quenching step. Successful
-31 20565 melting through the iiquid phase was demonstrated for most particles by a highly spherîcal bulk particle morphology.
[0189] The microspheroidal basait reagent powder “BD” has a molar Si/(A1, Fe3+) of 7.84, and molar cementitious reagent formula of (Ca,Mg)2.66*(Na,K)o.23*(Al, Fe3+)i*SÎ7.84 and CaO of 9.66 wt.% (CaO,MgO of 14.04%). Individual particles were observed to be highly spherîcal and smooth, roundness R is greater than 0.8, and D{3,2] is 8.0 gm as measured by laser diffraction. [0190] A 116 g mixture was made containing 1.53 moles of water, 0.09 moles NasO + K2O, 0.75 moles S1O2 and 0.17 moles ΑΙ2Ο3 + Fe2O3. The source of AI2O3 + Fe2Ü3 isthe microspheroidal basait powder prepared above. The source of S1O2 is also the basait powder and potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxide. The oxide mole ratios are provided in Table 7.
[0191] Table 7: Oxide mole ratios
| (Na2O,K2O)/SiO2 SiCh/tAhOj, Fe2Û3) H2O/(A12O3, Fe2Û3) (Na2O,K2O)/(A12Oî, Fe2O3) H2O/(Na2O,K2O) | 0.11 4.41 9.00 0.53 18.06 |
[0192] 110 g of sand was added to the mixture, and the sample was cast into cube molds, followed by 6 hours of sealed curing at 80 degrees Celsius. From three samples, the mean compressive strength of the mortar was determined to be 27.4 MPa with standard déviation of 2.22 MPa.
[0193] EXAMPLE 4: Coal tailings
[0194] A coal tailings sample acquired from Cape Breton, NS consists of approximately 60% resîdual coal and 40% minerai material. The înorganic fraction has the oxide composition provided in Table 8, shown below.
| [0195] | Table 8. Oxide Composition of Coal Tailings (XRF) |
| Oxide | Weight % (avg. of2 samples) |
| SiO2 AI2O3 FesOa MgO CaO Na2O K2O | 52.48 21.76 15.74 1.29 1.57 0.28 3.08 |
-3220565
[0196] Dried coal tailings with measured D[3,2] of 9.9 pm were fed through a vitrification apparatus that combusted excess coal and heated the inorganic material through a liquid phase change to approximately 1450°C} followed by a rapid quenching step. The coal fraction in the feedstock added considérable energy to the process: the flame power increased at least 46% processing coal tailings compared to an “inert” basait processed at the same mass flow rate. [0197] Successful melting through the liquid phase was demonstrated for inorganic particles by a highly spherical bulk particie morphology, with mean roundness (R) >0.8, and D[3,2] is 11.2 pm.
[0198] The microspheroidal coal tailings reagent powder has a molar Si/(A1, Fe3+) of 5.66, and molar cementitious reagent formula of (Ca,Mg)o38’(Na,K)o.io*(Al, Fe3+)rSis.66 and CaO of 1.7 wt.% (CaO,MgO of 2.56%) .
[0199] A 45 g mixture is made containing 0.57 moles of water, 0.04 moles N320 + K2Ü, 0.42 moles SiÛ2 and 0.12 moles AI2O3 + Fe2Û3. The source of AI2O3 + Fe2Û3 is the coal tailings microspheroidal powder prepared above. The source of SiO2 is also the coal tailings powder and sodium silicate. The source of sodium oxide is sodium silicate and sodium hydroxîde. The oxide mole ratios are provided in Table 9, shown below.
[0200] Table 9: Oxide mole ratios
| (Na2O,K2O)/SiO2 | 0.11 |
| SiO2/(AhO3, Fe2O3) | 4.45 |
| H2O/(AI2O3, Fe2O3) | 4.85 |
| (Ν32Ο,Κ2Ο)/(Α12Ο3, Fe2O3) | 0.49 |
| H2O/(Na2O,K2O) | 14.25 |
[0201] The mixture was cast into a cube mold, followed by 6 hours of sealed curing at 80 degrees Celsius. The sample was demolded and found to hâve a compressive strength of 21 MPa and a glossy ceramic-like surface.
[0202] EXAMPLE 5: Dredged Sédiment
[0203] A sédiment sample was acquired from the middle of Vancouver Harbour, BC to represent an example of dredged sédiment. The sample has the oxide composition provided in Table 10, shown below.
[0204] Table 10. Oxide Composition of sédiment (XRF)
Oxide Weight %
-3320565
SiO2 A12O3 FesCh MgO CaO Na2O K2O
67.06 12.69
5.62
2.4
2.98
2.69
1.64
[0205] The sample was dried and found to hâve a mass médian diameter, D50, of 47 pm.
Next, the sample was sieved to remove particles not passing 75 pm.
[0206) This powder was fed through a vitrification apparatus that heated the material through a liquid phase change to approximately 1450°C, followed by a rapid quenching step.
[0207] Successful melting through the liquid phase was démonstrated for most particles by a highly spherical bulk particle morphology. The microspheroidal sédiment reagent powder has a molar Si/(A1, Fe3+) of 11.49, and molar cementitious reagent formula of (Ca,Mg)i.55*(Na,K)o sj*(A1, Fe3+)i*Sii 1.49 and CaO of4.42 wt.% (CaO,MgO of 7.14%).
[0208] Indîvîdual particles are highly spherical and smooth, with mean roundness (R) >0.8, and D[3,2] of 11.8 pm.
[0209] A 98 g mixture is made containing 0.89 moles of water, 0.09 moles Na2O + K2O, 0.8 moles SiO2 and 0.13 moles AI2O3 + Fe2O3. The source of AI2O3 + Fe2O3 is the microspheroidal sédiment powder prepared above. The source of SiO2 is also the sédiment powder and potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxide. The oxide mole ratios are provided in Table 11.
[0210] Table 11: Oxide mole ratios
| (Na2O,K2O)/SiO2 | 0.12 |
| SiO2((AhO3, FesOs) | 6.15 |
| H2O/(A12O3, Fe2O3) | 6.85 |
| (Na2O,K2O)/(Al2O3, Fe2O3) | 0.69 |
| H2O/(Na2O,K2O) | 9.19 |
[0211] 1 10 g of sand was added to the mixture, and the sample was cast into a cube mold, followed by 6 hours of sealed curing at 80 degrees Celsius. The compressive strength of the mortar cube was determîned to be 25 MPa.
[0212] EXAMPLE 6: Copper Mine Tailings
-3420565
[0213] A sample of copper porphyry flotation tailîngs was acquired from Argentina to represent an example of a globally abundant aluminosilicate waste material. The sample has the oxide composition provided in Table 12, shown below.
| [0214] | Table 12. Oxide Composition of sédiment (XRF) |
| Oxide | Weight % |
| SiO2 AI2O3 Fe2O3 MgO CaO Na2O K2O | 70.98 15.26 2.64 1.18 1.09 2.75 3.44 |
[0215] The sample was sieved to remove particles not passing 75 pm. This powder was fed through a vitrification apparatus that heated the material through a liquid phase change to approximately 1450°C, followed by a rapid quenchîng step. Successfu! melting through the liquid phase was demonstrated for most particles by a highly spherical bulk partîcle morphology. [0216] The microspheroidal mine tailings reagent powder has a molar Si/(A1, Fej+) of 14.2, and molar cementitious reagent formula of (Ca,Mg)o.6*(Na,K)o5*(AI, Fe3+)i*Siu.2 and CaO of 1.94 wt.% (CaO,MgO of 4.87%).
[0217| Individual particles are highly spherical and smooth, mean roundness (R) is greater than 0.8, and D[3.2] is 11.4 pm.
[0218] A 103.6 g mixture is made containing 0.76 moles of water, 0.11 moles Na2O + K2O, 1.04 moles SiO2 and 0.13 moles AI2O3 + Fe2Û3. The source of AI2O3 + Fe2Û3 îs the microspheroidal tailings powder prepared above. The source of SÎO2 is also the tailings powder and potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxide. The oxide mole ratios are provided în Table 13, shown below.
[0219] Table 13: Oxide mole ratios
| (Na2O,K2O)/SiO2 | 0.10 |
| SiO2/(AI2O3, Fe2O3) | 8.64 |
| H2O/(AI2O3, Fe2Ü3) | 7.78 |
| (Na2O,K2O)/(A12O3, Fe2O3) | 0.89 |
| H2O/(Na2O,K2O) | 9.67 |
-35 20565
[0220] 110 g of sand was added to the mixture, and the sample was cast into a cube mold, followed by 6 hours of sealed curing at 80 degrees Celsius. The compressive strength of the mortar cube was determined to be 18 MPa.
[0221] EXAMPLE 7: Waste Concrète
[0222] Structural concrète cores were sampled from a mid-rise condominium construction site in Vancouver, BC. The material has the oxide composition provided in Table 14, shown
| below. | |
| [0223] | Table 14. Oxide Composition of a Structural Concrète (XRF) |
| Oxide | Weight % |
| SiO2 | 56.61 |
| AI2O3 | 13.94 |
| FesOs | 5.15 |
| MgO | 1.42 |
| CaO | 12.55 |
| Na2O | 3.55 |
| K2O | 1.48 |
| [0224] | The sample was sieved to remove particles not passing 75 pm. This powder was fed |
through a vitrification apparatus that heated the material through a liquid phase change to approximately 1450°C, followed by a rapid quenching step.
[0225] Successful melting through the liquid phase was demonstrated for most particles by a highly spherical bulk particle morphology.
[0226] The microspheroidal concrète reagent powder has a molar Si/(A1, Fe3+) of 12.3, and molar cementitious reagent formula of (Ca,Mg)3.o6*(Na,K)o.7*(Al, Fe3+)i*Si12.3 and CaO of 12.55 wt.% (CaO,MgO of 13.97%).
[0227] Individual particles are highly spherical and smooth, mean roundness (R) is greater than 0.8, and D[3,2] is 10.0 pm.
[0228] A 100 g mixture is made containing 1.27 moles of water, 0.08 moles Na2O + K2O, 0.73 moles SiO2 and 0.13 moles AI2O3 + Fe2Oj. The source of Α120ϊ + Fe2Û3 is the microspheroidal concrète powder prepared above. The source of SÎO2 is also the concrète powder and potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxide. The oxide mole ratios are provided in Table 15, shown below.
-3620565
[0229] Table 15: Oxide mole ratios
| (Na2O,K2O)/SiO2 | 0.11 |
| SiO2/(Al2O3, Fe2O3) | 7.59 |
| H2O/(A12O3, Fe2O3) | 10.79 |
| (Na2O,K2O)/(AI2O3, Fe2O3) | 0.86 |
| H2O/(Na2O,K2O) | 15.46 |
[0230] 100 g of sand was added to the mixture, and the sample was cast into a cube mold, followed by 6 hours of sealed curing at 80 degrees Celsius. The compressive strength of the mortar cube was determined to be 27 MPa.
