chemistry’s cathedrales chemische producten · innovatiekracht & kenniseconomie duurzaam...

Woudschoten, Chemieconferentie2 en 3 november 2007

De ideale chemische fabriek:“… klein maar fijn”

Jaap C. SchoutenCapaciteitsgroep Chemische Reactortechnologie

Faculteit Scheikundige TechnologieTU Eindhoven (TU/e)

[email protected]/scr

“Procestechnologie”Fysische ChemieThermodynamica

StromingsleerFysische Transportverschijnselen

Stof- en WarmteoverdrachtReactiekinetiek & Katalyse

Chemische ReactortechnologieScheidingstechnologie

Proces- en ProductontwerpProcesdynamicaProcesregeling

Process Systems EngineeringTechnische BedrijfskundeTechnologie Management

Chemistry’s Cathedrales Chemische producten

Poeders

Vloeistoffen

Producten

Gassen

… en nog veel meer

Chemische industrieNederland:

40 miljard euro omzet70.000 arbeidskrachten500 bedrijven3% BNP10% personeel industrie20% exportaandeel

Chemische industrie

Energieverbruik industrie 2005Totaal: 1179 PJ

Voedings- en genotmiddelden: 69 Raffinaderijen: 192 Kunstmestindustrie: 92 Overige chemische industrie: 607

Duurzaamheid

Balkenende: “Duurzaamheid is eenbelangrijk item in het regeerakkoord.“

Al Gore: “Een ongemakkelijke waarheid.”

SusChem (2006): Integrated and sharedvision of a more sustainable futureEuropean chemical industry

Kyoto protocol (1997): Beperking uitstoot broeikasgassen; CO2;‘global warming’

Innovatieplatform (2003): Innovatiekracht & Kenniseconomie

Duurzaam Produceren

minder grondstoffenminder afval

minder energieveiliger

goedkoper

Verbeteringen met een factor 2 tot 5 zijn nodig binnen een tijdshorizon van 5-10 jaar

Technologische Doorbraken

”Green & Smart”

Statement

“Future leading European process technology will be based on a wide-spread implementation and use of intensified, high-precisionprocess equipment and devices, including corresponding adaptation of plant management, supply chain organization, logistics planning, and market and business models.”

Statement

“There exists a strong need to develop flexible, intensified, on-site production plants situated in Europe, highly integrated in the value chains and employed on a routine basis for numerous chemical process applications over a wide range of production scales.”

“Chemicals processing closer toconsumer, shop, supplier, community”

Smart Systems & DevicesforChemical Transformationsand Physical Separations

… towards the Small-Scale Chemical Plant …

Present ! Future !

Disciplines:

microsystems engineeringrobotica & control

reaction & catalysis engineeringorganic chemistryseparations engineeringchemical process designmicrofluidics & fluid dynamicsspectroscopy & analytics

micromechanicsmaterials science

Key issues:reactor miniaturisationmodular systemsbench top unitsscale-upinstrumentationsensors & actuatorsanalysis & controlintegrated microfluidicsnovel chemistrydifferent functionalitiessmart materials

The Staying Power of Europe’s Chemical Industry

Arthur D. Little (2005) & CEFIC (www.cefic.be):

• Europe is world’s largest chemicals producer, exporter, importer, and consumer• Production (2004; excl. Pharma; 1.304 Trillion Euro):Europe 36%; USA 24%; Asia 13%; Japan 10%; China 8%

• Western-Europe is at the centre of technological innovation

• US and Europe own 70% of global intellectual property

• Benelux has the highest density of engineering institutes in the world• Benelux: 640,000 inhabitants per institute• Saudi Arabia: 5,000,000 inhabitants per institute• China: 24,000,000 inhabitants per institute

Of course (but …):• Europe’s economic growth rate below world average• wages significantly above world average• strict regulations & legislation• R&D investments too low• no sufficient innovative power

KennisOnderwijsOnderzoekInnovatie

“Bulk” to “Specialties”“Large Volume” to “High Added Value”

Personnel (fte) Turnover (M Euro)2002 2005 2002 2005

13 companies 62988 62398 16.8 16.2(‘large’ & ‘small’) -0.94 % -3.37 %

4 large companies(more than 1000 fte; 60737 59667 16.1 15.2 (~ 260 Euro/fte)routine-based, labour; -1.76 % -5,69 %ASML, NedCar, ….)

