w  Requirements for heterogeneous catalysts

w  Overview on different Solid catalytic materials
§  Bulk Catalysts
§  Supported Catalyst

-Catalyst design and manufacture – w  Preparation methods
-Catalytic Solids- w  Guidelines: what is the most adequate catalyst for a
given process?

The ideal heterogeneous catalyst The ideal heterogeneous catalyst

w  Mono-dispersed, structured w  Supported


Heterogeneous Catalysts by
w  Functionality
–  Oxidation: TiO2
–  Hydrogenation: Pt/Al2O3
–  Acidic: FCCC cat: FAU/ZSM-5
–  Basic: MgO
–  Multifunctional: i.e. Pt/MOR (hydrogenation + acidity)
w  Structure
–  Unsupported: Raney Nickel (hydrogenation)
–  Supported: Au/TiO2 (oxidation)
–  Structured: zeolite
–  Non-structured: Al2O3

Heterogeneous Catalysts: design Heterogeneous Catalysts: design

w  How to choose the most appropriate catalyst for a given reaction

w  Required information?

w  Main reaction Mechanism
w  Possible by-products (mechanism)
w  Functionalities required
w  Affinity of reactants and products
w  Stability of reactants and products
w  Thermodynamics
w  …


Heterogeneous Catalysts: design Heterogeneous Catalysts: design

w  Common support elements (Oxide form in most cases)

Heterogeneous Catalysts: design Heterogeneous Catalysts: design
w  Reducibility of oxides w  Reducibility of oxides




Heterogeneous Catalysts: design Heterogeneous Catalysts: design

w  Common RedOx catalysts w  Common hydrogenation catalysts

Heterogeneous Catalysts: design Heterogeneous Catalysts by Reactor

w  Common CO insertion catalysts


e.Heterogeneous Catalysts by Reactor Moving bed reactor w  Fixed-bed catalysts –  relatively large particles (several mm) –  mechanical strength important (fines formation) w  Moving-bed catalysts –  idem fixed-bed –  spherical particles (to flow smoothly) w  Slurry-reactor catalysts –  powders (25 µm) –  attrition resistance important –  usually high density important (for easy settling) w  Fluidised-bed and entrained-flow reactor catalysts –  powders (20 .200 µm).g. well-controlled size distribution –  attrition residence important w  Structured catalytic reactors. monoliths Heterogeneous Catalysts: Heterogeneous Catalysts: requirements requirements w  Minimal Pressure drop w  Minimal Pressure drop w  Minimal Pore Diffusion Resistance Use of Porous w  Minimal Catalysts/Supports Pore Diffusion Resistance Shaping w  Maximal Mechanical Strength w  Maximal Mechanical Strength w  Minimal Cost w  Minimal Cost 5 .

Most common Hydrogenation Good mechanical strength Ring Minilith Wagon wheel Trilobe Extrudates Hydrodesulphurisation Low pressure drop. costs Gauzes Ammonia oxidation Low-surface-area catalysts Other high-T processes Ammonia Oxidation: Pt Gauzes Monoliths Monolith Reactor for water treatment New gauze Used gauze -330 kJ/mol 6 . For formaldehyde Low-surface-area catalysts Pellets Carbon monoxide shift Regular shape. Low pressure drop Ethylene oxide production Small diffusion length Surface-volume ratio a’ Mechanical strength Monoliths Exhaust gas cleaning Low pressure drop. Insensitive to Monolith Monolith Foam Pressure drop dust. Poor strength Rings Steam reforming High strength. Shape of industrial Catalysts Catalyst Shapes Spheres Hydrodesulphurisation Low manufacturing costs Methanation Relatively high pressure drop Impregnated noble-metal Large diffusion length Irregular granule Sphere Pellet Extruded Ammonia synthesis Not common Granules cylindrical Silver cat. Small diffusion length ceramic metallic Pore-diffusion resistance Manufacture methods.

Monoliths Examples of Catalyst Manufacture Catalyst Preparation Mo salt Fe salt Silicate Acid Ni-Al alloy w  Bulk catalysts w  Supported catalysts Precipitation gelling Formation clear sol Melting –  Supports Cooling •  Silica Drying Gelling •  Alumina Grinding Water wash Crushing •  Zeolites Screening •  Metal Organic Frameworks Hydrothermic treatment Ripening Drying •  Activated Carbon Leaching (pH ~ 14) Drying –  Attachment of active phase Pelleting •  Co-precipitation •  Impregnation Calcining •  Deposition-precipitation •  Chemical vapour deposition (CVD) Fe-moylbdate SiO2 Raney Nickel •  Sol-gel method 7 .

esrf.eu/Industry/case-studies/raney-nickel/raney- nickel-1) Ammonia Synthesis: Iron Oxide Cat iron-ore H2. 14) (a) the inner microstructure of a Ni-77. diluted O2 undersized particles electric furnace reduction passivation casting table screen -Catalyst Supports- crushing stabilized catalyst 8 . NiAl3. Hydrogenation Catalyst and eutectic phases respectively (http://www. (b-d) 3D distribution of the Ni2Al3. Bulk Catalyst: Raney Nickel Bulk Catalyst: Raney Nickel Mixing w  Porous Ni-Al alloy Melting w  High activity Cooling w  High settling rate Crushing w  Regeneration difficult Screening w  Unsatisfactory reproducibility Exposure to NaOH w  Pyrophoric solution (pH ca.5at%Al droplet.

