New catalysis advances for a sustainable energetic development_Jens R. Nielsen
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New catalysis advances for a sustainable energetic development_Jens R. Nielsen
- 1. Catalysis Advances for Sustainmable Energy Jens Rostrup-Nielsen Haldor Topsøe A/S
- 2. CATALYSIS WILL PLAY KEY ROLE
- 3. Energy sources Natural gas Coal Oil Syngas Synfuel Methanol DME Hydrogen EthanolBiomass Automotive FC Solar Wind hydro Electric power via thermal Electric power via FC Heating Electric applications Energy carriers Energy conversion Nuclear Gasoline diesel Automotive ICE Electric power
- 4. Energy sources Natural gas Coal Oil Syngas Synfuel Methanol DME Hydrogen EthanolBiomass Automotive FC Solar Wind hydro Electric power via thermal Electric power via FC Heating Electric applications Energy carriers Energy conversion Nuclear Gasoline diesel Automotive ICE Electric power
- 5. Energy sources Natural gas Coal Oil Syngas Synfuel Methanol DME Hydrogen EthanolBiomass Automotive FC Solar Wind hydro Electric power via FC Heating Electric applications Energy carriers Energy conversion Nuclear Gasoline diesel Electric power Electric power via thermal Automotive ICE
- 6. Oil reserves and price level The challenge is investment and environment Kilde: IEA, 2005
- 7. Flared gas: 5% of production 2 mio bpd synfuels ca. 50 Sasol GTL plants
- 8. New role for coal?
- 10. Biomass conversion • Fermentation: 1. generation, 2. generation to ethanol • Catalytic conversion of sugars to fuels • Transesterfication of oil to biodiesel + glycerol • Hydrogenation of oil to synfuel, green diesel • Pyrolysis or steam conversion to ”oil” • Hydrotreating of ”oil” to synfuel, green
- 11. HDS - Hydrodesulphurisation + 2 H 2 + H 2 S S Hydrodesulphurisation
- 13. The synfuel cycle G a s if ic a t io n S t e a m r e f o r m in g A T R Coal CnHm Syngas H2 F - T T IG A S M T G D M E M e O H M e t h a n a t io n CH4
- 14. SOFC - high flexibility Kerosene Diesel Syngas Methanol Ethanol Biogas (landfil) gas Bio (digestive) gas Hydrogen SOFC Nat. gas Oil Coal Biomass Solar Wind Agricul. Power ηel = 40-50%
- 16. Electrons or hydrogen or ? El grid Electric cars FC cars ICE cars Wind Bio Natural gas H2
- 17. Chemical recuperation of nuclear energy HTR Eva Adam ADAM / EVA Energy Transportation System. Kernforschungsanlage Jülich 1970-85
- 18. Concentrated solar power Imaging the sun Imaging the Moon
- 19. Routes for solar hydrogen Concentrated solar energy Solar thermolysis Solar thermochemical cycles Solar reforming Solar cracking Solar gasification H2OH2O H2O Fossil fuels (NG, oil, coal) CO2/C sequestration Solar hydrogen Adopted from Steinfeld/Solar Energy 78 (2005) 605
- 20. TOOLS FOR CATALYSIS It is the know-how which counts
- 21. Mittasch
- 22. Input from Surface Science
- 23. Noble Art of Characterisation There is a risk that we learn more and more about less
- 24. In Situ Methods Today it is possible to study the catalyst structure during operation
- 25. Formation of Whisker CarbonFormation of Whisker Carbon In Situ HRTEMIn Situ HRTEM (CH4/H2 = 1:1, P = 5 mbar, T = 720°C)(CH4/H2 = 1:1, P = 5 mbar, T = 720°C)
- 26. Particle migration and coalescence H2, 600°C Ni/MgAl2O4
- 27. Ostwald ripening H2, 700°C– Atom migration – Vapour migration Ni/MgAl2O4
- 28. Nucleation of whisker carbon
- 29. Cs-corrected HRTEM of Au/TiO2 CM300 (300keV), Cs = 1.4mm Titan (300kV), Cs ≈ 0.0mm 2nm 2nm Confidential Uncorrected image Cs-corrected image
- 30. What is a site ?
- 31. Gas-induced shape changes in Cu nanocrystals on ZnO H2 H2O/H2= 1:3 CO/H2=1:6 P=1.5 mbar, T= 220 ºC (111) (110) P.L. Hansen et al. Science 295, 2053 (2002)
- 32. Michel Boudart “A catalyst is a complex and resilient self- assembly in space and time…. to treat an active site or a catalyst as a dead object in time with a fixed structure in space is a wrong model of the catalytic cycle”.
- 33. In situ EXAFS, Mössbauer and FTIR measurements: MoS2-like; ~10-20 Å at 400°C; Co substituted at S Mo Co Co9S8 MoS2-like nanoparticles ”Co-Mo-S” Co:Al2O3 Al2O3 (alumina) support Topsøe, et al. (1981) Co-Mo-S model Based on in situ characterisation studies
- 34. Bright brim Region with high eletron density (metallic character) Topsøe researchers with Besenbacher’s group (2001) Important discovery: MoS2 has metallic brim states!!