[0231] EXAMPLE 8: Quarried Aggregate
[0232] Granodioritic crusher dust from an aggregate quarry near Vancouver, Canada was sampled for the following experiment. The sample has an oxide composition (SEM-EDX) of approximately SiO2-73%; A12O3-15%, Fe2O3-3%; MgO-0%; CaO-2%; Na2O-3%; K2O-4%. The rock was further crushed and milled to a fine powder completely passing 75 pm.
[0233] The resulting powder was processed by an in-flight vitrification apparatus that heated the material through a liquid phase change to approximately 1450°C, followed by a rapid quenchîng step.
[0234] Successful melting through the liquid phase was demonstrated for most particles by a highly smooth and spherical bulk particle morphology.
[0235] Individual particles are highly spherical and smooth, mean roundness (R) is greater than 0.8, and D[3,2] Îs 9.3 pm. The microspheroîdal granodîorite glass reagent powder has a molar Si/(A1, Fe3+) of 16.0, and molar cementitious reagent formula of (Ca,Mg)2.5*(Na,K)4 4*(Al, Feî+)i*Sii6.o and CaO of 2 wt.% (CaO,MgO of 2%).
[0236] A 105 g mixture is made containing 1.53 moles of water, 0.1 moles Na2O + K2O, 0.93 moles SiO2 and 0.12 moles A12O3 + Fe2O3. The source of A12O3 + Fe2O3 is the microspheroîdal aggregate powder prepared above. The source of SÎO2 îs also the aggregate powder and potassium silicate. The source of potassium oxide is potassium silicate and potassium hydroxide. The oxide mole ratios are provided in Table 16.
[0237] Table 16: Oxide mole ratios (Na2O,K2O)/SiO2 0.1
-3720565
SiO2/(Al2O3, Fe2O3)
H2O/(A12O3î Fe2O3) (Na2O,K2O)/(Al2O3, Fe2O3)
Η2Ο/(Ν32θ,Κ2θ)
8.0
10.8 0.9
12.9
[0238] The mixture above was cast as a paste into a cube mold, followed by 24 hours of sealed curîng at 80 degrees Celsius. The compressive strength of the paste cube was determined to be 11 MPa, showing that the material gains strength with heat curing, as expected. The lower relative strength can be explained by the omission of sand (as in mortar), and higher unmolten quartz minerai content compared to other examp les (quartz melts at > 1600°C), which acts as a relatively inert fi lier.
[0239] Summary of Examples 1 to 8
[0240] Table 17 below summarizes the main findings of examples 1-8 and also provides a compati son against the performance of two fly ashes; one commercial ly available Type F fly ash that has been beneficiated (B-FA), and fly ash of Type F composition sampled directly from a coal power plant in Nova Scotia, Canada. A visual représentation of the roundness R distributions is provided in Figure 5.
-3820565
| [0241] | Table 17: | Summary of Examples 1 to 8 | |||||||
| Mortar | |||||||||
| Particle | Compressive | ||||||||
| Size | R (Roundness) | Strength | |||||||
| D[3,2] | |||||||||
| Example | Sample | Material | Type | (Pm) | Mean | StDev | n | (MPa) | |
| 1 | PUM-1 | Pumice | Feedstock | 0.79 | 0.21 | 201 | <1 | ||
| Processed | 11.0 | 0.86 | 0.11 | 128 | H | ||||
| 2 | B-FC | Basait | Feedstock | 0.80 | 0.15 | 151 | |||
| Processed | 10.5 | 0.89 | 0.10 | 160 | 19 | ||||
| 3 | BD-1 | Basait | Feedstock | 0.75 | 0.16 | 1326 | |||
| Processed | 8.0 | 0.91 | 0.08 | 230 | 27 | ||||
| Coal | |||||||||
| 4 | VJ | Tailings | Feedstock | 0.73 | 0.17 | 561 | |||
| Processed | 11.2 | 0.89 | 0.06 | 652 | 21 | ||||
| 5 | FRS | Sédiment | Feedstock | 0.79 | 0.66 | 2383 | |||
| Copper | |||||||||
| Mine | |||||||||
| 6 | LA-01 | Tailings | Feedstock | 0.68 | 0.21 | 1414 | |||
| Processed | 11.4 | 0.90 | 0.08 | 294 | 18 | ||||
| Demolished | |||||||||
| 7 | SC-01 | Concrète | Feedstock | 0.78 | 0.14 | 627 | |||
| Processed | 10.0 | 0.88 | 0.10 | 238 | 27 | ||||
| SV- | Felsic | ||||||||
| 8 | AGG | Aggregate | Feedstock | 0.78 | 0.16 | 2564 | |||
| Processed | 9.3 | 0.88 | 0.07 | 951 | 11 | ||||
| Fly Ash | Direct from | ||||||||
| L-FA | (Type F) | Power Plant | 3.9 | 0.83 | 0.13 | 1505 | 2.2 | ||
| Fly Ash | |||||||||
| B-FA | (Type F) | Bénéficiât ed | 5.1 | 0.87 | 0.07 | 797 | 23 |
R - roundness (unîtless), as defined by Takashimizu & liyoshi (2016), n —number ofparticles analyzed.
[0242] EXAMPLE 9: Use of Synthetic Cementitious Reagent as Alternative SCM
[0243] Mîcrospheroidal basait sample “BD” of Example 3 above was further processed by pulverizing the powder in a ring mil! for 5 minutes, causing the coarsest particles to break and thereby increase reactive surface area. The D[3,2] particle size was determined to be 3.6 pm by laser diffraction analysis. Interestingly, small spheres <10 pm tend to act as bail bearings in the mil! and resist breakage. The reagent’s strength activity index was compared to a commercîally
-3920565 available hîgh-quality Type F fly ash with an oxide composition SiO2-52.09%; AI2O3-18.58%, Fe2O3-4.25%; MgO-2.98%; CaO-lO.25%; Na2O-6.03%; K2O-1.72%.
[0244] Following ASTM C618, 50 mm cubes were cast of a Portland cernent control mix, Portland cernent with fly ash (20% and 40% replacement), and Portland cernent with cementitious reagent BD powder (also 20% and 40% replacement). Table 18 provides the compressive strength results at 7 and 28 days. The performance of the BD mix at 20% replacement was comparable with the commercial Type F fly ash and the strength activity index was acceptable. The BD mix was easîly workable and mixed without trouble. Notably, both the BD reagent and fly ash produce very useable mortar strengths greater than 40 MPa after 28 days at 40% replacement of Portland cernent. BD cementitious reagent can therefore be consîdered a suitable fly ash replacement in terms of compressive strength.
[0245] Table 18: Strength of Portland cernent with cementitious reagent BD powder
| Compressive Strength | Strength Activity Index | |||
| 7 days | 28 days | Ratio to control (7 days) | Ratio to control (28 days) | |
| Control | 45.4 | 60.8 | ||
| FA-20 | 38.6 | 48.4 | 85% | 79% |
| FA-40 | 29.2 | 42 | ||
| BD-20 | 38.4 | 50.8 | 84% | 83% |
| BD-40 | 26.4 | 44 | ||
| Minimum requirement of ASTM C618 | 75% | 75% |
[02461 Cementitious material
[0247] According to some embodiments, a novel method of production and uses of cementitious reagents, geopolymer reagents and supplementary cementitious materials (SCM) provides significant advantages over the known methods and formulas.
[0248] According to some embodiments, a cementitious reagent comprises the oxide
Formula 1:
(CaO,MgO)a*(Na2O,K2O)b«(A12O3,Fe2O3)C’(SiO2)d [Formula 1] wherein a is about 0 to about 4, b îs about 0.1 to about 1, c is 1, and d is about 1 to about 15.
-4020565
[0249] Advantageously, the cementitious reagent in accordance with the présent invention is formulated from abundant rocks, minerais and compounds of suitable composition. Preferably the CaO content is lower that about 30 wt.% in order to reduce the CO2 impact of cernent.
[0250] In some embodiments, the cementitious reagent is in the form of a non-crystalline solid. In embodiments, the cementitious reagent is in a powder form comprising a particle size distribution with a D50 (médian diameter) of approxîmately 20pm or less, or preferably I0pm or less.
[0251] In embodiments, the cementitious reagent comprises at least one of the following properties: a content of 45%~100%, and preferably 90-100%, X-ray amorphous solid; and molar composition ratios of (Ca,Mg)o-i2*(Na,K)o.O5-i*(Al, Fe3+)i*Sii-2o.
[0252] In some embodiments, the cementitious reagent comprises less than about 10 wt.% CaO. In another embodiment, the cementitious reagent comprises more than about 30 wt.% CaO. The composition of cementitious reagent with respect to molar ratio of (Na, K), and Ca may be varied to obtain certain advantages depending on the binder requîrements. For example, a cementitious reagent with less than about 10 wt.% CaO îs suitable for use in heat-cured geopolymer and as a fly ash substitute. In the alternative, a cementitious reagent with greater than about 30 wt.% CaO has hydraulic properties and may be added to geopolymer resin to allow ambient-temperature curing of geopolymer cernent, and directly replaces blast furnace slag in blended Portland cernent.
[0253] In some embodiments, the cementitious reagent is a low-calcium containing cementitious reagent with a molar composition of Si/(Fe3+,Al) between 1-20, and with a CaO content of about 10 wt.% or less. Preferably such cementitious reagent is 40-100% X-ray amorphous, more preferably about 80- about 100% X-ray amorphous, even more preferably 100% non-crystalline. Such low-calcium containing cementitious reagent may find numerous commercial applications, for instance, as a pozzolanic admixture in hydraulic cernent, and/or as a reagent in geopolymer binders and cements.
[0254] In another embodiment. the cementitious reagent is a high-calcium containing cementitious reagent with a molar composition of SiZ/Fe^Al) between 1 -20, and CaO content of about 10- about 50 wt.%, preferably about 20- about 45 wt.%. Preferably such cementitious reagent is 40-100% X-ray amorphous, more preferably about 80- about 100% X-ray amorphous, even more preferably 100% non-crystalline. Such a high-calcium containing cementitious
-41 20565 reagent may fînd numerous commercial applications, for instance as a hydraulic admixture in blended hydraulic cernent, and/or as a reagent in geopolymer binders and cements.
[0255] In another embodiment, the cementitïous reagent is an intermediate-calcium containing cementitïous reagent with a molar composition of Si/(Fe3+,Al) between 1-20, and CaO content of about 10- about 20 wt.%. Preferably such cementitïous reagent is about 40-1 00% X-ray amorphous, and preferably about 80- about 100% X-ray amorphous, and even more preferably 100% non-crystalline. Such an intermediate-calcium containing cementitïous reagent may fînd numerous commercial applications, for instance as a cementitïous reagent with désirable intermediate hydraulic and pozzolanic propertïes.