car exhaust treatment. light alkanes-to-aromatics. SCR Magnesium aluminate Steam reforming. after-burning Activated carbons Oxychlorination. pore structure) Silica Polymerisation. hydrotreating. hydrocracking. –  carrier active phase –  stability at reaction conditions methanol synthesis. methanation. condensation Cordierite monoliths Car exhaust. hydrocracking. Catalyst Supports Catalysts Supports and Applications Alumina Hydrogenation. hydrodemetallisation –  active phase support interaction –  inert/reactive Silica-alumina Ammoxidation. selective oxidation. reforming. –  stabilizes active phase –  stability at regeneration conditions methanation.size methanol-to-gasoline process. alkene methathesis –  access to active sites –  texture (surface area. cyclisation. hydrogenation (fine chemicals) . isomerisation. dehydrogenation –  heat capacity –  thermal conductivity Zeolites FCC. hydrogenation. oxidation. isomerisation. methanol synthesis 9 . dehydrogenation. w  Function w  Important properties FCC. –  mechanical strength organic synthesis –  cost Catalysts Supports and Applications Diatomceous earth SO2 oxidation. hydrogenation Clays Hydrogenation.Supports with “non periodic” porosity- Titania Selective oxidation. low-temperature CO shift. steam reforming. dewaxing. –  shape.

-O-Si-O-Si-O + OH- Washing.7 -Si-OH + -O-Si-OH -Si-O-Si.+ H+ -O-Si-OH Gelation Generation of Si-O-Si bonds -O-Si-OH + -O-Si-O.+ OH- 10 .Production of Silica (Porous SiO2) Production of Silica (Porous SiO2) Silicate anions Start from solution Na-silicate H+ Polymerisation Formation of silanol groups -O-Si-O. Drying Formation of ring structures Formation of Silica Particle Formation of Gels: Sol-Gel Method Colloidal solution Gel Solution of micelles (Hydro) gel pH ?? Surface charge depends on pH pH < 4 -Si-OH2+ pH > 9 -SiO - Porous structures can be formed at pH 6 .

soluble high pH. porosity reduced w  Can this be prevented? Washing •  exchange water for less polar fluid (e.g.. Silica Production Process Drying Silicate Acid w  Critical step •  capillary forces cause compression Mixing •  pores collapse. alcohol) •  dry under supercritical conditions Drying w  After drying •  at low Temperature : hydrophilic Milling •  at high temperature: concentration of silanol groups low hydrophobic Classifi- cation Packaging Production of Alumina Fumed Silicas (Porous Al2O3) SiCl4 + 4 H2 + O2 SiO2 + 4 HCl Al is amphoteric* Hydrogen To HCl absorption low pH. soluble Oxygen (air) Cyclone solution of Al2(SO4)3 solution of Al(OH)3 Mixer base acid Burner Vaporiser precipitate precipitate Silicon tetrachloride Pyrogenic silica Cooler Deacidification *can react either as an acid or as a base 11 .

precipitation of precipitation of precipitation of precipitation microcrystalline boehmite gel crystalline boehmite gel bayerite gel gibbsite gel AlO(OH) AlO(OH) Al(OH)3 Al(OH)3 ageing at pH 8 and 353 K ageing at high pH 2 4 6 8 10 12 14 pH Heating above 770 K Amorphous Al2O3 γ-Al2O3 η-Al2O3 χ-Al2O3 Poorly crystallised pseudo boehmite Amorphous precipitate Crystallized bayerite plus amorphous material Crystallised hydrargillite spinel structure: cubic close packing Heating at about 1170 . θ-Al2O3 δ-Al2O3 α-Al2O3 dependent on conditions Heating above 1370 K α-Al2O3 corund structure: hexagonal close packing Applications of Alumina Pore Size/Volume Distributions Wide-pore Silica γ-Alumina α-Alumina ZSM-5 12 .3 SO3 Na2O.Al2O3 Al-oxide amphoteric Soluble at low and high pH pH < 2 pH > 12 + + Base Acid solubility at 3 < pH < 6 at 6 < pH < 8 at 8 < pH < 11 Al3+ Region of AlO2. Precipitation Regions of Aluminium Formation of Different Aluminas Compounds Al-sulphate solution Na-aluminate solution Al2O3.1270 K Several precipitates.

w  Positive w  Negative polymers –  stable at all pH. T –  chemical reactivity (O2. Activated Carbons Activated Carbon Carbonaceous material peat. biomass.) High T –  high adsorption capacity –  mechanically weak Pyrolysis –  wide variety textural properties –  fines –  "soft" ligand Porous material –  not much erosion pumps. etc –  inert H 2O Partial gasification Additional porosity Activated carbon Structure of Activated Carbons Functional Groups 13 . coal.. sugar.