9 small companies(less than 1000 fte; 2251 2688 0.70 1.02 (~ 348 Euro/fte)high-tech, specialized; +19,41 % +31,29 %NedStack, ….)

(Bron: Technisch Weekblad 37 (9), 4 maart 2006) Big Opportunities !!


Source: Oliver Sparrow,WCCE7, Glasgow, 2005

Bron: Chemical Engineering Progress, January 2002, p. 27S.

Jobs of U.S. chemical engineering students three years after graduation (Bron: Chemical Engineering Progress, January 2002, p. 27S)

Een snel veranderende wereld …

• Chemie is overal• Duurzaamheid (energie)• CO2 en klimaatbeheersing• Kleinschalige productie• Innovatiekracht van Europa• High-tech, complexiteit

Een reactoris een apparaat waarin de ene chemische stofwordt omgezet via een chemische reactiein een andere chemische stof

Voorbeelden van “geroerde tank reactoren”

Chemische reactor

… voorziet involdoende reactie-

en verblijftijd

… voert warmtetoe of af

… zorgt voor grotekontaktoppervlakkenen fasegrensvlakken

Chemische reactor A multiphase reactor …

• … enables the necessary reaction time

• guidance of flow with high precision – reaction rate• residence time set accurately – selectivity

• … removes or adds heat

• surface-to-volume ratio – smart geometries• heat conduction – choice of reactor material

• … provides phase interfaces

• surface-to-volume ratio – energy dissipation• mass and heat transfer – multiphase flow• catalysis – activity per unit reactor volume

Stirred TankReactor

Slurry Bubble Column

GasLiquidSolidReactors

… zorgt voor grotekontaktoppervlakkenen fasegrensvlakken

Chemische reactorEen reactor is een apparaat waarin de ene chemische stof wordtomgezet via een chemische reactiein een andere chemische stof

… voorziet involdoende reactie-

en verblijftijd

… voert warmtetoe of af

G. AgricolaeDe Re Metallica,

1556

Anno 1556Anno 2007

… een duidelijke noodzaak voor innovatieve

reactorconcepten ...

Bron: A. Stankiewicz, TU Delft

A+B+C

D+E

agl asCg

CB

Gas Liquid Solid

Gas Liquid Solid

A gg gl l gl s s t r

H H Hr Ck a k a k a mL kη

−⎛ ⎞

− = + + +⎜ ⎟⎜ ⎟⎝ ⎠

11

Rea

ctio

n ra

te

Catalyst concentration

… mass transferlimited

… kineticallylimited



−⎛ ⎞

− = + + +⎜ ⎟⎜ ⎟⎝ ⎠

11



−⎛ ⎞

− = + + +⎜ ⎟⎜ ⎟⎝ ⎠

11

Gas-Liquid-SolidReactions

The Continuous Quest for Innovative Reactor Concepts

Source: )

Multiple Spinning Disks Reactor• interdisk distance ca. 10-100 μm• fine gas-liquid dispersions• excellent heat & mass transfer• catalytically active disks• high reaction rates• reaction & separation

Multiple Spinning Disks Reactor

“Rotating Chemical Plant”

MEMS:Micro ElectricalMechanical Systems


0

20

40

60

80

1900 1950 2000

Year

HTU

, cm

Rocks

Nutter Rings

Intalox SaddlesBerl Saddles

Rashig Rings

SulzerStructured

(Data: Ed Cussler, WCCE7, Glasgow, 2005)

Larg

er k

x a


0

20

40

60

80

1900 1950 2000

Year

HTU

, cm

Rocks

Nutter Rings

Intalox SaddlesBerl Saddles

Rashig Rings

SulzerStructured

Holy Grail(to be found in 2011)

Larg

er k

x a

2025

conc

entr

atie

temperatuur

afstand

G L S

conc

entr

atie

temperatuur

afstand

G L S

SmartStructuredReactors


(Data: Ed Cussler, WCCE7, Glasgow, 2005)Can we stir a bit harder!smarter!