[0256] One important advantage of optimizing Na/K in the cementitïous reagent in accordance with the présent is in: 1) SCM applications where free lime in hydraulic cernent will exchange with soluble alkalïs and coordinate with sialate molécules from cementitïous reagent to create some extent of relatively stable alkalï aluminosilicate polymerization that greatly ïmproves Chemical propertïes of traditional hydraulic cements; and 2) the fact that geopolymer reagents with sïgnifïcant Na/K contents require less soluble silicate hardener than would otherwise be necessary, thus decreasïng the soluble silicate requïrement (and cost) of a geopolymer mix design.
[0257] Method of préparation
[0258] In some embodiments, aluminosilicate materials are selected as a feedstock for producing cementitïous reagent. Figure 1 shows exemplary steps necessary to produce cementitïous reagent from aluminosilicate materials, in accordance with an embodiment of the présent invention.
(0259] Briefly, an aluminosilicate material 101 is selected, and its Chemical composition is analyzed 102 and evaluated. The feedstock may be analyzed by any suitable quantitative or semi-quantitative methods such as XRF, XRD with Rietveld Refinement, LIBS, EDS, wet Chemical analysis, and varions other existing methods to déterminé the feedstock elemental composition.
[0260] If the selected composition is not acceptable, the material is amended, blended (e.g. in a vessel prîor to thermochemical processing), or sorted 103, for example, through addition of a composition adjustment material 104. As used herein, the term “composition adjustment material” refers to any solid or liquid material with a composition suitable for preferentially
-4220565 altering the bulk composition of aluminosilicate material with respect to one or several ofthe éléments Ca, Na, K, Al, Fe, and Si.
[0261] As described above, composition adjustment materials that introduce calcium (Ca) may be comprised of CaCOa, Ca(OH)2, CaO, CaCl, calcium silicate minerais and compounds, calcium aluminum silicate minerais and compounds, waste portland cernent products, wollastonite, gehlenite, and other melilite group minerai compositions.
[0262] As described above, composition adjustment materials that introduce aluminum (Al) may be comprised of aluminous rocks, minerais, soîls, sédiments, by-products, and compounds including one or more of kaolinite, halloysite and other aluminum-rich/alkali-poor clay minerais, AhSÎOs polymorphs, chloritoid, staurolite, gamet, corundum, mullite, gehlenile, diaspore, boehmîte, gîbbsite, and nepheline and other feldspathoids. Other materials that may be used include aluminum métal, bauxite, alumina, red mud (alumina refinery residues).
[0263] As described above, composition adjustment materials that introduce iron (Fe) may be comprised of îron-rich rocks, minerais, soîls, sédiments, by-products, and compounds such as olivine, chlorite minerais (chamosite, clinochlore, etc.), pyroxenes, amphiboles, goethite, hématite, magnetite, ferrihydrite, lepidicrocite and other iron oxy-hydroxide compositions, îronrich clay and phyllosilicate minerais, and elemental iron.
[0264] Sorting 105 may also be used as a composition adjustment method 103 and any undesirabîe waste material may be dîscarded.
[0265] The resultîng solid aluminosilicate material comprising a désirable composition is next heated 106. The heating is carrîed ont to reach a heating température above a liquid phase température to obtain a liquid, for instance at about 1000-1600°C, or about 1300-1550°C. Any suitable method or apparatus may be used for the heating and for obtaining the liquid including, but not limited to, in-flight melting and/or batch melting. This may be achieved by using, for instance, a plasma furnace, an oxy-fuei furnace, an arc furnace, a reverberatory furnace, a rotary kiln and/or a solar furnace. Typically, a furnace température of 1000-1600°C is needed, and most typîcally 1300-15 50°C, to obtain the desired liquid phase.
[0266] If desired, a fluxing material may be added to the solid aluminosilicate material to lower its melting point and/or to induce depolymerization of the liquid. The fluxing material may be mixed with the solid aluminosilicate material prior to heating (e.g. vessel) or during the heating. Common fluxing materials that may induce depolymerization in melts, and/or lower
-43 20565 melting température include CaF2, CaCO3, waste glass, glass cullet, glass frit, alkali-bearing minerais (e.g. feldspars, zeolites, clays, and feldspathoid minerais), borate salts, halogen compounds (fluoride and chloride bearing salts) and calcium salts.
[0267] Next, the aluminosîlicate liquid is quenched 107 to obtain a solid. In embodiments, the quenching step comprises reducing température of the liquid significantly below the glass transition, for instance at 500°C or lower, or preferably below 200°C or lower. In embodiments, the quenching is done rapidly, i.e. the température is reduced at a rate of about 102 K8’1 - 106 K3'1 (preferably at a rate of >103 5 K3'1). Any suitable method may be used for the quenching including, but not limited to, contacting the molten material with a sufficient stream of adequately cool air, with steam, or with water to produce a non-crystalline solid.
[0268] Next, the solid is crushed and/or pulverized in order to reduce particle size 108 and obtain the cementitious reagent 109.This may be carried out using any suitable method or apparatus including, but not limited to, a bail mill, a roller mill and a vertical roller mill.
Preferably the particle size is reduced to obtain a fine powder useful in cementitious applications. In embodiments, the powder comprises a particle size distribution with D50 (médian diameter) of approximately 20μηι or less, or preferably lOgm or less. Such a particle size is generally désirable to ensure sufficient reactivïty and consistent material properties.
[0269] Uses of the cementitious reagent
[0270] One related aspect concerns the broad relevance of the cementitious reagent described herein. Approprîate compositions of engineered cementitious reagent may be used interchangeably în sîgnificant proportion in both geopolymer cements and hydraulic cements (i.e. cements that react with water).
[0271] Accordingly, embodiments described herein encompass geopolymer cements and hydraulic cements comprising at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%. or at least 25 wt.%, or at least 30 wt.%, or at least 40 wt.%, or at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or more, of a cementitious reagent as described herein.
[0272] In accordance with another aspect, some embodiments relate to a supplementary cementitious material (SCM) comprising a cementitious reagent as defined herein. In embodiments, the SCM comprises about 5 wt. % to about 50 wt.% (preferably at least 20 wt. %) of the cementitious reagent as defined herein.
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[0273] In accordance with another aspect, some embodiments relate to a supplementary cementitious material (SCM) comprising one or more of the following properties: it comprises less than about 35 wt. % CaO, with appréciable content of Na/K (e.g. at least 2 wt. %, preferably at least 5 wt.%) and Al content (e.g. at least 5 wt.%) and is in the form of a non-crystalline solid. [0274] In accordance with another aspect, some embodiments relate to a solid concrète, comprising a cementitious reagent as described herein, i.e. comprising about 5 wt. % to about 50 wt.% (preferably at least 20 wt. %) of the cementitious reagent as described herein.
[0275) In accordance with another aspect, some embodiments relate to a blended hydraulic cernent that is distinguishable from Portland cernent. For instance, solid-state 29SÎ NMR spectroscopy can differentiate blended hydraulic cernent with low iron (<5 wt.%) according to the présent invention from Portland cernent (having dominant CSH binder constituent) by the amount and type of connectivity of silica tetrahedra în the cured cements. Indeed, cured Portland cernent binder phases are characterized by low coordination and hydrated sites (Ql, Ql(OH), Q2, and Q2(OH)), insignificanttetrahedral Al substitution, and no higher coordination (i.e. no Q3 and Q4 sites). The blended hydraulic cernent with cementitious reagent according to the présent invention will show the typical CSH-related sites above in addition to unique features such as: aluminum substitution (e.g. Q2(l Al)), and a “higher” level of coordination than Portland cernent (i.e. branching). For instance, a blended hydraulic cernent according to the présent invention can comprise at least a Q3 level of coordination (e.g, (Q3(2 Al), Q3(l Al), Q3(0 Al)). In embodiments the blended hydraulic cernent according to the présent invention contains a measurable proportion (>1 wt. %) of three-dimensional cross-linking (Q4 sites) which îs not known in conventional hydraulic cements. In accordance with another aspect, the présent invention relates to a geopolymer binder comprising a cementitious reagent as defined as defined herein, i.e. comprising about 5 wt. % to about 90 wt.% (preferably at least 20 wt. %, at least 30 wt. %, at least 50 wt. %, at least 75 wt. %,) of the cementitious reagent as defined herein.
[0276] In accordance wîth another aspect, some embodiments relate to solid geopolymer concrète comprising about 5 wt. % to about 50 wt.% (preferably at least 20 wt. %) of the cementitious reagent as defined herein.
[0277] Those skilied în the art can appreciate that the présent invention advantageously provides means to produce versatile low-COs cementitious reagents from abundant, cheap natural materials. Another significant advantage is the création of a single reagent that meets
-45 20565 today’s spécification standards for alternative SCMs, while also meeting the needs of the growing geopolymer market.
[0278] Aluminosilicate materials
[0279] As described herein, some embodiments provide a method for thermochemical processing of aluminosilicate materials to produce a solid cementitious reagent that may advantageously be used as an alternative supplementary cementitious material (SCM) in blended hydraulic cernent and/or as a geopolymer solid reagent in geopolymer binders (thus eliminatîng the need for some or ali of MK-750, fly ash, GGBFS, and other common solid reagents).
[0280] In some cases, an aluminosilicate material is used to produce a non-crystalline cementitious reagent as defined herein. In some embodiments, an aluminosilicate material is used to produce at least one of a supplementary cementitious material (SCM) and a geopolymer reagent.
[0281] As used herein, the term “aluminosilicate material” refers to a material comprising aluminum and/or Fe3+, and Silicon dîoxide selected from natural rocks and minerais, dredged materials, mining waste comprising rocks and minerais, waste glass, alumînosilicate-bearing contaminated materials and aluminosiliceous industrial by- products. An aluminosilicate material according to the présent invention is preferably in the form of a crystalline solid (e.g. at least 50 wt. %, or at least 60 wt. %, or at least 70 wt. %, or at least 80 wt. %, or at least 90 wt. %, or 100 wt. % crystalline solid). In embodiments, the aluminosilicate material comprises at least 2 wt, % (Na2O,K2O), or at Ieast 3 wt. % (Na2O,K2O), or at least 4 wt. % (Na2O,K2O), or at least 5 wt. % (Na2O,K2O), at least 6 wt. % (Na2O,K2O), or at least 7 wt. % (Na2O,K2O), or at least 8 wt. % (Na2O,K2O), or at least 10 wt. % (Na2O,K2O), or at least 12 wt. % (Na2O,K2O), or at least 15 wt. % (Na2O,K2O), or at least 20 wt. % (Na2O,K2O).
[0282] In some embodiments, the aluminosilicate material is selected from dredged sédiments, demolished concrète, mine wastes, glacial clay, glacial deposits, fluvial deposits, rocks and minerai mixtures, for instance rocks and minerai mixtures composed of some or ail the éléments Ca, Na, K, Fe, Al and Si.
[0283] In some embodiments, aluminosilicate materials are selected as a feedstock for producing cementitious reagent. The feedstock may be analyzed by quantitative or semiquantitatîve methods such as XRF, XRD with Rietveld Refinement, L1BS, EDS, wet Chemical analysis, and various other existing methods to détermine the feedstock elemental composition.
