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3-3-2017
Challenge the future
Delft University of Technology
1 GREEN ELECTRICITY-BASED PROCESSING AND FLOW CHEMISTRY THE INEVITABLE SYMBIOSIS
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About TU Delft 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 1st in Europe (ex aequo) in chemical engineering
Ranked 6th in the world 2nd in Europe in chemical engineering
Process Technology Institute
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Intensified Reaction & Separation Systems TOWARDS PERFECT REACTORS AND SEPARATORS VIA FUNDAMENTAL CONCEPTS OF PROCESS INTENSIFICATION
• Alternative energy forms for intensification of reaction and separation systems
• Intensified processes for advanced solid materials
Leslie van LeeuwenSecretary
Burak Eral Advanced Solid
Materials
Guido Sturm Alternative
Energy Forms
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Electricity-Driven Chemical Plants and Power-to-Chemicals
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Chemical industry – doomed to the steam boiler?
Why using fossil resources as energy source instead of raw material?
American Chemistry Council, "Energy," published 2011, American Chemistry Council.
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BIOMASS WATER SUN EARTH WIND WASTE
In the post-oil age the widest available, sustainable form of energy.
The future is green electricity
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Power-to-Chemicals concept
Chemicals as:
• Green energy-based products
• High-capacity green energy storage
(Source: R. van de Sanden, presented at Conférence de l’Institut Coriolis pour l’Environnement de l’École Polytechnique 2013)
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Can we envisage green electricity-based processing plants?
?
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(http://petrowiki.org/Electromagnetic_heating_of_oil)
The structure of the electrothermic oil recovery process where the 480 volt power is fed to a downhole contractor through an insulated production pipe. Applied on commercial scale for many years
Not as new as it may seem!
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Electric fields
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Electric fields - surface creation
Basic methods for surface area generation in electric field; (a) – via charged nozzle or orifice, (b) – via droplet breakage in a strong electric field [Ptasinski 1992]
200 to 500 times increase in the surface area per unit volume reported
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Electric fields - enhanced coalescence
Eow [2003] Wärtsilä’s Vessel Internal Electrostatic Coalescer (a), integrated with VectoGray’s Low Water Content Coalescers and installed in a subsea unit (b) (courtesy of Wärtsilä http://www.wartsila.com/products/marine-oil-gas/gas-solutions/oil-separation/wartsila-viec
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Orientation with electric field – feasibility considerations
T [K]
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Could micro-/millichannel systems help?
- - - - - - - - - - -
++++++++++++
1 2
Laser Induced Fluorescence(LIF) detection
(a) (b)
Eorientation
skimmerpiezovalve
Molecular jet
To pumps
fluorescence
+V
-V• Lower voltages
• Influence of rigid walls?
• How “warm” could we work?
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(C. Tsouris, et al., AIChEJ, 49, 2181-2186 (2003))
Electro-hydrodynamic mixing (Oak Ridge National Laboratory)
No electric field: mixing length > 5,000 µm Strong electric field (2 kV/mm) : mixing length < 150 µm
Electric Fields and Flow Chemistry Systems
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Electro-hydrodynamic mixing (New Jersey Institute of Technology)
DC current AC current
(A. O. El Moctar, et al., Lab Chip, 2003, 3, 273-280)
Electric Fields and Flow Chemistry Systems
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Magnetic fields
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Magnetically stabilised fluidized beds
Fluidized bed Magnetically stabilized bed Fixed bed
Small particle size with low ΔP Yes Yes ---
High reactor efficiency --- Yes Yes
Continuous solids throughput Yes Yes ---
Counter-current contacting --- Yes ---
Avoids entrainment from bed --- Yes Yes (from Lucchesi, et al. 1979)
Purification of caprolactam - catalyst consumption decreased by 60% [Meng 2003].
