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1
MSc Course on Process Intensification
INTRODUCTION TO PROCESS
INTENSIFICATION:
PHILOSOPHY AND BASIC PRINCIPLES
Giorgos Stefanidis / Andrzej
Stankiewicz
2
MSc Course on Process Intensification
T
ertia
ry
Quaternary
Neogene
Paleogene
Cretaceous
Jurassic
Triassic
Permian
Carboniferous
Devonian
Silurian
Ordovician
Cambrian
Precambrian
Cenozoic
Mesozoic
Paleozoic
4500
600
500
400
300
200
100
NOW
SOURCES OF OIL:
FORAMINIFERA
3
MSc Course on Process Intensification
THE OMNIPRESENT CHEMISTRY:
FROM THE CRADLE TO THE GRAVE …AND BEYOND!
4
MSc Course on Process Intensification
Consumption of chemical products is rapidly
increasing
• new types of chemical and biochemical products
brought to the market
• new markets open in different parts of the world
for already existing products
Main reasons
• rapid growth in world’s population
• growth in consumers’ wealth
• growth in consumers’ needs
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MSc Course on Process Intensification
OIL
PRODUCTION
FORECAST
(U.S. Energy Information Administration)
GENERATION << CONSUMPTION
INPUT ≈ 0 OUTPUT ≈ 0
1 generation ahead 3 generations ahead
12 EIA World Conventional Oil Production Scenarios
0
10
20
30
40
50
60
70
80
90
1900 1925 1950 1975 2000 2025 2050 2075 2100 2125
Billion
Barrels
per
Year
History
Mean
Low (95 %)
High (5 %)
3 %
Growth
1 %
Growth
Peak Range 46 yrs or 91 yrs
2021 2067
USGS Estimates of Ultimate Recovery
Ultimate Recovery
Probability BBls
-------------------- ---------
Low (95 %) 2,248
Mean (expected value) 3,003
High (5 %) 3,896
2 %
Growth
0 %
Growth
Decline
R/P = 10
2112
Note: U.S. volumes were added to the USGS foreign volumes to obtain world totals.
900 Billion Bbls
Moves Peak 10
Years
From 2037 - 2047
(J. A. Moulijn)
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MSc Course on Process Intensification
THE NON-SUSTAINABLE MANKIND
o WE WILL ESSENTIALLY USE UP ALL THE WORLD’S OIL
RESOURCES BY 2050 (S. A. Nelson)
o WE WILL ESSENTIALLY USE UP ALL THE WORLD’S GAS
RESOURCES BY 2070 (P.-R. Baquis)
o WE WILL ESSENTIALLY USE UP ALL THE WORLD’S COAL
RESOURCES BY 2500 (S. A. Nelson)
SOME FORECASTS:
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MSc Course on Process Intensification
Steam Cracker - Cathedral of the Chemical Industries of 20th Century
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MSc Course on Process Intensification
How to solve the resources problem?
OPTION 1:
o start exploitation of extraterrestrial resources
- still in the S-F stage and may remain so
OPTION 2:
o develop technically and economically feasible
processes based on the renewable feedstocks
(“green”, biomass-based processes)
9
MSc Course on Process Intensification
Some open questions to OPTION 2:
• do we have enough arable land to feed mankind AND to
provide energy AND to supply raw materials
simultaneously?
• what will we do with by-products, such as CO2?
• how will this “new farming” influence environment?
• what will be repercussions of genetic manipulations?
• when will this all be feasible?
• what about inorganic chemical products?
How to solve the resources problem?
10
MSc Course on Process Intensification
OPTION 3:
o develop innovative methods and technologies that
would DRASTICALLY increase the EFFICIENCY of
chemical and biochemical processes
• FACTOR 4 (Von Weizsacker, 1998)
• FACTOR 10 (Schmidt-Bleek, 1993)
• FACTOR 20? (AllChemE – Alliance for Chemical
Sciences and Technologies in Europe, 2001)
How to solve the resources problem?
11
MSc Course on Process Intensification
G. Agricola, De Re Metallica, 1556
Chemical Process Industry, 2012
• THIS IS NOT THE WAY
TO BOOST EFFICIENCY
• PROCESS INNOVATION
IS CLEARLY NEEDED
12
MSc Course on Process Intensification
Innovation = Unproven Solutions
(“Plant manager never wants to be the first”)
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MSc Course on Process Intensification
Process industry is facing numerous challenges
Source: Roland Berger
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MSc Course on Process Intensification
Natural
Resources
Goods and
Services
Pollution, Waste
and Environmental
Disturbances
Only 25 wt% of
what goes into
the pipe comes
out as goods
and services
(Source: World Resource Institute)
ISSUES OF CONCERN FOR CHEMICAL INDUSTRY:
MATERIAL EFFICIENCY OF MANUFACTURING
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MSc Course on Process Intensification
Industry Sector Product tonnage Tons by-product/ton product
Oil refining 106
– 108
< 0.1
Bulk chemicals 104
– 106
1 - 5
Fine chemicals 102
– 104
5 – 50+
Pharmaceuticals 10 – 103
25 – 100+
(R. Sheldon, 1992)
ISSUES OF CONCERN FOR CHEMICAL INDUSTRY: ENVIRONMENT
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MSc Course on Process Intensification
Laws and Regulations
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MSc Course on Process Intensification
Cost
2012
Our technology X
Legislative
and
regulatory
constrains
> 2020
Is our technology X able to
sustain the compliance with
future legislative and
regulatory constrains?
Identified possible improvements versus expected
developments in legislation
Laws and regulations
18
MSc Course on Process Intensification
ISSUES OF CONCERN FOR CHEMICAL INDUSTRY: SAFETY
Union Carbide, Bhopal,
December 3, 1984
BASF, Oppau/Ludwigshafen,
September 21, 1921
AZF, Toulouse,
September 21, 2001
TERRORISM – THE
PLAGUE OF THE
21ST CENTURY:
IS CHEMICAL
INDUSTRY SAFE
ENOUGH?
19
MSc Course on Process Intensification
AZF, Toulouse,
September 21, 2001
License to Operate
20
MSc Course on Process Intensification
ISSUES OF CONCERN FOR CHEMICAL INDUSTRY: PUBLIC IMAGE
ONLY TOBACCO
AND NUCLEAR
SECTORS HAVE
WORSE PUBLIC
IMAGE
21
MSc Course on Process Intensification
• sooner or later a critical limit will be reached
• competitors will follow
• the only way to go beyond that limit and gain
significant long-term advantage over the competitors
is via innovative technological development
TIME
C
OSTS
Operational excellence
Breakthrough in technology
ISSUES OF CONCERN FOR EUROPEAN CHEMICAL INDUSTRY: COST
SQUEEZING THE COSTS
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MSc Course on Process Intensification
Process Intensification
One of PI definitions
A set of often radically innovative
principles (“paradigm shift”) in process
and equipment design, which can bring
significant (more than factor 2) benefits
in terms of process and chain efficiency,
capital and operating expenses, quality,
wastes, process safety, etc.