Ni Acetylene + HCl to vinyl chloride HgCl2 Acetylene + HAc to vinyl acetate Zn(OCOCH3)2 -Supports with ”periodic” porosity- Ordered Mesoporous materials Ordered Mesoporous materials synthetic strategies main properties Liquid crystal templating 3 – 30 nm pores Wide variety in terms of composition (Si. Microporous and Mesoporous Materials 125 (2009) 170– 223 14 . Pd. organics…) Self assembly Nanometric building blocks Sheet-folding mechanism Cool et al. Reactions with Carbon-supported Catalysts Reaction Active Phase Hydrogenations Pt.. Al. Ti.

org/databases/ Zeolites •  Microporous aluminosilicates •  Crystalline •  Molecular sized pores •  Over 150 framework types •  Tunable interactions •  Thermally / Chemically robust •  No swelling •  Catalysis •  Separation •  Adsorbents •  Membranes 15 . Zhou. Z.. L. Int. 2007. Shan. Chem. 713–714. Marchese. Ed. Maschmeyer. W. 2001. Angew.iza-structure. Zeolites http://www. C. d. v. Chem. N. 46. 2879 –2882 and T. Ordered Mesoporous materials Ordered Mesoporous materials functionalization TUD-1 Grafting One-pot synthesis J. Jansen.. Commun. Puil Asefa et al.

C3 ü  Fair thermal stability ü  Fast coking rate ü  Mainly C2 and C3 SAPO-34 (8MR) 3D 16 . C3. C6 •  P ü  High thermal stability •  Cr ü  Low coking rate •  … ü  Wide product distribution ZSM-5 (10MR) 3D •  Ion Exchange: •  Pt •  Pd •  … Methanol •  As supports for nanoparticles MTP C2. C4. Kinetic Diameters of Molecules Compared with Zeolite Pore Size Zeolites: catalytic activity Zeolites: pore size vs. C5. performance •  Isomorphic substitution: MTO •  Al C2.

E.6 Å y x z * Kumita.3 .. Marcus. (2005). performance ZSM-58 SAPO-34 Vs. J. D. 41-48 F... Gascon.C4H6 n C4H10 ZSM-58 (DDR. performance Zeolites: pore size vs. 8MR) 3D: 4. * Haw. Stavitski. Y. J. Kapteijn. C 2H 4 C 3H 6 SAPO-34 (CHA..8 x 3. A. Moulijn.8 Å CH4 2-C4H8 C5 1.4 x 3. J. 34. Top. Appl Catal A (2010) Industrial Production of Early Zeolite Synthesis Method Na Aluminosilicate Zeolite Alumina Alkali Hydroxide Silica Gel 373 K Zeolite 17 .. 8MR) 3D: 3. In Cat. Zeolites: pore size vs.

Preparation of H-Zeolite from Na. Ion-Exchange of Zeolite Y for Na Removal Zeolite NaY sieve NH4+ or 1st RE3+ Exchange solution Filtration & Na+ washing solution Heating NH4+ or 2nd RE3+ Na+ Exchange solution solution Filtration & washing Final drying Zeolites Classified by their Trends in Catalytic Cracking Catalyst Si/Al Ratio Performance (1946) ts ca (1955) 10 (1964) s ou (1968-72) ph ts Coke yield (wt% on FF) or ca 9 am s ou s st ing a ph in l y ck um or 8 ta ra ca rc am al e lite ris w a Lo Y) (1980’s) in o + 7 Ze tes -H- um oli (RE al Ze es h olit ) ig 6 e SY H ez s (U ctiv cat s ele ctiv e 5 C o ke e sele co k hly 4 Hig 50 60 70 80 Conversion (vol%) 18 .

9.. Nature 2009. 5737.4 nm Burton et al. ChemCatChem 3 (2011) 67–81. Chem. 30 19 . J. Eur. van Donk et al.2 nm alternatives SSZ-53: 14 MR 1. Hierarchical Zeolites Trends in Catalytic Cracking Catalyst ü  Effective ü  Scalable → Industrial importance S. 498. Improving diffusion in zeolites Ultra large pore zeolites approaching the meso-region ITQ-37: 18 MR 2.5748 Corma et al. 2003.

Phys. Catal. 7304 –7306 Corma et al. 186 (1999) 57-63 Delaminated zeolites Solid-State Reactions in Y Zeolite During maximizing external surface area. Chem. B 2004. minimizing diffusion pathlength Steaming Effect of delamination: Ti-MWW in the epoxidation of alkanes Si Si O OH H2O Si O Al O Si Si OH HO Si + Al(OH)3 O OH Si Si Si(OH)4 Non-framework H2O species From other parts of the lattice (creating meso-pores) Si O Si O Si O Si O Si Tatsumi et al. Ultra large pore zeolites Delaminated zeolites FCC on SSZ-53 maximizing external surface area. 108. Ed. Chem. US Ernst et al. 19126-19131 20 . minimizing diffusion pathlength (MWW) N-decane cracking on SSZ-53 Hexamethylenimine SiO2 Hexadeciyltrimethylammonium Layered zeolite precursor HCl. 2007. Angew. Int. 46. J. J.

20 (2008) 946-960 Hierarchical zeolites Hierarchical zeolites Selective leaching of Si or Al Desilication Dealumination + /H m ea St OH - Desilication Al Si Perez-Ramirez et al. 37. Chem. Chemistry-A European Journal. 14. Mater. 2530–2542 Weckhuysen.. Chem. Rev. Hierarchical zeolites Carbon templating Christensen et al. 2008. 2008. 1718-1725 21 . Soc.

