instrumentations for monitoring microreaction processes · betriebsversammlung ict 18.10.1999 9 sl...
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Betriebsversammlung ICT 18.10.1999
1
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CPAC Satellite Workshop, March 2006
Instrumentations for Monitoring Microreaction Processes
Stefan Löbbecke
Fraunhofer Institute for Chemical Technology ICTPfinztal, Germany
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motivation
Monitoring the Chemistry• products
• conversion
• mechanism
• thermokinetic data
• …
Monitoring Process Parameters• T, p, flow, pH, …
Monitoring Fluid Dynamics• flow distribution
• residence time distribution
• …
Betriebsversammlung ICT 18.10.1999
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motivation
process diagnosticsmechanistic, kinetic studies
safety analysis
…
qualification of microfluidic structures
mixing performance
RTD
…
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www.microreaction-technology.info
motivation
process optimizationparameter screenings
automation
Betriebsversammlung ICT 18.10.1999
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challenges
spatial resolution
time resolution
sensitivity
…
interfacing
hold-up
thermal control
…
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online infrared spectroscopy: using silicon microreactors
Betriebsversammlung ICT 18.10.1999
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↓ reactant 1
reactant 2 ↓
↑ product
online infrared spectroscopy: using silicon microreactors
mixing principle:split-and-recombine
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online infrared spectroscopy with FTIR microscopy
Betriebsversammlung ICT 18.10.1999
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hydrolysis of benzoyl chlorideO Cl
+ H2O
O OH
+ HCl
benzoic acid (product; reference)
benzoyl chloride (educt; reference)
reactor outlet
online infrared spectroscopy with FTIR microscopy
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nitration of N,N‘-dialkyl substituted ureas
NR
H
O
N R
H
NR
NO2
O
N R
H
NR
NO2
O
N R
NO2
+
nitrating agent
(e.g. HNO3, HNO3/H2SO4,
N2O5, ...)
N N
R
NO2
R
NO2
DNDA (energetic plastiziser)
R = alkyl
+ ...
(S)
macroscopic batch reactor: -20°C/-30°C; mixtures of mono- and dinitro substituted
ureas; other by-products; target product < 10%
microreactor: room temperature; one main product with selectivity > 95%
Betriebsversammlung ICT 18.10.1999
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reactor entrancereactor centerreactor outlet
nitration of dialkyl subst. thioureas: online analysis in microreactors
synthesis of N-nitroso-N,N´-diethyl-urea: reaction progress along a microreactor channel
1722
15301480
NC2H5
H
O
N C2H5
NO
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concentration profiles in individual microreactor channels
channel 4
00,010,020,030,040,050,06
1 2 3 4 5 6position
conc
entr
atio
n D
ND
EH /
(m
ol/L
)channel 1
00,010,020,030,040,050,06
1 2 3 4 5 6position
conc
entrat
ion
DN
DEH
/ (m
ol/L
)
channel 6
0
0,010,02
0,030,04
0,050,06
1 2 3 4 5 6position
conc
entr
atio
n D
ND
EH /
(m
ol/L
)
nitration of dialkyl subst. thioureas: online analysis in microreactors
Betriebsversammlung ICT 18.10.1999
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thermography: monitoring of the entire microreaction process
L RP
nitration of ureas with N2O5/CH2Cl2
• „micro hot spots“
• fluctuations in flow behavior, inhomogeneous flow distribution
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Re-designed microfluidic split-and-recombine structures
out
in 2
in 1in 1 in 2out
(patented by MERCK, WO 96/30113 )
Corporate TechnologyAutomation & Drives
Betriebsversammlung ICT 18.10.1999
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• homogenous flow distribution
• improved mixing quality
Corporate TechnologyAutomation & Drives
Re-designed microfluidic split-and-recombine structures
