EP2692460A1 - Teilchenförmige Feuerfestmaterialzusammensetzungen zur Verwendung bei der Herstellung von Gussformen und -kernen, Verfahren zu ihrer Herstellung und entsprechende Verwendungen - Google Patents
Teilchenförmige Feuerfestmaterialzusammensetzungen zur Verwendung bei der Herstellung von Gussformen und -kernen, Verfahren zu ihrer Herstellung und entsprechende Verwendungen Download PDFInfo
- Publication number
- EP2692460A1 EP2692460A1 EP12178533.1A EP12178533A EP2692460A1 EP 2692460 A1 EP2692460 A1 EP 2692460A1 EP 12178533 A EP12178533 A EP 12178533A EP 2692460 A1 EP2692460 A1 EP 2692460A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cores
- additive
- broken material
- binder
- zeolites
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 169
- 239000000203 mixture Substances 0.000 title claims abstract description 159
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 149
- 239000000463 material Substances 0.000 claims abstract description 130
- 230000000996 additive effect Effects 0.000 claims abstract description 121
- 239000011230 binding agent Substances 0.000 claims abstract description 92
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 89
- 239000010457 zeolite Substances 0.000 claims abstract description 77
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000010438 heat treatment Methods 0.000 claims abstract description 71
- 239000000470 constituent Substances 0.000 claims abstract description 48
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000011819 refractory material Substances 0.000 claims abstract description 10
- 239000004576 sand Substances 0.000 claims description 94
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 85
- 239000000725 suspension Substances 0.000 claims description 44
- 238000005245 sintering Methods 0.000 claims description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910001679 gibbsite Inorganic materials 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- -1 brewsterite Chemical compound 0.000 claims description 16
- 229920001568 phenolic resin Polymers 0.000 claims description 14
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000007423 decrease Effects 0.000 claims description 8
- 229910052680 mordenite Inorganic materials 0.000 claims description 6
- 150000002895 organic esters Chemical class 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 4
- JEWHCPOELGJVCB-UHFFFAOYSA-N aluminum;calcium;oxido-[oxido(oxo)silyl]oxy-oxosilane;potassium;sodium;tridecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.[Na].[Al].[K].[Ca].[O-][Si](=O)O[Si]([O-])=O JEWHCPOELGJVCB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052908 analcime Inorganic materials 0.000 claims description 3
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 3
- 229910052676 chabazite Inorganic materials 0.000 claims description 3
- 229910052675 erionite Inorganic materials 0.000 claims description 3
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 229910001683 gmelinite Inorganic materials 0.000 claims description 3
- 229910001690 harmotome Inorganic materials 0.000 claims description 3
- 229910052677 heulandite Inorganic materials 0.000 claims description 3
- 229910001711 laumontite Inorganic materials 0.000 claims description 3
- 229910001723 mesolite Inorganic materials 0.000 claims description 3
- 229910052674 natrolite Inorganic materials 0.000 claims description 3
- 229910001743 phillipsite Inorganic materials 0.000 claims description 3
- 229910001744 pollucite Inorganic materials 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 229910052679 scolecite Inorganic materials 0.000 claims description 3
- 229910001761 stellerite Inorganic materials 0.000 claims description 3
- 229910052678 stilbite Inorganic materials 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 144
- 238000012360 testing method Methods 0.000 description 86
- 239000000523 sample Substances 0.000 description 83
- 239000006101 laboratory sample Substances 0.000 description 58
- 239000013074 reference sample Substances 0.000 description 47
- 230000008569 process Effects 0.000 description 45
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 43
- 239000000428 dust Substances 0.000 description 27
- 239000000377 silicon dioxide Substances 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 16
- 229910052700 potassium Inorganic materials 0.000 description 16
- 239000011591 potassium Substances 0.000 description 16
- 239000004927 clay Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 229910001680 bayerite Inorganic materials 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 7
- 239000002956 ash Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- 229960002622 triacetin Drugs 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001681 doyleite Inorganic materials 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910001682 nordstrandite Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000004449 solid propellant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 description 2
- 239000001087 glyceryl triacetate Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000007431 microscopic evaluation Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 102000054765 polymorphisms of proteins Human genes 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- YVKMMZAFUFUAAX-UHFFFAOYSA-N aluminum;tetrahydrate Chemical compound O.O.O.O.[Al] YVKMMZAFUFUAAX-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 101150038956 cup-4 gene Proteins 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000005335 volcanic glass Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
- B22C1/186—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
- B22C1/188—Alkali metal silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
- B22D29/001—Removing cores
- B22D29/003—Removing cores using heat
Definitions
- the invention relates to particulate refractory compositions for use in the manufacture of foundry moulds and cores, methods of preparing same and corresponding uses.
- the invention relates to a method of preparing a particulate refractory composition (hereinafter according to the terminology typically used in practice also referred to as "sand") for use in the manufacture of foundry moulds and cores from spent foundry moulds or cores formed of refractory material and an alkaline binder containing alkali metal ions.
- a particulate refractory composition i.e. sand
- the invention relates to a particulate refractory composition for use in the manufacture of foundry moulds and cores, obtainable by a method according to the first aspect of the invention.
- the invention relates to a method of making a foundry mould or core, wherein a particulate refractory composition is used which is prepared according to the method of the invention.
- the invention relates to the use of certain suspensions
- Broken material from spent foundry moulds and cores is a useful starting material according to the present invention, and is in many cases a material fabricated by (i) bonding foundry sand (particulate refractory composition) with a phenolic resin binder in strong alkaline aqueous solution (i.e., an alkaline phenolic resin binder), wherein the binder has been cured with a liquid or gaseous organic ester or with carbon dioxide gas, to give a foundry mould or core, and (ii) breaking said mould or core after use, i.e. breaking the spent foundry mould or core.
- the resin is a mixture of organic (phenolic resin) and inorganic (hydroxide) compounds.
- an alkaline inorganic binder e.g. (i) modified silicates in combination with inorganic oxides and (ii) water glass binders comprising silicon dioxide and alkali metal oxides in a defined ratio
- the inorganic binder is then cured as known in the art (e.g. with carbon dioxide or by heat).
- alkaline phenolic resins for the making of foundry cores and moulds is known for many years. Examples are cold setting processes (so called No-Bake systems) wherein the binder is cured with liquid or gaseous esters. Liquid or gaseous esters are for example di- or triacetin, methyl formate, gamma-butyrolactone, epsilon-caprolactone and propylene carbonate. Other processes comprise binders for core making that are cured by gassing with carbon dioxide.