Foam Catalyst Support• electrochemistry• catalyst activation• mass and heat transfer• cascade catalysis, mini-plants• fine-chemistry, biocatalysis

Solid Foam Structured Reactor

surface area: 500 – 4500 m2/m3

pore size: 5.1 – 0.254 mmvoidage: 88 – 97 %

Co/counter current operation: trickle, bubble, and pulse flow

--

Co-current bubble flow

Co-current pulse flow

Open-celled reticulated materialUniform and isotropicInterconnecting pores10 – 100 pores per linear inch (ppi)Well-defined pore sizes: 0.25 – 5 mmHigh voidage: 88 – 97%High geometric surface area: 103 – 104 m2/m3

Any shape possibleCarbon, metal, ceramics, plasticCommercially available

What is a Solid Foam ?

Foam geometricallyrepresented by an so-called interlinked tetrakaidecahedra(Fourie, 2002)

20 ppi10 ppi

45 ppi 100 ppi

1 cm

What is a Hairy Foam ?

100 ppi10 ppi

1 cm

Porous packed bed Inverse packed bed

Hairy Foam

+ =

Solid Foam + Carbon NanoFibres = Hairy Foam

solid foam structure

foam surface

metal catalyst

carbon nanofibers

reactor scale

101 10-1 10-2 10-3 10-6 10-8 10-9 m

Full control at multiple length scales

I-Trickle III-PulseII-Bubble

G L

Counter-current flowLarge concentration gradientsHigh gas-liquid mass transfer Flow limited by flooding

G L

Co-current up-flowHigh flow rates achievableNo floodingHigh gas-liquid mass transferIntense mixing

III-PulseII-Bubble

Solid Foam Reactor: Flow Regimes

Gas-Liquid mass transfer:• liquid-wetted foam surface inside gas bubble/slug• outer surface of gas bubble/slug

Contact time determines mass transfer coefficient kL

Higbie’s penetration theory:

10 ppi 40 ppi

as = 1080 m2/m3 as = 4300 m2/m3

Gas-Liquid mass transfer:co-current up-flow

e

LL t

Dk⋅

=π

2


Source: )

Micro Reactors• micro-channel diameter: 20 - 500 μm

channel length: 1 - 50 mmS/V: 1,000 – 50,000 m2/m3

• manufacturing by micro-machiningin metal, silicon, polymers, glass, etc.

• deposition of catalytic active layer,anodic oxidation, sol-gel method, etc.

• integration with mixers, heat exchangers, membranes, etc.

• integration with sensors/actuators:temperature and flow sensors, gasanalysis, process monitoring

Functions of a (micro) reactor

• Enable the necessary reaction time

• guidance of flow with high precision – fast reactions• residence time set accurately - selectivity

• Remove or add heat

• large surface-to-volume ratio – intrinsic property• heat conduction - choice of reactor material

• Provide phase interfaces

• large surface-to-volume ratio - intrinsic property• mass and heat transfer – multiphase flow• catalysis – activity per unit volume

annularslug-annular

slug

bubbly

churn

Liqu

id s

upe

rfic

ial v

eloc

ity,

Gas superficial velocity,

Gas-liquid flow regimes in a microchannel (1 mm ID)

Multiphase Flow in Microchannels

100 μm

50 μm

45 mm

20 mm

8 mm

1 mm

“Smooth mixer”

Gas

Liquid

Liquid 1 mm

“T-mixer ”

Liquid

Liquid

Gas

Gas-liquid flow in a microchannel

Inlets Outlet

Hole for heating rod Glass chip

Window for viewingmixer and channel

InletsOutletH

ole forheating

rodGlass

chipWindow

forviewing

mixer and channel

Compression lid

O - ring

InletsO

utletGlass

chipod

Compression lid

O - ring

1 mm“Smooth mixer”GasLiquidLiquid1.mm“T-mixer ”LiquidLiquidGas(Note that the superficial gas velocity is given at 1 bar and 200C)10-110010110210310-210-1100101

Gas velocity (U g) [m/s]

Liqu

id v

eloc

ity (U

l) [m

/s]

• Taylor/Annular• Taylor/Ring• Annular • Taylor• Churn• Ring

10-1 100 101 102 10310-2

10-1

100

101

Ga

s

ve

lo

ci

ty

(

Ug)

[

m/

s]

Li

qu

id

v

el

oc

it

y

(U

l)

[m

/s

]•

Ta

yl

or

/A

nn

ul

ar•

Ta

yl

or

/R

in

g•

An

nu

la

r

•T

ay

lo

r•

Ch

ur

n•

Ri

ng

Gas-liqu

id flow in

a microch

ann

el

GL

Three regions for gas-liquid mass transfer:• directly from the bubble through the liquid film

