Professional Documents
Culture Documents
If University Logo is required, please adjust size to fit below the line, e.g.
Fischer-Tropsch synthesis
Synthesis gas
Originating from carbon source: Natural gas Biomass Oil residue Coal
Industrial FT-catalysts
Cobalt-based catalysts: supported on Al2O3/SiO2/TiO2 noble metal promoter (Pt, Ru, Re)
Iron-based catalyst: fused catalyst co-precipitated catalyst (promoters: K, Cu, SiO2) Kinetics inhibited by water limited conversion per pass Less stable Water-gas shift activity (H2/CO)optimum (250oC) =1.2 1.3 Less sensitive to poisons (S in ppm levels) Cheap
Kinetics not inhibited by water high conversion per pass High stability Low water-gas shift activity (H2/CO)optimum = 2.1 Highly sensitive to poisons (S in ppb level) Costly
Iron-based catalysts could be better suited for synthesis gas: derived from dirty feedstock with low H2/CO
If University Logo is required, please adjust size to fit below the line, e.g.
Cu
Si
EDX-mapping of spray-dried ARGE-type of catalyst, J. Malherbe, MSc-thesis, University of Cape Town (2006)
If University Logo is required, please adjust size to fit below the line, e.g.
Promoters
Promoter: Compound with no or negligible catalytic activity on its own which enhances the activity/modifies the selectivity obtained over the catalytically active phase Classification of promoters [1]: Chemical promoter (K2O) electronic modification of the catalytically active site Reduction promoter (Cu) facilitation of the formation of the catalytically active phase during activation Structural promoter (SiO2) dispersing the catalytically active phase maintaining dispersed catalytically active phase
[1] M.E. Dry, Stud. Surf. Sci. and Catal. 152 (2004), 196 M.E. Dry, Stud. Surf. Sci. and Catal. 152 (2004), 533
If University Logo is required, please adjust size to fit below the line, e.g.
Potassium as a promoter
Catalyst activity
Data: A. Blignaut, MSc thesis University of Cape Town (2007) Supported Fe-catalyst (10% Fe/SiO2); Activation: H2 (350oC for 16 hrs); Reaction conditions: 270oC, 20 bar , (H2/CO)in = 2; FCO,0/W = 10.7 mmol/min/gFe [1] S. Li, A. Li, S. Krishnamoorthy, E. Iglesia, Catal. Lett. 77 (2001), 197
If University Logo is required, please adjust size to fit below the line, e.g.
Potassium as a promoter
Undesired products - Selectivity for CO2 and methane
H2O + CO CO2 + H2
Data: A. Blignaut, MSc thesis University of Cape Town (2007) Supported Fe-catalyst (10% Fe/SiO2); Activation: H2 (350oC for 16 hrs); Reaction conditions: 270oC, 20 bar , (H2/CO)in = 2; FCO,0/W = 10.7 mmol/min/gFe
If University Logo is required, please adjust size to fit below the line, e.g.
Potassium as a promoter
Olefin formation
Data: A. Blignaut, MSc thesis University of Cape Town (2007) Supported Fe-catalyst (10% Fe/SiO2); Activation: H2 (350oC for 16 hrs); Reaction conditions: 270oC, 20 bar , (H2/CO)in = 2; FCO,0/W = 10.7 mmol/min/gFe
If University Logo is required, please adjust size to fit below the line, e.g.