- the alkaline phenolic resin binder is usually prepared by mixing phenol and formaldehyde in a defined molar ratio under alkaline conditions.
- the defined molar ratio typically is in the range of from 1.5 : 1.0 to 2.2 : 1.0.
- the molar ratio of hydroxide (e.g. potassium hydroxide) and phenol (KOH : phenol) is usually in the range of from 0.2 : 1.0 to 1.2 : 1.0.
- No-Bake systems known for manufacturing foundry moulds and cores comprising alkaline phenolic resin binders. Such foundry moulds and cores can be used in casting processes to finally give (after the respective mould or core has been used) the broken material which is an appropriate starting material for the purposes of the present invention. Broken material from spent foundry moulds or cores, wherein the moulds or cores have been produced according to a No-Bake process, are a useful starting material in methods of the present invention.
- Betaset process is similar to the Alphaset process but the ratio between hydroxide and phenols may vary from 0.2 : 1 to 1.2 : 1 and curing of the resin binder is accomplished by gaseous esters (e.g. methyl formate).
- gaseous esters e.g. methyl formate
- the amount of hydroxide is for example between 20 and 25 % by weight referred to the dry weight of the composition.
- the curing of a phenolic binder can also be carried out by applying an inorganic curing agent.
- the use of carbon dioxide is disclosed in US 4,977,209 .
- the amount of hydroxide in such a process is for example 30 % by weight referred to the dry weight of the composition.
- Broken material from spent foundry moulds or cores, wherein the moulds or cores have been cured with carbon dioxide, are also a useful starting material in methods of the present invention.
- Foundry moulds and cores manufactured according to one of the above mentioned processes have in common that a high amount of alkalinity is present in said mixtures.
- Advantages of these water-based systems are, next to the competitive binder costs, technological advantages like good collapsibility and a good casting finish as well as low emissions during core and mould making and casting.
- Disadvantages are that the binders are supplemented with high amounts of hydroxides.
- This high alkalinity mainly remains in the spent foundry sands after casting, in particular in the form of oxides and hydroxides of alkali metals.
- Conventional reclamation methods e.g. mechanical attrition
- washing of the sand to remove soluble alkaline components would be an ideal solution to clean the sand.
- such washing process is not practicable as it would create vast quantities of polluted waste water as well as high energy costs for drying the sand.
- foundry sands partate refractory composition for use in the manufacture of foundry moulds and cores
- foundry moulds and cores partate refractory composition for use in the manufacture of foundry moulds and cores
- One known conventional method of sand reclamation is a mainly mechanical reclamation and comprises attrition of the bonded sand from spent foundry moulds or cores to break up sand lumps into individual particles.
- attrition When working with (reclaimed) sand obtained after attrition, the strength of moulds and cores made with ester- or carbon dioxide-cured phenolic resins are generally far inferior compared to the strength obtained with new sand or reclaimed sand from other processes. This is also true for sand obtained from heat-, ester- or CO 2 -curing silicate systems (i.e. inorganic systems).
- Conventional attrition processes allow only a reclamation rate of approximately 70 to 85 % and in practice demand addition of new or otherwise reclaimed sand (e.g. through thermal reclamation at high temperatures) to maintain acceptable performance levels.
- a further step of sand reclamation can involve a heat treatment following the mechanical attrition to completely remove (decompose) all organic impurities and residues.
- a known technique is to heat the sand in a fluidized bed (further details are provided below in the specification).
- heat treatment can lead to agglomeration of the sand grains and preventing the fluidized bed from properly functioning. This negative effect is sometimes described as fritting or sintering of the fluidized bed.
- This fritting/sintering process is a physicochemical process resulting in the formation of solidified objects which means the fusion or agglomeration of particulated, powdery substances (e. g. sand grains) under increased temperatures. In the context of the present invention, this fritting/sintering process is undesirable and should be avoided.
- alkaline metal oxides and hydroxides e.g. sodium and/or potassium hydroxide and oxide, respectively
- This glass covers the surfaces of the sand grains and forms bridges between individual grains that lead to the above described fritting/sintering process (agglomeration).
- fritting/sintering dramatically reduces the refractoriness of the substrate.
- EP 2 191 908 A1 discloses the use of silicon oils as additives for improved mechanical reclamation of sands. According to own experiments, this additive does not remove the alkalinity and is therefore not ideal.
- EP 0 949 978 B1 discloses the use of carbohydrates as additives added prior to heat treatment to prevent sand grain fusion. However, this method in own experiments proved unsuccessful as no potassium is removed and the potassium content of the reclaimed sand became too high with intensive reuse therefore compromising the rebond strength and refractoriness.
- WO 94/05448 discloses the use of additives like halogen acids, sulphuric acid, boric acid and ammonium salts of these acids that react with potassium compounds to form salts that have a melting point of at least 550 °C, preferably above 700 °C.
- the unacceptable disadvantage of this process in own experiments was that a high degree of corrosion was observed in the treatment plants.
- WO 94/26439 discloses the use of particulate active clay additives added prior to the heat treatment. It is disclosed that the strength levels obtained with reclaimed sand are improved and that the level of elutable alkali is dramatically reduced after the reclamation process. However, in own experiments (compare example 3.1) it has been found that with this additive the strength levels drop with each reclamation cycle and was too low to manufacture cores or moulds. Furthermore, EP 1 753 560 B1 discloses that this process suffers from the disadvantage that very fine clay particles are retained with the treated sand with a resultant lack of potassium (or other alkali) removal.
- WO 2005/107975 A1 discloses the use of pozzolanic additives such as volcanic-, fuel-and fly ashes as well as calcined bauxite to reduce fritting/sintering of the fluidized bed of a thermal reclamation unit.
- a common characteristic of the pozzolanic additives is their content of reactive SiO 2 . It is disclosed that the pozzolanic additives react with potassium and are removed after the reclamation process together with the dust.
- pozzolanic materials have a potential reactivity and that it is therefore difficult to prepare storage-stable suspensions.
- Another disadvantage is that the pozzolanic additives can be obtained from natural sources or are waste products which can have a varying composition making it more difficult to ensure stable and reproducible process conditions.
- pozzolans contain mostly fine materials and varying amounts of finely divided SiO 2 that, as shown by own experiments (further details are shown in example 4.), has a significant influence on the degree of fritting and glass formation and, therefore, should be avoided.
- a primary object of the present invention is to provide an alternative or improved method of preparing a particulate refractory composition for use in the manufacture of foundry moulds and cores from spent foundry moulds or cores formed of refractory material and an alkaline binder containing alkali metal ions.
