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The role of promoters in Enter title of Fe-based presentation here Fischer-Tropsch catalysts

E. van Steen, M. Claeys


Centre for Catalysis Research, Dept. Chemical Engineering, University of Cape Town, South Africa

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Fischer-Tropsch synthesis

Synthesis gas

Catalyst: Fe, Co (Ru, Ni)

Originating from carbon source: Natural gas Biomass Oil residue Coal

Desired products: Liquid fuels (wax hydrocracking) Chemicals (olefins, oxygenates)

F. Fischer, H. Tropsch, Brennstoff-Chem. 7 (1926), 97

decreasing C/H ratio

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
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Low temperature Fe-based FT-catalyst

ARGE catalyst (100 Fe/5 K2O/5 Cu/25 SiO2)


Fe

Cu

Si

EDX-mapping of spray-dried ARGE-type of catalyst, J. Malherbe, MSc-thesis, University of Cape Town (2006)

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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

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Potassium as a promoter
Catalyst activity

Activity enhancement: ca. 4 fold (based on 1st order kinetics)


Optimum potassium loading: ca. 12 mmol K/mol Fe corresponds to ca. 1 K/nm2 on catalytically active phase assuming no sintering (2 K/nm2 according to Li et al. [1]

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

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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

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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

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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

1.22 1.74 7.1 -2.66 1.28 -1.38

dFe-C in CO, jCO, o


q O, e qC in CO, e qCO, e

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

Presence of KO instead of K reduces effect of polarization on surface and upon CO adsorption

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

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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

Reduction behaviour affected by size as well [2]


[1] D.B. Bukur, D. Mukesh, S.A. Patel, Ind. Eng. Chem. Res. 29 (1990), 194 P. Cairns, PhD thesis, UCT (2008) [2] Z. Chonco, PhD thesis, UCT (in preparation)

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

pCO pH2 b pH2O

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

On bare iron carbide surface, copper will segregate

Copper as a promoter
Effect of co-adsorbed CO

Cu in Position I

Cu in Position II Cu stabilized by presence of CO Copper will segregate (thermodynamically)

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

-0.32/-0.34 -0.32/-0.45 -0.32/-0.47 -0.32/-0.31 16.6/17.3 18.0/13.5 17.0/4.4 18.1/23.5


0.76/3.128 0.76/2.198 0.76/ 2.272 0.75/3.945 0.71 0.75 0.72 0.80

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

Copper facilitates the reduction of iron with H2


Copper can be located on surface of Hgg carbide during Fischer-Tropsch synthesis BUT Copper as a promoter requires suitable catalyst pretreatment (e.g. CO activation) to prevent kinetically phase segregation Catalyst deactivation seems to be built into the system Copper may act as a chemical promoter (similar to potassium) charge transfer from Cu to adsorbed CO weakening C-O bond of nearby adsorbed CO enhanced charge on adsorbed CO enhanced polarization within adsorbed CO

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

Observed effects might be caused by migration of promoters


What effect can be ascribed to metal-support interactions?

[1] [2] [3] [4] [5]

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.

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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

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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

Reverse micelle precipitation


tetra ethoxy-silane in n-hexane

Flocculation with acetone re-dispersion in n-hexane

Surface modification
O-M-OR3 Fe(OH)3/ FeOOH O-M-(OH)3 Fe2O3

Calcination in air 350 oC

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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
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Silica as a promoter
Silica within the model system

Additional bands in the region 800-1150 cm-1

50 nm
Homogeneous Si-distribution

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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

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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

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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

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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

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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

lower degree of reduction with increasing Si-content

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
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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

Possibly tridentate ( FeO)3-SiOH bidentate ( FeO)2-Si(OH)2 monodentate FeO-Si(OH)3


Reduction in pure H2 (SV = 400 ml/min/g) at 350oC for 16 hrs; undiluted sample
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Silica as a promoter
Activation of model systems in H2 (in-situ XRD)

Reduction process: g-Fe2O3 Fe3O4 a-Fe Complete transformation to a-Fe at 350oC

Reduction process: g-Fe2O3 Fe3O4

a-Fe FeO

Complete transformation to a-Fe and FeO at 350oC

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
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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
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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)

Si/Fe 0 4 12 21 8.8 9.3 12.4

Fe3O4

FeO

Fe3C

Fe5C2 96.7

Fe7C3

mmol/mol x, wt.-% d, nm x, wt.-%


8.2 6.3 3.5 6.2 10.1

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

Si 39.0 Fesurface in FeOx


19.1 0.37 34.1 0.57 38.7 0.30

13.3 10.6 7.2

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
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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

250oC 100 20 bar 39.0 600 ml(NTP)/min/gcat 3.3 2


11.8 96.7 39.0

3.3

20.9 15.4 70.9 22.8

Fe5C2

x, wt.-%

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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

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Silica as a promoter
Secondary olefin reactions during FT-synthesis

Expected: increase XCO, decrease in olefin content Si addition results in increased hydrogenation

Expected: increase XCO, decrease in 1-olefin content

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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
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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)

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Promoters in Fe-based FT-catalysts


Conclusions
Promoters may affect: crystallite size and/or crystal phase of catalyst precursor activation process (noticeably copper, silica) may result in change in surface area of catalytically active phase

phases present in catalyst (e.g. metallic copper, iron silicate) Cooperative effect between phases

chemical promotion (if promoter is near the catalytically active site


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ACKNOWLEDGEMENTS

Department of Science and Technology

fuels & chemicals from synthesis gas : state of the art


Autumn School : 29 31 March 2012 Syngas Convention : 1 4 April 2012
2012 Vineyard Hotel & Spa Cape Town South Africa www.syngasconvention.com

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