Potassium as a promoter
A molecular picture
Bader charge analysis Charge Atom Carbide surface K adsorbed Potassium 0.61 Fe-atoms Ridge R1 0.28 0.16 R2 0.28 0.10 R3 0.28 0.11 R4 0.28 0.18 Valley V1 0.22 0.20 V2 0.22 0.20 V3 0.22 0.22 V4 0.22 0.23
R1 V1 R2 V2
R3 V3 R4 V4
Potassium on carbide surface leads to reduced positive charge on ridge Fe atoms in Fe5C2(100)0.00 surface
Data: J. Cariem, MSc thesis University of Cape Town (in preparation) See also: D. Sorescu, Surf. Sci. 605 (2011), 401
VASP-spin polarized parameters: Surface: Fe40C16(100)0.00 PAW-RPBE; Ecut-off: 450 eV; s = 0.1 eV If University Logo is required, please k-points spacing <:0.04 -1; F = 0.02 eV/ adjust size to fit below the line, e.g.vacuum:22 ; dipole corrected
Potassium as a promoter
CO adsorbed in iron carbide
V3
Carbide surface Eads, eV dC-O, K-promoted Carbide surface
-1.61
1.17 1.79 2.9 -1.83 1.51 -0.32
-2.09
V4
Data: J. Cariem, MSc thesis University of Cape Town (in preparation) See also: D. Sorescu, Surf. Sci. 605 (2011), 401
VASP-spin polarized parameters: Surface: Fe40C16(100)0.00 PAW-RPBE; Ecut-off: 450 eV; s = 0.1 eV If University Logo is required, please k-points spacing <:0.04 -1; F = 0.02 eV/ adjust size to fit below the line, e.g.vacuum:22 ; dipole corrected
Potassium as a promoter
Speciation of K during Fischer-Tropsch synthesis
Potassium is usually viewed as metallic potassium on iron carbide surface Potassium might be present as KO at prevailing FT-conditions
V3
VASP-spin polarized parameters: Surface: Fe40C16(100)0.00 PAW-RPBE; Ecut-off: 450 eV; s = 0.1 eV If preparation) Data: J. Cariem, MSc thesis University of Cape Town (in University Logo is required, please k-points spacing <:0.04 -1; F = 0.02 eV/ adjust size to fit below the line, e.g.vacuum:22 ; dipole corrected
Bader charge analysis Charge Atom K adsorbed KO adsorbed Oxygen -0.88 Potassium 0.61 0.72 Fe-atoms Ridge R1 0.16 0.51 R2 0.10 0.44 R3 0.11 0.11 R4 0.18 0.18
Potassium as a promoter
Conclusion
Potassium on a carbide surface: is likely to be associated with surface oxygen (KO adsorbed instead of K)
V3
enhances the polarization within co-adsorbed CO strengthened CO adsorption enhanced CO-dissociation reduced hydrogenation reduced extent of secondary olefin hydrogenation reduced extent of secondary double bond isomerisation reduced methane selectivity facilitation of CO-bond dissociation enhanced activity
If University Logo is required, please adjust size to fit below the line, e.g.
Copper as a promoter
Copper is known to be a reduction promoter (see e.g. [1]) for catalyst activation in H2 Copper in co-precipitated catalyst precursor in the form of copper ferrite [2] 1st reduction peak: 345oC
CuFeO2 + H2 Cu + Fe3O4 + H2O
325oC
CuFe2O4 + 1 H2 Cu + Fe3O4 + 1 H2O
435 oC (shoulder)
Fe2O3 + H2 Fe3O4 + H2O
Copper as a promoter
Chemical promotion by copper upon activation in CO?
increasing Cu-loading with increasing Cu-loading k increases (factor 1.6) possible due to sizes?
2 k pCO pH
rCOH2
b decreases (factor 0.5) chemical promotion (?) Conversion of synthesis gas to Fischer-Tropsch products as a function of space time for catalysts activated in CO (270oC, 1.3 MPa) tested at 270oC and 1.3 MPa with (H2/CO)inlet =0.67
R..J. OBrien, B.H. Davis, Catalysis Letters 94 (2004), 1
Copper as a promoter
Can copper be stable near active site?