- the method should avoid or at least alleviate at least some problems or disadvantages associated with the prior art methods discussed above.
- this object is achieved by a method of preparing a particulate refractory composition for use in the manufacture of foundry moulds and cores from spent foundry moulds or cores formed of refractory material and an alkaline binder containing alkali metal ions, the method comprising the following steps:
- zeolites refers to both and does not distinguish between natural and synthetic zeolites if not stated otherwise.
- a definition of natural and synthetic zeolites is given below in the specification.
- Al(OH) 3 sometimes erroneously called hydrate of alumina (in German: Tonerdehydrat), is found in nature as the mineral gibbsite (monoclinic; also known as hydrargillite) and its three, much more rare polymorphs: bayerite (hexagonal), doyleite and nordstrandite. Closely related are aluminium oxide hydroxide, AIO(OH), differing only by loss of water. These compounds together are the major components of the aluminium ore bauxite. Freshly precipitated aluminium hydroxide forms gels, which is the basis for application of aluminium salts as flocculants in water purification. This gel crystallizes with time.
- aluminium hydroxide The naming for the different forms of aluminium hydroxide is ambiguous and there is no universal standard. All four polymorphisms have a chemical composition of aluminium trihydroxide (an aluminium atom attached to three hydroxide groups).
- Gibbsite is also known as hydrargillite, with gibbsite used most commonly in the United States and hydrargillite used more often in Europe. In 1930 it was referred to as ⁇ -alumina trihydrate to contrast it with bayerite which was called ⁇ -alumina trihydrate (the alpha and beta designations were used to differentiate the more- and less-common forms respectively).
- ⁇ -alumina trihydrate the alpha and beta designations were used to differentiate the more- and less-common forms respectively.
- a symposia on alumina nomenclature attempted to develop a universal standard, resulting in gibbsite being designated ⁇ -Al(OH) 3 and bayerite becoming ⁇ -Al(OH)3 and nordstrandite being designated Al(OH) 3 .
- ⁇ and ⁇ prefixes refer to hexagonal, close-packed structures and altered or dehydrated polymorphisms respectively, with no differentiation between nordstrandiate and doyleite.
- Alkyl hydroxide refers to any of the above mentioned different forms of aluminium hydroxide. For preferred forms see below.
- Al(OH) 3 aluminium oxide hydroxide
- AIO(OH) aluminium oxide hydroxide
- Al(OH) 3 aluminium oxide hydroxide
- AIO(OH) exists in two forms: ⁇ -AlO(OH) (Diaspor) and ⁇ -AlO(OH) (Böhmit).
- Aluminium hydroxide is capable to form aluminates upon reacting with alkali metal hydroxides.
- the generic formula of such compounds is M[Al(OH) 4 ], wherein M means the alkali metal ion.
- said additive comprising one or more particulate constituents selected from the group consisting of aluminium hydroxide, synthetic zeolites and natural zeolites reduces the likelihood of fritting/sintering of the sand grains and does not disturb the flowability of a fluidized bed in a reclamation unit. Furthermore, said additives do not bind sand particles.
- the constituents of said additives are typically fully removable from the mixture after heat treatment by dedusting, and along with the dust/fines advantageously a high amount of alkali metal ions (for example potassium ions) can be removed.
- the method according to the invention is preferably a method (as described above), wherein the alkaline binder containing alkali metal ions is an organic binder.
- Alkaline organic binders are typically prepared by mixing phenol and formaldehyde in defined molar ratios under alkaline conditions to obtain resols (phenol formaldehyde resins).
- the defined molar ratio (formaldehyde : phenol) typically is in the range of from 1.5 : 1.0 to 2.2 : 1.0.
- the molar ratio of hydroxide (e.g. potassium hydroxide) and phenol (KOH : phenol) is usually in the range of from 0.2 : 1.0 to 1.2 : 1.0.
- the resulting alkaline organic resin binders are usually employed in Alphaset, Betaset and CO 2 -curing processes (as defined above).
- the method of the invention and the additives used therein, in particular the additives designated as being preferred, is particularly useful in cleaning the surfaces of particulate material (sand) from such organic binders.
- the properties of a (cleaned) particulate refractory composition, reclaimed from spent foundry moulds or cores formed of refractory material and an alkaline organic binder containing alkali metal ions are close to the properties of the corresponding virgin particulate refractory composition, i.e. the particulate refractory composition present before first contact with binder.
- the particulate refractory composition reclaimed from spent foundry moulds or cores can be optionally mixed with virgin particulate refractory composition.
- the alkaline organic binder which is to be removed in the reclamation process
- the alkaline organic binder is a binder as defined above.
- the method according to the invention is preferably a method (as described above), wherein the alkaline binder containing alkali metal ions is an inorganic binder.
- the method of the invention and the additives used therein, in particular the additives designated as being preferred are also useful in cleaning the surfaces of particulate material (sand) from such inorganic binders.
- the properties of a (cleaned) particulate refractory composition, reclaimed from spent foundry moulds or cores formed of refractory material and an alkaline inorganic binder containing alkali metal ions are improved compared to a particulate refractory composition, reclaimed from spent foundry moulds or cores formed of refractory material and an alkaline inorganic binder containing alkali metal ions not treated according to the method of the invention.
- the alkaline inorganic binder (which is to be removed in the reclamation process) is usually selected from the group consisting of (i) modified silicates in combination with inorganic oxides and (ii) water glass binders comprising silicon dioxide and alkali metal oxides in a defined molar ratio.
- the molar ratio of silicon dioxide to e.g. sodium oxide typically is in the range of from 2.3 : 1 to 3.0 : 1.
- Cores and moulds manufactured with said organic alkaline or inorganic alkaline binders (as defined above) are in most cases excellent starting materials for the method of the invention.
- the fritting/sintering during the heat treatment can be reduced by means of the addition of additives comprising one or more particulate constituents selected from the group consisting of aluminium hydroxide, synthetic zeolites and natural zeolites.
- the method (as described above, in particular as preferably described) is preferably a method, wherein the amount of constituents in the additive is selected such that sintering and/or fritting is reduced during the heat treatment in comparison with a method not comprising mixing the broken material with an additive but being otherwise identical.
- the skilled person will typically conduct a number of simple experiments in order to identify an appropriate amount of constituents in the additive, i.e.
- the appropriate additive formulation type and amount of additive constituent
- an appropriate amount of additive for a given type and amount of spent foundry mould or core.
