Nanocatalysts in Refining & Petrochemical Processes


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Principle of catalysis

Nanocatalysis in Petroleum Refining and
Petrochemicals Industries

Research Activities on Nanocatalysts


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Nanocatalysts in Refining & Petrochemical Processes

  1. 1. Nanocatalysts in Refining & Petrochemical Processes Gerard B. Hawkins Managing Director
  2. 2. Introduction Principle of catalysis Nanocatalysis in Petroleum Refining and Petrochemicals Industries Research Activities on Nanocatalysts Conclusion Table of Contents
  3. 3. 3 Introduction  Catalysts systematically have been used at least since the beginning of the industrial age. In a sense, all catalysis is nanoscale, since it involves chemical reactions at the nanoscale, and today their use is widespread in industries such as petroleum refining, petrochemicals and other chemical industries.
  4. 4. 4 Introduction  The focus on principle of catalyst, cleaner fuels, and lower cost petrochemicals has driven the refining and petrochemical industries towards improvements in conventional catalysts and, in several cases, to the introduction of new nanocatalysts.
  5. 5. 5 Growth in the worldwide nanocatalysts market is driven by the ever-increasing demand from polymer manufacturers, refining and petrochemical industries.  Nanomaterials offer many possibilities as catalysts to meet future demands in catalytic process technologies in petroleum refining, petrochemical, and synthetic fuels production of the future. Introduction
  6. 6. 6 Principle of catalysis Many experimental studies on nanocatalysts have focused on correlating catalytic activity with particle size. While particle size is an important consideration, many other factors such as geometry, composition, oxidation state, and chemical/physical environment can play a role in determining NP reactivity. The exact relationship between these parameters and NP catalytic performance may be system dependent, and is yet to be laid out for many nanoscale catalysts.
  7. 7. 7 Principle of Catalysis • Catalyst is a substance that increases the rate of a chemical reaction by reducing the required activation energy, and alter the required reaction temperature. C + catalyst A + B + catalyst ΔG Ea′
  8. 8. 8 Principle of Catalysis • Catalyst provide a site for the reactants to be activated and interacted together while leaving the catalyst surface unchanged after the reaction. C + catalyst A + B + catalyst ΔG Ea′
  9. 9. 9 Principle of Catalysis • Normally catalyst surface must have the high active energy, right structure, and enough spaces. C + catalyst A + B + catalyst ΔG Ea′
  10. 10. 10 Catalysis: in Chemical Indusrty Applications Catalysis Petroleum refining Petro- chemicals Fertilizer& Inorganic chemicals Pharma- ceutical Fine & Agro chemicals Environ- mental protection
  11. 11. 11 Industrial Catalyst Developments Industrial application Side Stream stage Pilot stage Lab work
  12. 12. 12 Key Elements of Development & Commercialization of Catalysts • Research & Development • Innovation/Intellectual Property Rights • Pilot scale efforts, scale up & process economics • Product & Process technology development
  13. 13. 13 Key Elements of Development & Commercialization of Catalysts • Process engineering / Instrumentation/Construction • Process licensing • Manufacture • Marketing • Technical services
  14. 14. 14 Refinery Catalysts Catalytic Reforming of naphtha • Metal-Acid bifunctional Catalyst, •UOP (Platinum), Total (Tin), Chevron (Rhenium), Exxon (iridium). Hydrotreating Process •Sulfur metal-type catalysts (Mo, W) with (Co, Ni). Hydrocracking Process •The bifunctional metal sulfide phase catalyst,of the same type as the HD catalysts. •Amorphous (Silica–aluminas) by the Y zeolite exchanged with alkaline earth ions.
  15. 15. 15 Refinery Catalysts Isomerization of Light Alkane •Brønsted superacid catalyst (HAlCl4), the first to be used industrially. •Bifunctional Pt based, supported on chlorinated alumina or on Mordenite catalysts. Alkylation of Isobutane-Butane •Liquid Acid Catalysts, (H2SO4 and HF) are still used today. •Solid acid catalysts, Acid Zeolites (Shell, Akzo), Triflic Superacid on porous silica (Topsoe), and Solid Acid (UOP). Oligomerization of Olefins into Petroleum Cuts • Phosphoric Acid supported on Silica (SPA), zeolite (ZSM-5). •Ni-Mordenite, Mesoporous Silica-Alumina, Acid Resin, Ni-based in the liquid phase.
  16. 16. 16 World Consumption of Petroleum Refining and Chemical Processing catalysts
