andrzej stankiewicz at basf science symposium 2015

6-3-2015

Challenge the future

Delft University of Technology

1 BASF 150 years

FUNDAMENTAL APPROACHES OF PROCESS INTENSIFICATION

FOR ENERGY-EFFICIENT MANUFACTURING

6-3-2015



2 BASF 150 years

nked

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

6-3-2015



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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5 BASF 150 years

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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6 BASF 150 years

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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8 BASF 150 years

STRUCTURE

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9 BASF 150 years

STRUCTURE: examples

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10 BASF 150 years

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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12 BASF 150 years

ENERGY

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13 BASF 150 years

ENERGY: examples

+ -

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14 BASF 150 years

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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15 BASF 150 years

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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16 BASF 150 years

• Undissipated energy can be recycled

Mastering the microwaves – Traveling Wave Reactor

Uniform energy distribution with energy efficiency >90%

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17 BASF 150 years

SYNERGY

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18 BASF 150 years

SYNERGY: examples

TiO2 support

Pt catalyst

Silicalite-1 coating

TiO2 support

Pt catalyst

Silicalite-1 coating

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19 BASF 150 years

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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22 BASF 150 years

TIME: examples

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23 BASF 150 years

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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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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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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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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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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31 BASF 150 years

THE FUTURE

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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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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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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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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



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)

andrzej stankiewicz at basf science symposium 2015

Science

years energy

tu delft university

years structure

years kochergin

years heart

years process data

years nypro plant

total energy