600 “DrySyn” beta à Deff = 13. 825–831 (2012) Ordered mesoporous zeoles “Dry Synthesis” Metal Organic Frameworks §  Crystalline porous materials consisting of metal ions linked together by BETA-TUD-1 vs Microporus Beta (alkylation of organic ligands aromatics) 1.200 Deff = 2.000 0.00 1.(porous) coordination polymers . Ordered mesoporous zeoles “Dry Synthesis” Silica-alumina particle Particle with zeolite crystals (1) (2) Incipient Conversion Wetness Process Impregnation Mesopore Solid oxide Filled with zeolite Mesopore Ultrasmall forming agents Unconverted molecular solid oxide sieve crystals Perez-Ramirez et al.400 Commercial beta 0.8 * 10-5 cm2/sec 0.50 2.800 0.200 Experimetal 1.hybrid inorganic–organic frameworks .5 * 10-5 cm2/sec 0.50 1.00 0.000 Calculated K (app).00 §  May also be referred as: Particle size (mm) . Nature Chemistry 4. (1/sec) 0.zeolite imidazolate frameworks 22 .

60 ml/g 20 µm Cages-windows 3D 3000-4000 m2/g Tmax = 350o C 23 .paddlewheel cluster Corrugated pores. cages-windows Free coordination sites on CuII Tmax : 250 °C 1300 m2/g 0. Metal Organic Frameworks Metal Organic Frameworks Straight channels 3D Cages-windows 3D Structure: MIL-101 (Material Institute Lavoisier) Structure: [Cu3(BTC)2] HKUST-1 Cu .

U. J. Gascon. % Benzaldehyde Ethyl cyanoacetate Ethyl (E)-α-cyanocinnamate 50 40 30 Blank (solvent) 20 ü  Liquid phase 10 0 ü  Near room temperature 0 10 20 30 40 50 60 70 80 90 100 110 120 130 T ime. 24 . Kapteijn.D. (2009) 261. min ü  Base catalyzed ü  Strong dependence on the solvent J. van Klink.06 mmol) C O O .G.P. Aktay. Infinite channels with a minimum diameter of 3 Ångström. M. F. Catal. Heranndez-Alonso. y x z Catalysis on MOFs Zeolites versus MOFs Grafting Open Metal Sites x z y Semiconductor Functional x Photocatalysis Organic Sites z y Encapsulation Porosity: permeability without structural collapse.M.H2O 90 C C2H5 C C2H5 80 O O 70 60 Aniline (0.2 mmol) Y ie ld. 75. z x x Metal Complexation yz y z y x Basic Catalysis: Knoevenagel condensation Basic Catalysis on MOFs containing -NH2 x y CN H CN H IRMOF-3 100 z H2C C C O IRMOF-3 2500 (0.

Aktay... % 50 EtOH 40 Cyclohexane CycloC6 30 20 Polarity -Inclusion of the active phase - Toluene 10 Toluene 0 0 10 20 30 40 50 60 70 80 90 100 110 120 130 Time. J.. M. Basic Catalysis on MOFs containing -NH2 100 DMSO 90 DMSO 80 70 EtOH DMF 60 DMF Yield.. 75. van Klink. pH Mixed oxides homogeneous or Drier and nucleation heterogeneous –  ripening time calciner and carbonates –  nucleation promotors Mill –  .D. Filter –  T .P. Catal. growth Precipitation and ageing Powder mixing bin Weighing Coprecipitation mixed oxides machines Catalyst pellets Pelleting machine 25 . U.M... Gascon.cB. Heranndez-Alonso.G. Kapteijn. F. min J.... (2009) 261. Production of Catalysts by (Co)Precipitation Precipitation Mixed metal Sodium nitrates tank carbonate tank Solution solution w  Parameters supersaturated solution –  nature salts –  cA.

Bucket conveyor Drip chute w  Wetting of support with solution precursor Wet impregnation Tipper Bucket –  "Wet" Excess solution Drive wheel –  "Dry" Amount of solution=Pore Volume w  Drying To drying Bucket filter –  Critical. Fe/Al Supports for catalysts Basic support Mg/Al Catalyst Preparation by Impregnation of supports Impregnation a. Cu/Zn/Mg/Al relatively high Higher Alcohol Synthesis Cu/Co/Zn/Al. Cu/Co/Zn/Cr dispersion –  high thermostability Fischer-Tropsch Co/Cr. Impregnating •  bursting support solution •  interaction compounds Dry impregnation Spray header •  sintering Support to be impregnated Rotating drum 26 . Ni/Mg/Al –  high loading possible –  at high loadings Methanol synthesis Cu/Zn/Al. Zn/Cr. Catalysts Prepared by Coprecipitation Coprecipitation Reaction Catalytic elements w  Positive w  Negative Catalysts –  components well –  difficult scale-up mixed on an atomic –  at low loadings Hydrogenation Ni/Al scale relatively low dispersion Steam reforming Ni/Al. tendency towards "egg-shell" catalyst Impregnating solution w  Calcination Impregnating basin –  Critical b.