(European Roadmap of Process Intensification, 2007)
23
MSc Course on Process Intensification
PI - fundamental benefits
• Energy savings (20 – 80%)
• CapEx and OpEx savings (20 –
80%)
• Selectivity and yield increase (up to
>10 times)
• Significant process safety increase
(reactor volume & inventory of
chemicals decreased 10-1000 times
+ better reaction control)
(2006 study by SenterNovem, Dutch Energy
and Environmental Agency)
ENERGY
MATERIALS
RISK AND
HAZARD
COST
WASTE
REDUCING
NUISANCES
(ODOUR, NOISE,
ETC.)
24
MSc Course on Process Intensification
Lower costs due to PI
 land costs (much higher production capacity and/or
number of products (plants) per unit of manufacturing
area);
 other investment costs (cheaper, compact
equipment, reduced piping etc.);
 costs of raw materials (higher yields/selectivities);
 costs of utilities (energy in particular);
 costs of waste-stream processing (less waste in
general).
25
MSc Course on Process Intensification
Lower costs due to PI
26
MSc Course on Process Intensification
Shorter time to the market = lower cost
Possible solution: a continuous lab-scale plant as
a commercial-scale production unit
Do not forget: in continuous operation 1 ml/s = 30 t/year!
Advantages:
 FDA approval procedures of drug
technology take place only once:
the lab-scale is the commercial-
scale.
 Process development takes place
only once, with no scale-up via a
pilot plant to the industrial scale.
Example: How to shorten time to the market
in pharmaceutical technologies?
Result:
 Start of the commercial
production speeded up, in
some cases even by
several years.
 Time to the market
shortened - patent time
better utilized.
27
MSc Course on Process Intensification
Union Carbide, Bhopal,
December 3, 1984
LESSON LEARNED:
Process could have
been intensified to
contain a total
inventory of less than
10 kg of MIC, instead
of 41 tons!
Intensified
means:
SAFER!
PI AND SAFETY
28
MSc Course on Process Intensification
SHORT HISTORY OF PI
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MSc Course on Process Intensification
Origins of Process Intensification
FROM NASA’s
SPACE PROGRAM
TO INNOVATIVE
CHEMICAL PLANTS
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MSc Course on Process Intensification
• Term “Process Intensification” appeared in early
1960’s
• Mostly East-European publications on METALLURGY
• “Process Intensification” = “Process Improvement”
• Comes to chemical engineering literature in 1970’s
(Leszczynski, 1973, Romankov, 1977, Kleemann and Hartmann, 1978)
• still East-European domain
• still “Process Intensification” = “Process Improvement”
History of process intensification
31
MSc Course on Process Intensification
• 1983 - Colin Ramshaw from ICI New Science Group
describes studies on application of centrifugal fields
(so-called “HiGee”) in distillation processes
• PI = “devising exceedingly compact plant which reduces both the
“main plant item” and the installations costs”
• 1983 - Annual Research Meeting of IChemE entitled
Process Intensification held at UMIST, Manchester
• first paper presented at that meeting concerned
PROCESSING OF GOLD ORE using intensive methods
• PI = “order-of-magnitude reductions in process plant and
equipment” (Heggs)
History of process intensification
32
MSc Course on Process Intensification
• 1980’s and early 1990’s – mainly British discipline
• primarily focused on four areas: the use of centrifugal forces,
compact heat transfer, intensive mixing and combined technologies
• 1995 - 1st Conference on Process Intensification
• Process Intensification Network – PIN-UK
• late 1990’s – growing interest and activities in different
parts of the world
• research centers in US (PNNL, MIT), France (Greth CEN),
Germany (IMM), UK (BHR), China (HighGravitec) and many
more…
• industry enters the scene – first applications at Eastman, Dow,
DSM, Sulzer and many more…
History of process intensification
33
MSc Course on Process Intensification
• PI placed clearly in
sustainability context
• First university courses,
books, international
conferences, journal
• National networks in UK,
NL and DE
• Numerous industrial
initiatives
• EFCE establishes of the
Working Party on Process
Intensification
• PI in FP7
• European Roadmap for PI
Awareness of the importance of PI has grown
strongly in last 10 years
The 3rd European Process
Intensification Conference
Manchester Conference Centre, UK
34
MSc Course on Process Intensification
POSITION OF PI
35
MSc Course on Process Intensification
molecules
ps
ns
ms
s
min
h
day
week
month
time
scale
1 pm 1 nm 1µm 1mm 1 m 1 km length scale
molecular
clusters
particles,
thin films
single and multi-
phase systems
process units
plants
site
enterprise
Chemical scales
small
large
After W. Marquardt (2000)
PI versus Process Systems Engineering
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MSc Course on Process Intensification
37
MSc Course on Process Intensification
Process Intensification versus Process Systems
Engineering and Process Optimization
Process Optimization Process Systems Engineering
Interdisciplinarity
Process Intensification
Performance improvement of
existing concepts
Model, numerical method
Weak (interface with applied
mathematics)
Multi-scale integration of
existing and new concepts
Model, software
Modest (mostly applied
mathematics and informatics,
chemistry)
Development of new concepts
of process steps and
equipment
Experiment, phenomenon,
interphase
Strong (chemistry & catalysis,
applied physics, mechanical
engineering, materials science,
electronics, etc.)
Focus
Aim
38
MSc Course on Process Intensification
P
I
ROCESS
NTENSIFICATION
EQUIPMENT
METHODS
REACTORS
EQUIPMENT FOR
NON-REACTIVE
OPERATIONS
MULTIFUNCTIONAL
REACTORS
HYBRID
SEPARATIONS
ALTERNATIVE
ENERGY SOURCES
OTHER
METHODS
- spinning disk reactor
- static mixer reactor
- monolithic reactor
- microreactor
- static mixer
- compact heat exchanger
- rotating packed bed
- centrifugal adsorber
- heat-integrated reactors
- reactive separations
- reactive comminution
- reactive extrusion
- fuel cells
- membrane absorption
- membrane distillation
- adsorptive distillation
- supercritical fluids
- dynamic (periodic)
reactor operation
- centrifugal fields
- ultrasounds
- solar energy
- microwaves
- electric fields
- plasma technology
EXAMPLES:
PI as a technology toolbox
39
MSc Course on Process Intensification
Different stages of technical development
Conventional
Performance
of
technology
Embryonic Growth Mature Aging
Natural limit of technology
Loop
reactor
Centrifugal
extractor
Stirred
vessel
Mixer
settler
Shell&tube
Hex
Filter
Centrifuge
One
stage
dest
Conical
dryer
Micro
distillation
Static
mixer
Flash
dryer
Micro
extraction
Micro
reactor
Micro
Hex
Micro
wave
dryer
Micro
mixer
RPB
SDR
(R. Reintjens)
PI technologies on maturity S-curve
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MSc Course on Process Intensification
FUNDAMENTALS OF
PROCESS INTENSIFICATION
41
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
Fundamentals of Process Intensification
PRINCIPLES
(GOALS)
APPROACHES
SCALES
maximizing the
effectiveness of
intra- and
intermolecular
events
42
MSc Course on Process Intensification
What’s wrong with current reactors?
