WELCOME

TO

CL 641: Process Intensification and Integration

(July Nov 2017)

INSTRUCTOR
Dr. Nageswara Rao Peela
Room 304, Department of Chemical Engineering
(email: peelanr@iitg.ernet.in, Phone: XXX3526)

Teaching Assistants
Mr. Ponnala Rambabu (Research Scholar)
Mr. Velaga Bharath (Research Scholar)
 About Me
Research Interests
Heterogeneous Catalysis and reaction
engineering
Biomass conversion to value added chemicals
Bio-oil up-gradation to transportation fuels
Metal encapsulated zeolites
Optofluidic devices for Hydrogen production

Website: http://www.iitg.ernet.in/chemeng/nrp.html
 CL 641 - TEXTBOOKS/RESOURCES
Texts/Reference books:
D. Reay, C. Ramshaw and A. Harvey, Process intensification:
engineering for efficiency, sustainability and flexibility, (1st Ed.)
Butterworth-Heinemann, Burlington, 2008
A. Stankiewicz and J.A. Moulijn (Editors); Re-engineering the
chemical processing plant: process intensification; Marcel
Dekker, New York, 2004.
K. Boodhoo and A. Harvey (Editors) Process intensification for
green chemistry: engineering solutions for sustainable
chemical processing; John Wiley, West Sussex, 2013
F.J. Keil (Editor) Modeling of process intensification; Wiley-VCH
verlag, 2007
R. Smith, Chemical Process: Design and Integration, (8th Ed.)
John Wiley & Sons, Chichester, 2005
 Evaluation Scheme

Component Weightage (%)

4 Class Tests (Closed book, best 3) 3x10 = 30

Mid-Sem Exam (Closed book) 20
End-Sem Exam (Closed book) 30
Term Project 20
 What I expect of you
General Expectations
Ask question(s) whenever something is not clear to
you
Help each other understand the course material
Arrive on-time for class
Provide me with feedback/suggestions on how
the course and my delivery can be improved
 Course Contents
Sl. # of Lectures
Lecture Topic (Tentative)
No. (tentative)
1 Introduction, principles and approaches of 4
PI.
Approaches:
Structure
Synergy
Energy and
Time
2 Special Domain (Structure): 10
Design and Applications of:
Microchannel reactors
Monlithic reactors and
structured Reactors
 Course Contents (Continued)
Sl. # of Lectures
Lecture Topic (Tentative)
No. (tentative)
3 Functional Domain (Synergy): 10
Reactive separations: (Reactive
distillation, Reactive extraction,
Reactive absorption, Dividing-Wall
Column for Reactive Distillation,
Reaction with Membrane Separation)
Heat integrated reactors
4 Thermodynamic Domain (Energy): 8
Electric field,
Magnetic field,
Microwave,
Hi-gee (Spinning disc Reactor),
Cavitational Reactor
 Course Contents (Continued)
Sl. # of Lectures
Lecture Topic (Tentative)
No. (tentative)
5 Inline and High Intensity Mixers 2
6 Simulated moving bed Chromatography 2
7 Implementation of PI at industrial level 2

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Context
Rapid Depletion of Petroleum
Environment
Safety of Chemical Plants
Out-dated technologies (A large scope for
improvement)
Cost
 Context: Rapid Depletion of Petroleum

Depletion rate depends on:

New technologies with higher efficiency
% of alternative energy resources
http://www.eia.gov/pub/oil_gas/petroleum/feature_articles/2004/worldoilsupply/oilsupply04.html
Context: Environment
 Context: Safety

Methylisocynate leakage HPCL blast in Visakhapatnam, Aug,

Nearly 3,800 dead and 2013
2720 permanently
disabled
 Context: Safety

Did we learn any

lessons?
 Context: Out-dated Technologies

No much difference in technologies used in 2012 to

those used in 1500s
 Context: Costs

At some point of time a critical limit will be reached

with the conventional technologies.
 Process Intensification (PI)
Definition:
Ramshaw (1983): devising an exceedingly compact plant
which reduces both main plant item and installation costs.
Cross and Ramshaw (1986): strategy of reducing the size of
chemical plant needed to achieve a given production
objective.
ERPI (2008): provides radically innovative principles
(paradigm shift) in process and equipment design which can
benet (often with more than a factor two) process and chain
efciency, capital and operating expenses, quality, wastes,
process safety and more.

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Process Intensification

Sky-scraping distillation towers of the naphtha-cracking unit

are replaced by a compact, clean and tidy indoor plant
 Questions

What are the areas where PI is possible?

What is the role of PI to mitigate above
mentioned problems?
What are the constraints in applying PI to
industry?
 Benefits from PI
Cheaper Processes

Smaller Equipment/Plant

Safer Processes
Benefits
Less Energy consumption
from PI
Shorter time to market

Less waste/by-products

Better Company Image

 Benefits from PI: Costs
Land costs
Other investment costs
Costs of raw materials
Costs of utilities
Costs of waste processing

Up to 50% of cost saving can be achieved by using PI.