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[0284] EXAMPLE 10: Using Drcdged Sédiments
[0285] A sampie of sédiments was taken from the tidal lower reaches of the Fraser River, Vancouver, BC. The sample is composed of fine sand, silt and clay size fractions. The mineralogy ofthe sample is given in Table 19 (determined by XRD with Rietveld refinement) and the major éléments’ oxide composition was estimated from the mineralogy (Table 20).
[0286] Table 19. Mineralogy of Fraser River Sedinient Sample
| Phase | Weight % |
| quartz-low andesine albite-low illite/musc 2ml clinochlore augite orthoclase actinolite dolomite kaolinite | 42 16 13 11 5 4 4 4 2 2 |
[0287] Table 20. Oxide Composition (estimated from mineralogy)
| Oxide | Weight % |
| SÎO2 A12O3 Fe2O3 FeO MnO MgO CaO Na2O K2O CO2 H2O | 73.0 11.9 0.2 L5 0.0 3.1 3.3 2.6 1.4 0.9 2.2 |
[0288] Fraser river sédiment (FRS) was dried, classified, and the fraction passing 120pm was fed to a vitrification apparatus that heated the material through the melting point to approximately 1450°C, followed by a quenching step to cool the powder. The resulting FRSglass powder was ground in a bail mill to D50 <20pm. The X-ray amorphous component of the obtained powder was 52%. The mineralogy results yield an estimated molar Si/(A1, Fe3+) of
-4720565
11.46, and molar cementîtîous reagent composition of (Ca,Mg)i.25·(Na,K)o.34’(Al, Fe^rSi11.46 and CaO of 3.3 wt.%. This may be qualified as a “low-Ca cementîtîous reagent”.
[0289] Heat-cured geopolymer binder: 5 parts of the low-Ca cementîtîous reagent was mixed with 1 part potassium silicate solution (Molar ratio SiO2:K2OM.45J. The paste was mixed thoroughly, placed in a sealed mold and cured at 80°C for 4 hours. The resulting hardened paste achieves at least 20 MPa compressive strength in a cylinder compression test.
[0290] Ambient-cured geopolymer binder: 5 parts of the low-Ca cementîtîous reagent was mixed with Ipart potassium silicate solution (Molar ratio SiO2:K2O=l .45), 1 part water, and 1.5 parts finely ground CaSiOj. The silicate solution was mixed with the CaSiOs powder and allowed to react for 15 minutes. The resulting paste was mixed thoroughly with the FRS glass powder and water, then placed in a sealed mold and cured at 20°C for 7 days. The resulting hardened paste achieves at least 20 MPa compressive strength in a cylinder compression test. [0291] Ambient-cured SCM application in Portland Cernent: a sériés of Portland cernent mortar cubes were cast from a 50:50 mix of cernent and sand. The low-Ca cementîtîous reagent was substituted at 0%, 20%, 40%, 60% and 80% în place of Portland cernent in the mortar mix. The cubes were cured for 7 days at 100% humidity and the compressive strength of the cubes is presented în Table 21. Up to 60% replacement of ordinary Portland cernent (“OPC”) yields useable compressive strength for many applications while proportionally reducing CO2 footprint of the mortar.
[0292] Table 21: 7-Day Compressive Strength, SCM Application
FRS Cementîtîous Reagent (%) Compressive Strength (MPa ± 10)
0% (100% OPC)40
20% (80% OPC)37.5
40% (60% OPC)30
60% (40% OPC)15
80% (20% OPC)3.5
[0293] EX AMPLE 11: Using Demolished Concrète
[0294] A core of structural concrète was sampled from a 2019 mid-rise housing development in Vancouver, BC. The minerai composition of the concrète (including fine and coarse aggregate) is given in Table 22 (XRD with Rietveld refinement), and the bulk elemental composition is calculated from the mineralogy in Table 23.
-4820565
[0295] Table 22. Mineralogy of concrète sample
| Phase | Weight % |
| albite-low (calcian) quartz-low albite-low orthoclase calcite *CSH gel estimate clinozoisite actinolite clinochlore 11 biotîte IM ettringite C2S beta brownmîllerite (Al) gypsum | 31 21 11 8 8 6 3 3 3 2 2 2 1 l |
| [0296] Oxide | Table 23. Oxide Composition (estîmated from mineralogy) Weight % |
| SiO2 AI2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O co2 h2o | 64 13 0 1 0 2 11 5 2 4 4 |
[0297] The concrète was crushed and pulverized to a powder with D50 of about 20pm. The powder was fed through a vitrification apparatus that heated the material through the melting point to approximately 1450°C, foilowed by a quenching step. The resulting glassy particles were finely ground to a powder with D50 of approximately 5- 15pm.
[0298] The mineralogy results of this powder yield an estîmated molar Si/(A1, Fe3+) of 9.88, and molar cementitious reagent composition of (Ca,Mg)2.79,(Na,K)o,55*(AI, Fej+)i*SÎ9 88 and CaO of 11 wt.%. This may be qualified as an “intermediate-Ca cementitious reagenf’.
-4920565 ,0299] Ambient-cured geopolymer cernent: Cernent paste was thoroughly mixed by weight using the powdered concrète glass (2.5 parts), a potassium silicate solution with molar ratio SiO2:K2O=l .45 (0.74 parts), and water (0.08 parts). The paste was then placed în cylinder molds and cured at 20°C. Setting time was estîmated by Vîcat needle pénétration test. Initial setting occurred at 51 minutes, and final setting time was 195 minutes.
[0300] Compressive strength of a mortar mix comprising 50:50 of the ambient-cured geopolymer cernent and sand was measured by compressing cylinders to failure. After 3 days, compressive strength attained approximately 25 MPa, and tensile strength was approximately 2 MPa (by split cylinder method).
[0301] To test hîgh heat performance, a sample of the original structural concrète and a 1 cm diameter cast cylinder of geopolymer were subjected to 750°C în air for 2 hours. The Portland cernent concrète decrepitated and tumed to powder upon handling, but the geopolymer mortar cylinder remained intact with no visible cracks or defects.
[0302] The novei methods, Systems, apparatus, and formulations presented herein provide numerous benefits as detaîled throughout. In some instances, the novel formulation and processes resuit in a particle, powder, or reagent that is particularly use fui as a replacement for traditîonal cementitious additives in hydraulîc cernent or geopolymer cernent compositions. The novel formulation may comprise a molar composition, in which:
| [0303] | ---------------------= 0.295 to about 0.605 Si +Λ l+Fe+(Ca+Mg) + (Wa+K} |
| [0304[ | --------———---- = 0.190 to about 0.340 Si ï -\-Fs g) + (Να+Κ ) |
| [0305] | Fe —-----------—---- = 0 to about 0.16 Sî+j4 + (Na+A) |
| [0306] | --------Ca+Mg--------= 0 to about 0.215, and Si +Al+Fe+(£a+Mg)+(Na+K) |
| [0307] | --------Na+K--------= o.O4 to about 0.24 Si+Al+Fe+(Ca+Mg)+(Na+K') |
| [03081 | While the novel formulas presented herein resuit in a unique material that is especially |
suited for the purposes described throughout, it can be difficult to differentîate the material by its individual elemental ranges or a région on a ternary diagram alone, due to the fact that ternary diagrams are limited to visualization of exactly three compositîonal parts and ail the elemental parts of the total composition hâve interdependent relationshîps.
-5020565
[0309] As geochemical compositions are classîfied as compositional data, a transformation (centered logratio transformation - CLR) from the Simplex to the Euclidean space was applied to the 7-part compositions, preserving the information encoded în molar compositions in a way that standard statistical methods can handle.
[0310[ On the CLR représentation of Chemical data, a Random Forest classification was completed, and from this prédictive mode!, the 8-rule classification set (presented below) was extracted. Using this rule set, fly ash and the described feedstock compositions are separated, despite the fact that there may appear to be compositional overlap between these materials on ternary diagrams. A classification model such as this is useful to accurately represent or classîfy compositions exceedîng 3-dimensional data.
[0311] Modeling the Novel Formulation and Material
[0312] The described glassy reagent (“Novel Feedstock”, or alternative cementitious material “ACM”) is differentiated from fly ash in several important characteristics, such as timetemperature hîstory, manufacturaility at nearly any location, and a relative!y lower values of problematic heavy métal contaminants. Major element Chemical composition of embodiments described herein is also readily differentiated statistically from fly ash using compositional rules. By way of example, a statistical model was buîlt using fly ash compositional data from the literature, and expected suitable feedstock compositions as described herein. The classification rules were generated from a subsample as training data, and tested on remaining compositions (fly ash, and the novel compositions described herein) to assess accuracy and prédictive power of the classification rules. In the model below, fly ash is predicted correctly 94% ofthe time on 331 global compositions of fly ash from the literature, and the other 6% were classîfied as “outside the rule set”. No fly ash samples were misclassîfîed as the novel feedstock geological material described herein. The model was applied to more than 70,000 compositions of natural geological materials that fit in the disclosed molar composition range, and the model predicts the novel feedstock described herein with 99% success rate. Less than 1% of the compositions tell under the category of “outside the rule set”. Clearly there are significant and predîctable différences between the novel feedstocks described herein and other by product reagents, such as fly ash. Composition alone, represented in centered log ratio coordînates (CLR) is highly accurate in discemîng the chemistry of the described glassy particles from fly ash.
[0313] Application of the model
-51 20565
[0314] To apply the model below;
1. Measure bulk Chemical composition of a gîven glassy sample by any suitable analytical method and provide molar % of Si, Al, Fe, Ca, Mg, Na and K.
2. Convert molar data to CLR coordinates for the 7 éléments.
3. Apply the foliowing conditions sequentially to predict whether the sample is Fly Ash, or a Terra reagent, respectively.
[0315] Note: If a condition is not satisfied, apply next condition. If no conditions apply to given composition, ELSE predicts that the sample is outside of the model’s rule set and cannot be confidently predicted.