- the appropriate additive and amount of additive will also be determined by the apparatus available for mixing and heat treatment etc.
- the person skilled in the art knows methods which can be used to verify the appropriate amount and type of constituents in the additive.
- the concepts of DIN 51730 for example provide a method (Testing of solid fuels - Determination of fusibility of fuel ash) to verify the results achieved with defined amounts and types of constituents in the additive by determining the cross sectional area values of specimens manufactured with heat treated broken material. These cross sectional area values indicate the progress of fritting/sintering in dependence of the temperature (see example 4. and Figure 1 ).
- the skilled person can take pictures of heat treated broken material with an optical microscope to analyse the surfaces of heat treated particles (compare 3.1 under the heading Examples). Such an analysis advantageously shows whether the surfaces are clean or still covered by remaining binder material. Both methods are suitable to determine the appropriate amount and type of constituents in the additive, in particular for broken material (sand) which has been obtained from spent foundry moulds or cores formed of refractory material and an alkaline binder containing alkali metal ions.
- An optical analysis using a microscope is a preferred method to analyze sand grain particles and to identify whether and to which extent sintering and/or fritting has occurred (in comparison with a method not comprising mixing the broken material with an additive but being otherwise identical).
- the method according to the invention preferably relates to a method (as described above, in particular as designated as being preferred), wherein the heat treatment is at a temperature in the range of from 400 to 750 °C, more preferably 450 to 670 °C, even more preferably 530 to 650 °C, most preferably 580 to 600 °C.
- the method of the invention and the additives used therein, in particular the additives designated as being preferred, is particularly useful in cleaning the surfaces of broken material (sand) from remaining binder material.
- This cleaning process is preferably carried out at a temperature between 400 to 750 °C because in this temperature range the heat treatment ensures a complete burning/combustion of the remaining binder.
- the burning process (this means the quantity of burned/combusted binder material) depends on the type of binder that has been used to manufacture the broken material and the temperature used during heat treatment.
- the method according to the invention surprisingly showed an excellent burning/combustion of alkaline organic binders (as defined above, in particular as designated as being preferred).
- especially preferred methods of the invention relate to a method (as described above, in particular as designated as being preferred) wherein the alkaline binder containing alkali metal ions is an organic binder, and wherein the heat treatment is at a temperature at which the binder is burned/combusted.
- Temperatures below 400°C usually (i) do not guarantee a complete burning/combustion of the residual binders (in particular organic binders) during heat treatment and/or (ii) lead to emissions in the exhaust gases due to unburned binder material. These emissions usually comprise volatile organic compounds because at lower temperatures the binder material (e.g. resin) may be removed from the broken material (sand grain surface) by for example vaporization but temperature is insufficient to destroy the binder vapor, which will be passed to the atmosphere. Furthermore, broken material (sand) obtained after heat treatment below 400 °C exhibits insufficient binding properties (which means an insufficient binding strength upon manufacturing moulds and cores with such broken material). On the other hand, temperatures above 750 °C strongly increase the likelihood of fritting/sintering of the broken material during heat treatment.
- temperatures above 750 °C strongly increase the likelihood of fritting/sintering of the broken material during heat treatment.
- the method according to the invention can be carried out in various scales and may e.g. include mixtures (comprising the broken material and an additive comprising or consisting of one or more particulate constituents selected from the group consisting of aluminium hydroxide, synthetic zeolites and natural zeolites) of less than 1 kg (e.g. 500 g) up to 15 tonnes.
- the method according to the invention can be carried out as a batch process or as a continuous process. Both processes can be performed in a thermal reclamation unit (this means a thermal reclamation unit particular for sand reclamation) capable of providing suitable temperatures during heat treatment. In most cases, the thermal reclamation unit advantageously provides stable and reproducible treatment conditions during the heat treatment.
- Continuous operating thermal reclamation units can be (but are not necessarily) part of a thermal reclamation plant which is commercially available (e.g. Richards/Omega Alkaline Phenolic Thermal Sand Reclamation Plant typically comprising a PXG "Phoenix" thermal reclamation unit; Omega Foundry Machinery Ltd.).
- the Alkaline Phenolic Thermal Sand Reclamation Plant (as commercially offered) is typically made in standard unit sizes from 0.25 tons per hour to 12.0 tons per hour, in increments of 0.25 tons per hour, and is advantageously designed to treat broken material obtained from moulds and cores cured with alkaline phenolic ester type binders.
- the method according to the invention (as described above, in particular as designated as being preferred) preferably relates to a method carried out in a thermal reclamation unit, more preferably in a continuous operating thermal reclamation unit.
- the binder preferably is an alkaline resol phenol-aldehyde resin binder, preferably as used in a method of bonding foundry sand with phenolic resin binder in alkaline aqueous solution, wherein the binder is cured with an liquid or gaseous organic ester or with gaseous carbon dioxide.
- Such resin binders and corresponding methods of bonding foundry sand with said binders are for example disclosed in EP 0 556 955 B1 , EP 0 085 512 B1 , US 4,980,394 and US 4,977,209 , and broken material from moulds and cores manufactured accordingly are preferred starting materials in methods according to the invention.
- such broken material shows an excellent burning/combustion of said binders during the heat treatment step (at temperatures as defined above, in particular as designated as being preferred). Fritting and/or sintering is avoided or at least significantly reduced. Another advantage is that costs for dumping spent broken material can be significantly reduced as well as the amount of virgin sand (this means fresh or new sand before first contact with a binder) which is typically added in practice in order to maintain excellent properties of the sand mixture used.
- the additive preferably comprises its constituents suspended in water.
- the additive In order to mix the additive with broken material from spent foundry moulds or cores the most practical way is to add the additive as a suspension.
- One advantage is that a suspension can be accurately and easily dosed. Furthermore, the addition of a suspension prevents dust formation and guarantees homogenous mixing with the substrate.
- additives as preferably used in the method according to the invention are preferably suspensions of (i) aluminium hydroxide in water or (ii) synthetic zeolites in water or (iii) natural zeolites in water or (iv) mixtures of synthetic and natural zeolites in water or (v) mixtures of aluminium hydroxide and synthetic zeolites in water or (vi) mixtures of aluminium hydroxide and natural zeolites in water or (vii) mixtures of aluminium hydroxide and natural and synthetic zeolites.
- said suspensions (i) to (vii) are advantageously storage-stable and usually exhibit a defined composition of constituents. This ensures stable and reproducible process conditions in a method according to the invention.
- a suspension of, e.g., aluminium hydroxide in water can be prepared by mixing aluminium hydroxide in water by means of a high-performance mixer.
