1. TPR and TPS Temperature Programmed Reduction (TPR)
characterisation of oxidic catalysts and other reducible catalysts
qualitative information on oxidation state
quantitative kinetic data
optimisation of catalyst pretreatment
Temperature Programmed Sulphiding (TPS)
similar to TPR
Catalysis and Catalysts - TPR and TPS

2. Examples of TPR Reduction of oxidic species: MO + H2 M + H2O
Study of coke deposits:
Reduction of sulphides:
MO + H2 M + H2O
coke + H2 hydrocarbons + H2O
MS + H2 M + H2S
Catalysis and Catalysts - TPR and TPS

3. Thermodynamics G0 (kJ/mol) T (K)
Catalysis and Catalysts - TPR and TPS
T (K)

4. Equipment for TPR reactor H / Ar FID molsieve TCD 2
Catalysis and Catalysts - TPR and TPS

5. TPR of 9.1 wt% CoO/Al2O3 e d c b a j i h g f o n m l k Temperature (K)
Temperature (K)
Temperature (K)
Temperature (K)
Catalysis and Catalysts - TPR and TPS

6. TPR Patterns of Reference Materials
TCD
CoAl2O4
FID
Co3O4
CoO
Temperature (K)
Catalysis and Catalysts - TPR and TPS

7. Influence of ‘hard’ and ‘soft’ Ions
CoMoO4
CoAl2O4
Co3O4
Temperature (K)
Catalysis and Catalysts - TPR and TPS

8. TPS of MoO3/Al2O3 Reactions: MO + H2  M + H2O MO + H2S  M + H2O + S
MO + H2S  MS + H2O
M + H2S  MS + H2
Catalysis and Catalysts - TPR and TPS

9. TPS of MoO3/Al2O3 100 mg, 4.5 atoms/nm2 200 mg, 2.2 atoms/nm2e
100 mg, 4.5 atoms/nm2
200 mg, 2.2 atoms/nm2
400 mg, 1.0 atoms/nm2
800 mg, 0.5 atoms/nm2
400 mg, carrier d c b a
50% H2S conversion
Catalysis and Catalysts - TPR and TPS
Time (min) Temperature (K)

10. TPS of MoO3/Al2O3 100 mg 4.5 atoms/nm2 H2 H2S H2O Temperature (K)
Catalysis and Catalysts - TPR and TPS
Temperature (K)

11. Molecular Scheme of Sulphiding+ H 2 - I V
Catalysis and Catalysts - TPR and TPS

12. Modelling of TPR Patterns
Catalysis and Catalysts - TPR and TPS

13. Kinetic Models for Reduction
Catalysis and Catalysts - TPR and TPS

14. Catalysis and Catalysts - TPR and TPS

15. TPR of Fe2O3 H2/Ar saturated with 3% H2O 7.0 mg 15.9 mg dry H2/Arc b a
Temperature (K)
Catalysis and Catalysts - TPR and TPS

16. TPR of Fe2O3 as a Function of Heating Rate
10.0 K/min
0.08 mg
Dry H2/Ar f
5.0 K/min
0.19 mg e
2.0 K/min
0.91 mg d
1.0 K/min
1.8 mg c b
0.5 K/min
2.8 mg a
0.2 K/min
3.6 mg
Temperature (K)
Catalysis and Catalysts - TPR and TPS

17. TPR of Fe2O3 as a Function of Heating Rate
10.0 K/min
0.17 mg
Wet H2/Ar (3% H2O) e
5.0 K/min
0.33 mg d
2.0 K/min
0.90 mg c
1.0 K/min
1.5 mg
0.5 K/min
2.6 mg b
0.2 K/min
7.0 mg a
Temperature (K)
Catalysis and Catalysts - TPR and TPS

18. Arrhenius Plots from TPR of Fe2O3
(K-1 s-1) b c
-15
-16
-17
-18
-19 a
dry series main peak
Ea = 111 kJ/mol
wet series main peak
wet series low T peak
(10-4 K-1)
Catalysis and Catalysts - TPR and TPS

19. Calculated Fe3O4  Fe TPR Peaks2 1
(10-2 K-1)
Temperature (K) a b c d e f
three-dimensional nucleation (Avrami Erofeev);
f() = 3(1-) [-ln(1-)]2/3
two-dimensional phase boundary;
f() = (1-)1/2
two-dimensional nucleation (Avrami Erofeev);
f() = 2(1-) [-ln(1-)]1/2
three-dimensional phase boundary;
f() = (1-)2/3
unimolecular decay;
f() = (1-)
Three-dimensional diffusion (Jander);
f() = [3(1-)2/3]/[2(1-(1-)1/3)]
Catalysis and Catalysts - TPR and TPS

20. Comparison of Measured and Calculated Fe3O4  Fe TPR Peaks a b
Temperature (K)
three-dimensional nucleation (Avrami Erofeev);
f() = 3(1-) [-ln(1-)]2/3
calculated
Wet series
Dry series
Catalysis and Catalysts - TPR and TPS