[0316] Rules
1. For glassy material with bulk CaO oxide équivalent wt.% <35%, AND
2. Bulk mol % ratio Si/Al > 2,
[0317] Notably, Rule 1 above can be used to rule out slag as a feedstock, and Rule 2 can be used to rule out metakaolin, kaolinîte, and other 1:1 clay rich feedstocks. Apply the foliowing conditions to closed, CLR transformed molar sample compositions using the logic IF (condition =TRUE), THEN (prédiction), ELSE (move to next condition) as shown in Table 24 below:
[0318] Table 24
| Condition | Prédiction |
| Si>0.40109 & Si<=l. 18718 & Al<=0.52677 & Al<=0.40675 & Ca<=-0.40656 & Ca<=-0.7324 | Novel Feedstock |
| Al>0.5364 & Al>0.55929 & Ca>-4.65173 & Na<=-1.2763 & Mg<=-0.7076 & K>-4.1446 | Fly Ash |
| Si>0.43721 & Fe<=0.31807 & Fe>-2.32162 & Ca<=-0.08759 & Mg>-1.80049 & Mg>-1.47036 | Novel Feedstock |
| Al<=0.52677 & Ca<=-0.31475 & K>-1.52367 | Novel Feedstock |
| Si<=0.44413 & K<=-2.12091 | Fly Ash |
| Fe>-1.19597 & Ca<=-0.36227 & Na>-1.79741 & Na<=-0.18124 & Mg>-2.7976&K<=-1.87031 | Novel Feedstock |
| Al>0.5364 & Fe>-2.59819 & Mg<=-0.7076 & Mg>-6.29972 & Mg<=-0.93309 & K>-4.10525 | Fly Ash |
| ELSE | Outside rule set |
[0319] FIG. 11 illustrâtes the région of the novel 7-part molar compositions in a complété set of ternary diagrams. The circled areas highlight the différences between the Novel Feedstock and global fly ash samples from the literature. Examples As illustrated, the top row of four
-5220565 ternary diagrams represents the Si perspective, and is shown in more detail in FIG. 12. With reference to FIGS 11-15. a black outline of samples indicates the alternative cementitious material (“ACM”) described herein, whîch may also be referred to as the Novel Feedstock. ACM Compositions of Examples 1-8 are shown as black dots labelled with the number corresponding to the example composition (numbers and compositions summarized in Table 17). The grey outline shown in the figures represents a 90% confidence interval of fly ash samples, based on 331 unique samples (same as were categorized using the above statîstîcal model). [0320] The second row of figures in FIG. 11 represents ternary diagrams from the Al perspective, and is shown in further detail in FIG 13.
[0321] The third row of figures in FIG. 11 represents ternary diagrams from the Fe perspective, and is shown in further detail în FIG. 14.
[0322] Finally, the last row of FIG. 11 represents a ternary dîagram from the Ca+Mg perspective, and is shown in greater detail in FIG. 15.
[0323] FIGS 11-15 illustrate the Novel Feedstock as it relates to global fly ash compositions and cleariy shows that the two material populations are highly distinguishable from each other even on elemental molar ternary diagrams. The areas of apparent overlap between the Novel feedstock and fly ash are shown to be differentiated in the higher dimensional classification model provided herein. The Novel Feedstocks or ACM described herein are not particularly alkali résistant and partieipate in a reaction with alkali hydroxides or lime as a reagent.
[0324] FIG. 16 illustrâtes a schematic flow diagram of the process 1600 of making an alternative cernent concrète using a relative!y small décentraiized in-flight minikiln. The minikiln can be located at any suitable place, and because of the size and nature of the minikiln, is especially suited to be col located at an aggregate quarry, at a concrète bat ch plant, in-between a quarry and a concrète batch plant, or any other suitable location to mînimize, or at least reduce, the transportation time and distance typically required for concrète batch plants relying on Portland cernent.
[0325] At 1602, an aluminosilicate aggregate is provided, as described herein. The aggregate material may be any suitable aluminosilicate material, and may be specifically mined for the intended purpose, or may be waste material, such as mine tailings, ground concrète, or some other type of aggregate. At block 1604, the aluminosilicate material is milled to a powder, as described herein.
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[0326] At block 1606, a mi lied aluminosilicate material may be stored, shipped, or provided to an input of a minikiln as described herein. At block 1608, energy is added to the milled aluminosilicate aggregate, such as combustion of an air/fuel mixture, a torch, industrial heat, or some other form of energy to increase the température of the aggregate. In some embodiments, the aluminosilicate partîcles are optionally amended, blended (e.g. in a vessel prior to thermochemical processing), for example, through addition of a composition adjustment material in order to reach desired ratio(s) with respect to one or several of the éléments Ca, Mg, Na, K, Al, Fe, and Si.
[0327] At block 1608, the energy causes the aluminosilicate aggregate to melt, which in some cases, occurs in-flight, such as where the aggregate is entrained within a column of air and/or air/fuel within a melting chamber.
[0328] At block 1612, after the aggregate is melted and quenched, the feedstock becomes glassy aluminosilicate partîcles. In some cases, the partîcles are substantially spheroidal with a roundness R > 0.8.
[0329] At block 1614, the partîcles are combined with other ingrédients at a concrète batch mixing plant, which may be collocated wîth the minikiln in some instances. At block 1616, Additives may be added to the concrète, such as hardener, ambient cure reagent, admixtures, plasticizers, reinforcement materials, and the like. At block 1618, sand and coarse aggregate may be added to the cernent as is known in the art.
[0330] At block 1620, the final concrète mixture is formed and ready to be used.
[0331] According to some embodiments, a method of cernent production decreases cernent transportation distance (and therefore cost) compared to conventional methods. Some embodiments allow for decentralized production of an Alternative Cernent Material (ACM) in close proximity to an aluminosilicate aggregate quarry and a concrète batch plant. This ACM may be advantageously used as a primary reagent in a suitable alternative cernent formulation that can be used to make cost-effective and CO2-reduced concrète.
[0332] Alternatively, the ACM may be used as an alternative supplementary cementitious material (ASCM) to replace a proportion of Portland cernent în conventional concrète and thereby reduce cost and environmental impact of resulting concrète.
[0333] FIG. 17 illustrâtes a typical Portland cernent plant 1702 in which the cernent may typically be shipped over long distances to reach concrète batch plants 1704. Similarly,
-5420565 aggregate from quarries 1706 may also be shipped long distances to reach their destination at concrète batch plants 1704. The time and energy to ship these dense and voluminous products dramatically increases the cost associated with manufacturing concrète as well as contributes to the overall CO2 émissions associated with concrète production.
[0334] FIG. 18 illustrâtes an alternative arrangement 1800 that utilizes the ACM described herein. In some instances, an ACM minikiln 1802 can be collated at an aggregate quarry 1706 site. In this way, the aluminosilicate material mined at the aggregate quarry 1706 can be processed at the ACM minikiln 1802 on-site without transporting the aggregate to a remote location. The ACM and sufficient aggregate can then be sent to the concrète batch plant 1704, which may be in much closer proximity.
[0335] FIG. 19 illustrated an alternative arrangement 1900 that utilizes the ACM described herein. In the illustrated embodiment, and ACM minikiln 1802 can be collocated with a concrète batch plant 1704. Accordingîy aggregate from an aggregate quarry 1706 can be delivered to the concrète batch plant 1802 and the aggregate can be used by the ACM minikiln 1802 as described herein, and also be used as the coarse aggregate in the concrète mix.
[0336] FIG. 20 illustrâtes an alternative arrangement 2000 that utilizes the ACM described herein. In the illustrated embodiment, an ACM minikiln 1802 is located between an aggregate quarry 1706 and a concrète batch plant 1704. In this arrangement, aggregate can be delivered to the ACM minikiln, which utilizes the aggregate to formulate ACM as described herein, and the ACM and additional aggregate can be shipped to a concrète batch plant.
[0337] The minikiln architecture allows a distributed system that takes advantage of the smaller, and even portable nature, of the ACM minikiln. Rather than relying on a single centralized Portland cernent plant that must ship cernent long distances, a number of ACM minikilns can replace a Portland cernent plant and reduce shipping times and costs dramatically. The illustrated embodiments of FIGS 17-20 offer an architecture that is nimble, efficient, and reduces waste by locating the ACM minikiln in close proximity to the aggregate quarry, the concrète batch plant, or both.
[0338] Suitable feedstock compositions and the process of converting the feedstock to microspheroidal glassy particles hâve been disclosed in Applicant’s copending applications having Serial Number 62/867,480, filed on June 27, 2019 and Serial Number 63/004,673, filed April 3, 2020, the entire disclosures of which are hereby incorporated by reference in their
-55 20565 entirety. Suitable feedstocks are generally rocks and minerais bearing a proportion of both aluminum and Silicon oxides. Ordinary construction aggregate materials used in concrète are suitable. économie, and conveniently located for use as an idéal cernent feedstock. Previously, it was not possible to make a cementitious material from such ordinary crystalline aluminosilicate materials.
[0339] One particular advantage of using aluminosilicate aggregate as ACM feedstock is that the material is cheaply and abundantly available.
[0340] Another particular advantage is that aluminosilicate aggregate quarries exist widely, and generally there is no need for permitting of new quarries to make ACM by the présent method in most markets.
[0341] Another particular advantage of using aluminosilicate aggregate as ACM feedstock is that a minîkiln (for example as described in Applicant’s copending application having Serial Number 63/004,673) may be collocated at or very near the aggregate quarry, or concrète batch plant, or both, thus minimizing transportation costs of cernent. This great advantage cornes about because cernent from large centralized kilns travels on average 5-10 times further than aggregate (supply of which is décentraiized); a natural conséquence of widespread aggregate availability, low price of aggregate, and high price of shipping aggregate.
[0342] Another particular advantage of using aluminosilicate aggregate as ACM feedstock is that frequently quarries hâve abundant byproduct material available that is “off-specification”, meaning that there is no common use for that particular gradation, despite such materials sharing generally identical composition with the main quarry products. Such byproduct materials are very cheaply available at both crushed stone aggregate quarries, as well as sand and grave) quarries.
[0343] Another particular advantage of the décentraiized ACM minikilns is that capital cost per unit of throughput is expected to be similar to conventional rotary cernent kilns, though the absolute scale of capital requirement is on the order of 1/10th what it would be for Portland cernent production.
[0344] Another particular advantage of the décentraiized ACM minikilns îs that operating expenditures per unit of throughput are not expected to exceed the corresponding expenses in manufacture of Portland cernent. Thereby, ACM production is cost-competitive with Portland cernent at a smaller scale of production, yet requires 5-10 times less shipping expense.
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[0345] The présent disclosure includes the following numbered clauses.
]0346] Clause 1. Solid microspheroidal glassy particles, wherein said particles comprise one or more of the following properties: mean roundness (R) > 0.8 ; and less than about 40% particles having angular morphology (R < 0.7).
[0347] Clause 2. The particles of clause 1, wherein said particles comprise a mean roundness (R) of at least 0.9.
[0348] Clause 3The particles of clause l or 2, wherein less than about 30% particles, or less than about 25% particles, or less than about 20% particles, or less than about 15% particles, or less than about 10% particles hâve an angular morphology (R < 0.7).
[0349] Clause 4. The particles of any one of clause l to 3. wherein said particles comprise the mean oxide Formula 1: (CaO}MgO)a*(Na2OfK2O)b*(Al2O3,Fe2O3)c*(SiO2)d [Formula 1] wherein a is about 0 to about 4, b is about 0.1 to about 1, c is 1, and d is about 1 to about 20.
[0350] Clause 5. The particles of any one of clauses 1 to 4, wherein said particles comprise one or more of the following properties: (î) a content of 45%-100%, and preferably 90-100%, Xray amorphous solid; and (ii) molar composition ratios of (Ca,Mg)o-i2*(Na,K)o.o5-i*(Al, Fe3+)i-Sii-20.