Position I h: 1.295 dCu-Fe(sur): 2.581 2.603 2.692 dCu-Fe(ss): 2.436 dCu-C(ss): 3.252 Eads = 0.60 eV ZPE = 0.02 eV Bader charge (q) on copper: -0.16 e
Position II h: 1.155 dCu-Fe(sur): 2.582 2.584 2.592 dCu-Fe(ss): 2.565 2.587 dCu-C(ss): 2.550 Eads = 0.46 eV ZPE = 0.02 eV Bader charge (q) on copper: -0.17 e
VASP-spin polarized parameters: PAW-RPBE; Ecut-off: 500 eV; s = 0.1 eV k-points spacing <:0.04 -1; F = 0.02 eV/ vacuum: 13 ; dipole corrected
Copper as a promoter
Effect of co-adsorbed CO
Cu in Position I
VASP-spin polarized parameters: PAW-RPBE; Ecut-off: 500 eV; s = 0.1 eV k-points spacing <:0.04 -1; F = 0.02 eV/ vacuum: 13 ; dipole corrected
Copper as a promoter
Kinetics of copper migration
Copper has a high mobility over clean carbide surface Estimated hopping frequency at FT-conditions: 1.6.107 s-1 (550K)
VASP-spin polarized parameters: PAW-RPBE; Ecut-off: 500 eV; s = 0.1 eV k-points spacing <:0.04 -1; F = 0.02 eV/ vacuum: 13 ; dipole corrected
Copper as a promoter
Kinetics of copper migration co-adsorbed CO
Energy barrier for Cu-migration increases with increasing CO coverage Cu migration at high CO-coverage requires a displacement of adjacent CO molecules (electro-static interaction)
VASP-spin polarized parameters: PAW-RPBE; Ecut-off: 500 eV; s = 0.1 eV k-points spacing <:0.04 -1; F = 0.02 eV/ vacuum: 13 ; dipole corrected
Copper as a promoter
Kinetics of copper migration co-adsorbed CO
Energy barrier for Cu-migration increases with increasing CO coverage Kinetic stabilization can be obtained at high coverage of the on top sites with CO (QCO,top 1) This high coverage on the on-top sites is achieved VASP-spin polarized parameters: during FT-synthesis PAW-RPBE; Ecut-off: 500 eV; s = 0.1 eV
k-points spacing <:0.04 -1; F = 0.02 eV/ vacuum >11.4 ; dipole corrected Average time: TST D Einstein relation
Copper as a promoter
Does copper affect CO on sites nearby?
1 2 3 4 1 2 3 4
1
q O, , dC-Oe qFe-CO, e dC in CO, q e jCO, o qFe, e dCu-C in CO,
-1.83/-1.84 -1.83/-1.86 -1.83/-1.92 -1.83/-1.83 1.162/1.163 1.162/1.176 1.162/1.177 1.162/1.160 1.51/ 1.51 1.51/ 1.41 1.51/ 1.45 1.51/ 1.52 1.828/1.812 1.829/1.837 1.828/1.808 1.829/1.826
Increased CO-bond length for CO nearby Cu Increased polarization of the CO (qCu-COco-adsorbed = 0.34 e; similar to effect of K)
VASP-spin polarized parameters: PAW-RPBE; Ecut-off: 500 eV; s = 0.1 eV k-points spacing <:0.04 -1; F = 0.02 eV/ vacuum >11.4 ; dipole corrected
Copper as a promoter
Conclusions
1 2 3 4 1 2 3 4
Silica as a promoter
Structural promoter [1] Enhancing mechanical strength Reducing sintering BUT metal-support interactions [2,3] K-migration [4,5] more intimate Fe-Cu contact [5] Observed effects: limited reducibility reduced activity enhanced stability change in product selectivity
M.E. Dry, Stud. Surf. Sci. Catal. 152 (2004),196. H. Dlamini, T. Motjope, G. Joorst, G. ter Stege, M. Mdleleni, Catal. Lett. 78 (2002), 201. M. Qing, Y. Yang, B. Wua, J. Xu, C. Zhang, P. Gao, Y. Li, J. Catal. 279 (2011), 111. M.E. Dry, G.J. Oosthuizen, J. Catal. 11 (1968) 18. H.-J. Wan, B.-S. Wu, Z.-C. Tao, T.-Z. Li , X. Ana, H.-W. Xiang, Y.-W. Li, J. Mol. Catal. A: Chemical 260 (2006), 255.