• through the bubble caps to the liquid slug

• from the liquid slug through the liquid film

⎛ ⎞⎜ ⎟⎜ ⎟⎝ ⎠gl gl

gls ls

-1

v s go s1

k ak a +k= a 1

a+

k

Reference:Kreutzer et al., PhD thesis, TU Delft, 2001

Taylor flow and Mass transfer

Channel diameter: 100 μm

Film layer: 4-5 μm

Film volume: 17%of channel volume

Controlled formulation of monodisperse double emulsions in a multiple-phase microfluidic system (Nisisako, 2005)

Micro Product Engineering

A micro-reactor for preparing uniform molecularly imprinted polymer beads (Zourob, 2005)


Polymer vesicles from double emulsions (Hayward, 2006)


High-throughput microreactor

IN

UIT

StromingsverdelerMicroreactor+ Coatings Koeling/monsterkamer

40 mm

Chemische industrie

Lonza, Sigma-Aldrich, Bayer, DSM,Roche, Novartis, Uhde, Clariant,Degussa, Organon, Quest, …Corning, LioniX, Micronit, Mikroglass,IMM, Syntics, Ehrfeld BTS, FZK,Fraunhofer, Velocys, …

(Courtesy: Prof.dr. V. Hessel, TU/e & IMM) (Courtesy: Prof.dr. V. Hessel, TU/e & IMM)

Numbering Up:increasing capacity by adding micro-channels, not by changing critical processdimensions (not new: “Heatric heat-exchangers”)

Scale Out:replication of devices (“circuit board”)

Modular Plants:integration of processing units (“Lego”)

Micro System Scale-Up

Tonkovich et al. (Velocys)Chem. Eng. Res. Des.83(A6) 634-639 (2005)

1. Full-scale reactor system designproduction rate: 8 m3 (STP) H2 / sec

2. Experimental validation

3. Parallelisation of microchannels

4. Design of commercial plant

5. Economic analysis

Scale-Up of Steam Methane ReformingMicrochannel Reactor

1.2.

3. 4.

5.

Fuel Processing forHydrogen & Electricity

MiRTH-e Fuel Processor:

Brandstofcel

Cu/ZnO/Al2O3CH3OH + H2O 3 H2 + CO2 (+ 0.5% CO)

CO + H2 + O2 CO2 + H2OPt/Ru/Al2O3

Methanol Fuel Processor – Fuel Cell System

Vaporizer

HeatexCooler

CO Prox

Burner

Reformer Fuel

Cell

methanolwater

exhaust

airair

75-100 °C 170 °C270 °C 60 °C100 We

electricity

MiRTH-e Fuel Processor:Hydrogen and Electricity Production

CO ProxHeatex

Design targets:• CO concentration< 10 ppm• Heat recovery > 80 % heat exchanger

high temperatureheat exchanger

low temperatureheat exchanger

250 °C

60 °C130 °C

170 °C

Prox reactor130-170 °C

200 °C

Vaporizer

HeatexCooler

CO Prox

Burner

Reformer Fuel

Cell

methanolwater

exhaust

air

75-100 °C 170 °C250 °C 60 °C100 We

electricity

air

MiRTH-e Fuel Processor:Hydrogen and Electricity Production

Specifications:• 53 microstructured plates• Volume: 60 cm3

• Mass: 150 g• 1.5 g Pt/Ru/Al2O3 catalyst• coating thickness: 50 μm

Experimental conditions:• simulated reformate gas:

H2/CO2/H2O/CO/O2 =56/ 18 / 10 /0.5/0.9 %

• coolant gas: nitrogen

5.5 cm

CO ProxHeatex #2

0

10

20

30

40

50

60

70

80

20 30 40 50 60 70Time on stream [hrs]

CO

[ppm

]

100

120

140

160

180

200

Tem

pera

ture

(°C

)

TinTout

3 SLMλ = 3

4 SLMλ = 2.7

1.5 SLMλ = 3

CO ProxHeatex #2: Catalyst Activity and Heat Recovery

40

60

80

100

0 2 4 6

reformate flow rate (SLM)

heat

reco

very

(%)

CO concentration < 20 ppm Heat recovery > 80 %

De ideale chemische fabriek:“… klein maar fijn”

Laboratory for Chemical Reactor Engineering

www.chem.tue.nl/scr

chemistry’s cathedrales chemische producten · innovatiekracht & kenniseconomie duurzaam...

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