Nanocatalysts in Refining & Petrochemical Processes

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

8


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


Normally catalyst surface must

have the high active energy, right

structure, and enough spaces. C + catalyst

A + B + catalyst G

Ea

10

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

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

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

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


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


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

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

31

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


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


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


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


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.

Slide Number 1Slide Number 2Slide Number 3Slide Number 4Slide Number 5Slide Number 6Slide Number 7Slide Number 8Slide Number 9Slide Number 10Slide Number 11Slide Number 12Slide Number 13Slide Number 14Slide Number 15Slide Number 16Slide Number 17Slide Number 18Slide Number 19Slide Number 20Slide Number 21Slide Number 22Slide Number 23Slide Number 24Slide Number 25Slide Number 26Slide Number 27Slide Number 28Slide Number 29Slide Number 30Slide Number 31Slide Number 32Slide Number 33Slide Number 34Slide Number 35Slide Number 36Slide Number 37Slide Number 38Slide Number 39Slide Number 40Slide Number 41Slide Number 42Slide Number 43Slide Number 44Slide Number 45Slide Number 46Slide Number 47Slide Number 48Slide Number 49Slide Number 50Slide Number 51

Technology

Nanocatalysts in Refining & Petrochemical Processes