Example: Reactive Distillation
 Benefits from PI: Safety
PI ensures safety
Smaller equipment
Lesser equipment
Better control
Efficient heat removal
Uniform distribution of gas-liquid flow

The first solution to a process safety problem should

always be to get rid of the hazard, but not control it.
 Benefits from PI: Time to Market
Conventional approach:
Stirred talk Bigger stirred tank Even bigger tank
Scale-up is not straightforward

PI approach
Batch to continuous
Process development only once
The lab scale technology is the commercial-scale technology

Better utilization of patent life.

Status of PI
Underlying Principles of PI
Typical Chemical Process

Reactants

Undesirable
Bi-products
A Conventional Chemical Reactor
Mass
Transfer Fluid
Heat Mechanics Safety
Transfer

REACTANT(S) PRODUCT(S)
REACTOR

Thermodynamics
Reaction Economics
Kinetics
 Chemical Reactor with PI

REACTANT(S) PRODUCT(S)
REACTOR

Reaction Economics
Kinetics

This view suffers from the drawbacks of using

old paradigms
PI Toolbox
 Principles or Goals of PI
Principle 1: Principle 2:
Maximizing the
Giving each
effectiveness of
molecule the same
intra- and
processing
intermolecular
experience
events

Principle 3: Principle 4:
Optimizing the driving Maximizing
forces and maximizing synergistic effects
the specific surface areas from partial
to which these forces processes
apply

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Challenges at Molecular Level

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Principle 1: Maximize the Effectiveness of
Intra- and Intermolecular Events
Collision theory says, effectiveness of reaction
depends on:
Number/frequency of collisions
Geometry of approach
Mutual orientation of molecules
Their energy

Decides the conversions, selectivities, and side-

products

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Principle 1: Maximize the Effectiveness of
Intra- and Intermolecular Events

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

Principle 1: Maximize the Effectiveness of
Intra- and Intermolecular Events
+ =

= 0

Maxwell Boltzmann
Distribution
 Principle 2: Same Processing Experience to
Each Molecule

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Principle 3: Optimizing the driving forces
and maximizing the specific surface areas
to which these forces apply

Counter-current HE Co-current HE
HT is more in the case of Counter-current HE
as compared to that in Co-current HE
Stankiewicz, Trans. IChemE, Part A: Chem Eng. Res. Des. 84(A7) (2006) 511
 Principle 4: Maximizing synergistic effects
from partial processes

Stankiewicz, Trans. IChemE, Part A: Chem Eng. Res. Des. 84(A7) (2006) 511
 Approaches of PI
Approach 1: Approach 2:

ENERGY
STRUCTURE
(Thermodynamic
(Spatial domain)
domain)

Approach 3: Approach 4:

SYNERGY TIME
(Functional domain) (Temporal domain)

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Summary: PI Principles and Approaches

Switching from batch to continuous processing also comes under

temporal approach of PI

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Methods for
controlling
molecular alignment
and orientation
Orientation control via Alignment and
nano-structural orientation control via
confinement external field
Shape-selective catalysts Molecular beam
Molecular Catalysts Electric fields
(Cyclodextrins) Magnetic fields
Imprinted Catalysts Non-resonant laser
Liquid Crystals

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 STRUCTURE: Molecular Reactors

Cyclodextrins
Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465
 STRUCTURE: Molecular Reactors

Br

Br

Bromination of
acetamidobenzene
Barr et al., J. Incl. Phen. Macrocyclic Chem. 50 (2004) 19.
 STRUCTURE: Molecular Reactors
4-Hydroxybenzoic acid synthesis

Komiyama and Hirai J am Chem Soc 106 (1984) 174.

 STRUCTURE: Molecular Reactors
4-Hydroxybenzoic acid synthesis

Komiyama and Hirai, J am Chem Soc 106 (1984) 174.

 Shape Selective Catalysis by Zeolites

Controlled placement of reactant molecules

(Source: HS Fogler)
 Static Mixer Reactor

HTM: Heat Transfer

Medium

Efficient Mixing + Heat removal can be carried out using

Static-mixer-reactor.
Ex.: Nitration, Neutralization and Polymerization reactions
 Static Mixer (with Solid-catalyzed
Reaction)

Corrugated Plate Static Mixer

Efficient Mixing + solid-catalyzed reaction can be

carried out using open-crossflow-structure catalysts.
Ex.: KATAPAK
 Monolithic Reactor
Megnesia:Silica:Alumina = 2:5:2

Catalytic converter in a vehicle

Very low P (1 2 OM lower)
1.5 4 times high geometrical area
100% Catalyst efficiency
Metallic or nonmetallic bodies forming a multitude of
straight, narrow channel of uniform shapes.
Ex.: Catalytic converter
Nijhuis et al., Catal. Rev. 43 (2001) 345.
 Monolithic Reactor

Nijhuis et al., Catal. Rev. 43 (2001) 345.