Chem. 0. O. O.1 pH pH < PZC pH = PZC pH > PZC Surface Charge positive neutral negative 0 γ-Alumina Species MOH2+ MOH MO- Adsorption anions cations PZC 6 7 8 9 10 Alumina 8-9 pH increase pH Silica ~3 10% Alumina/Silica ~ 5 Active-Phase Distributions Active-Phase Distributions Example: Ni on α-Alumina Uniform Egg-shell Egg-white Egg-Yolk J. Adsorption from [Pt(NH3)4]2+ Relation between PZC and Surface Charge solution Lower pH pH = P ZC Hi gher pH Adsorbed [Pt(NH3)4]2+ (mmol/g) H H+ H H+ H H+ H H H O.3 O O O O O O Si O Si O Si Si O Si O Si Si O Si O Si Silica gel 0. Soc.. 131 (46).2 0. pp 16932–1693 27 . 2009. Am.

Impregnation of γ-Alumina with Pt Processes during Impregnation Influence of Coadsorbing Ions Solution flow into pores adsorption diffusion a b c Adsorption/desorption + diffusion adsorption Increasing citric acid concentration Pt/Al2O3 Al2O3 evaporation Drying Homogeneous Deposition Homogeneous Deposition Precipitation Precipitation w  Applicable in precipitation upon increasing pH –  example: Ni2+ Ni(OH)2 w  Upon heating (370 K) urea in water decomposes slowly: CO(NH2)2 + 3 H2O CO2 + 2 NH4+ + 2 OH- w  pH increases slowly throughout particle –  homogeneous loading 28 .

–  $$ Example: Synthesis of Mesoporous Zeolites -Examples: Catalyst Engineering- 29 . How to choose the most adequate Catalyst? –  Selectivity –  Activity –  Stability –  $$ -Concluding remarks.

Tailored Isomerization Process Problem Refinery è Gasoline SR (l/h)G LOW RON ! Further processing is needed: SR-Jet •  Reforming •  Oxygenate addition SR-Diesel •  Isomerization Major Refinery Gasoline Process C6 Isomerization nC6 30 2MP 74 23DMB 105 •  Higher branched isomers have higher octane numbers M M M H+ H+ •  Pt/HMOR: bifunctional isomerization catalyst H+ H+ H+ H+ •  Acid site: isomerization/cracking •  Metal site: de(hydrogenation) è AIM: Selective production of M M dibranched isomers 3MP 76 22DMB 94 30 .1..

zeolite channel (≈7 Å) à  higher packing efficiency è selectivity towards dibranched isomers? 31 . Thermodynamic limitations Catalyst requirements •  Acid + metal functionality in close proximity •  Amount of dibranched isomers is limited by thermodynamic gas phase equilibrium Equilibrium conditions are not known •  •  Active at low T to maximize the production of di- •  Low selectivity at high T 60% branched isomers 50% nC6 3MP 2MP 23DMB 22DMB •  Stability Fraction (mol%) 40% 30% “State of the art” Catalyst: Pt / Chlorinated alumina 20% selectivity conversion 10% TRADE OFF 0% 300 350 400 450 500 T (K) 550 600 650 700 Problem: Acidity loss because of Cl leaching Hypothesis: confinement effects Zeolite candidate: Mordenite (MOR) (10MR) Isomerization packing entropy •  Molecular simulations à  higher number of dibranched isomers can be packed into a 1D.

H2O/MOR(wt)=10. T=25oC. high-Si Pt/HMOR 10% H2. 0.5oC/min 0.6wt%Pt/H-MOR Catalyst performance Pt NP formation: impact on stability 50% 60% Fraction (mol%) 40% nC6 23DMB 50% 30% 90% 80% 20% 40% 70% 10% n C 6 conversion 60% 0% 30% 50% 470 480 490 500 510 520 470 480 490 500 510 520 T (K) T (K) 40% 30% 25% Fraction (mol%) 20% 20% H2. high-Si Pt/HMOR 15% 0% 0 500 1000 1500 2000 2500 3000 3500 10% 22DMB time [s] 5% 0% 470 480 490 500 510 520 T (K) 32 . Proposed catalyst: Pt/HMOR Catalyst preparation High-Si MOR NH4MOR + NaMOR 1) Ion exchange: t=24h. 0.5C/min. 1M NH4NO3 2) Pt inclusion: (NH4)2[PtCl4] 3) Calcination in air at T=550oC for 8h. 8h at T=450C. 10C/min. Tmax=400C.

.1 g. solvent n-decane O OH H2 H2 100 100 100 + H 2O relative concentration (%) a) b) Pd/SiO2 Pd/SiO2 4-isobutylacetophenone 1-(4-isobutylphenyl) ethanol 4-isobutylethylbenzene 80 80 80 (4-IBAP) (4-IBPE) (4-IBEB) SIBPE(%) YIBPE(%) 60 60 60 Ibuprofen 40 40 40 IBAP IBPE ‘In-house’ prepared Pd/SiO2 by wet impregnation method 20 20 20 IBEB •  Commercial SiO2 support (particle size 35-74 µm) Regenerated catalyst 0 0 0 •  2. J.Catal. this in one of the few all-zeolite based processes (catalysis + separation) Hydrogenation Isobutyl-acetophenone Results Slurry Reactor . pH2=20 bar. wcat=0.5 % Pd/SiO2 0 50 100 150 200 0 20 40 60 80 100 •  Pd crystallite size: 2-4 nm 7.Selective hydrogenation First plant using Pt/ HMOR catalyst built in 1993 Several plants operating worldwide. semi-batch IBAP conditions C4-IBAP=0.5 nm t (min) XIBAP(%) •  Pd dispersion: 30% Kinetics: LH-type •  Batch slurry reactor A. Quintanilla et al. HYSOMER process (Shell) 2. T=373 K. 257(2008)55-63 33 .27 mol/L.

