View
0
Download
0
Category
Preview:
Citation preview
Woudschoten, Chemieconferentie2 en 3 november 2007
De ideale chemische fabriek:“… klein maar fijn”
Jaap C. SchoutenCapaciteitsgroep Chemische Reactortechnologie
Faculteit Scheikundige TechnologieTU Eindhoven (TU/e)
J.C.Schouten@tue.nlwww.chem.tue.nl/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
The Staying Power of Europe’s Chemical Industry
The Staying Power of Europe’s Chemical Industry
The Staying Power of Europe’s Chemical Industry
The Staying Power of Europe’s Chemical Industry
“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 !!
The Staying Power of Europe’s Chemical Industry
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
A gg gl l gl s s t r
H H Hr Ck a k a k a mL kη
−⎛ ⎞
− = + + +⎜ ⎟⎜ ⎟⎝ ⎠
11
A gg gl l gl s s t r
H H Hr Ck a k a k a mL kη
−⎛ ⎞
− = + + +⎜ ⎟⎜ ⎟⎝ ⎠
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
The Continuous Quest for Innovative Reactor Concepts
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
The Continuous Quest for Innovative Reactor Concepts
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
The Continuous Quest for Innovative Reactor Concepts
(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
The Continuous Quest for Innovative Reactor Concepts
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)
Micro Product Engineering
Polymer vesicles from double emulsions (Hayward, 2006)
Micro Product Engineering
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
Recommended