- Limited control upon molecules
effective
collision
Energizing molecules via conductive
heating, or turning snooker into pinball
• non-selective
• amplifies random motions and collisions
• produces temperature gradients
ineffective
collision
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MSc Course on Process Intensification
A snooker game with molecules: how to hit the right one,
with right energy, at right orientation?
(www.drmackay.org)
CHALLENGE:
control of the geometry
of approach and mutual
orientation of
molecules at the
moment of collision
CHALLENGE:
the most efficient way of
supplying energy
(amount, form, position
and moment ) to let
reactants molecules
selectively overcome
activation energy barrier
44
MSc Course on Process Intensification
…or is our thinking about
reactions and reactors not
limited by the traditional,
macroscopic temperature-
based approach to reaction
kinetics?
T
R
Ea
e
k
k 

 0
Where are the limits of reaction rate?
CATALYST
HEATING
?
(Simpson et al. 1996; Kandel & Zare, 1998; Hoffman, 2000)
Laser-induced vibration: C-H bond
stretching, making the target
molecule “bigger” for collisions +
introducing stripping collisions:
reaction rate increase >100x
45
MSc Course on Process Intensification
Methods for controlling molecular
alignment and orientation
Orientation control via nano-
structural confinement
Alignment and orientation
control via external fields
Imprinted catalysts
Shape-selective catalysts
Liquid crystals
Molecular reactors (cyclodextrins)
Stark’s effect methods (electric field)
Molecular beam
Non-resonant laser
Brute force methods
Magnetic
Electric
Femtosecond
Adiabatic
Control of spatial orientation of molecules and geometry
of collisions
• Molecules get immobilized
• Structures confining the access
• “Take it or leave it”
• Molecules move
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MSc Course on Process Intensification
(A)- Orientation of a molecular beam of carbonyl sulphide molecules moving along the z-axis by a
hexapole electric field (left) followed by their dissociation by a laser beam acting along the x-axis (from
Rakitzis, et al, 2004); (B) - Probability plot of the molecular orientation of the OCS molecule; dotted
arrows are proportional to the orientation probability of the OCS dipole moment along each direction.
(A)
(B)
Control of spatial orientation of molecules and geometry
of collisions
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MSc Course on Process Intensification
Multi-beam hexapole
honeycomb device for orienting
molecules in static electric field
(Shimizu, 2003)
Control of spatial orientation of molecules and geometry
of collisions
A “multitubular reactor” of the future?
48
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
Fundamentals of Process Intensification
PRINCIPLES
(GOALS)
APPROACHES
SCALES
giving each molecule
the same processing
experience
49
MSc Course on Process Intensification
What’s wrong with current reactors?
- Limited control upon molecules
. Illustration of the energy distribution problem in molecules, in relation to the yield of simple parallel reactions. A
stirred-tank reactor with conductive heating generates energy distribution due to temperature gradients, which
translate to both material and energy losses.
P
S
P*
P
W
W*
N Reaction coordinate
Energy
A
B
C
D
N
Temperature
Topt
W
S
Creation of waste
product W, leads
to losses of P
Ineffective
collisions, lead to
losses of energy
50
MSc Course on Process Intensification
Giving each molecule the same processing history
time

time

(a) (b)
Stirred-tank reactor with a heating jacket (a) contradicts the 2nd principle of Process Intensification. The
residence time of molecules is widely distributed and both concentration and temperature non-uniformities
are present. On the other hand, a plug-flow reactor with a gradientless, volumetric (e.g. microwave) heating
(b) enables a close realization of that principle.
51
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
PRINCIPLES
(GOALS)
APPROACHES
SCALES
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
Fundamentals of Process Intensification
52
MSc Course on Process Intensification
Surface to volume ratio depends on diameter
D
L
D
L
D
V
A 4
4
2








 






D (m) 1 0,1 0,001
A / V (m2/m3) 4 40 4000
Enhance mass and heat transfer by increasing
the transfer area
Optimizing the driving forces and maximizing the
specific surface areas to which those force apply
(R. Reintjens)
53
MSc Course on Process Intensification
How to catch up with the Nature and
generate ultra-high-interface systems?
Capillary blood vessels
D (m) 0.00001
A/V (m2/m3) 400,000
D (m) 0,0001
A / V (m2/m3) 40000
Optimizing the driving forces and maximizing the
specific surface areas to which those force apply
54
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
PRINCIPLES
(GOALS)
APPROACHES
SCALES
maximizing
synergistic effects
from partial
processes
Fundamentals of Process Intensification
55
MSc Course on Process Intensification
Example: catalytic function + separation function
Agar, 1999
methanol + ammonia monomethylamine + dimethylamine + trimethylamine
(MMA) (DMA) (TMA)
catalyst
catalyst +
membrane
Selectivity
(MMA+DMA)/TMA
2
5
ordinarySi-Al catalyst
Carbon molecular sieve
layer (~ 0.5 nm pores)
Maximizing synergistic effects from partial processes
56
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
PRINCIPLES
(GOALS)
APPROACHES
SCALES
STRUCTURE
(spatial
domain)
Fundamentals of Process Intensification
57
MSc Course on Process Intensification
STRUCTURE
STRUCTURE: examples
58
MSc Course on Process Intensification
Example: Microreactor for manufacturing
of a specialty product (DSM)
Photos courtesy of DSM and
Forschungszentrum Karlsruhe
Stirred Tank Reactor: the
reactants are mixed in a large
vessel, and the heat is
removed through the jacket or
a heat transfer coil.
Traditional technology PI technology Benefits
• Equipment content 3 litres
vs 10 m3
• 20% higher selectivity 
20% higher material yield
• Process more reliable
because continuous instead
of batch
• Same capacity (1700 kg/h)
Microreactor: the reactants are
mixed, and the heat is removed
through thousands of micro
channels, fabricated by
micromachining or lithography
STRUCTURE
59
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
PRINCIPLES
(GOALS)
APPROACHES
SCALES
ENERGY
(thermodynamic
domain)
Fundamentals of Process Intensification
60
MSc Course on Process Intensification
ENERGY
ENERGY: examples
+
-
61
MSc Course on Process Intensification
Photos courtesy of Dow Chemical Company;
A system of absorption-
stripping columns: the main
product (HClO) has to be
removed as quickly as
possible from the reaction
environment to prevent its
decomposition.