- suspending agents and thickeners are optionally added to the suspension in order to avoid or minimize sedimentation and to improve mixing with the broken material, in particular sand.
- Zeolites can be added as further active ingredient.
- additional additives e.g. surfactants
- the resulting aluminium hydroxide suspension contains a total amount of solid material of about 20 to 70 %, preferably 35 to 55 %, more preferably 40 to 50 % by weight based on the total amount of the suspension.
- at least 70 %, preferably at least 75 % by weight, based on the total amount of solid material in the suspension is natural zeolite.
- At least 90 %, preferably at least 95 % by weight, based on the total amount of solid material in the suspension is selected from the group consisting of aluminium hydroxide and zeolite.
- a suspension of natural and/or synthetic zeolites in water likewise shows excellent results, in particular if the suspension is homogeneously mixed with the broken material prior to the heat treatment.
- the steps of preparing a suspension of natural and/or synthetic zeolites in water correspond to the steps of preparing a suspension of aluminium hydroxide in water.
- Aluminium hydroxide can be added as further active ingredient.
- Preferred zeolite suspensions contain a total amount of solid material of about 20 to 60 %, preferably 30 to 50 %, more preferably 35 to 45 % by weight based on the total amount of aluminum hydroxide in the suspension.
- at least 90 %, preferably at least 95 % by weight, based on the total amount of solid material in the suspension is selected from the group consisting of aluminium hydroxide and zeolite.
- a suspension of a mixture of aluminium hydroxide and natural and/or synthetic zeolites in water shows equally excellent results if the suspension is homogeneously mixed with the broken material prior to the heat treatment.
- a similar positive effect of reducing the likelihood of fritting/sintering as described throughout this specification for the use of aluminium hydroxide as well as for the use of zeolites (in particular if said compounds are suspended in water) in the method of the invention has been found also for the use of a mixture of aluminium hydroxide and natural and/or synthetic zeolites (in particular in aqueous suspensions).
- the steps to prepare a suspension of a mixture of aluminium hydroxide and natural and/or synthetic zeolites in water correspond to the steps of preparing either a suspension of aluminium hydroxide in water or of zeolites in water.
- the aforementioned aspects concerning the preparation of an aluminium hydroxide suspension and a zeolite suspension also apply to the preparation of a suspension comprising a mixture of aluminium hydroxide and natural and/or synthetic zeolites.
- suspensions are preferably employed for preparing the mixture which is then subjected to heat treatment at a temperature as defined above.
- the method according to the invention relates to a method (as described above, in particular as designated as being preferred), wherein the broken material is mixed with an additive comprising aluminium hydroxide and/or one or both of synthetic zeolites and natural zeolites.
- an additive comprising aluminium hydroxide and/or one or both of synthetic zeolites and natural zeolites.
- at least one constituent of an additive as used in a method according to the invention is mixed with said broken material.
- a mixture of preferred constituents in a suspension advantageously decreases even more the likelihood of fritting/sintering of the broken material (in particular sand) during heat treatment compared to broken material mixed with a suspension comprising either aluminium hydroxide or natural and/or synthetic zeolites.
- the mixing of broken material and additive according to the method of the invention can be for example performed in a thermal reclamation plant (see above).
- a thermal reclamation plant provides excellent results when employed in the method of the invention.
- said mixing can be also performed in a separate step in other typical mixing units as known to the skilled person, and the resulting mixture can subsequently be subjected to heat treatment in a thermal reclamation unit
- the mixture simultaneously with being subjected to said heat treatment is preferably fluidized in a fluidized bed apparatus or moved (preferably mixed) in a thermal sand reclamation unit.
- the heat treatment of the mixture in a method according to the invention leads to the burning/combustion of remaining binder material. It is therefore preferred that the mixture is stirred up or moved in order to improve the effects of the heat treatment.
- the heat treatment in the method according to the invention is more preferably carried out using fluidization of the mixture in a fluidized bed or movement (mixing movement) in a thermal sand reclamation unit such as a rotary reclamation apparatus.
- a rotary reclamation apparatus is for example disclosed in US 6,286,580 B1 . Fluidization of the mixture in the method according to the invention is more preferably achieved in a thermal reclamation unit or a thermal reclamation plant (as described above). The skilled person is familiar with the appropriate conditions in order to carry out such heat treatment step.
- solid matter (preferably dust and fines) containing alkali metal ions is preferably removed from the mixture during and/or after the heat treatment, so that the concentration of alkali metal ions in the remaining mixture decreases.
- the process of removing solid matters preferably separates the mixture in at least two fractions: (i) a sand fraction comprising the desired heat treated (broken) material and (ii) dust and fines which comprise alkali metal ions and reaction products of constituents of the additives with alkali metal ions.
- a preferred removing step is a dedusting step carried out to remove dust and fines.
- Dust and fines can be removed for example by using a sieve with a defined mesh size.
- a dedusting step using a sieve is preferably used if the method according to the invention is carried out in small scales (e.g. laboratory scales).
- dedusting can be advantageously combined with the use of a fluidized bed.
- a fluidized bed In a fluidized bed the mixture behaves as a fluid.
- a characteristic of a fluidized bed is that an object with a higher density than the bed will sink, whereas an object with a lower density than the bed will float. This property can be increased by applying a negative pressure to the fluidized bed.
- Such a fluidized bed allows the removal of dust and fines of lower density (dedusting), and its use is therefore preferred in the method of the present invention.
- a dedusting step to remove dust and fines which contain alkali metal ions can be carried out during and/or after the heat treatment. Said alkali metal ions are effectively removed, probably because constituents in the additives used in the method according to the invention advantageously react and bind alkali metal ions (in particular potassium ions) and form compounds which are thermally more stable in the temperature range applied to the fluidized bed. The formation of such thermally stable compounds prevents fritting/sintering of the fluidized bed, and said compounds can be removed by dedusting.
- dedusting during and/or after heat treatment effectively decreases the concentration of alkali metal ions in the mixture.
- Dedusting can be for example carried out in a thermal reclamation unit (as well as in a thermal reclamation plant) (see above) in combination with a filter unit appropriate to remove dust and fines.
- said solid matter comprises particulate constituents of said additive and/or reaction products thereof.
- the amount of alkali metal ions may vary and depend on the specific broken materials.
- the amount of constituents in the additive may not fully react with the alkali metal ions and residual amounts of constituents may remain in the mixture.
- These remaining constituents are preferably removed during dedusting.
- remaining additive constituents are fully removed.