[0351] Clause 6. The particles of any one of clauses 1 to 5, wherein said particles are 40100% X-ray amorphous, more preferably about 80- about 100% X-ray amorphous, even more preferably 100% non-crystalline.
[0352] Clause 7. The particles of any one of clauses 1 to 6, wherein said particles comprise less than about 10 wt.% CaO.
[0353] Clause 8. The particles of any one of clauses 1 to 6, wherein said particles comprise more than about 30 wt.% CaO.
[0354] Clause 9. The particles of any one of clauses 1 to 6, wherein said partiele comprises a high-calcium content with a molar composition of Si/(Fe3+,AI) between 1-20, and CaO content of about 10- about 50 wt.%, preferably about 20-45 wt.%.
[0355] Clause 10. The particles of any one of clauses 1 to 6, wherein said particle comprises an intermediate-calcium content with a molar composition of Si/(Fe3-i-,Al) between 1-20, and CaO content of about 10- about 20 wt.%.
[0356] Clause 11. A cementitious reagent comprising a mixture of microspheroidal glassy particles as defîned in any one of clauses 1 to 10.
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10357] Clause 12. A cementitïous reagent comprising a mixture of microspheroîdal glassy particles, wherein said particles comprises one or more ofthe following propertïes: (i) mean roundness (R) > 0.8; (iï) less than about 20% particles having angular morphology (R < 0.7); (iîi) the oxide Formula 1 as defined in claim 4; (ïv) a content of 45%-100%, and preferably 90-100%, X-ray amorphous solid; and (v) a molar composition ratios of (Ca,Mg)ou2*(Na,K)o.o5-i*(Al, Fe3+)i‘Si 1-20; and (vi) a low calcium content of about <10wt% CaO, or an intermediate calcium content of about 10 to about 20% wt% CaO, or a high calcium content of >30wt% CaO.
[0358] Clause 13. The cementitïous reagent of clause 12, wherein said cementitïous reagent is in the form of a non-crystalline solid.
[0359] Clause 14. The cementitïous reagent of clause 12 or 13, wherein said cementitïous reagent is in the form of a powder.
[0360] Clause 15. The cementitïous reagent of any one of clauses 12 to 14, wherein said cementitïous reagent comprises particle sïze distribution with D[3,2] of about 20pm or less, more preferably 1 Opm or less, or most preferably 5pm or less.
[0361] Clause 16. The cementitïous reagent of any one of clauses 12 to 15, wherein said mixture of particles comprises the oxide Formula 1 : (CaO,MgO)a*(Na2O,K2O)b*(A12Oj,Fe2O3)c’(SiO2)d [Formula 1] wherein a is about 0 to about 4, b is about 0.1 to about 1, c îs 1, and d is about 1 to about 20.
[0362] Clause 17. The cementitïous reagent of any one of clauses 12 to 16, wherein said cementitious reagent comprises less than about 10 wt.% CaO.
[0363] Clause 18. The cementitious reagent of any one of clauses 12 to 16, wherein said cementitious reagent comprises more than about 30 wt.% CaO.
[0364] Clause 19. The cementitious reagent of any one of clauses 12 to 16, wherein the cementitious reagent is a high-calcium containing cementitious reagent with a molar composition of Si/(Fe3+,Al) between 1-20, and CaO content of about 10- about 50 wt.%, preferably about 2045 wt.%.
[0365] Clause 20. The cementitious reagent of any one of clauses 12 to 16, wherein the cementitious reagent is an intermediate-calcium containing cementitïous reagent with a molar composition of Si/(Fe3+,Al) between I -20, and CaO content of about 10- about 20 wt.%.
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[0366] Clause 21. The cementitious reagent of any one of clauses 12 to 20, wherein the cementitious reagent is about 40-100% and preferably about 80- about 100% X-ray amorphous, and even more preferably 100% non-crystalline.
[0367] Clause 22. A geopolymer binder comprising a cementitious reagent as defined in any one of clauses 11 to 21.
[0368] Clause 23. A supplementary cementitious material (SCM) comprising a cementitious reagent as defined in any one of claims 11 to 21.
[0369] Clause 24. The SCM of claim 23, comprising at least 20 wt.% of said cementitious reagent.
[0370] Clause 25. A solid concrète, comprising a cementitious reagent as defined in any one of clauses 11 to 20.
[0371] Clause 26. Use of the microspheroidal glassy particles as defined in any one of clauses 1 to 10 and/or of the cementitious reagent of any one of claims 11 to 20, to manufacture a geopolymer binder or cernent, a hydraulic cernent, a supplementary cementitious material (SCM) and/or solid concrète.
[0372] Clause 27. A method for producing a cementitious reagent from aluminosilicate materials, comprising the steps of: (i) providing a solid aluminosilicate material; (ii) in-flight melting/quenching said solid aluminosilicate material to melt said material into a liquid and thereafter to quench said liquid to obtain a molten/quenched powder comprising solid microspheroidal glassy particles; thereby obtaîning a cementitious reagent with said powder of microspheroidal glassy particles.
[0373] Clause 28. The method of clause 27, wherein said method further comprises step (iii) of grinding said powder of microspheroidal glassy particles into a finer powder.
[0374] Clause 29. The method of clauses 27 or 28, wherein said powder comprises particle size distribution with D[3,2] of about 20pm or less, more preferably 1 Opm or less, or most preferably 5gm or less.
[0375] Clause 30. The method of any one of clauses 27 to 29, wherein said particles comprise one or more of the following properties: a mean roundness (R) of at least 0.7; less than about 20% particles of angular morphology; the oxide Formula 1 as defined in claim 4; a content of 45%-100%, and preferably 90-100%, X-ray amorphous solid; molar composition ratios of (Ca,Mg)o-i2*(Na,K)o.o5-i*(Al, Fe3+)i*Sii-20; and a calcium content of less than about 10 wt.% CaO.
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[0376] Clause 31. The method of any one of clauses 27 to 30, wherein said cementitious reagent comprises one or more ofthe following properties: is reactive in cementitious Systems and/or în geopolymeric Systems; delîvers workable low yield stress geopolymer cernent mîxes below 25 Pa when a cernent paste has an oxide mole ratio of HzO/CNazOjKïO) < 20 ]; requîtes water content in cernent paste such that the oxide mole ratio FhO/fNasO^O) < 20; and delîvers a cernent paste with higher workability than an équivalent paste with substantially angular morphology, given the same water content.
[0377] Clause 32. The method of any one of clauses 27 to 31, further comprising the step of adjustîng composition of a non-ideal solid aluminosilicate material to a desired content of the éléments Ca, Mg, Na, K, Al, Fe, and Si.
[0378] Clause 33. The method of clause 32, wherein said adjustîng comprises blending saîd non-ideal aluminosilicate material with a composition adjustment material in order to reach desired ratio(s) with respect to one or several of the éléments Ca, Mg, Na, K, Al, Fe, and Si. [0379] Clause 34. The method of any one of clauses 27 to 33, further comprising the step of sorting said solid aluminosilicate material to obtain a powder of aluminosilicate particles of a desired size.
[0380] Clause 35. The method of any one of clauses 27 to 34, further comprising the step of discardîng undesirable waste material from said solid aluminosilicate material.
[0381] Clause 36. The method of any one of clauses 27 to 35, wherein said in-flight melting comprises heating at a température above a liquid phase température to obtain a liquid.
[0382] Clause 37. The method of clause 36, wherein said température îs about 1000-1600°C, or about 1300-1550°C.
[0383] Clause 38. The method of any one of clauses 27 to 37, further comprising addîng a fluxing material to the solid aluminosilicate material to lower its melting point and/or to induce greater enthalpy, volume, or depolymerization of said liquid.
J0384] Clause 39. The method of clause 38, wherein the fluxing material îs mixed with said solid aluminosilicate material prior to, or during said melting.
[0385] Clause 40. The method of any one of clauses 27 to 39, wherein said in-flight melting/quenching comprises reducing température of said liquid below température of glass transition to achîeve a solid.
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[0386] Clause 41. The method of clause 40, wherein said in-flight melting/quenching comprises reducing température of said liquid below about 500°C, or preferably below about 200°C or lower.
[0387] Clause 42. The method of clause 41, wherein reducing température of said liquid comprises quenching at a rate of about 102 K5'1 to about 106 Ksl, preferably at a rate of>10J 5 Ks1.
[0388] Clause 43. The method of clause 41, wherein quenching comprises a stream of cool air, stearn, or water.
[0389] Clause 44. The method of any one of clauses 27 to 43, further comprising reducing particle size of said powder of solid microspheroidal glassy particles.
[0390] Clause 45. The method of clause 44, wherein reducing particle size comprises crushîng and/or pulverizing said powder in any one of a bail mill, a roller mill, a vertical roller mill.
[0391[ Clause 46. The method of any one of clauses 27 to 45, further comprising separating quenched solid particles from hot gases in a cyclone separator.
[0392] Clause 47. An apparatus for producing microspheroidal glassy particles, comprising: a burner; a meltîng chamber; and a quenching chamber.
[0393] Clause 48. The apparatus of clause 47, wherein the melting chamber and the quenching chamber are first and second sections of the same chamber, respectively.
[0394] Clause 49. The apparatus of clauses 47 or 48, wherein said apparatus is configured such that solid particles are flown in suspension, melted in suspension, and then quenched in suspension in said apparatus.
[0395] Clause 50. The apparatus of any one of clauses 47 to 49, wherein said burner provides a flame heating solid particles in suspension to a heating température suffi cîent to substantially melt said solid particles into a liquid.
[0396] Clause 51. The apparatus of any one of clauses 47 to 50, wherein said burner comprises a flame that is fueled with a gas that entrains aluminosilicate feedstock particles towards the melt/quench chamber.
[0397] Clause 52. The apparatus of clause 51, wherein the gas comprises an oxidant gas and a combustible fuel.
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[0398] Clause 53. The apparatus of any one of clauses 47 to 52, wherein said the quenching chamber comprises a cooling system for providing cool air inside the quenching chamber, said cool air quenching molten partîcles to solid mîcrospheroidal glassy partïcles.
[0399] Clause 54. The apparatus of clause 53, wherein said a cooling System comprises a liquid cooling loop positioned around the quenching chamber.
[0400] Clause 55. The apparatus of any one of clauses 47 to 54, wherein the apparatus further comprises a cyclone separator to collect mîcrospheroidal glassy partîcles.
[0401] Clause 56. The apparatus of any one of clauses 47 to 55, wherein the bumer comprises at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a solar concentrating furnace.
[0402] Clause 57. A method for producing a cementitious reagent from aluminosîlîcate materials, comprising the steps of: (i) providing a solid aluminosilicate material; (ii) in-flight melting/quenching said solid aluminosilicate material to melt said material into a liquid and thereafter to quench said liquid to obtain a molten/quenched powder comprising solid mîcrospheroidal glassy partîcles; thereby obtaîning a cementitious reagent with said powder of mîcrospheroidal glassy partîcles.