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5 10 15 200,0
0,1
0,2
0,3
0,4
E(t)
t / s
split-and-recombine Reaktor (type a) split-and-recombine Reaktor (type b)
(patented by MERCK, WO 96/30113 )(Design: Siemens, AuMµRes)
Re-designed microfluidic split-and-recombine structures: RTD
Betriebsversammlung ICT 18.10.1999
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online NIR and Raman spectroscopy
1000 1100 1200 1300 1400 1500 1600
0.0
0.1
0.2
0.3
0.4
Ext
inkt
ion
Wellenlänge [nm]
p2 4
(AOTF)-NIR monitoring of HNO3 consumption
wavelength / nm
abso
rban
ce
O
Cl HOOC
O
Cl HOOC
NO2
nitrating agent
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CH3
CH3
NO2
CH3CH3
NO2NO2
+ +HNO3
CH3
NO2O2NCH3
NO2
NO2
+ +
online spectroscopy: quantitative analysis during process screenings
2000 1750 1500 1250 1000 750 500 250
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
Inte
nsitä
t
Shift /cm-1
HNO3
Toluol
2-Nitro
3-Nitro
4-Nitro
Reaktion-mischung
Inte
nsity
reaction mixture
Betriebsversammlung ICT 18.10.1999
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online spectroscopy combined with defined quenching and subsequent HPLC/GC analysis: chemometric calibration for quantitative analysis
for homogeneous reaction mixures for heterogeneous reaction mixures
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quantitative online Raman spectroscopy: nitration of toluene
D e s ir a b il i ty
B: T
empe
ratur
2 . 0 2 . 5 3 . 0 3 . 5 4 . 0
1 5 .0 0
1 7 .5 0
2 0 .0 0
2 2 .5 0
2 5 .0 0
0 . 0 0 0
0 .0 0 0
0 .0 0 0
0 .0 0 0
0 . 0 0 0 0 .0 0 0
0 . 0 0 1
0 .0 0 1
0 . 0 0 1
0 . 0 0 1 0 .0 0 1
0 . 0 0 1
0 .0 0 1
0 . 0 0 1
0 .0 0 1
0 . 0 0 1
0 . 0 0 1
0 . 0 0 1
0 . 0 0 1
0 .0 0 1
0 . 0 0 1
0 . 0 0 2
0 . 0 0 2
P r e di c t i o 5 . 2 4 9 E - 0 0 3
p-nitrotoluene
stoichiometry
flow
tem
pera
ture
CH3
NO2
CH3
NO2
Betriebsversammlung ICT 18.10.1999
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ATR-MIR(UV/VIS) NIR
Raman
microreactorinlet 1
inlet 2 residence time unit
quench reactor
offline-analysis
quenching agent
quantitative online spectroscopy for screening purposes
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ATR-FTIR
Raman
UV/Vis/NIR
Betriebsversammlung ICT 18.10.1999
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0
1
2
3
4
5
0 1 2 3 4 5predicted /mol-%
mea
sure
d /m
ol-%
0
1
2
3
4
5
0 1 2 3 4 5predicted /mol-%
mea
sure
d /m
ol-%
0.9770.9779correlation
0.2090.1965RMSECV /mol-%RamanNIR
NIR
3-nitrotoluene
Raman
RMSECV: Root Mean Square Error of Cross Validation
quantitative monitoring of individual species in reaction mixtures
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goal: determination of thermodynamic and kinetic parameters of strong exothermic reactions
calorimetric monitoring of microreaction processes
new approach:
combined use of microreactors and thermoelectric modules
•safe processing
•small hold-ups
•improved heat transfer characteristics
development of a µL-flowthrough
calorimeter on basis of microreactors
embedded between Seebeck and
Peltier elements
Betriebsversammlung ICT 18.10.1999
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reactants quench and products
cryostat
metal housing
µL-flowthrough calorimeter »concal« on basis of microreactors embedded between Seebeck and Peltier elements
thermofoil for calibration
set-up of the continuous µL calorimeter (»concal«)
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use of a special designed, flat split-and-recombine microreactor made of glass
quench
outletinlet 1
inlet 2
set-up of the continuous µL calorimeter (»concal«)
Betriebsversammlung ICT 18.10.1999
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nitration of toluene with 100% fuming HNO3 (offline analysis by GC)
toluene flow / (mL/min)
P (
mea
sure
d)
/W
50°C
examplary measurements
NO2
NO2
NO2
+ +HNO3
• heat (power) increases linear with volume flow
• from slope: calculation of ∆HR
• varied residence time: 4s - 32s
• conversion even at 4s: 100% → short time constant!