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Model system for metal-support interaction
Classical systems Multi-component Fe-based Fischer-Tropsch catalysts Iron supported on silica
Model systems on purpose introduction of metal-support interactions on the iron oxide precursor
activation in H2
activation in CO
Fischer-Tropsch synthesis
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Synthesis of model system mimicking metal-support
Reverse micelle solution Water: surfactant (PEDGE) = 0.3 g/g oil phase: n-hexane aqueous phase: 0.5 M iron nitrate Reverse micelle solution Water: surfactant (PEDGE) = 0.3 g/g oil phase: n-hexane aqueous phase: 2 M (NH4)2CO3
Surface modification
O-M-OR3 Fe(OH)3/ FeOOH O-M-(OH)3 Fe2O3
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Crystallite size and crystal phase of calcined models
Main phase: maghemite (with some hematite content) High Silica-loading decrease in average crystallite size Silica prevents formation of large Feoxide crystallites spacer
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Silica within the model system
50 nm
Homogeneous Si-distribution
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Silica within the model system
band at 952 cm-1 ( FeO)2-Si(OH)OH (in samples Si/Fe > 10)
50 nm
Homogeneous Si-distribution
[1] X. Yang, P. Roonasi, R. Jolstr, A. Holmgren, Colloids Surf. A: Physicochem. Eng. Aspects 343 (2009), 24
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Silica within the model system
band at 952 cm-1 ( FeO)2-Si(OH)OH (in samples Si/Fe > 10) band at 1020 cm-1 oligomeric surface silicate species (in samples Si/Fe > 16)
50 nm
Homogeneous Si-distribution
[1] X. Yang, P. Roonasi, R. Jolstr, A. Holmgren, Colloids Surf. A: Physicochem. Eng. Aspects 343 (2009), 24
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Silica within the model system
band at 952 cm-1 ( FeO)2-Si(OH)OH (in samples Si/Fe > 10) band at 1020 cm-1 oligomeric surface silicate species (in samples Si/Fe > 16) band at 1085 cm-1 strongly linked Si-O-Si absent in samples
50 nm
Homogeneous Si-distribution
[1] X. Yang, P. Roonasi, R. Jolstr, A. Holmgren, Colloids Surf. A: Physicochem. Eng. Aspects 343 (2009), 24 [2] E. Vinogradova, M. Estrada, A. Moreno, J. Colloid Interface Sci. 298 (2006), 209
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Silica within the model system
band at 952 cm-1 ( FeO)2-Si(OH)OH (in samples Si/Fe > 10) band at 1020 cm-1 oligomeric surface silicate species (in samples Si/Fe > 16) band at 1085 cm-1 strongly linked Si-O-Si absent in samples
Additional band at 865 cm-1 clearly visible at low loading possibly tridentate ( FeO)3-SiOH
50 nm
Homogeneous Si-distribution
[1] X. Yang, P. Roonasi, R. Jolstr, A. Holmgren, Colloids Surf. A: Physicochem. Eng. Aspects 343 (2009), 24 [2] E. Vinogradova, M. Estrada, A. Moreno, J. Colloid Interface Sci. 298 (2006), 209
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Activation of model systems in H2(TPR)
Degree of reduction
(reduction at 350oC for 16 hrs in H2 (400 ml/g/min): Si/Fe mmol/mol 0 2 4 12 16 21 degree of reduction % 91.9 80.1 76.8 62.1 61.1 58.4
42
56.7
introduction of Si formation of hard-to-reduce species lower degree of reduction after reduction at 350oC
TPR-condition: 5% H2 in Ar (SV = 1250 ml/min/g); heating rate 10oC/min
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Activation of model systems in H2 - FTIR
Broad band in region 860-930 cm-1 No band at 1085 cm-1 absence of strongly linked Si-O-Si (extraneous silica) No band at 1020 cm-1 absence of oligomeric silicate species
Silica as a promoter
Activation of model systems in H2 (in-situ XRD)
a-Fe FeO
Reduction in pure H2 (SV = 400 ml/min/g); heating rate 0.5oC/min up to 350oC; undiluted sample
Silica as a promoter
Activation of model systems in H2 (in-situ XRD)
Si/Fe
a-Fe
Fe3O4
x, wt.-% 6.4 d, nm 10
FeO
x, wt.-% d, nm
mmol/mol x, wt.-% d, nm Si/Fe, mmol/mol Si 0 100 39.0 Fesurface in FeOx 93.6 33.1 4 4 0.67 12 12 21 21 42 42 70.8 0.44 60.7 0.50 52.1 0.81 30.4 29.3 27.4
With increasing29.2content: Si 11.7 decrease in metal surface area (up to 25%) 39.3 10.4
47.9 10.6
Reduction in pure H2 (SV = 400 ml/min/g); heating rate 0.5oC/min up to 350oC kept for 16 hrs; undiluted sample
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Activation of model systems in CO (in-situ XRD)
Activation in CO leads to: a mixture of carbides residual iron oxides (both magnetite and wstite) Graphite Activation process appears sequential: Fe2O3 Fe3O4
If University Logo is required, please adjust size to fit below the line, e.g.