  17. 17. 17 The Challenges of Refining and Petrochemical Industries • Constraints in feedstock with respect to availability, quality and cost. • Eco friendly processes & products: stringent emission levels. • Need for conserving energy. • Waste minimization/effective treatment.
  18. 18. 18 The Challenges of Refining and Petrochemical Industries •Catalysts with higher efficacy: activity/selectivity/ life. • Process improvements: milder conditions/fewer steps. • produce essential fuels and chemicals at an acceptable cost. •Reduce costs in face of competitive pressures, and to meet the changing demand of customers.
  19. 19. Nanocatalysis in Petroleum and Petrochemicals Industries • Objective of Nanocatalysts Research. • Nanocatalysts Preparation Methods. • Benefits of Nanocatalysts in Chemical Industry. • Global Market for Nanocatalysts. • Applications of Nanocatalysts. Research Activities on Nanocatalysts Conclusion 19
  20. 20. 20 Nanocatalysts in Petroleum and Petrochemical Industries
  21. 21. 21 Nanocatalysis in Petroleum and Petrochemical Industries • Objective of Nanocatalysis Research : is to produce catalysts with 100% selectivity, extremely high activity, low energy consumption, and long lifetime. • The approaches: Precisely controlling the size, shape, spatial distribution, surface composition, electronic structure, and thermal and chemical stability of the individual nanocomponents. • Nanoparticles: have a large surface-to-volume ration compared to bulk materials, a few billionths of a meters in dimension to speed up chemical reactions, they are attractive candidates for use as catalysts.
  22. 22. 22 Nanocatalysis in Petroleum and Petrochemical Industries The key point for the nano- materials lies in that it has high surface area of the crystal, thus to give higher atomic utilization ratios, the surface electronic and steric properties all changes. Doping heteroatoms over the nano-materials surface would give much large effect.
  23. 23. 23 Nanocatalysis in Petroleum and Petrochemical Industries
  24. 24. 24 Nanocatalysis Preparation Methods •Chemical Reduction Method. Reduction of transition metal salt in solution to form the nanoparticales. •Thermal, Photochemical and Sonochemical Reduction Method. •Decomposition of the precursor organometallic salt to the zerovalent form. •Ligand Displacement Method. •Displacement of ligand in the organometallic complex. •Condensation of Metal Vapor Method. •Evaporation of transition metal vapors at reduced pressure and subsequent co- condensation of these metals at low temperature with organic vapors. •Electrochemical Reduction Method. •Precursor metal ions are reduced at the cathode using anode as the metal source Homogeneous Nanocatalyst Preparation Methods (for Colloidal):
  25. 25. 25 Nanocatalysis Preparation Methods Heterogeneous metal nanocatalyst are prepared by adsorption of nanoparticles onto support, witch involves functionalization of support to adsorb nanoparticle on to them. Heterogeneous Nanocatalyst Preparation Method:
  26. 26. 26 Benefits of Nanocatalysts in Chemical Industry Increasing selectivity and activity of catalysts by controlling pore size and particle characteristics. Replacement of precious metal catalysts by catalysts tailored at the nanoscale and use of base metals, thus improving chemical reactivity and reducing process costs.
  27. 27. 27 Global Market for Nanocatalysts Sectors Market, % (2005) Refining / Petrochemicals Chemicals / Pharmaceuticals Food Processing Environmental Remediation 38.0 % 19.6 % 19.0 % 13.4 % $ 3.3 b $ 3.7 b
  28. 28. 28 Applications of Nanocatalysts Nanomaterials offer many possibilities as catalysts to meet future global demands in the following catalytic process technology: Petroleum refining. Petrochemical industry. Synthetic fuels production. Polymer manufacturing. Pharmaceutical, chemical, food processing.
  29. 29. 29 Biomass gasification to produce high syn gas and biomass pyrolysis for bio-oil Nano NiO/γ- Al2O3 Production of biodiesel from waste cooking oil Solid acid nanocatalysis of Al0.9H0.3PW12O40 with surface area of 278 m2/g Green Diesel production using Fischer-Tropsch (Fe and Co) powders 10-50nm, promoted by Mn, Cu and alkalis. Improved economic catalytic combustion of JP-10 aviation fuel Hexanethiol monolayer protected Palladium clusters < 1.5nm Industrial Applications of Nanocatalysts
  30. 30. 30 Hydrogen production by steam reforming of ethanol over nanostructured catalyst Mesoporous In2O3, particle size 2-3 nm. Adsorptive desulfurization and bio desulfurization of fossil oils Nano Al2O3 with surface area 339m2/g. Hydrodesulfurization of diesel Nano NiMo/Al hexagonal, by supercritical deposition method. Industrial Applications of Nanocatalysts
  31. 31. 31 Applications of Nanocatalysts ~ 0.1- 1.0 mm Microchan nel