• measured ∆HR = 110 kJ/mol (Lit.: 105-135 kJ/mol)
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NH3C
NO2
O
N CH3
NO2
nitrating agent
NH3C
H
O
N CH3
H
nitration of N,N‘-dimethyl urea
urea flow / (mL/min)
P (
mea
sure
d)
/W
10°C
heat (power) increases linear with volume flow
controlled measurement of extremely high reaction enthalpies, here: ∆HR = 280 kJ/mol (reaction
mixture) => decomposition reactions in parallel
safe processing even under conditions of decomposition
fast quantitative screening for safety analyses of exothermic reactions
examplary measurements
Betriebsversammlung ICT 18.10.1999
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detection limits and time constants
comparison of different commercially available reaction calorimeters with respect to their
relative detection limits (W/L) and time constants
Std. RC: RC1 (Mettler), Sysalco (Systag), Simular (HEL); CPA 200 (Chemisens), autoMate (HEL, small scale); C80 DRC (Setaram);
DSC: Differential Scanning Calorimeter)
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enhancing spatial resolution and sensititvity
Betriebsversammlung ICT 18.10.1999
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thermo foil
microreactor
heat
heat
n Seebeck elements
Seebeck
element
Peltier element
enhancing spatial resolution and sensititvity
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1
2
3
1
2
3
measurement of mixing enthalpy, e.g. acetone/water
acetone flow/ (mmol/s)
P (
mea
sure
d) /
W
∆Hm 601 J/mol, Lit.: 575-620 J/mol
xacetone: 0.2
enhancing spatial resolution and sensititvity
Betriebsversammlung ICT 18.10.1999
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automated microreaction system: AuMµRes
Corporate TechnologyAutomation & Drives
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microstructured mass flow sensor based on the Coriolis princple
Corporate TechnologyAutomation & Drives
(flow-through design, corrosion resistant)
microstructured mass flow and density
sensor based on the Coriolis princple
microstructured process sensors: mass flow
Betriebsversammlung ICT 18.10.1999
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microstructured process sensors: mass flow
microstructured mass flow sensor and density
based on the Coriolis princple
Corporate TechnologyAutomation & Drives
(flow-through design, corrosion resistant)
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mass flow sensor for density measurements
0,0150
0,0180
0,0210
0,0240
0,00 0,20 0,40 0,60 0,80 1,00
density / (g/cm3)
1/f R
²
resonance frequency depends on density (here: water/ethanol mixtures)
Corporate TechnologyAutomation & Drives
microstructured process sensors: mass flow
Betriebsversammlung ICT 18.10.1999
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flow–through design
pressure range 0-10 bar
temperature range < 200°C
dead volume < 0.5 µL
corrosion resistant
Corporate TechnologyAutomation & Drives
microstructured process sensors: pressure + temperature
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Jürgen Antes
Dusan Bošković
Wolfgang Ferstl
Klaus Huber
Horst Krause
Gunnar Kronis
Eric Marioth
Slobodan Panić
Harald Polifke
Björn Richert
Daniel Schifferdecker
Frank Schnürer
Heike Schuppler
Maud Schwarzer
Wenka Schweikert
Tobias Türcke
…
Financial support:
Federal Ministry of Eduction and Research (BMBF)
ICT staff:Acknowledgements