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Delft University of Technology
1 BASF 150 years
FUNDAMENTAL APPROACHES OF PROCESS INTENSIFICATION
FOR ENERGY-EFFICIENT MANUFACTURING
6-3-2015
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Delft University of Technology
2 BASF 150 years
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Founded in 1842 by King William II.
The oldest and largest University
of Technology in the Netherlands.
About TU Delft
University of the first Nobel Prize
winner in chemistry – Jacobus
Henricus van ‘t Hoff (1901).
The oldest and the largest
chemical and process
engineering community in
Dutch academia (18 full-time
Chairs; >150 PhD’s)
Ranked 8th in the world, 3rd in
Europe in chemical
engineering
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3 BASF 150 years
Heart of the plant, but the quest for energy efficiency begins here…
Separation technologies – one of definitions:
“…cleaning up the mess left by the
reaction engineering”
Consume > 40% of total energy in chemical &
related industries
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4 BASF 150 years
Energy in reactors: problems start at fundamental level
Energy distribution due to temperature
gradients, translates to both material AND
energy losses.
Energizing molecules via conductive heating, or turning snooker into pinball
• non-selective, does not energize selectively the molecules, just heats everything (bulk fluid, catalyst support, reactor elements, etc.) • amplifies random motions • produces temperature gradients
…plus…
(www.drmackay.org)
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Process data: Large production capacity: ca. 100 kton/annum Gas-liquid reaction Exteremly exothermic: -ΔH = 294 kJ/mol Temperatures: 140-180oC Pressures: 0.8 – 2 MPa Residence time: ca. 20 mins Conversion limited to ca. 10%, due to byproduct formation
Example: Cyclohexanone via cyclohexane oxidation
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NYPRO plant, Flixborough, June 1, 1974
Example: Cyclohexanone via cyclohexane oxidation Due to poor heat removal
Due to poor conversion
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7 BASF 150 years
Fundamentals Approaches of Process Intensification
10-16 10-10 10--6 10-4 10-2 100 102 m
Molecular processes
Catalyst/reaction processes, particles, thin films Processing units
Processing plant/site
Hydrodynamics andtransport processes,single- and multiphase systems
at all scales, from nano to macro
SPATIAL DOMAIN (STRUCTURE)
THERMODYNAMIC DOMAIN (ENERGY)
FUNCTIONAL DOMAIN (SYNERGY)
TEMPORAL DOMAIN (TIME)
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STRUCTURE
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STRUCTURE: examples
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Monolithic catalysts
Better mass transfer at lower pressure drop and lower power input
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11 BASF 150 years Kochergin and Kearney, 2006
Weak cation softening of juice from sugar beets
Conventional ion exchange
Fractal ion exchange
Resin bed depth(inches)
Exhaustion flow rate (bed
volumes/hour)
Maximum resin bed pressure drop (bar)
Regeneration flow rate (bed
volumes/hour
40 6
50 500
3.5-5.6
30 150
0.1
Overall capital cost
of the process
reduced by a factor of
2.5-3!Relative process
size 10 1
Intensification factor
6.5
10
>35
5
10
Fractal structures to minimize energy expenditure
Coppens and Van Ommen., 2003
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ENERGY
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ENERGY: examples
+ -
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Selective heating of catalytic sites with MW
Imperial College - MW heating of molybdenum catalyst on alumina support (X. Zhang et al., (2001))
• Lower bulk temperature • Better selectivity • Improvement in reactor thermal efficiency
Thermal images showing preferential absorption of microwaves by graphite surrounding a much colder pellet; (a) after 3 sec of heating; (b) after 5 sec of heating
Vallance SR, et al. (2012)).
• Room for development of tailored, energy-responsive catalysts
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Energy efficiency of the reactor
CuZnO/Al2O3
MW: Same reactor performance with lower net heat input (~10%)
0
0
0
Heat of reactionNet heat input
( )OUT
OUT
TrT
Tr i i
i T
HEfficiencyH n Cp T dT
∆= =
∆ +∑ ∫
(Durka, T. et. al., 2011)
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• Undissipated energy can be recycled
Mastering the microwaves – Traveling Wave Reactor
Uniform energy distribution with energy efficiency >90%
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SYNERGY
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SYNERGY: examples
TiO2 support
Pt catalyst
Silicalite-1 coating
TiO2 support
Pt catalyst
Silicalite-1 coating
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Photo courtesy of Dow Chemical Company;
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
ENERGY – High-Gravity technology
= energy saving
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20 BASF 150 years
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: reactive and hybrid separations
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21 BASF 150 years
TIME
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TIME: examples
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06 March 2015 23
James Bond at James Robinson, or SHAKEN, NOT STIRRED… Oscillatory Baffle Flow Reactor (NiTech Solutions) implemented at James Robinson
27 m
Replaced by…
2.5 m
TIME: forced dynamic operation of reactors
Reduction in: Space (20x)
Process time (20x) Capital cost (2x)
Energy and waste (many times)
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24 BASF 150 years
Reaction of methane over activated carbon using pulsed RF irradiation – effect of pulse time on selectivity (Ioffe et al., 1995)
TIME: influencing selectivity (hence energy)
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25 BASF 150 years
Back to cyclohexane case – could we think of other approaches?
