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Department of Chemical Engineering Institute of Technology, Nirma University

Chemists and Chemical Engineers Make the World a Better Place through Modern Developments in Heterogeneous Catalysis. Presented by S ANJAY P ATEL. Department of Chemical Engineering Institute of Technology, Nirma University. Content. Chemistry & Chemical Engineering

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Department of Chemical Engineering Institute of Technology, Nirma University

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  1. Chemists and Chemical Engineers Make the World a Better Place through Modern Developments in Heterogeneous Catalysis Presented by SANJAY PATEL Department of Chemical Engineering Institute of Technology, Nirma University

  2. Content • Chemistry & Chemical Engineering • History of Catalysis • Catalysis • Recent trends in Catalysis • Future trends in Catalysis • Summary

  3. Household commodities Gadgets Energy Demand Luxury Health All other Engg Industrial Chemicals Population Environment Alternative Fuels Research

  4. Chemistry and Chemical Engineering more Integrated to the Society Society: • Cleaner and safer processes • Well accepted and integrated processes Industry: • Speed-up processes • Energy and cost effective processes • New catalysts and catalytic processes • New technologies Academia: • New innovations • Deeper knowledge and understanding of phenomena • Control of phenomena

  5. Role of Catalysis in a National Economy • 24% of GDP from Products made using catalysts (Food, Fuels, Clothes, Polymers, Drug, Agro-chemicals) • > 90 % of petro refining & petrochemicals processes use catalysts • 90 % of processes & 60 % of products in the chemical industry • > 95% of pollution control technologies • Catalysis in the production/use of alternate fuels (NG,DME, H2, Fuel Cells, biofuels…)

  6. Why R&D in catalysis is important • For discovery/use of alternate sources of energy/fuels/raw material for chemical industry • For Pollution control • For preparation of new materials (organic & inorganic-eg: Carbon Nanotubes)

  7. Three Scales of Knowledge Application

  8. Some Developments in Industrial catalysis-11900- 1920s Industrial ProcessCatalyst 1900s: CO + 3H2 CH4 + H2O Ni Vegetable Oil + H2 butter/margarine Ni 1910s: Coal Liquefaction Ni N2+ 3H2 2NH3 Fe/K NH3 NO NO2 HNO3 Pt 1920s: CO + 2H2 CH3OH (HP) (ZnCr)oxide Fischer-Tropsch synthesis Co,Fe SO2  SO3 H2SO4 V2O5

  9. Industrial catalysis-21930s and 1940s 1930s:Cat Cracking(fixed,Houdry) Mont.Clay C2H4C2H4O Ag C6H6  Maleic anhydride V2O5 1940s:Cat Cracking(fluid) amorph. SiAl alkylation (gasoline) HF/acid- clay Platforming(gasoline) Pt/Al2O3 C6H6 C6H12 Ni

  10. Industrial catalysis-3 1950s C2H4Polyethylene(Z-N) Ti C2H4Polyethylene(Phillips) Cr-SiO2 Polyprop &Polybutadiene(Z-N) Ti Steam reforming Ni-K- Al2O3 HDS, HDT of naphtha (Co-Mo)/Al2O3 C10H8  Phthalic anhydride (V,Mo)oxide C6H6  C6H12 (Ni) C6H11OH C6H10O (Cu) C7H8+ H2 C6H6 +CH4 (Ni-SiAl)

  11. Industrial catalysis-4 1960s Butene Maleic anhydride (V,P) oxides C3H6  acrylonitrile(ammox) (BiMo)oxides Bimetallic reforming PtRe/Al2O3 Metathesis(2C3 C2+C4) (W,Mo,Re)oxides Catalytic cracking Zeolites C2H4 vinyl acetate Pd/Cu C2H4  vinyl chloride CuCl2 O-Xylene Phthalic anhydride V2O5/TiO2 Hydrocracking Ni-W/Al2O3 CO+H2O H2+CO2 (HTS) Fe2O3/Cr2O3/MgO --do-- (LTS) CuO-ZnO- Al2O3