- 36. Snapshots of the Whisker
- 37. Mechanism and Step Abild-Pedersen et al 2006
- 38. • INPUT FROM THEORY
- 40. DFT-calculations for CH4 Activation CH3,H CH2,2H CH,3H H,4H Graphene,4H C,5H,OH C,6H,O CO,6H 6H CO 3H2 H2OCH4 Ni(111) Ni(211) 300 200 100 0 -100 -200 Bindingenergy(kJ/mol) (JRN et al 2002)
- 41. Optimal Catalyst Ammonia Synthesis 1000 100 10 1 0.1 0.01 0.001 0.0001 0.00001 0.000001 -150 -100 -50 0 50 100 Relative nitrogen binding energy/kJ/mol TOF/s-1 Mo Fe Co Ni Os Ru 450°C 100 bar 3:1 H2/N2 10% N H 3 1% N H 3 0.1% N H 3 0.01% N H 3
- 42. THE ELECTRONIC FACTOR activation energy for CH4 activation (Abild Pedersen et al) 1.6 1.4 1.2 1.0 0.8 -1.9 -1.8 -1.7 -1.6 -1.5 d band center (eV) Ea(eV) Ni/Au(111) 2C/Ni(211) S/Ni(211) C/Ni(211) Ni(111) Ni(211) Nistrain(111)
- 43. Scaling model ΔE(CH4) = ΔE(C) + ξγ Abild-Pedersen
- 44. SCALING MODEL adsorption energies of CHx and of C (Abild Pedersen et al) -1 -2 -3 -4 -5 -6 -7 -7 -6 -5 -4 -3 -2 ∆EC (eV) ∆ECH x(eV) Fit: y=0.76x-1.2 Fit: y=0.75x-1.04 Fit: y=0.49x-1.24 Fit: y=0.25x+0.11 Fit: y=0.26x+0.14 Fit: y=0.47x-1.46 Ag Ag Au Au Cu Cu Au Au Ag Ag Ag Ag Au Au Cu Cu Ni Ni Ni Ni Ni Pt Pt Pt Pt Pd Pd Pd Pd Ru Ru Ru RuRh Rh Rh Rh Ir Ir Ir Ir Ir Ir Ru Pt Pt Rh Ni Pd Co Ru Cu Rh Ir Pd CHX
- 45. STEAM REFORMING OF CH4 ON Ni reaction scheme from DFT calculations (Jones et al) 2 1 0 CH 4(g)+ H 2O(g) Freeenergy/eV 673 773 973 1173 CH 3*+ H 2O(g)+ 0.5H 2(g) CH 2*+ H 2O(g)+ H 2(g) CH*+ H 2O(g)+ 1.5H 2(g) C*+ H 2O(g)+ 2H 2(g) C*+ OH*+ 2.5H 2(g)C*+ O*+ 3H 2(g) 3H 2(g)+ CO*3H 2(g)+ CO(g)
- 46. Activity for steam reforming (log10. TOF) as function of C and O adsorption energies. 500o C, 1 bar abs. Jones et al
- 47. Conclusions
- 49. Noble Art of Modelling The model is no better than the accuracy of the main constants involved
- 50. Multiple Approach • Development – Catalyst – Process – Catalyst production methods • Research to understand (and market) • Explorative research (2nd S-curve)
- 51. Catalyst R&D Basic research Fundamental studies Catalyst characterization Catalyst formulation Process development Scale-up Pilot operation Computer modeling Industry
- 52. A future for a hydrogen economy ?
Editor's Notes
- Topsøe works with the high temperature fuel cell (solid oxide fuel cell), but it is not dependent on hydrogen like the PEM fuel cell and can convert a number of fuels. Hence, it provides a high flexibility.
- One ton of ammonia synthesis catalyst will within its operational life produce ammonia which as fertilizer may produce food for 100 people in 10 years. Topsoe sells 4000 t of ammonia synthesis catalyst per year. The composition of the catalyst has been known for about 100 years. It is the know-how about its function and how to achieve the optimum surface structures during preparation and operation which is the competitive advantage.
- The success of surface science almost turned catalysis into the "noble art of characterization". There is a need to study reactions rather than characterizing sites. This is done by the ”in-situ” methods.
- The science of catalysis has provided much stronger tools for optimization and control of catalyst manufacture and operation. This is not the least the success of the socalled in-situ methods (Topsøe 2002) by which the catalytic reaction is studied at the same time as changes of the structure of the catalyst or surface intermediates can be identified. One example is the use of X-rays from synchrotron radiation. The figure shows the combined X-ray diffraction (XRD) and X-ray absorption (EXAFS) spectra of a methanol synthesis catalyst during activation (Clausen et al. 1993).
- The progress in theoretical methods has lead to a detailed understanding of many catalytic systems. The input from “ab-initio”, density functional theory based calculations has become well-established. The DFT-approach often gives precise explanations of catalysis on bi-metallic systems, promoted metal catalysts. This may lead to computer aided design of catalysts etc. The figure illustrates that stepped nickel surfaces Ni(211) are more reactive for methane activation than the ideal dense packed nickel surface Ni(111).
- The introduction of computer methods allowed much more sophisticated models to be used in the reaction engineering. These models have been the key to process innovation. The success almost turned catalysis into the ”noble art of modelling” with more and more complex differential equations with dimensionless parameters. It has brought many chemical engineers in front of the computer screen far from the reality of industrial problems.