Pressure-swing adsorption process for olefin-paraffin separation - ethylene recovery in the MSB was almost 4 times higher (50% versus 14%) than in the packed bed [Sikavitsas 1995]
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Magnetic Fields and Flow Chemistry Systems
• pumping of fluids • valves • mixing • sorting and separation • self-assembly and
patterning
(Pamme, N. (2005) Magnetism and microfluidics, Lab on a Chip, 6, 24-38)
Magnetic mixing with a permalloy rotor (400 mm length) controlled with a conventional benchtop stirrer plate
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Inductive heating
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How it works
Type of heating Power transmission [W/m2]
Convection 0.5 Irradiation 8 Heat conduction 20 Flame 1000 Inductive heating 30000
Kirschning, A., Kupracz, L. and Hartwig, J. (2012) New Synthetic Opportunities in Miniaturized Flow Reactors with Inductive Heating, Chem. Lett., 41, 562-570
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Induction-heated cracking unit developed at Shell (reproduced from Archibald, et al. 1952)
Coke formation in the inductively and conventionally heated catalysts (reproduced from Mulley, et al. 2015
Long history
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Inductive Heating and Flow Chemistry Systems
Residence times: 0.5 ml/min = 8 min; 0.2 ml/min = 20 min
ferromagnetic nanoparticles involved
Ceylan, S., Coutable, L., Wegner, J. and Kirschning, A. (2011) Inductive Heating with Magnetic Materials inside Flow Reactors, Chem. Eur. J., 17, 1884-1893
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Microwaves
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03 March 2017 25
Energy of electromagnetic field: microwaves
Courtesy: CEM Corporation, 2005
+ - Ionic conduction
Dipole rotation
c
λ
ε
H
= electric field = magnetic field = wavelength (12.2 cm for 2450 MHz) = speed of light (300,000 km/s)
ε
H
c λ
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Microwaves interaction with materials
www.cem.com
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Microwave effects in homogeneous reactions
(R. N. Gedye, et al., Can. J. Chem., 1988, 66, 17)
Some examples:
Reaction
Reaction time Product Yield
Conventional Microwave Conventional Microwave
Hydrolysis of benzamide to benzoic acid 1 h 10 min 90% 99%
Oxidation of toluene to benzoic acid 25 min 5 min 40% 40%
Esterification of benzoic acid with methanol 8 h 5 min 74% 76%
SN2 reaction of 4-cyanophenoxide ion with
benzyl chloride 16 h 4 min 89% 93%
Heck arylation of olefines 20 h 3 min 68% 68%
• Spectacular effects due to common reasons
• Very fast and effective heating
• Often wrong temperature measurements
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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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Microwaves and Flow Chemistry Systems
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• Spiral configuration optimizes microwave reactor coupling
Sturm G. et al., Exploration of rectangular waveguides as a basis for microwave enhanced continuous flow chemistries, CES, 2012
Challenge: How to achieve local uniformity?
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Travelling Wave Reactors
Coaxial cable: commonly used for signal transmission
Challenge: How to achieve local uniformity?
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• Undissipated energy can be recycled
Challenge: How to achieve high energy efficiency?
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Plasmas
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Investment cost SRO
(euro/Nm3h-1 H2)
H2 cost (euro/Nm3)
Investment cost SOFC-GT-SRO
system (euro/W) Chemical reactors 750-900 0.05-0.08 5.12 Plasma reactors 65 0.23 4.59
Comparison of the economy of steam reforming with oxygen (SRO) process in conventional and in plasma reactors
Cormier JM, Rusu I. Syngas production via methane steam reforming with oxygen: plasma reactor versus chemical reactors, J. Phys. D. Appl. Phys., 34, 2798-2803(2001).
Non-equilibrium plasma reactions
• Higher level of non-equilibrium results is better selectivity (compared to thermal
plasma)
• Cold gas (ambient – 1000K), very hot electrons (10,000K)
• Strong vibrational excitation
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• 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%!
Reactions with MW-induced plasma
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Brown coal gasification (pilot scale)
• Indonesian brown coal (10.7%
moisture, 32.5% volatiles, 22.5% ash,
34.3% fixed carbon)
• 70 μm powder
• 1700 oC inner wall temperature (exit at 1000 oC)
• 500 kW thermal power
• ~100% conversion
• 84% cold gas efficiency!
• 1145 l reaction chamber
Uhm, H.S. et. al., International Journal of Hydrogen Energy, 2014, 39, p. 4351-4355
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www.sunfire.de
Plasma processing and Flow Chemistry Systems: reliable ENGINEERING models are essential
http://repository.tudelft.nl/view/ir/uuid%3A4fd7b14d-293e-45c3-904b-5e52bfc429d5/ - publication pending
world’s first reduced model of the plasma-assisted CO2 splitting
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Microplasma reactor for ozone generation – cutaway view and a 48-channel planar array of Al/Al2O3 microchannels [ Kim M.H., Cho J.H., Ban S.B., Choi R.Y., Kwon R.Y., Kwon E.J., Park S.-J. and Eden J.G. (2013) Efficient generation of ozone in arrays of microchannel plasmas, J. Phys. D. Appl. Phys., 46, 305201].