Bi-functional F-T catalyst 100 CAT-HMDS 80 Pd/SiO2 SIBEP (%) 60 40 20 20 40 60 80 100 XIBAP(%) 34 ..Approach Selectivity improvement Control of selectivity by optimization of the relative adsorption strength of 4-IBAP and 4-IBPE Modification of the Silylation 1 Control of selectivity hydrophobic/ hydrophilic properties of Pd/SiO 2 HMDS Pd/SiO2 R R Si R R R Si R R R Si R R R Si R OH OH OH OH O O O O Pd Pd Modification Optimization Silica support Silica support Hydrophobic Adsorption 1 Properties Strength H 3C H CH3 N Si Si Silylation to increase hydrophobicity CH3 CH3 CH3 CH3 Hexamethyldisilazane (HMDS) Effect Silylation on Selectivity 3.

6 0.1 0. .1 C4 0 0 0.1 0..6 0.6 C2 C1 C 2H 6 C 3* 0.3 0.4 C 3H 8 0.7 weight fraction 0.9 1 chain growth probability.4 0.5 C5-C11 0.4 0.9 rp 0.2 C 4* 0 C4H10 0 0.7 0. T p H2/CO Kinetics & Mass Transport ? 35 .2 0. α Anderson-Schulz-Flory (ASF) Fischer-Tropsch synthesis distribution CO + 2H2 CnH2n+2 + H2O polymeric growth scheme 1 C* C20+ 0.5 0.2 C3 0. Fischer-Tropsch as key technology Fischer-Tropsch Synthesis rp rp w  Chain growth *Cn-1 *Cn *Cn+1 w  Termination rt Cn 1 0.2 0.5 0.8 methane α= wax rp + rt 0.6 0..4 0..8 C5-C9 C10-C20 α CH4 1-α mass fraction C4 C 2* C3 0.3 0.9 1 C 5* chain growth probability α .8 0.7 0.3 C2 C12-C21 Wn = nα n −1(1 − α )2 0..8 0.

velocys. Cambridge.com 2 CO → CO2 + Cads (Boudouard Carbon) www. Spivey (Eds.J. Oxygenates Syngas 320–340 Alkanes. 31 (2008) 746–754. re-injection H2:CO Adjustment CO2 H 2S §  High-quality clean fuels – new products §  Chemicals source in future? Fischer-Tropsch Syncrude Cooling/ Synthesis Separation w  Lower environmental impact §  More efficient utilization fossil resources Fischer-Tropsch Gas Loop §  Renewable. Alkenes. Fischer-Tropsch-Based Facility Diagram Gas-to-Liquid Conversion Syngas Fischer-Tropsch Fuel Raw Material Feed Preparation Products Natural Gas Fuels generation synthesis upgrading Coal Chemicals Biomass Coal. natural gas. E. 142 FTS Reactions Conventional FTS Reactors Low Temperature Shell Technology Sasol Technology FTS Metal Temperature [°C] Nature of Products Fe 200–250 Alkanes. FTS Technol.ws 36 . RSCPublishing. 2010..shell. Oxygenates Multitubular Reactor Slurry Reactor Co 170–220 Alkanes. w  Low Temperature FTS Co-Based Catalysts w  High Temperature FTS Fe-Based Catalysts w  Reactions: n CO + (2n+1) H2 → CnH2n+2 + n H2O (Enthalpy: ~-150 kJ per mole converted CO) n CO + 2n H2 → CnH2n + n H2O n CO + 2n H2 → CnH2n+2O + (n-1) H2O (Alcohols & Ethers) n CO + (2n-1) H2 → CnH2nO + (n-1) H2O (Aldehydes & Ketones) n CO + (2n-2) H2 → CnH2nO2 + (n-2) H2O (Carboxylic Acids & Esters) www. biomass Feed-to-Syngas Refinery Water Waste Conversion •  Remote natural gas resources •  Associated gas crude oil rigs Syncrude w  Flexible technology Gas Cleaning and Offgas §  Monetising alternative to flaring.co. oil.). in: J. Alkenes. Eng. Furimsky.biorefinery. Chem. de Klerk.com www.h2creative.uk CO + H2O  CO2 + H2 (Water-Gas-Shift Catalyzed by Fe) www. Guettel et al. contributes to sustainable society A. Some Alkenes and Oxygenates High Temperature R. Aromatics.Catalysis in the Refining of Fischer-Tropsch Syncrude.