- the total amount of said remaining constituents aluminium hydroxide and zeolites does preferably not exceed 10% by weight based on the total amount of aluminium hydroxide and zeolites comprised in the additive mixed with the broken material.
- the additive preferably comprises one or more particulate constituents selected from the group consisting of amorphous aluminium hydroxide (Al(OH) 3 ), monoclinic aluminium hydroxide (Al(OH) 3 ), and hexagonal aluminium hydroxide (Al(OH) 3 ), synthetic zeolites selected from the group consisting of synthetic mordenite, zeolite A, zeolite L, zeolite X, zeolite Y, ZM5 and ZSM11, and (other) zeolites of the pentasil family of zeolites, natural zeolites selected from the group consisting of analcime, barrerite, chabazite, brewsterite, clinoptilolite, edingtonite, erionite, ferrierite, gismondine, gmelinite, gonnardite, harmotome, heulandite, laumont
- Natural zeolites which can be employed in the method of the present invention are crystalline and naturally occurring alumosilicates. So far, there are 48 natural zeolites known. Zeolite minerals have been created through hydrothermal conversion of volcanic glasses and tuff-containing sediments, respectively.
- Natural zeolites are for example analcime, barrerite, chabazite, brewsterite, clinoptilolite, edingtonite, erionite, ferrierite, gismondine, gmelinite, gonnardite, harmotome, heulandite, laumontite, levynite, mesolite, mordenite, natrolite, paulingite, pentasil, phillipsite, pollucite, scolecite, stellerite, stilbite and wairakite.
- Synthetic zeolites which can be employed in the method of the present invention are compounds of the formula M 2 / z O Al 2 O 3 xSiO 2 yH 2 O, wherein M means a mono- or bivalent metal ions (preferably alkali or alkaline earth metal ions), hydrogen (H) or ammonium ions (NH 4 + ).
- water glass or liquid glass
- silicic acid-bulking agents colloidal silica
- colloidal silica colloidal silica
- Al 2 O 3 -containing e.g. aluminium hydroxide, aluminates, kaolinite
- alkali hydroxides e.g. sodium hydroxide
- Synthetic zeolites are for example synthetic mordenite, zeolite A, zeolite L, zeolite X, zeolite Y, ZM5, ZSM11, and (other) zeolites of the pentasil family of zeolites.
- the additive used in the method of the invention is free of puzzolanic constituents such as natural pozzolans occurring in volcanic ash and in volcanic tuff and synthetic pozzolanes, such as pulverized fuel ash, fly ash, gound granulated blast-furnace slag, condensed silica fume, amorphous silica and calcined bauxite.
- puzzolanic constituents such as natural pozzolans occurring in volcanic ash and in volcanic tuff and synthetic pozzolanes, such as pulverized fuel ash, fly ash, gound granulated blast-furnace slag, condensed silica fume, amorphous silica and calcined bauxite.
- the additive used in the method of the invention is free of free reactive silicon dioxide.
- the presence of reactive silicon dioxide (SiO 2 ) strongly favors fritting/sintering of the broken material.
- Reactive silicon dioxide (SiO 2 ) in particular is finely divided silicon dioxide providing a large surface area and, thus, an increased reactivity.
- Natural and synthetic zeolites have in common that they exhibit a cation exchange capacity.
- the cations compensating the negative charges of the AlO 4 -tetraeder, are floating in the hydrated lattice and therefore, are easily exchangeable against other cations.
- zeolites are capable to exchange alkali metal ions in an aqueous solution against other cations.
- zeolites can adsorb other molecules.
- a typical characteristic of zeolites is that they can release water molecules without modifying their crystal structure.
- the additives comprise particulate constituents.
- a screen accordinging to DIN ISO 3310 having a mesh size of 125 ⁇ m.More preferably, at least a part (preferably at least 80 to 90 % by weight, more preferably 95 % by weight based on the total amount of said constituents) of the particulate constituents selected from the group consisting of aluminium hydroxide (as defined above), synthetic zeolites (as defined above) and natural zeolites (as defined above) passes a screen (according to DIN ISO 3310) having a mesh size of 125 ⁇ m., which means that at least a part of aluminium hydroxide passes a screen (according to DIN ISO 3310) having a mesh size of 125 ⁇ m.and/or at least a part of synthetic zeolites passes a screen (according to DIN ISO 3310) having a mesh size of 125 ⁇ m. and/or at least a part
- Particulate constituents (as defined above, in particular as defined as preferably) preferably show an excellent reactivity with alkaline metal ions in the mixture according to the method of the invention and said particulate constituents which have not been reacted with said metal ions can be in most cases advantageously removed by dedusting.
- Particulate constituents exhibiting a particle size not passing a mesh size of less than 125 ⁇ m (the particle size is too large) show disadvantages during the dedusting process.
- such particulate constituents disadvantageously show an increased tendency to remain in the heat treated mixture and have a relatively small surface area available for reaction with alkaline materials to be removed from the broken material from spent foundry moulds or cores.
- a further important parameter during heat treatment of the mixture in the method according to the invention is the amount of additive to be used in the mixture.
- the total amount of aluminium hydroxide, synthetic zeolites and natural zeolites in the mixture is preferably in the range of from 0.1 to 3 % by weight based on the total weight of broken material, aluminium hydroxide, synthetic zeolites and natural zeolites. This concentration range is preferred to ensure an excellent ratio between said constituents and alkali metal ions.
- a concentration of less than 0.1 % by weight does in some cases not suffice (i) to decrease the likelihood of fritting/sintering of the broken material and (ii) to significantly decrease the concentration of alkali metal ions in the mixture.
- a concentration above 3 % by weight in some cases leads to a concentration of constituents in the mixture which cannot sufficiently be decreased by dedusting during or after heat treatment. According to own experiments particularly excellent results have been achieved when the total amount of aluminium hydroxide, synthetic zeolites and natural zeolites in the mixture is in the range of from 2.0 to 3.0 % by weight based on the total weight of broken material, aluminium hydroxide, synthetic zeolites and natural zeolites.
- a further important parameter is the period of time for subjecting the mixture to heat treatment.
- the method according to the invention preferably relates to a method (as described above, in particular as designated as being preferred), wherein the mixture is subjected to said heat treatment for a period of from 20 minutes to 12 hours, preferably from 15 minutes to 30 minutes.