FeCx FeO
Activation in pure CO (SV = 400 ml/min/g); heating rate 0.5oC/min up to 270oC; undiluted sample
Silica as a promoter
Activation of model systems in CO (in-situ XRD)
Fe3O4
FeO
Fe3C
Fe5C2 96.7
Fe7C3
d, nm
x, wt.-%
3.3 72.1
Si/Fe, mmol/mol
11.8 13.8 4 25.7 12 26.2 21
d, nm x, wt.-% d, nm x, wt.-% d, nm
11.7 3.6
50.4 38.8
42
32.4
4.4
18.0
6.0
4226.1
10.6
23.5 0.36
25.5
with increasing Si-content: increase in amount of iron oxide present in sample as small crystallites increase in surface area of carbides by up to 100%
(for samples with Si/Fe<42 mmol/mol) Activation in pure CO (SV = 400 ml/min/g); heating rate 0.5oC/min up to 270oC kept for 16 hrs; undiluted sample
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Fischer-Tropsch activity and selectivity testing
Packed bed reactor 0.1 g of model catalyst diluted with 6 g of SiC Activation in hydrogen Si/Fe = 0 Temperature: 350oC Calcined Red. in H2 Act. in CO Pressure: 1 bar x, wt.-% 100400 ml(NTP)/min/g Space velocity: cat Fe2O3 12.1 hrs Duration:d, nm 16
Fe3O4 Reaction conditions: d, nm Temperature: x, wt.-% a-Fe Pressure: d, nm Space velocity: x, wt.-% Feed: (H2/CO)inlet: Fe3C d, nm d, nm x, wt.-%
Spent
8.3
3.3
Fe5C2
x, wt.-%
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Fischer-Tropsch activity
CO-conversion maximum at Si/Fe = 12 mmol/mol (initial decrease possibly due to larger initial size of crystallites) CO2-selectivity increases upon addition of Si oxidic phases stabilized by Si resulting in higher WGS-activity
Silica as a promoter
Methane selectivity in Fischer-Tropsch synthesis
Increasing methane selectivity with increasing Si-loading Catalyst becomes more hydrogenating
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Secondary olefin reactions during FT-synthesis
Expected: increase XCO, decrease in olefin content Si addition results in increased hydrogenation
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Formation of branched products in FT-synthesis
Si addition results in decreased formation of branched products due to enhanced hydrogenation activity
If University Logo is required, please adjust size to fit below the line, e.g.
Silica as a promoter
Conclusions
Model system with on purpose iron-silica interaction in catalyst precursor leads to
stabilization of oxidic phases (in particular wstite) in reduced (H2) and CO-activated catalyst resulting in estimated Si/Fesurface in oxides = 0.3-0.7
smaller carbide crystallites (after activation in CO) overall increase in carbide surface area higher activity surface area related (?) Change in selectivity implying higher hydrogen availability (more methane, less olefins)
If University Logo is required, please adjust size to fit below the line, e.g.
phases present in catalyst (e.g. metallic copper, iron silicate) Cooperative effect between phases
ACKNOWLEDGEMENTS