GTOX. a multipurpose oxide + database. GTT Users Meeting, Herzogenrath K. Hack 1, T. Jantzen 1, Elena Yazhenskhik 2, Michael Müller 2
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1 GTOX a multipurpose oxide + database GTT Users Meeting, Herzogenrath K. Hack 1, T. Jantzen 1, Elena Yazhenskhik 2, Michael Müller 2 1, 2 IEK2-FZ Jülich
2 Contents of presentation A bit of history Components, Phases the Slag Atlas G-modelling Going down to the binary element systems Me-O Addition of P 2 O 5 and SO 3 Fields of Application Conclusions and future developments
3 HotVeGas project Phase I September 2007 August 2011 Phase II September 2011 August 2015 Phase III January 2016 December 2019 Partners: IEK-2, FZ Jülich Bergakademie Freiberg TU München
4 A bit of history-elephant s wedding Al 2 O 3 -K 2 O-Na 2 O-SiO 2 Al 2 O 3 -CaO-FeO-Fe 2 O 3 -MgO-SiO 2
5 The present state of GTOX database The GTOX database contains the assessment of the Al 2 O 3 -Al 2 S 3 -CaF 2 -CaO-CaS-CaSO 4 -CrO-Cr 2 O 3 -CrS-FeO-Fe 2 O 3 -FeS- K 2 O-K 2 S-K 2 SO 4 -Na 2 O-Na 2 S-Na 2 SO 4 -MgO-MgS-MgSO 4 -MnO-Mn 2 O 3 - MnS-P 2 O 5 -SiO 2 -TiO 2 -ZnO system Contents Slagatlas, Year Binary systems Ternary systems Quaternaries Slag components Components Solid solution phases Stoichiometric phases Total pages
6 G-modelling (Me1O) x (Me2O) y (A,B,C) x (D) y
7 Slag in GTOX database The associate species were described in the same way in similar systems in order to provide a handle for the use in multi-component systems. The composition of the associate speciesare as introduced by Spear taking two moles of cations per associate. System Associate species System Associate species with P 2 O 5 Description Me-O Cr-O Cr, Cr 2 O System Associate species with S MeO 2, Cr 2 O x : 3, Cr P 2 O 3 O 4 System Associate 5 System Al 2 O 3 -P 2 O 5 Associate Fe-O species with AlPO 4 (SGPS)-Berlinite species with MnO Fe, K,Na Fe Description 2 O 2, Fe x Description 2 O 3, Fe 3 O 4 Ca -S CaS Mn-O Mn, Mn 2 O 2, Mn MeO MeO 2 O x x : 3 :(K,Na), Mn MnO(:MeO) 3 O 2 O 4 Al Cr Fe -S 2 O 3 -MnO Al 2 O 23 O P 3 K 2 O 52 OCaO-Me Al CrPO FeS 2 MnO 4 AlKO 4,Al 4 K 2 O 2 O CaO-Al 3 2 O 3 7 CaAl 2 O 4 CaO-Cr Al 1:1 1:1, 2:1 Fe 2 O Mg -S 2 3 Na 3 P 2 O 2 O AlNaO 2 O 5 FePO MgS 4 (SGPS),Al 3 CaCr 4 Na 2 O 2 O 4 CaO-Fe 7 Cr 2 O 3 MnO Cr 2 MnO 2 O 3 CaFe 2 O 4 4 Fe 1:1 Mn-SCaO-P 2 O 3 K 2 O 2 O CaO-Mn FeKO 2 O 3 5 MnS Ca 3 P 2 O 8, Ca 2 P 2 O 7, CaP 2 CaMn 2 O 4 1:1 2 O 6 [Serena Fe 2 O 3 MnO CrO-Me Fe Fe 2011] 2 MnO 2 O 3 Na 2 O 2 O CrO-Al 3 2 O 3 CrAl 2 O 4 4 CrO-Fe FeNaO 2 Cr-SFeO-P 2 O 5 CrS 2 O 3 CrFe 2 O 4 Fe 3 P 2 O 8, Fe CrO-Mn 2 P 2 O 7, FeP 2 O 6 2 O 3 CrMn 2 O 4 MnO-SiO 2 MnSiO 3,Mn 2 SiO 4 3:1, 2:1, 1:1 1:1 and 1:2 MgO-P 2 O MgO-Me 5 (likewithca Mg 2 O MgO-Al 3 P 2 O 8 (SGPS), 2 O +2, Fe +2 Mg 3 MgAl andmg 2 P 2 O 7, MgP ) 2 2 O Na In 6 2 O-SiO total Na 2 Si 2 Oassociate 4 5, Na 4 SiO 4,Na 4 Si 2 O species MgO-Cr 2 O 3 MgCr 26 O 4 CaO-MnO-SiO ZnO-P 2 O 2 CaMnSi 5 Zn 3 P 2 O 2 O 8, MgO-Fe Zn 6 2 P 2 O 7, 2 OZnP 3 2 O MgFe 2 O 4 1:1:1 6 MgO-Mn 2 O 3 MgMn 2 O 4 MgO-MnO-SiO 2 FeO-Me 2 MgMnSi O 3 2 OFeO-Al 6 2 O 3 FeO-Cr 2 O 3 FeAl 2 O 4 FeCr 2 O 4 1:1:1 FeO-Mn 2 O 3 FeMn 2 O 4 K 2 O-SiO 2 K 2 Si 2 O 5, K 2 Si 4 O 9,K 4 Si 2 O 6 2:1,4:1(1:2), 1:1
8 Binary Fe-O and Mn-O systems
9 Description of the phase MeO MeO - (Al +3,Ca +2,Cr +3,Mn +2,Mn +3,Fe +2,Fe +3,Mg +2,Na +1, Zn +2,Va)(O -2 )
10 Description of the phase Zincite Zincite - (Ca +2,Cr +3,Mn +2,Mn +3,Fe +2,Fe +3,Mg +2,Zn +2,Va)(O -2 )
11 Description of the phase Spinel Spinel (Al +3,Cr +2,Cr +3,Fe +2,Fe +3,Mg +2, Ti +4, Mn +2,Zn +2 )(Al +3,Ca +2,Cr +3,Fe +2,Fe +3,Mg +2, Mn +2,Mn +3,Mn +4,Va) 2 (Cr +2, Fe +2, Mg +2,Va) 2 (O -2 ) 4