- the period (dwell time) of preferably from 20 minutes to 12 hours, more preferably from 15 minutes to 30 minutes affects the quality of the burning/combustion of remaining binder material. Even at sufficient temperatures (as defined above, in particular as designated as being preferred) the combustion of remaining binder material may be incomplete if the dwell time is too short. On the contrary, if the dwell time is longer than preferred the yield per time is decreased and energy costs for the heat treatment increase.
- thermal reclamation unit typically provides a 15 minutes bed residence time while the broken material (sand) is subjected to heat treatment in a fluidized bed.
- a residence time of from 10 to 30 minutes is generally preferred.
- the method of the invention allows for the preparation of an excellent particulate refractory composition for use in the manufacture of foundry moulds and cores from spent foundry moulds or cores in particular if the measures discussed above regarding the important parameters (temperature, concentration and dwell time; all parameters as defined above, in particular as designated as being preferred) are combined.
- the heat treatment is carried out at temperatures as defined above (in particular as designated as being preferred) and/or (preferably "and")
- the total amount of aluminium hydroxide, synthetic zeolites and natural zeolites in the mixture is in the range of from 0.1 to 3 % by weight, preferably in the range of from 2.0 to 3.0 % by weight based on the total weight of broken material, aluminium hydroxide, synthetic zeolites and natural zeolites and/or (preferably "and")
- the mixture is subjected to said heat treatment for a period of from 20 minutes to 12 hours, preferably from 15 minutes to 30 minutes.
- the invention relates to a particulate refractory composition for use in the manufacture of foundry moulds and cores, obtainable by a method (as described above, in particular as designated as being preferred) according to the invention.
- a method as described above, in particular as designated as being preferred
- Such a composition can be advantageously obtained if in the method of the invention a thermal reclamation unit (as defined above) is used for the heat treatment step.
- Particulate refractory compositions according to the invention in many cases comprise one or more particulate constituents selected from the group consisting of aluminium hydroxide, synthetic zeolites, natural zeolites, and reaction products of alkali oxides with aluminium hydroxide, synthetic zeolites and/or natural zeolites.
- the method of the invention preferably comprises a dedusting step to remove solid matters.
- Dedusting in particular relates to so-called "fines", i.e. to solid particles passing a 0,075 mm (75 ⁇ m) sieve, preferably a 0,125mm (125 ⁇ m) sieve.
- fines i.e. to solid particles passing a 0,075 mm (75 ⁇ m) sieve, preferably a 0,125mm (125 ⁇ m) sieve.
- a particulate refractory composition of the invention contains dust and fines.
- Said fines usually comprise remaining constituents (e.g. as aluminium hydroxide and/or zeolites) and/or reaction products thereof with alkali metal ions (as described above).
- the particulate refractory compositions for use in the manufacture of foundry moulds and cores according to the invention do not comprise aluminium-containing oxy anions.
- the present invention relates to a method of making a foundry mould or core comprising the following steps:
- the binder used in the method of making a foundry mould or core according to the invention is preferably a binder as discussed above.
- alkaline organic binders are typically prepared by mixing phenol and formaldehyde in defined molar ratios under alkaline conditions to obtain resols (phenol formaldehyde resins).
- the defined molar ratio (formaldehyde : phenol) typically is in the range of from 1.5 : 1.0 to 2.2 : 1.0.
- the molar ratio of hydroxide e.g.
- Typical alkaline inorganic binders are (i) modified silicates in combination with inorganic oxides or (ii) water glass binders comprising silicon dioxide and alkali metal oxides in a defined molar ratio.
- the molar ratio of silicon dioxide to e.g. sodium oxide typically is in the range of from 2.3 : 1 to 3.0 : 1.
- the binder is preferably cured with a liquid or gaseous organic ester or with gaseous carbon dioxide.
- Liquid or gaseous esters are for example di- or triacetin, methyl formate, gamma-butyrolactone, epsilon-caprolactone and propylene carbonate.
- Foundry moulds or cores manufactured according to the method of the invention advantageously show excellent properties in the foundry and casting processes, and after use they can be recycled as discussed above.
- spent foundry moulds or cores manufactured according to the method of the invention can be broken, and the resulting broken material can be used as starting material in a method of the present invention of preparing a particulate refractory composition for use in the manufacture of foundry moulds and cores.
- the invention relates to the use of a suspension comprising one or more particulate constituents selected from the group consisting of aluminium hydroxide, synthetic zeolites and natural zeolites
- “Additive A”, “Additive B”, and “Additive C” were prepared as known to one skilled in the art. This includes mixing of the respective materials (aluminium hydroxide and/or zeolite; water) with common suspension additives such as suspension agents, wetting agents and thickeners. Significant characteristics of “Additive A”, “Additive B”, and “Additive C” are summarized in Table 1. Table 1 "Additive A” (aluminium hydroxide) "Additive B” (zeolite) "Additive C” (aluminium hydroxide and zeolite) Solid content [% by weight] (5-7 g are dried for 10 min.
- Pilot plant trials were carried out in a Richards/Omega thermal pilot plant. The pilot trials were carried out as follows:
- Test samples obtained in step VI) of the second cycle are labeled as follows:
- the numbering of the laboratory samples and the reference samples, prepared in step g), is increased by one.
- the respective laboratory samples are designated "Laboratory sample A-II", “Laboratory sample B-II” and “Laboratory sample C-II” whereas the reference samples are designated “Reference sample Pozzolan II” and "Reference sample Clay II”.
- the resultant laboratory samples and reference samples prepared in step g) of the fourth cycle are designated "Laboratory sample A-IV", “Laboratory sample B-IV” and “Laboratory sample C-IV", “Reference sample Pozzolan IV” and "Reference sample Clay IV", respectively.
- the potassium content in the dust (K 2 O Dust ) in [%] of each sample obtained in step f) was determined by X-Ray refraction analysis as potassium oxide.
- a potassium removal rate (PRR, determined in [% by weight]) was calculated for each cycle (4 cycles in total) and indicates the calculated ratio of a dividend, which is the difference of the amount of potassium removed by removal of dust and the amount of potassium added by addition of the additive, to the divisor, which is the amount of potassium added by addition of binder, in the respective cycle.
- Table 5 Transverse strength levels in [N/cm 2 ] after 1 and 4 hours (after 4 cycles) "Laboratory sample A-IV” "Laboratory sample B-IV” "Laboratory sample C-IV” "Reference sample Pozzolan IV” "Reference sample Clay IV” 1h 113,3 31,7 71,7 106,7 n./a. 4h 181,3 66,3 131,3 180,0 n./a.
- a test sample "Carbophen” was prepared on the basis of a CO 2 -process as carried out by a person skilled in the art. The sample preparation was carried out as follows:
- step E the resulting sample in step E) is "Carbophen II".
