Anda di halaman 1dari 26

Industrial Catalysis

Arun Basrur
Süd-Chemie India Pvt. Ltd. (Clariant JV)
1st State Level Seminar Parul University
22 SEP 2017
This talk
Target audience
• Graduate and Post Grad Students

Objective
• Provide a flavor of catalysts & catalysis
• Impact on Society
• Touch upon inter-disciplinary nature of the
subject
• Cover current trends in this field
Some aspects about catalysts
• Catalysts are materials which alter {increase} the
rate of chemical reactions

• Vital to Global economy


– Worldwide demand 20.6 Bio US$ [2018] {1.3 x 10 5 Cr.
INR}
• Touch almost every walk of life yet little known to
the layman: Behind the scenes player

• “Heart” of the process


Aspects about catalysts…
• Preparation of HETEROGENEOUS catalysts described as an
‘ART’

• Catalysts – multicomponent – multifunctional:


‘OPTIMIZATION’ between multiple properties

• Catalysis multi-disciplinary

• Current Global R&D focus >> Sustainability, GHG


abatement, Green Processes; Water splitting, artificial
photosynthesis > Significant Global funding

• Vast intriguing subject – everlasting WOW factor


Diversity of application

Food - Fertilizer – Ammonia Clothing – Polyester; Acrylic Pollution control


7.5 Bn Population {1.34} GHG abatement / Sustainability

Energy - Fuels Medicine Plastics & Polymers


Transportation / Paints / Furnishing / Packaging / Communication / Entertainment
What catalysts can do

• Efficient chemical transformations > Better


productivity and economy

• Higher product selectivity than thermal reactions

• Less severe reaction conditions > Energy saving

• Clean ‘Green’ Chemistry


Example – Efficient transformation
Crude Oil Utilization
90%
• UOP Technologies
6 steps
6%

– 15 fold increase in yield of transportation fuels


derived from crude oil between 1920 to 2015

– Catalysts played an important role along with


engineering

– Reference: Six-Revolutions – Chapter 4 - The drive for


yield: www.uop.com
How catalysts work

• Chemical Reactions are transformations


• Existing chemical bonds break and new ones
are formed: Optimal bond strength of TS
Reactant + Catalyst  TS*  Product + Catalyst
SURFACE PHENOMENON
Diffusion
Adsorption R
Surface Reaction
Desorption TS
Diffusion
P
What catalysts cannot do
• Violate thermodynamics
– BUT can cheat thermodynamics: Molecular sieving

Zeolite
Thermodynamic Eq >>> 22 55 23
Shape selective Catalysis >> 0.05 0.25 99.7%
EB Ethylation
C2H4
& DEB
ZSM-5 Isomerization
EB DIETHYL BENZENE ISOMERS

• Are not eternal: Have life span


p-isomer diffusion
• Limited tolerance to poisons

• Magical Solutions>> Catalyst development is OPTIMAL COMPROMISE


Broad Types
Homogeneous Heterogeneous
• Same physical state as reactants and • Different physical state than
products reactants and products
PROS PROS
• High rates of reaction • Ease of separation
• Good control over selectivity
• Harsh reaction conditions
• Long life
• Defined structure
• Ease of disposal of spent catalyst

CONS CONS
• Mild reaction conditions • Diffusion limited – lower rates of
• Separation from product difficult reaction
• Expensive • Relatively lower selectivity
• Short life • Difficult to produce with
consistent quality & characterize
• Disposal of spent catalyst difficult
HAZARDOUS
Diversity of catalysts
• Materials ranging from single component system
– Ex: Sponge Nickel or Pt; -Al2O3
– Metal complexes
TO Multiple requirements to
service Diverse reaction
environments
• Highly Complex FORMULATIONS
– Supported metals
– Mixed oxides [6-10 elements]
– Metal ‘alloys’ Reactants
– Blends

• Adsorbents & Traps


– To remove impurities from feed streams Flow is important
Microstructure / Morphology
• Catalysis = Surface Phenomenon
WHICH
• Active phase and Carrier / Substrate for dispersion, ONE?
mechanical & thermal stability
• High surface area >> ‘Porosity’ Internal surface / ‘Nano’
Power of POROSITY = Power of SIZE

Reference: www.researchgate.net Reference: www.nano.gov


Pore Size & dP
• Size: Nano packing > less void space > Unmanageable Back
Pressure
• 1.0 mm particles > External surface area low > Porosity necessary
• Size of reactant and product molecules [Diffusivity]

Opt. Reactant-Catalyst collisions

Reference: www.researchgate.net Ind. Eng. Chem. Res. 34 (1995) pp 2202


Porous or Nano???
Sp. Surface area = f{1/Pore size}
Nanomaterials - Au active only in nanosize