[0403] Clause 58. A method for producing mîcrospheroidal glassy partîcles, comprising the steps of: providing an in-flight meltîng/quenchîng apparatus, said apparatus comprising a bumer, a melting chamber and a quenching chamber; providing solid partîcles; flowing said solid partîcles in suspension in a gas to be bumed by said burner; heating said solid partîcles into said melting chamber to a heating température above liquid phase to obtain liquid partîcles in suspension; quenching said liquid partîcles in suspension to a cooling température below liquid phase to obtain a powder comprising solid mîcrospheroidal glassy partîcles.
[0404] Clause 59. The method of clause 58, wherein the melting chamber and the quenching chamber are first and sections of the same chamber, respectively.
[0405] Clause 60. The method of clauses 58 or 59, wherein said heating température îs about 1000-1600°C, or about 1300-1550°C.
[0406] Clause 61. The method of any one of clauses 58 to 60, wherein cooling température is below 500°C, or below 200°C.
[0407] Clause 62. The method of any one of clauses 58 to 61, wherein said solid partîcles comprise aluminosilicate materials.
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[0408] Clause 63. The method of any one of clauses 58 to 62, wherein said burner comprises a flame that is fueled with a gas that entrains the solid particles towards the melting chamber.
[0409] Clause 64. The method of clause 63, wherein the gas comprises an oxidant gas and a combustible fuel.
[0410] Clause 65. The method of any one of clauses 58 to 64, wherein said quenchîng comprises providing cool air inside the quenching chamber.
[0411] Clause 66. The method of any one of clauses 58 to 65, further comprising collecting said powder with a cyclone separator.
[0412] Clause 67. Use of an apparatus comprising at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a solar concentrating furnace, for producîng microspheroîdal glassy particles.
[0413] Clause 68. Use of an apparatus comprising at least one of a plasma torch, an oxy-fuel burner, an air-fuel burner, a biomass burner, and a solar concentrating furnace, for producîng a cementitious reagent from aluminosilicate materials
[0414] Clause 67. Ail novel compounds, compositions, processes, apparatuses, Systems methods and uses substantially as hereinbefore described with particular references to the Examples and the Figures.
[0415] Headings are included herein for reference and to aid in locating certain sections. These headings are not intended to limit the scope of the concepts described therein, and these concepts may hâve applicability in other sections throughout the entire spécification. Thus, the présent invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
[0416] The singular forms “a”, “an” and “the” include corresponding plural references unless the context clearly dictâtes otherwise. Thus, for example, reference to a solid microspheroîdal glassy particle includes one or more of such particle, and reference to the method includes reference to équivalent steps and methods known to those of ordinary ski 11 în the art that could be modified or substituted for the methods described herein.
[0417] Unless otherwise indicated, ail numbers expressing quantities of ingrédients, reaction conditions, concentrations, properties, and so forth used in the spécification and claims are to be understood as being modified in ail instances by the term “about”. At the very least, each numerical parameter should at least be construed in light of the number of reported significant
-63 20565 digits and by applying ordinary rounding techniques. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the présent spécification and attached claims are approximations that may vary depending upon the properties sought to be obtained.
Notwîthstandîng that the numerical ranges and parameters setting forth the broad scope of the embodiments are approximations, the numerical values set forth in the spécifie examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors resulting from variations in experiments, testing measurements, statïstical analyses and such.
[0418] It is understood that the examples and embodiments described herein are for illustrative purposes only and that varions modifications or changes in light thereof will be suggested to persons ski lied in the art and are to be included within the présent invention and scope of the appended claims. A person of ordinary skill in the art will recognize that any process or method disclosed herein can be modified in many ways. The process parameters and sequence of the steps described and/or illustrated herein are given by way of example only and can be varied as desired. For example, while the steps illustrated and/or described herein may be shown or discussed in a particular order, these steps do not necessarily need to be performed în the order illustrated or discussed.
{0419] The various exemplary methods described and/or illustrated herein may also omit one or more of the steps described or illustrated herein or comprise additional steps in addition to those disclosed. Further, a step of any method as disclosed herein can be combined with any one or more steps of any other method as disclosed herein.
[0420] Unless otherwise noted, the terms “connected to” and “coupled to” (and theîr dérivatives), as used in the spécification and claims, are to be construed as permitting both direct and indirect (i.e., via other éléments or components) connection. In addition, the terms “a” or “an,” as used in the spécification and claims, are to be construed as mean in g “at least one of.” Finally, for ease of use, the terms “including” and “having” (and their dérivatives), as used in the spécification and claims, are interchangeable with and shall hâve the same meaning as the word “comprising.
[0421] The processor as disclosed herein can be configured wîth instructions to perform any one or more steps of any method as disclosed herein.
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[0422] As used herein, the term “or” is used inclusively to refer items in the alternative and in combination.
[0423] As used herein, characters such as numerals refer to like éléments.
[0424] Embodiments of the présent disclosure hâve been shown and described as set forth herein and are provided by way of example only. One of ordînary skîl 1 in the art will recognize numerous adaptations, changes, variations and substitutions without departing from the scope of the présent disclosure. Several alternatives and combinations of the embodiments disclosed herein may be utilized without departing from the scope of the présent disclosure and the inventions disclosed herein. Therefore, the scope ofthe presently disclosed inventions shall be defïned solely by the scope of the appended claims and the équivalents thereof.
Claims (87)
1. A method for producing a cementitious reagent from aluminosîlicate materials, comprising the steps of:
providing a solid aluminosîlicate material;
milling the solid aluminosîlicate material to hâve a particle size distribution with D[3,2] of less than 20 pm;
meltîng, by in-flight melting, of the aluminosîlicate material in a kiln; and quenching, by in-flight quenching, of the aluminosîlicate material to produce solid microspheroidal glassy particles.
2. The method of claim 1, wherein the solid microspheroidal glassy particles having a mean roundness (R) of at least 0.8.
3. The method of claim 1, wherein the cementitious reagent has a molar composition ratios of (Ca,Mg)o-i2*(Na,K)o.o5-i*(Al, Fe3+)i«Sîi-2o.
4. The method of daim 1, further comprising controlling an in-flight quenching profile to produce the solid microspheroidal glassy particles that are greater than 80% X-ray amorphous.
5. The method of claim 1, wherein the aluminosîlicate material incîudes one or more ofthe éléments Ca, Na, K, Al, Fe, and Si and further comprising the step of adjusting a composition of the aluminosîlicate material to modify a content of one or more of the éléments Ca, Na, K, Al, Fe, and Si.
6. The method of claim 1, further comprising the step of locating the kiln at an aggregate quarry.
7. The method of claim 1, further comprising the step of locating the kiln at a concrète batch plant.
8. The method of claîm 1, further comprising the step of locating the kiln at a mine.
9. A cementitious reagent comprising:
-6620565 microspheroidal glassy particles having a mean roundness (R) > 0.7, and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, wherein:
about 0.4 <-------------------< about 0.9;
Si+Al+Fe+Ca+Mg+Na+K about 0.1
-------------------< about 0.3; and
Si+AU- Fe+Ca+ Mg+ Na+K wherein the molar composition comprises (Ca,Mg)o-i2*OMa,K)o.o5-i*(Al,Fej+')j*Sii-2o·
10. The cementitious reagent of claim 9, wherein the cementitious reagent comprises a powder.
11. The cementitious reagent of claim 9, wherein the cementitious reagent is at least about 40% x-ray amorphous.
12. The cementitious reagent of claim 9, wherein the microspheroidal glassy particles are at least about 40% x-ray amorphous.
13. The cementitious reagent of claim 9, wherein the microspheroidal glassy particles hâve a mean roundness (R) of at least 0.9.
14. The cementitious reagent of claim 9, wherein less than about 50% of the microspheroidal glassy particles hâve a mean roundness (R) of less than 0.7.
15. The cementitious reagent of claim 9, wherein the microspheroidal glassy particles hâve a Sauter mean diameter D[3,2] of about 20 micrometers or less.
16. The cementitious reagent of claim 9, wherein the molar composition comprises
0 <--------—--------< about 0.2.
Si+Al+Fe+Ca+Mg+Na+K
17. The cementitious reagent of claim 9, wherein the molar composition comprises
0 <------ca+Mg------< about q.4
Si+Al+Fe+Ca+Mg+Na+K
18. The cementitious reagent of claim 9, comprising less than about 10 wt.% CaO.
-6720565
19. The cementitious reagent of claim 9, wherein the molar composition comprises about 0.01 <-------Na+κ------- about 0.2.
Si+A1+Fe+Ca+Mg+Na+K
20. The cementitious reagent of claim 9, wherein the cementitious reagent is substantially free of fly ash.
21. A solid concrète comprising from about 5 wt.% to about 50 wt.% of the cementitious reagent of claim 9.
22. A cementitious reagent comprising:
microspheroidal glassy particles having a mean roundness (R) > 0.7, and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, wherein :
about 0.4
Si+Al+Fe+Ca+Mg+Na+K about 0.9;
about 0.1
Si+Al+Fe+Ca+Mg+Na+K about 0.3; and wherein the cementitious reagent has a molar ratio Si/(Fe3+, Al) of between about
1 and about 20, and a CaO content of about 10 wt.% or less.
23. The cementitious reagent of claim 22, wherein the cementitious reagent comprises a powder.
24. The cementitious reagent of claim 22, wherein the cementitious reagent is at least about 40% x-ray amorphous.
25. The cementitious reagent of claim 22, wherein the microspheroidal glassy particles are at least about 40% x-ray amorphous.
26. The cementitious reagent of claim 22, wherein the microspheroidal glassy particles hâve a mean roundness (R) of at least 0.9.
27. A cementitious reagent comprising:
microspheroidal glassy particles having a mean roundness (R) > 0.7, and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, wherein :
about 0.4
Si+Al+Fe+Ca+Mg+Na+K about 0.9;
-6820565 about 0.1
-------------------< about 0.3; and
Si+Al+Fe+Ca+Mg+Na+K wherein the cementitious reagent has a molar ratio Si/(Fe3+, Al) of between about
1 and about 20, and a CaO content of between about 20 wt.% and about 45 wt.%.
28. The cementitious reagent of claim 27, wherein the cementitious reagent is at least about 40% x-ray amorphous.
29. A concrète batch mixture comprising:
55-95 wt.% solid aggregate;
0.01-11.25 wt.% ambient cure reagent; and
2-32 wt.% cementitious reagent, wherein the cementitious reagent comprises:
microspheroidal glassy particles having a mean roundness (R) > 0.7, and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, where:
about 0.4
-------------------< about 0.9; and
Si+A!+Fe+Ca+Mg+Na+K about 0.1 < < about 0.3
Si+Al+Fe+Ca+Mg+Na+K
30. The concrète batch mixture of claim 29, wherein the ambient cure reagent comprises Portland cernent or calcic slag.
31. The concrète batch mixture of claim 29, further comprising a solution of an alkali silicate hardener characterized by a molar ratio Me2O/SiO2 < 1, wherein Me is Na or K.