in: J.2–2 0.Catalysis in the Refining of Fischer-Tropsch Syncrude. FTS Product Refining GTL Coupling F-T and catalytic cracking? Low Temperature Hydrocracking Diesel FTS Coal 180–250°C Wax (>C20) Syngas Natural Gas Biomass High Temperature Oligomerization Isomerization Gas FTS Hydrogenation Syngas Olefins (C3–C11) (H2 + CO) Typical process conditions of crude oil and FTS hydrocrackers Hydrocracker Type Fischer-Tropsch Description Conventional Mild FT Wax Temperature [°C] 350–430 380–440 325–375 Synthesis Pressure [Mpa] 10–20 5–8 3. Cambridge.5–7 -1 n CO + 2n H2 (-CH2-)n + n H2O LHSV [h ] 0. 2010. E. Spivey (Eds. Furimsky.). de Klerk. RSCPublishing.J.2–2 0.5–3 3 -3 H2:feed [normal m m ] 800–2000 400–800 500–1800 Reactor Technology Tricle Bed Tricle Bed Tricle Bed Product Conversion [%] 70–100 20–40 20–100 Cracking Fuel A. Contact states between FTS and zeolite phases Coupling F-T and catalytic cracking? Acid sites FTS sites Downstream Homogeneous Zeolite-coated Zeolite-supported separate zeolite physical mixture catalyst catalyst bed with zeolite More intimate contact between FTS and zeolite phases 37 .

J. Appl. FTS Base Catalyst Approach 1 Catalyst Synthesis CARiACT Q-10 SiO2 (FUJI SILYSIA CHEMICAL LTD. 456 (2013) 11-22 38 . 456 (2013) 11-22 S. Appl.) Shape Spherical Particle Size [mm] 0. vand Dijk. J. J. Sartipi.E.075–0.500 w  Support SiO2 2 Surface Area [m /g] 291 3 Pore Volume [cm /g] 1. Kapteijn. Catal. F. Catal. Gascon.E. Sartipi. Gascon.35 Pore Diameter [nm] ~15 w  Catalyst 10 wt% Co/SiO2 Incipient Wetness Impregnation Static Calcination in Air: 2 h @ 400°C 500 µm XRD 2 -1 Catalyst Surface Area [m g ] Co [wt%] Phases Crystal Size [nm] SiO2 291 – Amorphous – 10 wt% Co/SiO2 229 9.  H-ZSM-5 Coated Co/SiO2 H-ZSM-5 Coated Co/SiO2 (Without TEOS) 2.025 Al(NO3)3·9H2O 1 / 0 TEOS Co/SiO2 4 EtOH : 60 H2O 100 µm 5 µm Static Calcination in Air: 5 h @ 500°C (1°C min-1) H-ZSM-5 Coated Co/SiO2 1. vand Dijk. A. A. J.25 TPAOH 0.  H-ZSM-5 Coated Co/SiO2 (Without TEOS) S.31 Co3O4 27 Core-Shell Catalyst-Direct Hydrothermal Procedure Core-Shell Catalyst-Direct Hydrothermal Procedure Gel Composition 24 h @ 180°C 0. Kapteijn. F.

J. Sartipi. F. Chen et al.E-02 y/– 5 1. Appl.E-01 10 1. Catal. J. Chem. 456 (2013) 11-22 S. vand Dijk. Mater. vand Dijk. Product Selectivity FTS Experiments FTS Experiments 25 ■ n-Paraffin /// Isoparaffin and Olefin 1. J. Appl. Gascon.. 22 (2012) 17381–17403. A. J. Sartipi. F.E-05 Middle: H-ZSM-5 Coated Co/SiO2 1 3 5 7 9 11 13 15 Right: Co/SiO2 + H-ZSM-5 n/– S. A. J. Kapteijn.E.E. Kapteijn. 39 . 456 (2013) 11-22 Approach 2: Zeolites as supports for Challenge FT synthesis w  Question: Are microporous zeolites suitable supports for FTS catalyst formulation? Ø  High metal loading → Agglomeration on crystallite surface Ø  Diffusion limitations → Over-cracking Ø  Coke deposition in micropores → Low catalyst stability w  Answer: Introducing mesopores to the zeolite crystallites Hierarchy L. Gascon. Catal.E-03 0 2 5 8 11 14 17 20 23 26 Carbon Number 1.E-04 Co/SiO2 H-ZSM-5 coated Co Left: Co/SiO2 Co/SiO2 + H-ZSM-5 1.E+00 20 Selectivity [%] 15 1.

Catal.08 cm3 g-1 Si/Al = 16 Acid treatment Extra. van der Linden. Gascon. VP Santos. M. (2013). Makkee. J. MJ Valero-Romero. mesoH-ZSM-5(aw) Extra-framework framework Al Acid treatment Extra- Al removal Extra-framework framework Al Smeso = 314 m2 g-1 Al removal 1575 1550 1525 1500 ν / cm-1 1475 1450 1425 Vmeso = 1. van der Linden. 
 F. Kapteijn. VP Santos.08 cm3 g-1 Si/Al = 41 Pyridine adsorption-FTIR H-ZSM-5 Base treatment Base treatment Smeso = 309 m2 g-1 mesoH-ZSM-5(a) Vmeso = 1. Gascon. B. 179. 179. H-ZSM-5-supported Co H-ZSM-5-supported Co Brønsted Lewis Smeso = 52 m2 g-1 Vmeso = 0.09 cm3 g-1 Si/Al = 39 S. (2013). Sartipi. B. 305. Catal. J. Kapteijn. Sartipi. Gascon. Parashar. J. H-ZSM-5-supported Co 20 nm Base treatment Impregnation 20 nm 50 nm Acid treatment Extra- Extra-framework framework Al Al removal 20 nm S. F. MJ Valero-Romero. Kapteijn. Makkee. K. 305. M. 40 . VP Santos. Sartipi. Catal. MJ Valero-Romero. (2013). J. J. K. 179. M. 
 S. Parashar. B. Parashar. 305. 
 F. J. Makkee. K. van der Linden.