Win-Win situation
‘COMPROMISE’
• Carrier: Sacrifice nanosize, get
moderate porosity & surface area
• Get high Pd ‘active’ surface area
‘Nano’

• HR-TEM of Pd / -Alumina: Ref: Applied Catalysis B:


Environmental 97 (2010) 57–71
Selection of actives
• Reactivity for main reaction and side reactions
– Match properties with classical organic reaction mechanism
• Properties of elements/compounds
– Electronegativity
– % d character
– Acid-base character
– Redox character
– {Semi}conductor
– Melting Point

First
Approximation

Plots Reference: www.researchgate.net


Selection of carrier / substrate
MELTING / FUSION

– Thermal stability
• High reaction temperature 950-
1100◦C; [Steam Reforming]
• Frequent or Continuous catalyst
regeneration [Fast deactivation
– thermal shock] [FCC /CCR
naphtha reforming]
• REFRACTORY OXIDES /
CARRIERS
• ‘Sacrifice surface area’
– M-M & MSI Interaction
[Retard metal sintering] Photo Reference: Steam Reformer
GBH Enterprises
Carriers / substrates….

Mechanical strength / Abrasion resistance


– High pressure 150 bar g
– High reactant flow velocity; Moving bed, Fluid bed
reactors
– BINDERS
– Compaction
– ‘Sacrifice porosity’
BREAKAGE / POWDER

Picture reference: CFD-DEM simulation of


Circulating Fluidized reactor ; DCS Computing
Catalyst Deactivation

• Loss of active component


– Loss of surface area > Thermal Sintering
– Chemical Leaching
– Phase transformation

• Fouling
– Carbonaceous deposits
– Poisons {S, Cl, As, Hg, H2O}
• Temporary / Inhibition
• Permanent

• Loss of thermal mechanical strength: Increased


pressure drop
Pic Reference: www.researchgate.net
Catalyst Development
• Precipitation / Crystallization /
Impregnation
Preparation
• Drying / Calcination / Reduction

• Microstructure / Crystal phase


Characterization • Acidity / Dispersion / Reducibility

• Model reaction testing


Evaluation • Reaction Kinetics
Multi-disciplinary subject
Preparation: Carrier & Bulk catalysts
Equipment design
Selection / Precipitation / Crystallization
Kinetics
Design Mixing and Process controls
Scale-up
Solids recovery / Washing - channeling
Chemical Engineering
Supported cats: Impregnation / CVD
Uniform Drying / calcination / reduction
Material selection & analysis
Corrosion resistance
Inorganic & Organic Chemistry
Analytical Chemistry
Characterization
Spectroscopy
Physical Properties
Pulse Chemisorption / TP Techniques
Characterization
DSC-TG
Physical Chemistry
Physisorption
Chemical composition
Modeling – Simulation
Computer Programming
Performance Evaluation
Mathematics & Statistics
Reactor selection / Channeling
Heat & Mass transfer
HTS; Kinetic Modeling
Reactor Design - Engineering
Reactants Reactants

Coolant

• Mild to moderate heat • Highly exothermic reactions


changes; slow deactivation • Multi-tubular fixed bed – gradient catalysts
• Fixed Bed reactors • Fluid bed reactors
• Catalyst particle Dimension • Catalyst particle dimension 20-70m
1.2+ mm • High abrasion resistance
• Type of reactor • Loss of selectivity – back-mixing
• Heat and Mass transfer
• Managing heat of reaction
• Reaction Kinetics and Sizing reactor
Engineering Solutions
Fast deactivation: hours V. Fast deactivation: seconds scale
scale Moving bed or Circulating catalyst
Parallel fixed bed reactors reactors

Reaction Regeneration
Example – H2 production

ZnO Trap Thermally stable Fe-Cr Cu-Zn Ni Catalyst PSA


Co-Mo HDS Ni based catalysts Catalyst Catalyst
catalyst

Complexity - Train of catalysts and adsorbents working in tandem


Reference: nptel.ac.in/module2
Example - Naphtha Reforming
Multi-functionality: Pt-Sn/Cl-Alumina

Reference: What-when-how.com
State of the art
Catalyst preparation “An ART”
– Hitherto Limitations in determining structure-property correlations

ENABLERS: ART >>> SCIENCE


• ALD [Atomic Layer Deposition]
– Enables structuring the surface of the catalyst

• OPERANDO Spectroscopy
– Understanding of structure-activity relations under reaction
conditions

• High Throughput Screening


– Robotic Parallel synthesis and performance evaluation

• Models for catalyst design: Predictive modeling / DEM / DFT


Catalysis is Collaboration
THANK YOU