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Introduction Principle of catalysis Nanocatalysis in Petroleum Refining and Petrochemicals Industries Research Activities on Nanocatalysts Conclusion
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Nanocatalysts in Refining & Petrochemical Processes
Gerard B. Hawkins Managing Director
Introduction Principle of catalysis Nanocatalysis in Petroleum Refining and Petrochemicals Industries Research Activities on Nanocatalysts Conclusion
Table of Contents
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
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
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
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
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 G
Ea
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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 G
Ea
9
Principle of Catalysis
Normally catalyst surface must
have the high active energy, right
structure, and enough spaces. C + catalyst
A + B + catalyst G
Ea
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Catalysis: in Chemical Indusrty Applications
Catalysis
Petroleum refining
Petro- chemicals
Fertilizer& Inorganic chemicals
Pharma- ceutical
Fine & Agro
chemicals
Environ- mental
protection
11
Industrial Catalyst Developments
Industrial application
Side Stream stage
Pilot stage
Lab work
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
Key Elements of Development & Commercialization of Catalysts
Process engineering / Instrumentation/Construction
Process licensing
Manufacture
Marketing Technical services
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 (Silicaaluminas) by the Y zeolite exchanged with alkaline earth ions.
15
Refinery Catalysts
Isomerization of Light Alkane Brnsted 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
World Consumption of Petroleum Refining and Chemical Processing catalysts
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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.
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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.
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
Nanocatalysts in Petroleum and Petrochemical Industries
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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
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.
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Nanocatalysis in Petroleum and Petrochemical Industries
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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
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
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
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
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
Biomass gasification to produce high syn gas and biomass pyrolysis for bio-oil Nano NiO/- 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
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
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Applications of Nanocatalysts
~ 0.1- 1.0 mm
Microchannel
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)-13-(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
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
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
Synthesis of active nanocatalysts
Electrochemical deposition methods
Solgel or colloidal techniques
Depositionprecipitation and impregnation methods
Molecular cluster precursors
Methodologies investigated
36
Synthesis of active nanocatalysts Catalyst Prep by Fluidized Bed CVD Reactor
37
Synthesis of active nanocatalysts Catalyst Prep by Gs Phase Deposition
38
Synthesis of active nanocatalysts
TEM images of Pt NPs synthesized by encapsulation in PS-P2VP diblock copolymer micelles and supported on nanocrystalline ZrO2.
Gas-phase flow reactor for optimizing reaction parameters
Catalysts Characterization
42
GBHE Research Activities on Nanocatalysts
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
44
HDS of Diesel using Nano Mixed Oxide Catalysts
Size Particle ( nm )
Catalysts
25-90 CoMoOx/Al2O3
(acidic)
25-250 CoMoSx/Al2O3
(acidic)
25-90 CoMoOx/-Al2O3
25-100 CoMoSx/-Al2O3
10-65 MoO3
10-80 MoS
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 300-350C at atmospheric pressure.
All catalysts showed uniform crystallites, smaller particles were obtained after sulfidation process.
Nano MoS2 are agglomerated in a sphere-like structure.
46
HDS of Diesel using Nano Mixed Oxide Catalysts
SEM of Nano MoSx Catalyst
SEM of Nano CoMoOx/-Al2O3 Catalyst
Typical nano CoMoOx/-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.
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
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 Fr
eque
ncy
Low activity
Low stability
KOPRC 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:
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.
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