  12. Industrial catalysis-5 1970s Xylene Isom( for p-xylene) H-ZSM-5 Methanol (low press) Cu-Zn/Al2O3 Toluene to benzene and xylenes H-ZSM-5 Catalytic dewaxing H-ZSM-5 Autoexhaust catalyst Pt-Pd-Rh on oxide Hydroisomerisation Pt-zeolite SCR of NO(NH3) V/ Ti MTBE acidic ion exchange resin C7H8+C9H12C6H6+C8H10 Pt-Mordenite

  13. Industrial catalysis-6 1980s Ethyl benzene H-ZSM-5 Methanol to gasoline H-ZSM-5 Vinyl acetate Pd Improved Coal liq NiCo sulfides Syngas to diesel Co HDW of kerosene/diesel.GO/VGO Pt/Zeolite MTBE cat dist ion exchange resin Oxdn of methacrolein Mo-V-P N-C6 to benzene Pt-zeolite

  14. Industrial catalysis-7 1990s DMC from acetone Cu chloride NH3 synthesis Ru/C Phenol to HQ and catechol TS-1 Isom of butene-1(MTBE) H-Ferrierite Ammoximation of cyclohexanone TS-1 Isom of oxime to caprolactam TS-1 Ultra deep HDS Co-Mo-Al Olefin polym Supp. metallocene cats Ethane to acetic acid Multi component oxide Fuel cell catalysts Rh, Pt, ceria-zirconia Cr-free HT WGS catalysts Fe,Cu- based

  15. Industrial catalysis-8 2000+ • Solid catalysts for biodiesel - solid acids, Hydroisom catalysts • Catalysts for carbon nanotubes - Fe (Ni)-Mo-SiO2 For Developed Catalysts MAINLY IMPROVEMENT IN PERFORMANCE by New Synthesis Methods & use of PROMOTERS

  16. Green Chemistry is Catalysis • Pollution control (air and waste streams; stationary and mobile) • Clean oxidation/halogenation processes using O2,H2O2 (C2H4O, C3H6O) • Avoiding toxic chemicals in industry (HF,COCl2 etc) • Fuel cells (H2 generation) Latest Trends

  17. Catalysis in Nanotechnology Methods of Catalyst preparation are most suited for the preparation of nanomaterials • Nano dimensions of catalysts • Common prep methods • Common Characterization tools • Catalysis in the preparation of carbon nanotubes Latest Trends

  18. Catalysis in the Chemical Industry • Hydrogen Industry(coal,NH3,methanol, FT, hydrogenations/HDT,fuel cell) • Natural gas processing (SR,ATR,WGS,POX) • Petroleum refining (FCC, HDW,HDT,HCr,REF) • Petrochemicals (monomers,bulk chemicals) • Fine Chem. (pharma, agrochem, fragrance, textile,coating,surfactants,laundry etc) • Environmental Catalysis (autoexhaust, deNOx, DOC) Latest Trends

  19. HETEROGENEOUS CATALYSISAN INRODUCTION

  20. Steps of Catalytic Reaction - Diffusion of Reactants (Bulk to Film to Surface) - Adsorption - Surface Reaction - Desorption & Diffusion of Products

  21. porous carrier (catalyst support) bed of catalyst particles reactants substrate product reactor reaction desorption adsorption products catalyst support active site

  22. Role of Chemists & Chemical Engineers Team Work

  23. Catalysts Preparation • Wet impregnation: • Preparation of precursors (Cu & Zn-nitrates) solution • Impregnation of precursors on alumina support • Rotary vacuum evaporation • Drying • Calcination • Reduction Rotary vacuum evaporator