- step J The homogenized, dustless particulate refractory composition obtained in step J) could be used to manufacture cores after both cycles.
- step F no fritting/sintering was observed for the broken material mixed with "Additive C", in both cycles.
- each particulate refractory composition of each sample was analyzed with respect to fritting/sintering. It was observed that severe fritting/sintering occurred in the reference sample "CORDIS Z". No fritting/sintering was observed in the test samples "CORDIS X” and “CORDIS Y", wherein the broken material was mixed with "Additive C” prior to heat treatment. Thus, no fritting/sintering is to be expected in the preparation of a particulate refractory composition for use in the manufacture of foundry moulds and cores, using "Additive C” to treat broken material obtained from the CORDIS-process.
- Example 4 Quartz sand (SiO 2 ) fritting/sintering
- Fine, powdery quartz sand (reactive SiO 2 ) was provided.
- test specimen from "Quartz I” and a test specimen from "Quartz II” were manufactured, suitable for analysis following the concepts of DIN 51730 (Testing of solid fuels - Determination of fusibility of fuel ash).
- the specimen had a cylindrical shape, a height of 3 mm and a diameter of 3 mm.
- test specimens obtained from the test samples "Quartz I” and “Quartz II” were subjected to a heat treatment (in the range of from 25 to 1650 °C) and were simultaneously analyzed following the concepts of DIN 51730 (Testing of solid fuels - Determination of fusibility of fuel ash). According to this analysis a cross sectional area (projection area) of a test specimen can be recorded in dependence of the temperature. During a heat treatment a test specimen shows various deformations and/or changes of the volume which leads to varying cross sectional area values (projection area values) in dependence of the temperature applied.
- Heating from 25 °C to 700 °C was done with 80 °C/min, from 700 to 1500 °C with 50 °C/min and from 1500 °C with 10 °C/min.
- the results of the analysis following the concepts of DIN 51730 are shown in Figure 1 .
- the two curves in Figure 1 show the correlation of the cross sectional area values (projection area values; in rel. %, where 100 % refer to the starting area values of each test specimen prior to heating) of test specimens from "Quartz I" and "Quartz II" and the temperature applied.
- the curves are labeled as follows: A refers to "Quartz I" and B refers to "Quartz II".
- the cross sectional area values (projection area) indicate the progress of fritting/sintering. Fritting/sintering can be observed by a decreasing projection area (due to volume contraction), where the area decrease is not accompanied by a change of the shape of the test specimen.
- FIG. 1 shows that in the presence of 10 % potassium hydroxide (KOH, solid) fine quartz sand (SiO 2 ) exhibits a clear tendency to form agglomerates (fritting/sintering products) (see “Quartz I” in Fig. 1 ). Fritting/sintering started at a temperature of approximately 475 °C and was intensified upon increased temperatures. In contrast, “Quartz II” did not show any signs of fritting/sintering.
- KOH potassium hydroxide
- SiO 2 fine quartz sand
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| EP20120178533 EP2692460B1 (de) | 2012-07-30 | 2012-07-30 | Teilchenförmige Feuerfestmaterialzusammensetzungen zur Verwendung bei der Herstellung von Gussformen und -kernen, Verfahren zu ihrer Herstellung und entsprechende Verwendungen |
| PCT/EP2013/059731 WO2014019726A1 (en) | 2012-07-30 | 2013-05-10 | Particulate refractory compositions for use in the manufacture of foundry moulds and cores, methods of preparing same and corresponding uses |
| TW102116964A TW201412431A (zh) | 2012-07-30 | 2013-05-13 | 用於鑄造模及模芯之製造之微粒耐火組合物、其製備方法及對應用途 |
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| EP20120178533 EP2692460B1 (de) | 2012-07-30 | 2012-07-30 | Teilchenförmige Feuerfestmaterialzusammensetzungen zur Verwendung bei der Herstellung von Gussformen und -kernen, Verfahren zu ihrer Herstellung und entsprechende Verwendungen |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3006136A1 (de) * | 2014-10-10 | 2016-04-13 | Hüttenes-Albertus Chemische Werke GmbH | Verwendung einer basischen zusammensetzung als infiltrationsmittel für den formstoff einer giessform zur vermeidung von weissen belägen (narbigen oberflächen) auf gussstücken, entsprechende verfahren, giessformen und kits |
| WO2020049174A1 (en) | 2018-09-07 | 2020-03-12 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Method of preparing a particulate refractory composition for use in the manufacture of foundry moulds and cores, corresponding uses, and reclamation mixture for thermal treatment |
| US11065676B2 (en) | 2017-04-07 | 2021-07-20 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Method for producing casting molds, cores and basic mold materials regenerated therefrom |
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| CN114669718B (zh) * | 2020-12-24 | 2024-08-30 | 金隆化学工业股份有限公司 | 黏结材积层制造的方法 |
| WO2024237147A1 (ja) * | 2023-05-12 | 2024-11-21 | 花王株式会社 | 無機コーテッドサンドおよびその製造方法、鋳造用鋳型、ならびに無機コーテッドサンドの保存安定性の向上方法 |
| WO2024237149A1 (ja) * | 2023-05-12 | 2024-11-21 | 花王株式会社 | 鋳型用鋳物砂およびその製造方法、鋳造用鋳型、ならびに鋳型用鋳物砂の保存安定性の向上方法 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3006136A1 (de) * | 2014-10-10 | 2016-04-13 | Hüttenes-Albertus Chemische Werke GmbH | Verwendung einer basischen zusammensetzung als infiltrationsmittel für den formstoff einer giessform zur vermeidung von weissen belägen (narbigen oberflächen) auf gussstücken, entsprechende verfahren, giessformen und kits |
| US11065676B2 (en) | 2017-04-07 | 2021-07-20 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Method for producing casting molds, cores and basic mold materials regenerated therefrom |
| WO2020049174A1 (en) | 2018-09-07 | 2020-03-12 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Method of preparing a particulate refractory composition for use in the manufacture of foundry moulds and cores, corresponding uses, and reclamation mixture for thermal treatment |
| US11311931B2 (en) | 2018-09-07 | 2022-04-26 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Method of preparing a particulate refractory composition for use in the manufacture of foundry moulds and cores, corresponding uses, and reclamation mixture for thermal treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201412431A (zh) | 2014-04-01 |
| EP2692460B1 (de) | 2015-02-25 |
| WO2014019726A1 (en) | 2014-02-06 |
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