32. The concrète batch mixture of claim 29, further comprising water.
33. A method comprising:
introducing a particulate feedstock into a chamber;
heating the feedstock within the chamber to form molten particles; and cooling the molten particles to form microspheroidal glassy particles having a mean roundness (R) > 0.7, and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, wherein:
about 0.4 _______________Si_______________
Si+Aî+Fe+Ca+Mg+Na+K about 0.9; and about 0.1 ____________Al____________
Si+A)+Fe+Ca+Mg+Na+K about 0.3;
-6920565 wherein the particulate feedstock is suspended within the chamber in a flame comprising an oxidant gas and a combustible fuel.
34. The method of claim 33, wherein the particulate feedstock is substantially free of fly ash.
35. The method of claim 33, further comprising blending the particulate feedstock with a composition adjustment material prior to heating the feedstock within the chamber.
36. The method of claim 33, further comprising milling the particulate feedstock prior to heating the feedstock within the chamber.
37. The method of claim 33, further comprising mixing the particulate feedstock with a fluxing material adapted to lower a melting point of the particulate feedstock prior to heating the feedstock within the chamber.
38. The method of claim 33, further comprising entraining the particulate feedstock in a gas stream.
39. The method of claim 33, wherein the particulate feedstock comprises mine tailings.
40. The method of claim 33, wherein the flame is stabilized by an annular flow of quench air.
41. The method of claim 33, further comprising milling the microspheroîdal glassy particles to a Sauter mean diameter D[3,2] of about 20 micrometers or less.
42. The method of claim 33, further comprising mixing the microspheroîdal glassy particles with one or more addîtives selected from the group consisting of hardeners, ambient cure reagents, admixtures, plasticizers, reinforcement materials, sand, and coarse aggregate.
43. A method comprising:
entrainîng solid particles of an aluminosîlicate feedstock in a gas stream comprising an oxidant gas;
adding a combustible fuel to the entrained particles to form a mixture;
flowing the mixture through a burner and forming a flame by combusting the combustible fuel;
-7020565 heating the aluminosilicate feedstock particles to a température sufficient to melt the solid particles and form molten particles; and cooling the molten particles to form microspheroidal glassy particles having a mean roundness (R) > 0.7, and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, wherein:
about 0.4
-------------------< about 0.9; and
Si+Al+Fe+Ca+Mg+Na+K about 0.1 ____________Al____________
Si+Al+Fe+Ca+Mg+Na+K about 0.3.
44. The method of claîm 43, wherein the aluminosilicate feedstock is substantially free of fly ash.
45. The method of claîm 43, further comprising blending the aluminosilicate feedstock with a composition adjustment material prior to heating the aluminosilicate feedstock prior to heating the aluminosilicate feedstock particles.
46. The method of claîm 43, further comprising milling the solid particles of the aluminosilicate feedstock prior to heating the aluminosilicate feedstock particles.
47. The method of claim 43, further comprising mixing the aluminosilicate feedstock with a fluxing material adapted to lower a melting point of the aluminosilicate feedstock particles prior to heating the aluminosilicate feedstock particles.
48. The method of claim 43, wherein the aluminosilicate feedstock particles are mine taîlings.
49. The method of claim 43, wherein the aluminosilicate feedstock particles are flown and melted in suspension and the molten particles are cooled in suspension.
50. The method of claim 43, wherein the molten particles are cooled at a cooling rate of about 102 Ks’1 to about 106 Ks'1.
51. The method of claim 43, wherein the cooling comprises contacting the molten particles with a stream containing a fluid selected from the group consisting of air, steam, and water.
52. The method of claim 43, wherein the microspheroidal glassy particles are at least about 40% x-ray amorphous.
-71 20565
53. A method comprising:
milling an aluminosilicate material to produce solid particles of an aluminosilicate feedstock;
introducing the solid particles of the aluminosilicate feedstock into a melt chamber;
heating the solid particles of aluminosilicate feedstock within the melt chamber to form molten particles; and cooling the molten particles within a quench chamber to form microspheroidal glassy particles, wherein the microspheroidal glassy particles hâve a mean roundness (R) > 0.7, and a molar composition containing Si and Al and optionally one or more of Fe,
Ca, Mg, Na, and K, such that:
about 0.4
-------------------< about 0.9; and
Si+Al+Fe+Ca+Mg+Na+K about 0.1 <---------—---------< about 0.3 auuui v.i si+Al+Fe+Ca+Mg+Na+K
54. The method of claim 53, wherein the aluminosilicate feedstock is substantially free of fly ash.
55. The method of claim 53, further comprising blending the aluminosilicate feedstock with a composition adjustment material.
56. The method of claim 55, wherein blending the aluminosilicate feedstock with the composition adjustment material is performed while heating the aluminosilicate feedstock particles within the melt chamber.
57. The method of claim 53, further comprising mixing the aluminosilicate feedstock with a fluxing material adapted to lower a melting point of the aluminosilicate feedstock particles prior to heating the aluminosilicate feedstock particles within the melt chamber.
58. The method of claim 53, further comprising entraining the solid aluminosilicate feedstock particles in a gas stream.
59. The method of claim 58, wherein the gas stream comprises an oxidant gas and a combustible fuel.
-72 20565
60. The method of claim 53, wherein the aluminosilicate feedstock particles are suspended in a flame comprising an oxidant gas and a combustible fuel.
61. The method of claim 60, wherein the flame is stabilized by an annular flow of quench air.
62. The method of claim 53, wherein the solid aluminosilicate feedstock particles are flown and melted in suspension and the molten particles are cooled in suspension.
63. The method of claim 53, wherein the molten particles are cooled at a cooling rate of about 102 Ks-1 to about 106 Ks'1.
64. The method of claim 53, wherein the cooling comprises contacting the molten particles with a stream containing a fluid selected from the group consisting of air, steam, and water.
65. The method of claim 53, further comprising milling the microspheroidal glassy particles to a Sauter mean diameter D[3,2] of about 20 micrometers or less.
66. The method of claim 53, wherein the microspheroidal glassy particles are at least about 40% x-ray amorphous.
67. The method of claim 53, further comprising collecting the microspheroidal glassy particles using a cyclone separator.
68. The method of claim 53, further comprising mixing the microspheroidal glassy particles with one or more additives selected from the group consisting of hardeners, ambient cure reagents, admixtures, plasticizers, rein forcement materials, sand, and coarse aggregate.
69. The method of claim 56, wherein blending the aluminosilicate feedstock with the composition adjustment material comprises altering a bulk composition of the aluminosilicate feedstock with one or more of Ca, Na, K, Al, Fe, and Si.
70. The method of claim 53, further comprising blending the microspheroidal glassy particles wîth a hydraulic cernent.
71. The method of claim 53, wherein the solid particles of the aluminosilicate feedstock are selected from one or more of dredged sédiments, demolished concrète, mine wastes, glacial clay, glacial deposits, fluvial deposits, and rocks and minerai mixtures.
-73 20565
72. The method of claim 53, further comprising adding the microspheroidal glassy particles as a reagent to a mixture.
73. A blended cernent comprising:
a binder composition inciuding Portland cernent, a supplémentai cementitious material, and metakaolin; and an alkali sulfate activator compound, the blended cernent comprising, as a percentage of the binder composition:
from about 40 wt.% to about 60 wt.% of the Portland cernent;
from about 40 wt.% to less than about 60 wt.% of the supplémentai cementitious material;
up to about 10 wt.% of the metakaolin; and up to about 7.5 wt.% ofthe alkali sulfate wherein the supplémentai cementitious material is not a by-product of an exîsting industrial process, wherein the supplémentai cementitious material comprises microspheroidal glassy particles having a mean roundness (R) >0.7 and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, such that their ratios are:
(Ca,Mg)o-i2*(Na,K) ο.05-ι·(Α1, Fe3+)l*Sii-20.
74. The blended cernent of claim 73, wherein the microspheroidal glassy particles are at least about 40% x-ray amorphous.
75. The blended cernent of claim 73, wherein the microspheroidal glassy particles hâve a Sauter mean diameter D[3,2] of about 20 micrometers or less.
76. The blended cernent of claim 73, wherein the supplémentai cementitious material îs free of fly ash.
77. The blended cernent of claim 73, comprising from about 1 wt.% to about 5 wt.% ofthe alkali sulfate.
78. The blended cernent of claim 73, wherein the alkali sulfate is selected from the group consisting of anhydrous sodium sulfate, sodium sulfate decahydrate, and potassium sulfate.
-7420565
79. The blended cernent of claim 73, comprising from about 1 wt.% to about 10 wt.% of the metakaolin.
80. A blended cernent comprising:
a binder composition including Portland cernent, a supplémentai cementitious material, and optionally metakaolin; and an alkali sulfate activator compound, wherein the blended cernent comprises, as a percentage of the binder composition:
from about 40 wt.% to about 60 wt.% of the Portland cernent;
from about 40 wt.% to less than about 60 wt.% of the supplémentai cementitious material wherein the supplémentai cementitious material is not a by-product of an existing industrial process;
up to about 1Û wt.% of the metakaolin; and up to about 7.5 wt.% of the alkali sulfate.
81. The blended cernent of claim 80, wherein the supplémentai cementitious material comprises microspheroidal glassy partîcles having a mean roundness (R) >0.7 and a molar composition containing Si and AI and optionally one or more of Fe, Ca, Mg, Na, and K, such that:
about 0.3 about 0.2
--------------------< about 0.6; and
Si+Al+Fe+Ca+Mg+Na+K
-------------------< about 0.35.
Si+AÏ+Fe+Ca+Mg+Na+K
82. The blended cernent of claim 80, wherein the supplémentai cementitious material comprises fly ash and microspheroidal glassy partîcles having a mean roundness (R) >0.7 and a molar composition containing Si and Al and optionally one or more of Fe, Ca, Mg, Na, and K, such that;
about 0.4 <
about 0.1
-------------------< about 0.9; and
Si+Al+Fe+Ca+Mg+Na+K
--------------------< about 0.3.
Si+AI+Fe+Ca+Mg+Na+K
83. The blended cernent of claim 80, wherein the supplémentai cementitious material is free of fly ash.
-7520565
84. The blended cernent of claim 80, comprising from about I wt.% to about 5 wt.% of the alkali sulfate.
85. The blended cernent of claim 80, wherein the alkali sulfate is selected from the group consisting of anhydrous sodium sulfate, sodium sulfate decahydrate, and potassium sulfate.
86. The blended cernent of claim 80, comprising from about 1 wt.% to about 10 wt.% of the metakaolin.
87. The blended cernent of claim 80, wherein the supplémentai cementitious material is formed by melting crystalline minerais.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62/867480 | 2019-06-27 | ||
| US63/004673 | 2020-04-03 | ||
| US63/025148 | 2020-05-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA20565A true OA20565A (en) | 2022-10-27 |
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