Traditional technology PI technology Benefits
• Equipment size
decreased by a factor of
ca. 40
• Ca. 15% higher product
yield
• 50% reduction of the
stripping gas
• 1/3 reduction in waste
water & chlorinated
byproducts
• Same processing
capacity
Reactive stripping in High-Gravity
(HiGee) Rotating Packed Beds:
the reactants are subjected to
intensive contact and the product is
immediately removed via stripping
using high-gravity forces in a rotating
apparatus with a specially designed
packing
Example: High-Gravity Rotating Packed
Bed for the production of
hypochlorous acid (Dow Chemical)
ENERGY
62
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
PRINCIPLES
(GOALS)
APPROACHES
SCALES
SYNERGY
(functional
domain)
Fundamentals of Process Intensification
63
MSc Course on Process Intensification
SYNERGY
SYNERGY: examples
TiO2 support
Pt catalyst
Silicalite-1 coating
TiO2 support
Pt catalyst
Silicalite-1 coating
64
MSc Course on Process Intensification
Example: Methyl acetate in multifunctional
reactor (Eastman Chemical)
28 pieces of equipment:
separation problem - two
azeotropes
Traditional technology PI technology Benefits
• Equipment from 28
reduced to 3
• reduced energy
consumption by ca.
85%
• reduced investment by
ca. 80%
Multifunctional
reactor column
including reactive
and extractive
distillation steps
SYNERGY
65
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
PRINCIPLES
(GOALS)
APPROACHES
SCALES
TIME
(temporal
domain)
Fundamentals of Process Intensification
66
MSc Course on Process Intensification
TIME
TIME: examples
67
MSc Course on Process Intensification
James Bond at James Robinson, or
SHAKEN, NOT STIRRED…
27 m
Replaced by…
2.5
m
Reduction in:
Space (20x)
Process time (20x)
Capital cost (2x)
Energy and waste (many times)
Quality defects
Example: Oscillatory Baffle Flow Reactor
TIME
68
MSc Course on Process Intensification
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
APPROACHES
SCALES
PRINCIPLES
(GOALS)
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
PRINCIPLES
(GOALS)
APPROACHES
SCALES
maximizing the
effectiveness of
intra- and
intermolecular
events
giving each molecule
the same processing
experience
optimizing the driving
forces and maximizing
the specific surface
areas to which these
forces apply
maximizing
synergistic effects
from partial
processes
STRUCTURE
(spatial
domain)
ENERGY
(thermodynamic
domain)
SYNERGY
(functional
domain)
TIME
(temporal
domain)
10-16
10-16
10-14
10-10
10--4
10--6
10-2
10-4
100
10-2
102
100
104
102
s
m
Molec ula r
proc es ses
Catalyst/reaction processes, particles,
thin films
Processing units
Processing
plant/site
Hydrodynamics and
transport processes,
single- and multiphase systems
Fundamentals of Process Intensification
69
MSc Course on Process Intensification
SUMMARIZING…
Fundamental principles and approaches of
Process Intensification are applicable to any
chemical process or operation. Intensification
needs simultaneous addressing the four
domains, as given below:
Domain Main focus
Process Intensification
concepts applied
Motivation
Spatial
Structured
environment
Milli- and microchannels;
structured (catalyst) surfaces
 well-defined geometry
 creating maximum specific surface area at
minimum energy expenses
 creating high mass and heat transfer rates
 precise mathematical description
 easy understanding, simple scale-up
Thermodynamic
Alternative
forms and
transfer
mechanisms of
energy
Electric and electromagnetic
fields
 manipulation of molecular orientation
 excitation of targeted molecules
 selective, gradientless and local energy
supply
Functional
Integration of
functions/steps
Combination of alternative
energy forms (e.g. electric
and laser fields), combination
of catalyst and energy source
or energy-absorbing material.
 synergistic effects
 better heat management
 increase of overall efficiency
 more compact equipment
Temporal
Timing of the
events,
introducing
dynamics
Dynamic (pulsed) energy
supply, millisecond contacting
 controlled energy input
 utilizing resonance
 increased energy efficiency
 side reactions minimized
STRUCTURE
TIME
SYNERGY
ENERGY
70
MSc Course on Process Intensification
(O. Levenspiel: Chemical Reactor Omnibook)
SUMMARIZING: about multidisciplinarity
Multidisciplinarity of R&D
approach is essential to
Process Intensification.
Collaboration between
chemical engineering and
other disciplines such as
chemistry & catalysis,
material science, applied
physics or electronics is
of crucial importance.
71
MSc Course on Process Intensification
Course program
Date Block Subject Lecturer
Mon 5 Nov
13.45–15.45
Fundamentals
Genesis of Process Intensification. Issues of
concern for Chemical Process Industry.
Definitions of Process Intensification.
Position of PI in Chemical Engineering
science, its boundaries and interrelations
with other ChemEng disciplines. Generic
principles of Process Intensification, its
scales and fundamental approaches (TIME-
STRUCTURE-ENERGY-SYNERGY).
Stefanidis/
Stankiewicz
Thurs 8 Nov
08.45 -10.45
Designing a Sustainable Chemical Plant
(including elements of Inherently Safer
Process Design) – presentation of PI project
assignments
Stefanidis/
Sturm
Mon 12 Nov
13.45–15.45
PI in Temporal
Domain
TIME Stefanidis
Thurs 15 Nov
08.45-10.45
PI in Spatial
Domain
STRUCTURE Stankiewicz
Mon 19 Nov
13.45–15.45
ENERGY – Part 1 Stefanidis
Thurs 22 Nov
08.45 -10.45
PI in
Thermodynamic
Domain ENERGY – Part 2 Stefanidis
Mon 26 Nov
13.45–15.45
SYNERGY – Part 1 Stankiewicz
Thurs 29 Nov
08.45 -10.45
PI in Functional
Domain
SYNERGY – Part 2 Stankiewicz
Mon 3 Dec
13.45–15.45
Reactive Distillation and Heat Integrated
Distillation
Kiss
(Akzo Nobel)
Thurs 6 Dec
08.45 -10.45
Photocatalytic and Ultrasonic Reactors
Van Gerven
(Katholieke
Universiteit
Leuven)
Mon 10 Dec
13.45–15.45
“FOCUS ON”
lectures by guest
experts:
Rotating Fluidized Beds
De Wilde
(Université
Catholique
de Leuven)
Thurs 13 Dec
08.45 -10.45
PI project assignments – mid-term
reporting/discussion
Students
Mon 17 Dec
13.45–15.45
PI project assignments – mid-term
reporting/discussion
Students
Wed 23 Jan
14.00-17.00
EXAMINATION
EXTRA EXAMINATION
72
MSc Course on Process Intensification
Present course
• 22 hours of lectures
• case study project (inc. 4 hrs mid-term review)
• 6 credit points:
- written examination (50%)
- case study project (50%)
Required minimum: grade 6 on written
examination AND grade 6 in total
• Daily help-desk/project supervision:
Guido Sturm, George Krintiras, Maryam Khodadadian
73
MSc Course on Process Intensification
Edited by: Andrzej
Stankiewicz
Jacob A. Moulijn
Book
Hard Cover | Illustrated
Print ISBN: 0-8247-4302-4
www.dekker.com
(Auxiliary)
Re-Engineering the Chemical
Processing Plant
Process Intensification
Lecture notes
(Auxiliary)
Process Intensification
Info Sheets (aid for the
case study project)
Present course - materials
Free on-line
reading via
TUD Library
74
MSc Course on Process Intensification
QUESTIONS?