12 Inclusion of P 2 O 5 and SO 3 Phosphates and Sulphates are double oxides 3MgO+P 2 O 5 =Mg 3 (PO 4 ) 2 2MgO+P 2 O 5 =Mg 2 (PO 4 ) 2 MgO+P 2 O 5 =Mg(PO 4 ) 2 CaO+SO 3 =CaSO 4
13 Modelling Isopleth section of α CaCa 2 SiO 4 : Motivation 2 SiO 4 -Ca 3 P 2 O 8 α-ca 2 SiO 4, modelled before with solubility for CrO and MgO (Ca 2+,Cr 2+,Mg 2+ ) 2 (Si 4+ )(O 2- ) 4? α -Ca 3 P 2 O 8 modelled before with solubility for MgO (Ca 2+,Mg 2+ ) 3 (P 5+ ) 2 (O 2- ) 8 W. Fix, H. Heymann, and R. Heinke, J. Am. Ceram. Soc., 52 [6] (1969).
14 Isopleth section Ca 2 SiO 4 -Ca 3 P 2 O 8 The following description was suggested for the phase C2S-C3P : (Ca 2+,Cr 2+,Mg 2+ ) 3 (Ca 2+,Va) 1 (P 5+,Si 4+ ) 2 (O 2- ) 8 W. Fix, H. Heymann, and R. Heinke, J. Am. Ceram. Soc., 52 [6] (1969). R. W. Nurse, J. H. Welch, W. H. Gutt, J. Chem. Soc., (1959).
15 Binary Cr-S and Fe-S phase diagrams
16 FeS-MgS and FeS-MnS phase diagrams
17 Quasi-binaries with Oldhamite Sulfide Pearson Symbol Space group Strukturbericht Prototype CaS cf8 Fm 3m B1 NaCl MgS cf8 Fm 3m B1 NaCl MnS cf8 Fm 3m B1 NaCl
18 Liquidus surface in MnO-MnS-SiO 2 D.-H. Woo and H.-G. Lee, J. Am. Ceram. Soc., 93 [7], (2010), pp MnO. MnS. 3SiO 2 25MnO. MnS. 9SiO 2 stoichiometric stoichiometric modelled by GTT modelled by GTT
19 Fields of Application: Cement making R.R. Dayal, F.P. Glasser, Sci. Ceram., Vol. 3, Edited by G.H. Stewart, Academic Press, New York, (1967), pp
20 Fields of Application: Cement making Belite Alite Lime W.H. Gutt, A.D. Russel, J. Mater. Sci., 12 [9], (1977), pp Tricalcium aluminate K 2 SO 4 also incorporated!
21 Fields of Application: Slagging and Fouling Composition of hard coal ashes Columbia South Afr. Russia USA Component Unit SKC SKK SKR SKU Al2O3 % CaO % Fe2O3 % K2O % MgO % Na2O % P2O5 % SiO2 % SO3 % TiO2 % Inclusion of TiO 2 See T. Jantzen
22 Fields of Application: Slagging and Fouling VerSi project: Melting behaviour of different Hard Coals
23 Fields of Application: Slagging and Fouling VerSi project: Melting behaviour of hard coal SKC
24 Fields of Application: Stainless steel-making Low C in steel: 2 Cr + 3 CO(g) = 3 C + Cr 2 O 3 Law of Mass Action: log a C = 1/3 log K(T) + 2/3 log a Cr 1/3 log a Cr2O3 + log P CO
25 Fields of Application: Steel dephosphorisation BofDePhos project
26 Fields of Application: Steel dephosphorisation BofDePhos project
27 Fields of Application: Steel dephosphorisation BofDePhos project
28 Fields of Application: Avoiding nozzle clogging Slag window
29 Fields of Application: Slag fluxing CaF 2 Addition of CaF 2 (Fluorspar) decreases melting temp. of slag. Fluorspar furthermore decreases viscosity of the slags.
30 Conclusions GTOX now covers 28 components in 104 sol comp. phases The liquid phase was evaluated using the associate species model (X j liq. constituents x i liquid species) Solids have been treated either as stoichiometric (X, G=G(T) only) or with a multi-sublattice approach (Y, G=G(T,y ji ). Fields of application ranging from coal combustion and gasification over cement making and metallurgy to special cases such as recycling of spent car catalysists Direct link to modelling of slag viscosities available
31 Future Developments Inclusion of Cu into oxide database together with Me-S database start into a Cu-metallurgy database DüSol-project production of fertilizers using solar energy Adding salts such as alkali-sulphates to oxide database more practical relevance for biomass combustion applications
32 Thanks for your attention
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