Introduction Principle of catalysis Nanocatalysis in Petroleum Refining and Petrochemicals Industries Research Activities on Nanocatalysts Conclusion

1. Nanocatalysts in Refining &
Petrochemical
Processes
Gerard B. Hawkins
Managing Director

2. Introduction
Principle of catalysis
Nanocatalysis in Petroleum Refining and
Petrochemicals Industries
Research Activities on Nanocatalysts
Conclusion
Table of Contents

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
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
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
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
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
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
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
Catalysis: in Chemical Indusrty
Applications
Catalysis
Petroleum
refining
Petro-
chemicals
Fertilizer&
Inorganic
chemicals
Pharma-
ceutical
Fine &
Agro
chemicals
Environ-
mental
protection

11. 11
Industrial Catalyst Developments
Industrial application
Side Stream stage
Pilot stage
Lab work

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
Key Elements of Development &
Commercialization of Catalysts
• Process engineering / Instrumentation/Construction
• Process licensing
• Manufacture
• Marketing
• Technical services

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
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
World Consumption of Petroleum
Refining and Chemical Processing catalysts

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
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. 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
Nanocatalysts in Petroleum
and Petrochemical Industries

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
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
Nanocatalysis in Petroleum
and Petrochemical Industries

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
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
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
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
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
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
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
Applications of Nanocatalysts
~ 0.1-
1.0
mm
Microchan
nel

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
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
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
Synthesis of active nanocatalysts
Electrochemical deposition methods
Sol–gel or colloidal techniques
Deposition–precipitation and impregnation methods
Molecular cluster precursors
Methodologies investigated

36. 36
Synthesis of active nanocatalysts
Catalyst Prep by Fluidized Bed CVD Reactor

37. 37
Synthesis of active nanocatalysts
Catalyst Prep by Gs Phase Deposition

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. Gas-phase flow reactor for optimizing reaction parameters

40. Catalysts Characterization

42. 42
GBHE Research Activities on
Nanocatalysts

43. 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. 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

45. 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.

46. 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.

47. 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. 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:

49. 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.

50. 50