  24. Catalysts Preparation Co-precipitation Wet Impregnation

  25. Calcined WI CuO/ZnO/Al2O3 Catalyst

  26. Calcined WI CuO/ZnO/Al2O3 Catalyst

  27. Calcined Co-precipitation Co/Al2O3

  28. Commercial Ni/Al2O3

  29. Spent Commercial Ni/Al2O3

  30. Commercial Fe2O3 catalyst

  31. Spent Commercial Fe2O3 catalyst

  32. Auto-catalysts Pt, Pd and Rh on the Metox metallic substrates Pervoskite LATEST Research

  33. Honey Comb Catalysts

  34. CATALYST CHARACTERIZATION • Bulk Physical Properties • Bulk Chemical Properties • Surface Chemical Properties • Surface Physical Properties • Catalytic Performance

  35. Bulk Chemical Properties • Elemental composition (of the final catalyst) • XRD, electron microscopy (SEM,TEM) • Thermal Analysis(DTA/TGA) • NMR/IR/UV-Vis Spectrophotometer • TPR/TPO/TPD • EXAFS

  36. Surface Properties • XPS,Auger, SIMS (bulk & surface structure) • Texture :Surface area- porosity • Counting “Active” Sites: -Selective chemisorption (H2,CO,O2, NH3, Pyridine,CO2);Surface reaction (N2O) • Spectra of adsorbed species (IR/EPR/ NMR / EXAFS etc)

  37. Physical properties of catalysts • Bulk density • Crushing strength & attrition loss (comparative) • Particle size distribution • Porosimetry (micro(<2 nm), macro(>35 nm) and meso pores

  38. Catalysts Characterization

  39. BET Surface Area Analyzer Major role of Chemical Engineer with Chemists for Hardware Surface area, Pore Volume, Pore Size & Pore size distribution

  40. 7.0E-3 200 CZCEA2 180 6.0E-3 CZA2 (STP) 160 -1 0-1 g 140 5.0E-3 A 3 -1 g 120 3 4.0E-3 100 Volume adsorbed, cm 80 3.0E-3 Pore volume, cm 60 2.0E-3 40 20 1.0E-3 0 0 100 200 300 400 500 600 700 000.0E+0 10 100 1000 Relative pressure, P/P 0 0 Pore diameter, A Surface Area and Pore size Distribution P2CZCeA P2CZCeA P3CZA N2 adsorption/desorption Isotherm Pore size distribution by BJH method Barret, Joyner, and Halenda (BJH) P2CZCeA Cu/Zn/Ce/Al:30/20/10/40 P3CZA Cu/Zn/Al:30/20/50

  41. Chemisorption Analyzer Dispersion, Metal Surface area and Metal Particle size; TPR, TPO, TPD

  42. TGA/DTA Analyzers Coke measurement & TPO

  43. Reactions involved in SRM process CH3OH + H2O ↔ CO2 + 3H2 CO2 + H2 ↔ CO + H2O CH3OH ↔ 2H2 + CO Reactions involved in OSRM process CH3OH + (1-p)H2O +0.5pO2↔ CO2 + (3-p)H2 ∆H0 = (49.5 - 242*p) kJ mol-1 CH3OH + 0.75H2O + 0.125O2↔ CO2 + 2.75H2 ∆H0 = -10 kJ mol-1 ∆H300 oC = 0 kJ mol-1 CH3OH + 0.5H2O + 0.25O2↔ CO2 + 2.5H2 ∆H0 = -71.4 kJ mol-1 CH3OH + 0H2O + 0.5O2↔ CO2 + 2H2 ∆H0 = -192 kJ mol-1 CH3OH + 1.5O2 ↔ CO2 + 2H2O∆H0 = -727 kJ mol-1

  44. Catalyst Activity Testing • Activity to be expressed as: - Rate constants from kinetics - Rates/weight - Rates/volume - Conversions at constant P,T and SV. - Temp required for a given conversion at constant partial & total pressures - Space velocity required for a given conversion at constant pressure and temp

  45. Operating Conditions for SRM & OSRM

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