Plasma processing and Flow Chemistry Systems: (catalytic) microplasmas
• low power operation
• very high catalytic surface area
• address short lifetime of vibrationally excited species (<10-7 s)
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Ultrasound
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Ultrasound effects on reactions
(L. H. Thompson, L. K. Doraiswamy, Ind. Eng. Chem. Res., 1999, 38, 1215-1249)
Reduction in reaction time Increase in the yield Switching of the reaction pathway Changing the product distribution
ReactionReaction time Product Yield
Conventional US Conventi
onal US
Diels-Adler cyclization 35 h 3.5 h 77.9% 97.3%
Reduction of methoxyaminosilane
no reaction 3 h 0% 100%
Epoxidation of long-chain unsaturated fatty esters
2 h 15 min 48% 92%
Oxidation of arylalkanes 4 h 4 h 12% 80%
Michael addition of nitroalkanes to monosubstituted α,β-unsaturated esters
2 days 2 h 85% 90%
Permanganate oxidation of 2-octanol 5 h 5 h 3% 93%
Synthesis of chalcones by Claisen-Schmidt condensation
60 min 10 min 5% 76%
Ullmann coupling of 2-iodonitrobenzene 2 h 2 h < 1.5% 70.4%
ReactionReaction time Product Yield
Conventional US Conventi
onal US
Diels-Adler cyclization 35 h 3.5 h 77.9% 97.3%
Reduction of methoxyaminosilane
no reaction 3 h 0% 100%
Epoxidation of long-chain unsaturated fatty esters
2 h 15 min 48% 92%
Oxidation of arylalkanes 4 h 4 h 12% 80%
Michael addition of nitroalkanes to monosubstituted α,β-unsaturated esters
2 days 2 h 85% 90%
Permanganate oxidation of 2-octanol 5 h 5 h 3% 93%
Synthesis of chalcones by Claisen-Schmidt condensation
60 min 10 min 5% 76%
Ullmann coupling of 2-iodonitrobenzene 2 h 2 h < 1.5% 70.4%
0
20
40
60
80
100
0 500 1000 1500 2000
% Y
ield
Residence Time(S)
Batch Silent sonicated
Batch to continuous: rate increase of 2.5xSilent to sonicated: rate increase of 8x
Overall rate increase of 20x
John et al., in progress
Ultrasound and Flow Chemistry Systems
US-assisted solvent extraction hybrid reactor has been demonstrated in an academic lab environment and is now being performed in a pharma lab environment.
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US-assisted crystallisation reactors have been demonstrated in the lab with improved nucleation rate and micromixing efficiency. Also the use of US to produce seeds and application of these seeds in an oscillatory baffle flow reactor has been shown. With respect to energy requirement, it has been shown that pulsed ultrasound (at only 10% of the duty cycle of a continuous irradiation) is able to achieve the same results as continuous sonication.
Saturated Soln. In
Slurry Out
Crystal Product
Ultrasound and Flow Chemistry Systems
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Light (photocatalysis)
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Photocatalysis
• 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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Photocatalysis and Flow Chemistry Systems
(P. J. Barthe, et al., EP 1415707)
• amount of TiO2 per unit reactor volume ca. 12 times higher than in conventional slurry batch photoreactors
• illuminated specific surface 4-400 times higher than in conventional photoreactors
(R. Gorges, et al., J. Photochem. Photobiol. A., 167, 95-99 (2004))
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Photocatalysis and Flow Chemistry Systems – clear improvements
Type of reactor Reaction time Yield of L-PCA
Bulk slurry 60 min 22
Titania-modified mirochannel chip 0.86 min 22
(G. Takei, et al., Catal. Commun., 6, 357-360 (2005))
L-pipecolinic acid from L-lysine
Intensification: ca. 70x
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How to efficiently illuminate multi-layer structures?
Photocatalysis and Flow Chemistry Systems – challenges when it comes to scale-up
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titania nanotubes
Solution to photon transfer problem: nano-illumination of the catalyst
FUTURE
TODAY
CATALYST
LED array
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Future outlook
START DATE 1st October 2015
DURATION 48 months
BUDGET 6 million €
10 PARTNERS in 8 countries
PROJECT WEBSITE: www.spire2030.eu/adrem
OVERVIEW
COORDINATOR: TU Delft (A. Stankiewicz)
MOTIVATION
FLARING OF METHANE IN REMOTE LOCATIONS
NOAA/VIIRS via SkyTruth NOAA/VIIRS via SkyTruth
GENERAL AIM: develop an highly innovative, economically attractive and resource- & energy efficient modular reactors for valorisation of variable methane feedstocks to higher hydrocarbons and liquid fuels
LONG TERM AIM: valorisation process based on green electricity
22.04.2016
REACTOR TYPES
MICROWAVE / RADIOFREQUENCY REACTOR GAS-SOLID VORTEX IN A STATIC GEOMETRY
NON-THERMAL PLASMA TEMPERATURE GRADIENT PLASMA REACTOR
This project has received funding from the European Union’s Horizon 2020 Research and Innovation Programme under the Grant Agreement No. 680777
• With green electricity becoming the most widely available, versatile energy form on Earth, the electricity-based methods can play an important role in the development of flexible, distributed production units for clean manufacturing of fuels and chemicals in various environments (electricity price will no more be a hurdle)
• Electricity-based methods are definitely able to intensify many industrially relevant processes by influencing local conditions on nano-/micro-scale and/or by bringing molecules into energy states not achievable with conventional heating.
SUMMARIZING…
• More symbiotic research between catalysis, physics and chemical engineering is postulated.
SUMMARIZING…
• Processes carried out in Flow Chemistry Systems can benefit from the application of electricity-based energy forms.
• On the other hand the well-defined, structured Flow Chemistry Systems may greatly contribute to a better fundamental understanding of the underlying physico-chemical phenomena and the energy field-material-medium interactions.
Source: www.siemens.com
• highly intermittent,
• time-scales ranging from minutes to months
The future is green electricity but…
Electricity-based processing methods are not enough!
Technologies for green electricity generation
Electricity-based processing methods
Integrated long- and short-term energy storage and recovery on-site
New, energy supply-related process instrumentation and control
New, region-dependent process plant design
Further reading
Due 2017 Just published