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Introduction_to_Process_Intensification_2012.pdf

  • 1. 1 MSc Course on Process Intensification INTRODUCTION TO PROCESS INTENSIFICATION: PHILOSOPHY AND BASIC PRINCIPLES Giorgos Stefanidis / Andrzej Stankiewicz
  • 2. 2 MSc Course on Process Intensification T ertia ry Quaternary Neogene Paleogene Cretaceous Jurassic Triassic Permian Carboniferous Devonian Silurian Ordovician Cambrian Precambrian Cenozoic Mesozoic Paleozoic 4500 600 500 400 300 200 100 NOW SOURCES OF OIL: FORAMINIFERA
  • 3. 3 MSc Course on Process Intensification THE OMNIPRESENT CHEMISTRY: FROM THE CRADLE TO THE GRAVE …AND BEYOND!
  • 4. 4 MSc Course on Process Intensification Consumption of chemical products is rapidly increasing • new types of chemical and biochemical products brought to the market • new markets open in different parts of the world for already existing products Main reasons • rapid growth in world’s population • growth in consumers’ wealth • growth in consumers’ needs
  • 5. 5 MSc Course on Process Intensification OIL PRODUCTION FORECAST (U.S. Energy Information Administration) GENERATION << CONSUMPTION INPUT ≈ 0 OUTPUT ≈ 0 1 generation ahead 3 generations ahead 12 EIA World Conventional Oil Production Scenarios 0 10 20 30 40 50 60 70 80 90 1900 1925 1950 1975 2000 2025 2050 2075 2100 2125 Billion Barrels per Year History Mean Low (95 %) High (5 %) 3 % Growth 1 % Growth Peak Range 46 yrs or 91 yrs 2021 2067 USGS Estimates of Ultimate Recovery Ultimate Recovery Probability BBls -------------------- --------- Low (95 %) 2,248 Mean (expected value) 3,003 High (5 %) 3,896 2 % Growth 0 % Growth Decline R/P = 10 2112 Note: U.S. volumes were added to the USGS foreign volumes to obtain world totals. 900 Billion Bbls Moves Peak 10 Years From 2037 - 2047 (J. A. Moulijn)
  • 6. 6 MSc Course on Process Intensification THE NON-SUSTAINABLE MANKIND o WE WILL ESSENTIALLY USE UP ALL THE WORLD’S OIL RESOURCES BY 2050 (S. A. Nelson) o WE WILL ESSENTIALLY USE UP ALL THE WORLD’S GAS RESOURCES BY 2070 (P.-R. Baquis) o WE WILL ESSENTIALLY USE UP ALL THE WORLD’S COAL RESOURCES BY 2500 (S. A. Nelson) SOME FORECASTS:
  • 7. 7 MSc Course on Process Intensification Steam Cracker - Cathedral of the Chemical Industries of 20th Century
  • 8. 8 MSc Course on Process Intensification How to solve the resources problem? OPTION 1: o start exploitation of extraterrestrial resources - still in the S-F stage and may remain so OPTION 2: o develop technically and economically feasible processes based on the renewable feedstocks (“green”, biomass-based processes)
  • 9. 9 MSc Course on Process Intensification Some open questions to OPTION 2: • do we have enough arable land to feed mankind AND to provide energy AND to supply raw materials simultaneously? • what will we do with by-products, such as CO2? • how will this “new farming” influence environment? • what will be repercussions of genetic manipulations? • when will this all be feasible? • what about inorganic chemical products? How to solve the resources problem?
  • 10. 10 MSc Course on Process Intensification OPTION 3: o develop innovative methods and technologies that would DRASTICALLY increase the EFFICIENCY of chemical and biochemical processes • FACTOR 4 (Von Weizsacker, 1998) • FACTOR 10 (Schmidt-Bleek, 1993) • FACTOR 20? (AllChemE – Alliance for Chemical Sciences and Technologies in Europe, 2001) How to solve the resources problem?
  • 11. 11 MSc Course on Process Intensification G. Agricola, De Re Metallica, 1556 Chemical Process Industry, 2012 • THIS IS NOT THE WAY TO BOOST EFFICIENCY • PROCESS INNOVATION IS CLEARLY NEEDED
  • 12. 12 MSc Course on Process Intensification Innovation = Unproven Solutions (“Plant manager never wants to be the first”)
  • 13. 13 MSc Course on Process Intensification Process industry is facing numerous challenges Source: Roland Berger
  • 14. 14 MSc Course on Process Intensification Natural Resources Goods and Services Pollution, Waste and Environmental Disturbances Only 25 wt% of what goes into the pipe comes out as goods and services (Source: World Resource Institute) ISSUES OF CONCERN FOR CHEMICAL INDUSTRY: MATERIAL EFFICIENCY OF MANUFACTURING
  • 15. 15 MSc Course on Process Intensification Industry Sector Product tonnage Tons by-product/ton product Oil refining 106 – 108 < 0.1 Bulk chemicals 104 – 106 1 - 5 Fine chemicals 102 – 104 5 – 50+ Pharmaceuticals 10 – 103 25 – 100+ (R. Sheldon, 1992) ISSUES OF CONCERN FOR CHEMICAL INDUSTRY: ENVIRONMENT
  • 16. 16 MSc Course on Process Intensification Laws and Regulations
  • 17. 17 MSc Course on Process Intensification Cost 2012 Our technology X Legislative and regulatory constrains > 2020 Is our technology X able to sustain the compliance with future legislative and regulatory constrains? Identified possible improvements versus expected developments in legislation Laws and regulations
  • 18. 18 MSc Course on Process Intensification ISSUES OF CONCERN FOR CHEMICAL INDUSTRY: SAFETY Union Carbide, Bhopal, December 3, 1984 BASF, Oppau/Ludwigshafen, September 21, 1921 AZF, Toulouse, September 21, 2001 TERRORISM – THE PLAGUE OF THE 21ST CENTURY: IS CHEMICAL INDUSTRY SAFE ENOUGH?