  32. 32. 32 Research Activities on Nanocatalysts Comparison of catalytic activities (turnover frequency, TOF, in s −1) for CO oxidation on a bilayer Au film [Mo(112)- 1×3-(Au, TiOx)], a bilayer Au NP [Au/TiO2(110)], and an hemispherical Au NP supported on high-surface area TiO2 with a mean particle size of ∼ 3 nm. The inserts show structural models using red and blue marks to indicate active sites.
  33. 33. 33 GBHE Research Activities on Nanocatalysts Factors that are presently believed to play a significant role in the catalytic reactivity of supported metal clusters; the structure (size and shape), chemical composition, oxidation state, interparticle interactions, reactivity of nanocatalysts,
  34. 34. 34 Synthesis of active nanocatalysts Thermal evaporation in vacuum Electron-beam lithography and pulsed laser deposition Buffer-layer assisted growth Chemical vapor deposition Gas condensation, ionized cluster beam deposition Methodologies investigated
  35. 35. 35 Synthesis of active nanocatalysts Electrochemical deposition methods Sol–gel or colloidal techniques Deposition–precipitation and impregnation methods Molecular cluster precursors Methodologies investigated
  36. 36. 36 Synthesis of active nanocatalysts Catalyst Prep by Fluidized Bed CVD Reactor
  37. 37. 37 Synthesis of active nanocatalysts Catalyst Prep by Gs Phase Deposition
  38. 38. 38 Synthesis of active nanocatalysts TEM images of Pt NPs synthesized by encapsulation in PS- P2VP diblock copolymer micelles and supported on nanocrystalline ZrO2.
  39. 39. Gas-phase flow reactor for optimizing reaction parameters
  40. 40. Catalysts Characterization
  41. 41. 42 GBHE Research Activities on Nanocatalysts
  42. 42. 43 Clean fuel distillates using supported Nanocatalyst Very active supported nanocatalyst were prepared for converting mixture of olefins into clean fuel distillates in the range of gasoline, jet fuel and diesel; free of sulphur, nitrogen and aromatic compounds. • Catalyst : Nano-transition metal oxides supported on non-metal oxide. • Durability : Long life time and it could be regenerated. •The fuel distillates : Free Sulfur, Nitrogen, and Aromatic. •Particle size : 25-300 nm. •Conversion : 99 % • Octane Number : 85 98
  43. 43. 44 HDS of Diesel using Nano Mixed Oxide Catalysts Size Particle ( nm ) Catalysts 25-90 CoMoOx/Al2O3 (acidic) 25-250 CoMoSx/Al2O3 (acidic) 25-90CoMoOx/γ-Al2O3 25-100CoMoSx/γ-Al2O3 10-65MoO3 10-80MoS
  44. 44. 45 HDS of Diesel using Nano Mixed Oxide Catalysts SEM of Nano MoSx Catalyst SEM of Nano MoO3 Catalyst •Nano catalysts showed good activities in HDS of thiophen at 300-350°C at atmospheric pressure. •All catalysts showed uniform crystallites, smaller particles were obtained after sulfidation process. •Nano MoS2 are agglomerated in a sphere-like structure.
  45. 45. 46 HDS of Diesel using Nano Mixed Oxide Catalysts SEM of Nano MoSx Catalyst SEM of Nano CoMoOx/γ-Al2O3 Catalyst •Typical nano CoMoOx/γ-Al2O3 fringes are visible with slab thickness between 5 to 10 nm and lengths up to 10nm. The long slabs were curved producing onion like.
  46. 46. 47 Supported Nanocatalysts Produce Additives for Gasoline and Jet Fuels • Novel supported metal oxide nanocatalysts were developed for gasoline and jet fuels additives to raise the octane number and improve the fuel combustion. • Dimerization of olefins reaction of significant number of carbon atoms ranging from (2 – 5) were carried out to produce branched alkylates of (C8) as additives. • Conversion : 95% • Yield : 65% to branched alkylates of (C8) • Octane number : 88-98
  47. 47. 48 New Method for Catalysts Preparation in Nano Scale • Stabilize the metal active components, and keep them in nano-scale level. • Adjust the metal and support interaction to give the right electronic property of the active cluster. • Give the right and even size of the active phase, to maximize the active sites. Metal Crystallite Size Frequency Low activity Low stability KOPR C Other More Site Few Sites In this method, the key point is to add proper organic compounds into the impregnation solution system, which can lead to:
  48. 48. 49 Conclusions  Nanomaterials offer many possibilities as catalysts to meet future demands in catalytic process technology in petroleum refining, petrochemical industry, and synthetic fuels production of the future.  The higher activity and better selectivity of nanocatalysts over traditional catalysts are attributed to their large specific surface area, high percentage of surface atoms and special crystal structures.  The development of nanocatalysts is increasingly supported by advances in preparation, characterization and testing of catalysts.
  49. 49. 50
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