HEX-Reactor

Very high heat exchange rates with HT coeff.s up to

7,500W/m2K and HT areas 2,200 m2/m3.
Decreases the by-product formation by 75% and processing
time by 98.6% (18 h 15 min) in a fine chemical process
 Microchannel plates and Micro-devices

Catalyst coated
microchannle plate Reformer
Integrated Device: Reformer, WGS,
Heat exchanger

Integrated Device with Heat exchanger Grooved plates to prevent heat

guiding plates transfer

HT coefficients up to 35,000 W/m2K are reported

 Energy

At Micro-scale At Macro-scale
Electric fields High-Gravity fields
Microwaves Electric fields
Photo-reactions (Light)
Ultra-sound
Hydrodynamic
Cavitation

Stankiewicz, Trans. IChemE, Part A: Chem Eng. Res. Des. 84(A7) (2006) 511
 Light: Single-Step Water Splitting
Eg = band gap energy
Reduction site e- = electron
h+ = hole
C.B. = conduction band
V.B. = valance band

H2O H2 + O2
Go = 237.13 kJ/mol
Constraints:
h > 3 eV
VB edge-Potential > 0.82 eV
Oxidation site CB edge-Potential < -0.41 eV
Maeda, ACS Cat. 3 (2013) 1486
Light: Z-Scheme Water Splitting
H2 Evolving cat.

A = electron acceptor
D = electron donor
Eg1 & Eg2 = band gap energies
e- = electron
h+ = hole
AE Membrane C.B. = conduction band
V.B. = valance band
O2 Evolving cat.
High-Gravity Fields: Spinning Disc Reactor

In this reactor all the three processes (Heat, mass

and momentum transfer) can be intensified.
HT coefficients up to 10,000 W/m2K are reported
 Electric Field: Electroemulsification
Energy saving 2 orders
of magnitude
Highly effective for high
viscous fluids

Karyappa et al., Langmuir 32 (2016) 46

 Goal 2: Same Processing Experience to
Each Molecule

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Approach 2 for Goal 2: Same Processing
Experience to Each Molecule
Microwave Heating:
Dipole rotation
Ionic conduction

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Synergy (functional)

At Micro-scale At Macro-scale
Bifunctional Catalysts Multifunctional
Encapsulating Reactors
homogeneous catalysts Hybrid separations
Sonochemistry
microwave heating

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

 Atomic Architecture Plays a Pivotal
Role in Emergent Materials
14 amu
3.0 Langmuir NH3
at 350K and UHV
Thick Ni
Intensity (arb. units)

Ni-Pt
Reaction:
2NH3 3H2 + N2
Pt-Ni-Pt

Pt(111)

350 400 450 500 550 600 650 700 750

Temperature (K)

Surface monolayer materials exhibit emergent behavior

Methods for predicting emergent materials are lacking
Hansgen, Chen, and Vlachos, Nature Chem. 2 (2010) 484
 Detailed Model-based Design of Bimetallic
Catalysts
Develop a microkinetic model
using descriptors
Perform optimization
Build databases of binding
energies using DFT
Employ informatics to match
database properties and
structures to optimization
results
Synthesize and evaluate
materials Reaction: 2NH3 3H2 + N2
Hansgen et al., Nature Chem. 2 (2010) 484
 Proposed Catalyst Design for Complex
Reactions

Objective: Synergistically
combine the strengths of
High-Throughput Experiments
and DFT calculations to
rationally predict core-shell
catalyst structures
Reaction chosen: C3H8 +5O2 3CO2 + 4H2O
Peela et al., ChemCatChem 5 (2013) 3712
 Volcano Plot of Propane Turnover
Frequency
Propane: 0.5 kPa
O2: 9.0 kPa
Equiv. ratio = 0.28
Alumina support

The volcano peak occurs at a carbon BE of -7.22 eV

(high) and an oxygen BE of -4.40 eV (low)
Cu data strongly support the fact that both C and O BEs
should be at optimal for high activity
Previous studies focused mainly on single descriptor
 Activity Comparison

Propane: 0.5 kPa

O2: 9.0 kPa
Equiv. ratio: 0.28
Cat. Wt.: 2 mg
Alumina Support
400 oC

Ag-Pd(1:3) showed the highest activity

This catalyst is cheaper
The method is successful in predicting bimetallic catalysts
Peela et al., ChemCatChem 5 (2013) 3712 66
 Reactive Distillation

RD is a combination of reaction and distillation

Reactive Adsorption: Rotating Cylindrical
Annulus Chromatographic Reactor
AB+C

Inlet of mobile phase is uniformly

distributed
Feed stream is stationary & confined
Adsorbed species take different
paths and can be collected at fixed
locations
 Coupled Membrane Reactor

Membrane reactors used for two simultaneous reactions

Zhu et al. Chem Commun 48 (2012) 7137
 Time

Manipulation of time Dynamic states

scale Oscillatory Baffled
Millisecond reactors reactors
Sonochemical reactors Sonochemical
reactors

Switching from batch to continuous processing also comes under

temporal approach of PI

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465

Continuous Oscillatory Baffled Reactor
Reverse-flow Reactor
 Summary: PI Principles and Approaches

Switching from batch to continuous processing also comes under

temporal approach of PI

Gerven and Stankiewicz, Ind. Eng. Chem. Res. 48 (2009) 2465