  • 19. 19 MSc Course on Process Intensification AZF, Toulouse, September 21, 2001 License to Operate
  • 20. 20 MSc Course on Process Intensification ISSUES OF CONCERN FOR CHEMICAL INDUSTRY: PUBLIC IMAGE ONLY TOBACCO AND NUCLEAR SECTORS HAVE WORSE PUBLIC IMAGE
  • 21. 21 MSc Course on Process Intensification • sooner or later a critical limit will be reached • competitors will follow • the only way to go beyond that limit and gain significant long-term advantage over the competitors is via innovative technological development TIME C OSTS Operational excellence Breakthrough in technology ISSUES OF CONCERN FOR EUROPEAN CHEMICAL INDUSTRY: COST SQUEEZING THE COSTS
  • 22. 22 MSc Course on Process Intensification Process Intensification One of PI definitions A set of often radically innovative principles (“paradigm shift”) in process and equipment design, which can bring significant (more than factor 2) benefits in terms of process and chain efficiency, capital and operating expenses, quality, wastes, process safety, etc. (European Roadmap of Process Intensification, 2007)
  • 23. 23 MSc Course on Process Intensification PI - fundamental benefits • Energy savings (20 – 80%) • CapEx and OpEx savings (20 – 80%) • Selectivity and yield increase (up to >10 times) • Significant process safety increase (reactor volume & inventory of chemicals decreased 10-1000 times + better reaction control) (2006 study by SenterNovem, Dutch Energy and Environmental Agency) ENERGY MATERIALS RISK AND HAZARD COST WASTE REDUCING NUISANCES (ODOUR, NOISE, ETC.)
  • 24. 24 MSc Course on Process Intensification Lower costs due to PI  land costs (much higher production capacity and/or number of products (plants) per unit of manufacturing area);  other investment costs (cheaper, compact equipment, reduced piping etc.);  costs of raw materials (higher yields/selectivities);  costs of utilities (energy in particular);  costs of waste-stream processing (less waste in general).
  • 25. 25 MSc Course on Process Intensification Lower costs due to PI
  • 26. 26 MSc Course on Process Intensification Shorter time to the market = lower cost Possible solution: a continuous lab-scale plant as a commercial-scale production unit Do not forget: in continuous operation 1 ml/s = 30 t/year! Advantages:  FDA approval procedures of drug technology take place only once: the lab-scale is the commercial- scale.  Process development takes place only once, with no scale-up via a pilot plant to the industrial scale. Example: How to shorten time to the market in pharmaceutical technologies? Result:  Start of the commercial production speeded up, in some cases even by several years.  Time to the market shortened - patent time better utilized.
  • 27. 27 MSc Course on Process Intensification Union Carbide, Bhopal, December 3, 1984 LESSON LEARNED: Process could have been intensified to contain a total inventory of less than 10 kg of MIC, instead of 41 tons! Intensified means: SAFER! PI AND SAFETY
  • 28. 28 MSc Course on Process Intensification SHORT HISTORY OF PI
  • 29. 29 MSc Course on Process Intensification Origins of Process Intensification FROM NASA’s SPACE PROGRAM TO INNOVATIVE CHEMICAL PLANTS
  • 30. 30 MSc Course on Process Intensification • Term “Process Intensification” appeared in early 1960’s • Mostly East-European publications on METALLURGY • “Process Intensification” = “Process Improvement” • Comes to chemical engineering literature in 1970’s (Leszczynski, 1973, Romankov, 1977, Kleemann and Hartmann, 1978) • still East-European domain • still “Process Intensification” = “Process Improvement” History of process intensification
  • 31. 31 MSc Course on Process Intensification • 1983 - Colin Ramshaw from ICI New Science Group describes studies on application of centrifugal fields (so-called “HiGee”) in distillation processes • PI = “devising exceedingly compact plant which reduces both the “main plant item” and the installations costs” • 1983 - Annual Research Meeting of IChemE entitled Process Intensification held at UMIST, Manchester • first paper presented at that meeting concerned PROCESSING OF GOLD ORE using intensive methods • PI = “order-of-magnitude reductions in process plant and equipment” (Heggs) History of process intensification
  • 32. 32 MSc Course on Process Intensification • 1980’s and early 1990’s – mainly British discipline • primarily focused on four areas: the use of centrifugal forces, compact heat transfer, intensive mixing and combined technologies • 1995 - 1st Conference on Process Intensification • Process Intensification Network – PIN-UK • late 1990’s – growing interest and activities in different parts of the world • research centers in US (PNNL, MIT), France (Greth CEN), Germany (IMM), UK (BHR), China (HighGravitec) and many more… • industry enters the scene – first applications at Eastman, Dow, DSM, Sulzer and many more… History of process intensification
  • 33. 33 MSc Course on Process Intensification • PI placed clearly in sustainability context • First university courses, books, international conferences, journal • National networks in UK, NL and DE • Numerous industrial initiatives • EFCE establishes of the Working Party on Process Intensification • PI in FP7 • European Roadmap for PI Awareness of the importance of PI has grown strongly in last 10 years The 3rd European Process Intensification Conference Manchester Conference Centre, UK
  • 34. 34 MSc Course on Process Intensification POSITION OF PI
  • 35. 35 MSc Course on Process Intensification molecules ps ns ms s min h day week month time scale 1 pm 1 nm 1µm 1mm 1 m 1 km length scale molecular clusters particles, thin films single and multi- phase systems process units plants site enterprise Chemical scales small large After W. Marquardt (2000) PI versus Process Systems Engineering
  • 36. 36 MSc Course on Process Intensification
  • 37. 37 MSc Course on Process Intensification Process Intensification versus Process Systems Engineering and Process Optimization Process Optimization Process Systems Engineering Interdisciplinarity Process Intensification Performance improvement of existing concepts Model, numerical method Weak (interface with applied mathematics) Multi-scale integration of existing and new concepts Model, software Modest (mostly applied mathematics and informatics, chemistry) Development of new concepts of process steps and equipment Experiment, phenomenon, interphase Strong (chemistry & catalysis, applied physics, mechanical engineering, materials science, electronics, etc.) Focus Aim
  • 38. 38 MSc Course on Process Intensification P I ROCESS NTENSIFICATION EQUIPMENT METHODS REACTORS EQUIPMENT FOR NON-REACTIVE OPERATIONS MULTIFUNCTIONAL REACTORS HYBRID SEPARATIONS ALTERNATIVE ENERGY SOURCES OTHER METHODS - spinning disk reactor - static mixer reactor - monolithic reactor - microreactor - static mixer - compact heat exchanger - rotating packed bed - centrifugal adsorber - heat-integrated reactors - reactive separations - reactive comminution - reactive extrusion - fuel cells - membrane absorption - membrane distillation - adsorptive distillation - supercritical fluids - dynamic (periodic) reactor operation - centrifugal fields - ultrasounds - solar energy - microwaves - electric fields - plasma technology EXAMPLES: PI as a technology toolbox