M. Catal. Makkee. nitrate. MJ Valero-Romero. J. 305. J. 179. Gascon. Sartipi. Gascon. (2013) 3. B. 
 F. Carbon nanotubes…) 2)  Selection of the metal precursor (i. MJ Valero-Romero. Catal. van der Linden. Gascon. Catal Sci Tech. F. Example 4: exploring the limits of metal nanoparticle Supported catalysts supported catalysts Most common preparation methods 1)  Synthesis of the support (i. (2013). Parashar.  Small nanoparticles iii. FTS activity/stability Product distribution 1. J. Parashar.E-03 XCO / % 80 70 Co/mesoH-ZSM-5(a) 1. M. Al2O3. Parashar. J. J. K.E-01 100 Co/mesoH-ZSM-5(aw) 1. F. M. Makkee.e. (2013).E-05 TOS / h 1 6 11 16 21 26 31 36 20 nm n/– S. K.E+00 w  CO conversion increases considerably over Co/mesoH-ZSM-5 20 nm 1.E-02 y/– 90 l Co/SiO2 1.  High nanoparticle loading (=high activity) a)  Wet impregnation ii.  Full accessibility of metal phase b)  Incipient wetness impregnation 4)  Calcination 5)  Reduction 41 . Kapteijn.e. van der Linden. Kapteijn. VP Santos. acetate…) Synthesis methodologies able to deliver: 3)  Impregnation i. Sartipi. Makkee. 305. Kapteijn. B. 
 S.E-04 60 Co/H-ZSM-5 Extra- framework Al ▲Co/mesoH-ZSM-5 50 0 5 10 15 20 25 30 35 1. 572—575 S. 179. Sartipi. K. VP Santos.

42 . 134. 16207.catalysts Supported catalysts q  Poor mechanical strength Ø  Supported catalysts q  Deactivation due to carbon deposits Ø  Small and homogeneous Fe nanoparticles q  Catalyst fragmentation – reactor fouling Ø  Avoid large. J Am Chem Soc 2012.catalysts Fischer-Tropsch .catalysts ü  Resistant to poisoning ü  Addition of WGS functionality (readjustment H2/CO ratio) ü  High Temperature operation – direct synthesis of short HC’s q  Poor mechanical strength q  Deactivation due to carbon deposits q  Catalyst fragmentation – reactor fouling 165 Fe based FTS . difficult to carbidice. Common CO insertion catalysts Fe based FTS . Fe particles Torres Galvis et al.

134. Nature Communications 2015 43 . 61/994..Supported catalysts MOFs as catalyst precursors •  MOF consist of highly dispersed metals •  Carbon based linkers act as spacers Very little synthetic control over particle size at increasing Fe loading Torres Galvis et al. Synthetic approach MOFs as catalyst precursors •  MOF consist of highly dispersed metals •  Carbon based linkers act as spacers U. J Am Chem Soc 2012.277 & Santos et al.S. 16207.

Nature Communications 2015 44 .S.277 & Santos et al. Nature Communications 2015 U. 61/994.S. 61/994...TEM Characterization . 61/994.TEM Catalytic performance FA concentration U.S.277 & Santos et al.Characterization . Nature Communications 2015 U. 61/994.TEM 40 wt% Fe!! 40 wt% Fe!! U.277 & Santos et al...S.277 & Santos et al. Nature Communications 2015 Characterization .

Catalytic performance Example 4: synthesis control.277 & Santos et al. 61/994. J Am Chem Soc 2012. 16207 2) Schulte et al. Nature Materials 14 (2015) 48-55 45 . ChemCatChem 2012. 4.. Towards new 2D materials 1) Torres Galvis et al. 134. Nature Communications 2015 Bottom-up synthesis of MOF nanosheets Rodenas et al.S. 350 U.

Nature Materials 14 (2015) 48-55 Rodenas et al. Nature Materials 14 (2015) 48-55 Bottom-up synthesis of MOF nanosheets Bottom-up synthesis of MOF nanosheets controlling particle morphology extending MOF scope Temperature à Co BDC Zn BDC Cu(1.4-NDC) Cu(2.6-NDC) Cu BDC Rodenas et al. Nature Materials 14 (2015) 48-55 46 . Bottom-up synthesis of MOF nanosheets Rodenas et al.

Rodenas et al. Nature Materials 14 (2015) 48-55 47 . Nature Materials 14 (2015) 48-55 Separation performance Final remarks. catalyst preparation w  Lot of room for improvement w  Information on different reaction aspects is a must w  Main reaction Mechanism w  Possible by-products (mechanism) w  Functionalities required w  Affinity of reactants and products w  Stability of reactants and products w  Thermodynamics w  … Rodenas et al.