1. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Catalysis: Concepts and Green Applications Lecture slides for Chapter 4: Heterogeneous catalysis Most of the graphics here were drawn using PowerPoint and Chemdraw (version Ultra 9.0). Feel free to modify and/or add your own pyrotechnics. Please send any feedback to feedback@catalysisbook.org

2. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.1 reactants products reactor catalyst support active site substrate adsorption reaction desorption bed of catalyst particles porous carrier (catalyst support) product

3. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.2 catalyst surface substrate A substrate B product C catalyst surface B A C

4. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.3

5. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.4 Fe [1,1,1 ] 1 2 3 4 5 log (reaction rate) Fe [1,0,0 ] Fe [1,1,0 ] dissociative N 2 adsorption NH 3 production

6. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.5 Fe surface K /K 2 O promoter ** 

7. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.6 Bulk catalysts Impregnated catalysts Hydrothermal synthesis (zeolites) Precipitation (silica/alumina) Fusion/ alloy leaching ( mixed oxides, Raney metals ) Sol-gel synthesis ( mixed oxides, supports ) Flame hydrolysis ( fumed oxides, supports ) Wet impregnation ( automotive exhaust catalysts ) Incipient wetness (Pt/Sn/Al 2 O 3 ) Vacuum pore impregnation (Bi/Pb/SiO 2 ) Ion-exchange (acidic zeolites) Anchoring/grafting (supported tm-complexes)

8. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.7 Support preparation/ precursor treatment Gelation Precipitation Impregnation Ion-exhcange Grafting/ anchoring Fusion/ alloy leaching Active phase preparation Post-treatment Drying Calcination Forming Extrusion Pelleting Filtration Activation

9. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.8 – Al(OH) 3 Ni Ni/Al alloy fusing at high temperature Al NaOH Ni sponge (Raney Ni)

10. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.9

11. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.10 autoclave 100 –150 °C gel sodium silicate sodium aluminate template H 2 SO 4 filtering, washing, drying, calcining ZSM5 crystals H-ZSM5 ion-exchange, drying, calcining

12. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.11 narrow channels wider cages

13. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.12 catalyst paste extrudatescatalyst pellets template cutting, drying, calcining

14. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.13 1 nm

15. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.14

16. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.15 V adsorbed Pressure P0P0 0 I P0P0 0 B II Pressure P0P0 0 III Pressure P0P0 0 V adsorbed Pressure P0P0 0 P0P0 0 IVVVI B

17. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.16 mass spectrometer temperature control unit thermal conductivity detector purge thermal conductivity detector reactant gas, e.g. H 2 purge catalyst sample oven 0 200 400 600 800 Temperature (°C) TCD signal CuO CeO 2 Ce 0.90 Cu 0.10 O 2 A B C

18. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.17 primary electron beam (100 – 400 KeV) backscattered electrons secondary electrons Auger electrons X-rays photons transmitted electrons diffracted electrons loss electrons catalyst sample Ag Au 18 nm Al 2 O 3 support

19. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.18

20. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.19 metal surface C O C O C O C O 11 22 33 44

21. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.20 catalytic converter ceramic monolith 1 mm 1  m  -alumina washcoat Pt/Pd/Rh catalyst

22. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.21 exhaust O 2 level engine operating cycle oxygen release oxygen uptake

23. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.22

24. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.23

25. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.24 aqueous phase organic phase reactants products aqueous phase recycle L = tppts

26. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.25

27. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.26

28. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.27

29. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.28 interface aqueous phase organic phase Q + X – + Y – X – + Q + Y – Q + X – + RY RX + Q + Y – RH org + OH – aq R – interface + H 2 O R – interface + Q + X – org Q + R – org + X – aq Q + R – org + R’X org R’R org + Q + X – org

30. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.29 organic solvent CaSO 4 layer CaF 2 particle CaF 2 + H 2 SO 4 CaSO 4 + 2HF Oct 4 NBr 25 °C

31. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.30 ethylene vaporiser reactor vapour recycle ethyl acetate light/medium ends recovery acetic acid acetic acid recycle distillation units

32. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.31 olefin feed pretreatment reactor system hydrogen alkylate product n-butane light ends alkylation moderate temperature regeneration alkylation

33. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.32 methanol reactor I separator I tri- glycerides reactor II separator II separator III > 98% glycerol FAME (biodiesel)

34. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.33 free fatty acids (FFA) methanol FAME (biodiesel) reactive distillation column solid acid catalyst > 99.9% water evaporator

35. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.34 hydrophobic surface with isolated acid site hydrophobic surface with adjacent acid sites hydrophilic surface with numerous acid sites

36. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.35 ethylbenzene condensate dehydrogenation reactor O 2 /air heat exchanger steam separator dehydrogenated mixture ethylbenzene recyclebenzene toluene styrene monomer (product) tar inhibitor

37. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.36

38. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.37 A Ni on FER zeolite B Enzyme immobilised on zeolite-Y C Zn particles (1 mm diameter) D Ru on mesoporous silica E Pd on microporous alumina F Macroporous silica/alumina G Pt on mesoporous polystyrene after first run before first run Pressure P0P0 V adsorbed 0

39. Catalysis/ Rothenberg, ISBN 978-3-527-31824-7. www.catalysisbook.org Figure 4.38