  • 39. 39 MSc Course on Process Intensification Different stages of technical development Conventional Performance of technology Embryonic Growth Mature Aging Natural limit of technology Loop reactor Centrifugal extractor Stirred vessel Mixer settler Shell&tube Hex Filter Centrifuge One stage dest Conical dryer Micro distillation Static mixer Flash dryer Micro extraction Micro reactor Micro Hex Micro wave dryer Micro mixer RPB SDR (R. Reintjens) PI technologies on maturity S-curve
  • 40. 40 MSc Course on Process Intensification FUNDAMENTALS OF PROCESS INTENSIFICATION
  • 41. 41 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems Fundamentals of Process Intensification PRINCIPLES (GOALS) APPROACHES SCALES maximizing the effectiveness of intra- and intermolecular events
  • 42. 42 MSc Course on Process Intensification What’s wrong with current reactors? - Limited control upon molecules effective collision Energizing molecules via conductive heating, or turning snooker into pinball • non-selective • amplifies random motions and collisions • produces temperature gradients ineffective collision
  • 43. 43 MSc Course on Process Intensification A snooker game with molecules: how to hit the right one, with right energy, at right orientation? (www.drmackay.org) CHALLENGE: control of the geometry of approach and mutual orientation of molecules at the moment of collision CHALLENGE: the most efficient way of supplying energy (amount, form, position and moment ) to let reactants molecules selectively overcome activation energy barrier
  • 44. 44 MSc Course on Process Intensification …or is our thinking about reactions and reactors not limited by the traditional, macroscopic temperature- based approach to reaction kinetics? T R Ea e k k    0 Where are the limits of reaction rate? CATALYST HEATING ? (Simpson et al. 1996; Kandel & Zare, 1998; Hoffman, 2000) Laser-induced vibration: C-H bond stretching, making the target molecule “bigger” for collisions + introducing stripping collisions: reaction rate increase >100x
  • 45. 45 MSc Course on Process Intensification Methods for controlling molecular alignment and orientation Orientation control via nano- structural confinement Alignment and orientation control via external fields Imprinted catalysts Shape-selective catalysts Liquid crystals Molecular reactors (cyclodextrins) Stark’s effect methods (electric field) Molecular beam Non-resonant laser Brute force methods Magnetic Electric Femtosecond Adiabatic Control of spatial orientation of molecules and geometry of collisions • Molecules get immobilized • Structures confining the access • “Take it or leave it” • Molecules move
  • 46. 46 MSc Course on Process Intensification (A)- Orientation of a molecular beam of carbonyl sulphide molecules moving along the z-axis by a hexapole electric field (left) followed by their dissociation by a laser beam acting along the x-axis (from Rakitzis, et al, 2004); (B) - Probability plot of the molecular orientation of the OCS molecule; dotted arrows are proportional to the orientation probability of the OCS dipole moment along each direction. (A) (B) Control of spatial orientation of molecules and geometry of collisions
  • 47. 47 MSc Course on Process Intensification Multi-beam hexapole honeycomb device for orienting molecules in static electric field (Shimizu, 2003) Control of spatial orientation of molecules and geometry of collisions A “multitubular reactor” of the future?
  • 48. 48 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems Fundamentals of Process Intensification PRINCIPLES (GOALS) APPROACHES SCALES giving each molecule the same processing experience
  • 49. 49 MSc Course on Process Intensification What’s wrong with current reactors? - Limited control upon molecules . Illustration of the energy distribution problem in molecules, in relation to the yield of simple parallel reactions. A stirred-tank reactor with conductive heating generates energy distribution due to temperature gradients, which translate to both material and energy losses. P S P* P W W* N Reaction coordinate Energy A B C D N Temperature Topt W S Creation of waste product W, leads to losses of P Ineffective collisions, lead to losses of energy
  • 50. 50 MSc Course on Process Intensification Giving each molecule the same processing history time  time  (a) (b) Stirred-tank reactor with a heating jacket (a) contradicts the 2nd principle of Process Intensification. The residence time of molecules is widely distributed and both concentration and temperature non-uniformities are present. On the other hand, a plug-flow reactor with a gradientless, volumetric (e.g. microwave) heating (b) enables a close realization of that principle.
  • 51. 51 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems PRINCIPLES (GOALS) APPROACHES SCALES optimizing the driving forces and maximizing the specific surface areas to which these forces apply Fundamentals of Process Intensification
  • 52. 52 MSc Course on Process Intensification Surface to volume ratio depends on diameter D L D L D V A 4 4 2                 D (m) 1 0,1 0,001 A / V (m2/m3) 4 40 4000 Enhance mass and heat transfer by increasing the transfer area Optimizing the driving forces and maximizing the specific surface areas to which those force apply (R. Reintjens)
  • 53. 53 MSc Course on Process Intensification How to catch up with the Nature and generate ultra-high-interface systems? Capillary blood vessels D (m) 0.00001 A/V (m2/m3) 400,000 D (m) 0,0001 A / V (m2/m3) 40000 Optimizing the driving forces and maximizing the specific surface areas to which those force apply
  • 54. 54 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems PRINCIPLES (GOALS) APPROACHES SCALES maximizing synergistic effects from partial processes Fundamentals of Process Intensification
  • 55. 55 MSc Course on Process Intensification Example: catalytic function + separation function Agar, 1999 methanol + ammonia monomethylamine + dimethylamine + trimethylamine (MMA) (DMA) (TMA) catalyst catalyst + membrane Selectivity (MMA+DMA)/TMA 2 5 ordinarySi-Al catalyst Carbon molecular sieve layer (~ 0.5 nm pores) Maximizing synergistic effects from partial processes
  • 56. 56 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems PRINCIPLES (GOALS) APPROACHES SCALES STRUCTURE (spatial domain) Fundamentals of Process Intensification
  • 57. 57 MSc Course on Process Intensification STRUCTURE STRUCTURE: examples
  • 58. 58 MSc Course on Process Intensification Example: Microreactor for manufacturing of a specialty product (DSM) Photos courtesy of DSM and Forschungszentrum Karlsruhe Stirred Tank Reactor: the reactants are mixed in a large vessel, and the heat is removed through the jacket or a heat transfer coil. Traditional technology PI technology Benefits • Equipment content 3 litres vs 10 m3 • 20% higher selectivity  20% higher material yield • Process more reliable because continuous instead of batch • Same capacity (1700 kg/h) Microreactor: the reactants are mixed, and the heat is removed through thousands of micro channels, fabricated by micromachining or lithography STRUCTURE
  • 59. 59 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems PRINCIPLES (GOALS) APPROACHES SCALES ENERGY (thermodynamic domain) Fundamentals of Process Intensification