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26 BASF 150 years
Importance of the material and of the design
1 200 1000 1650 14 000 Intensification
factor US/V (kW/m3.K)
2.5 400 400 2500 2000 Compactness S/V (m²/m3)
A few hours A few minutes A few minutes A few seconds -minutes A few minutes
Maximal residence
time
400 500 2500 660 7000 Overall heat coefficient U
(W/m².K)
Picture
Batch reactor Tubular reactor HEX reactor
Stainless steel (Alfa Laval)
HEX reactor Glass (Corning)
HEX reactor SiC (Boostec/LGC) Devices
Fluide R Fluide réactif
Fluide caloporteur
Fluide Caloporteur Fluide R é actif
Fluide Caloporteur
Fluide réactif
Fluide caloporteur
Fluide caloporteur
STRUCTURE/SYNERGY approach: Heat exchanger (HEX) reactors
(C. Gourdon, Rhodia Sustainability Conference, 2008)
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Delft University of Technology
27 BASF 150 years
ENERGY approach: light
• complete (100%) selectivity of cyclohexane oxidation to cyclohexanone (Sun et al., (1996))
• most important hurdle: low energetic efficiency, due to light absorption and dissipation between the source and the catalytic site
medium
activator
concentrator/facilitator
light source
reaction products
reagents
support
catalyst
photon transfer
mass transfer (Van Gerven, et al. 2009)
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Delft University of Technology
28 BASF 150 years
Titania nanotubes
Our solution to photon transfer problem: nano-illumination of the catalyst
FUTURE
TODAY
CATALYST
LED array
Photocatalytic reactors – the future
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Delft University of Technology
29 BASF 150 years
Cyclohexane to cyclohexanone, cyclohexene and cyclohexanol with high selectivities (47%, 20% and 19% respectively) using water as co-reactant. Oxidation is done by the OH* radicals coming from water dissociation by plasma. Low conversions warrant further system optimization.
ENERGY approach: low-temperature plasma
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Delft University of Technology
30 BASF 150 years
Challenge: non-thermal plasma reactor design
• Tar-free converting of biomass/waste to almost pure synthesis gas
Forward Microwave Power
4 kW 4kW
Plasma Agent N2 air Product Gas Composition 20
l/min 15 l/min
H2 13.6% 23.3% CO 16.6% 34.5% CO2 0.3% 4.4% CH4 0.1% 1.0% Energy Recovery (lower heating value vs. net microwave power)
99% 184%*)
*) we have started from energy recoveries of ca. 3%!
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Delft University of Technology
31 BASF 150 years
THE FUTURE
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Delft University of Technology
32 BASF 150 years
The future is bio, yet…
• Huge, batch-operated, highly diluted systems
• Plenty of water in circulation
• Energy-demanding DSP
Transonic oxygen injection at DSM - productivity of industrial fermenter doubled
• From batch to continuous
• In-situ product recovery
• More productivity per unit volume of fermentation broth
Can PI help microbiology?
(Pinto Mariano & Maciel Filho (2012))
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Delft University of Technology
33 BASF 150 years
• Renewable electricity as primary energy source for chemical plants? • Region-tailored process design?
The future is electricity In the post-oil age the widest available, sustainable form of energy.
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Delft University of Technology
34 BASF 150 years
Example: solar energy-driven desalination plant
Solar desalination plant by WRPC, Takenaka Corp. and Organo Corp.
TIME
STRUCTURE
ENERGY
SYNERGY All four PI domains addressed
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Delft University of Technology
35 BASF 150 years
Key issue:
Highly efficient distributed generation and high-capacity energy storage
The future
More on that: lecture by Prof. Marquardt
6-3-2015
Challenge the future
Delft University of Technology
36 BASF 150 years
SUMMARIZING…
Fundamental approaches of Process Intensification are applicable to any chemical process or operation and can deliver substantial increase in energy efficiency
Process Intensification is expected to play an important role in the long-term developments towards the future, renewable electricity-based chemical manufacturing
With its focus on innovative equipment and processing methods, Process Intensification delivers novel building blocks for tailor-made design of more sustainable, energy-efficient processes (next lecture)