  • 60. 60 MSc Course on Process Intensification ENERGY ENERGY: examples + -
  • 61. 61 MSc Course on Process Intensification Photos courtesy of Dow Chemical Company; A system of absorption- stripping columns: the main product (HClO) has to be removed as quickly as possible from the reaction environment to prevent its decomposition. Traditional technology PI technology Benefits • Equipment size decreased by a factor of ca. 40 • Ca. 15% higher product yield • 50% reduction of the stripping gas • 1/3 reduction in waste water & chlorinated byproducts • Same processing capacity Reactive stripping in High-Gravity (HiGee) Rotating Packed Beds: the reactants are subjected to intensive contact and the product is immediately removed via stripping using high-gravity forces in a rotating apparatus with a specially designed packing Example: High-Gravity Rotating Packed Bed for the production of hypochlorous acid (Dow Chemical) ENERGY
  • 62. 62 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems PRINCIPLES (GOALS) APPROACHES SCALES SYNERGY (functional domain) Fundamentals of Process Intensification
  • 63. 63 MSc Course on Process Intensification SYNERGY SYNERGY: examples TiO2 support Pt catalyst Silicalite-1 coating TiO2 support Pt catalyst Silicalite-1 coating
  • 64. 64 MSc Course on Process Intensification Example: Methyl acetate in multifunctional reactor (Eastman Chemical) 28 pieces of equipment: separation problem - two azeotropes Traditional technology PI technology Benefits • Equipment from 28 reduced to 3 • reduced energy consumption by ca. 85% • reduced investment by ca. 80% Multifunctional reactor column including reactive and extractive distillation steps SYNERGY
  • 65. 65 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems PRINCIPLES (GOALS) APPROACHES SCALES TIME (temporal domain) Fundamentals of Process Intensification
  • 66. 66 MSc Course on Process Intensification TIME TIME: examples
  • 67. 67 MSc Course on Process Intensification James Bond at James Robinson, or SHAKEN, NOT STIRRED… 27 m Replaced by… 2.5 m Reduction in: Space (20x) Process time (20x) Capital cost (2x) Energy and waste (many times) Quality defects Example: Oscillatory Baffle Flow Reactor TIME
  • 68. 68 MSc Course on Process Intensification STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) APPROACHES SCALES PRINCIPLES (GOALS) maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems PRINCIPLES (GOALS) APPROACHES SCALES maximizing the effectiveness of intra- and intermolecular events giving each molecule the same processing experience optimizing the driving forces and maximizing the specific surface areas to which these forces apply maximizing synergistic effects from partial processes STRUCTURE (spatial domain) ENERGY (thermodynamic domain) SYNERGY (functional domain) TIME (temporal domain) 10-16 10-16 10-14 10-10 10--4 10--6 10-2 10-4 100 10-2 102 100 104 102 s m Molec ula r proc es ses Catalyst/reaction processes, particles, thin films Processing units Processing plant/site Hydrodynamics and transport processes, single- and multiphase systems Fundamentals of Process Intensification
  • 69. 69 MSc Course on Process Intensification SUMMARIZING… Fundamental principles and approaches of Process Intensification are applicable to any chemical process or operation. Intensification needs simultaneous addressing the four domains, as given below: Domain Main focus Process Intensification concepts applied Motivation Spatial Structured environment Milli- and microchannels; structured (catalyst) surfaces  well-defined geometry  creating maximum specific surface area at minimum energy expenses  creating high mass and heat transfer rates  precise mathematical description  easy understanding, simple scale-up Thermodynamic Alternative forms and transfer mechanisms of energy Electric and electromagnetic fields  manipulation of molecular orientation  excitation of targeted molecules  selective, gradientless and local energy supply Functional Integration of functions/steps Combination of alternative energy forms (e.g. electric and laser fields), combination of catalyst and energy source or energy-absorbing material.  synergistic effects  better heat management  increase of overall efficiency  more compact equipment Temporal Timing of the events, introducing dynamics Dynamic (pulsed) energy supply, millisecond contacting  controlled energy input  utilizing resonance  increased energy efficiency  side reactions minimized STRUCTURE TIME SYNERGY ENERGY
  • 70. 70 MSc Course on Process Intensification (O. Levenspiel: Chemical Reactor Omnibook) SUMMARIZING: about multidisciplinarity Multidisciplinarity of R&D approach is essential to Process Intensification. Collaboration between chemical engineering and other disciplines such as chemistry & catalysis, material science, applied physics or electronics is of crucial importance.
  • 71. 71 MSc Course on Process Intensification Course program Date Block Subject Lecturer Mon 5 Nov 13.45–15.45 Fundamentals Genesis of Process Intensification. Issues of concern for Chemical Process Industry. Definitions of Process Intensification. Position of PI in Chemical Engineering science, its boundaries and interrelations with other ChemEng disciplines. Generic principles of Process Intensification, its scales and fundamental approaches (TIME- STRUCTURE-ENERGY-SYNERGY). Stefanidis/ Stankiewicz Thurs 8 Nov 08.45 -10.45 Designing a Sustainable Chemical Plant (including elements of Inherently Safer Process Design) – presentation of PI project assignments Stefanidis/ Sturm Mon 12 Nov 13.45–15.45 PI in Temporal Domain TIME Stefanidis Thurs 15 Nov 08.45-10.45 PI in Spatial Domain STRUCTURE Stankiewicz Mon 19 Nov 13.45–15.45 ENERGY – Part 1 Stefanidis Thurs 22 Nov 08.45 -10.45 PI in Thermodynamic Domain ENERGY – Part 2 Stefanidis Mon 26 Nov 13.45–15.45 SYNERGY – Part 1 Stankiewicz Thurs 29 Nov 08.45 -10.45 PI in Functional Domain SYNERGY – Part 2 Stankiewicz Mon 3 Dec 13.45–15.45 Reactive Distillation and Heat Integrated Distillation Kiss (Akzo Nobel) Thurs 6 Dec 08.45 -10.45 Photocatalytic and Ultrasonic Reactors Van Gerven (Katholieke Universiteit Leuven) Mon 10 Dec 13.45–15.45 “FOCUS ON” lectures by guest experts: Rotating Fluidized Beds De Wilde (Université Catholique de Leuven) Thurs 13 Dec 08.45 -10.45 PI project assignments – mid-term reporting/discussion Students Mon 17 Dec 13.45–15.45 PI project assignments – mid-term reporting/discussion Students Wed 23 Jan 14.00-17.00 EXAMINATION EXTRA EXAMINATION
  • 72. 72 MSc Course on Process Intensification Present course • 22 hours of lectures • case study project (inc. 4 hrs mid-term review) • 6 credit points: - written examination (50%) - case study project (50%) Required minimum: grade 6 on written examination AND grade 6 in total • Daily help-desk/project supervision: Guido Sturm, George Krintiras, Maryam Khodadadian
  • 73. 73 MSc Course on Process Intensification Edited by: Andrzej Stankiewicz Jacob A. Moulijn Book Hard Cover | Illustrated Print ISBN: 0-8247-4302-4 www.dekker.com (Auxiliary) Re-Engineering the Chemical Processing Plant Process Intensification Lecture notes (Auxiliary) Process Intensification Info Sheets (aid for the case study project) Present course - materials Free on-line reading via TUD Library
  • 74. 74 MSc Course on Process Intensification QUESTIONS?