Micro Process Technology and bulk chemical industry - focussing on lessons learnt PoaC Symposium The Dutch process on a chip and micro reactor meeting May 22, 2013 Conference Center ‘The Strip’, Eindhoven, Netherlands Dr. Ralf Böhling Chemical Engineering, BASF SE
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Micro Process Technology - Welkom bij NWO · - focussing on lessons learnt ... Chemical Engineering, BASF SE . Outline 1 Micro Process Technology @ BASF history and motivation 2 Lessons
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Micro Process Technology and bulk chemical industry
- focussing on lessons learnt
PoaC Symposium
The Dutch process on a chip and micro reactor meeting
May 22, 2013
Conference Center ‘The Strip’, Eindhoven, Netherlands
Dr. Ralf Böhling
Chemical Engineering, BASF SE
Outline
1 Micro Process Technology @ BASF
history and motivation
2 Lessons learnt
Deydrogenation, Mercaptoethanol,
Cyclohexane Oxidation
3 Applications and outlook
Heat exchanger, Reactor, Evaporator, Mixer
Inherently safe – enables operation in the
explosive regime
No hot spot – improved selectivity
Numbering up instead of scale up – easy
transfer to production scale
Fast mixing for improving selectivity
Some Advantages commonly
attributed to micro reactors ...
Micro Process Technology
Motivation
. . . .
Source: Presentation of F. Lippert, Process Intensification @ BASF, Sep 7 - 10, 2008, Kyoto/Japan
History of Micro Process Technology
World and BASF
0
100
200
300
400
2006
2004
2002
2000
1998
1996
1994
1992
1990
Publications
Patents
Dr. Wörz (BASF)
starts cooperation
with IMM (Prof. Ehrfeld)
and FZK (Prof. Schubert)
Fast liquid phase reactions,
Oxy-dehydrogenation
1. IMRET
in Frankfurt
Chairman
Dr. Jäckel BASF
Start of SOLEMIO
a BMBF founded project
Focus on
wall coated micro reactors
2008
Implementation of a
Heatric PCHE
as compact heat exchanger
Start of Operation
of a Heatric PCHE
as reactor for
fine chemicals
BMBF-Project
µ.Pro.Chem
BASF, Degussa,
IMM, BAM,
TU-Chemnitz
Bringing µ-reactors
into technical scale
EU-Projekt
F³-Factory
BASF, Bayer, Evonik,
KIT, Astra Zeneca….
Development of
modular continuous plant
Source: Presentation of F. Lippert, Process Intensification @ BASF, Sep 7 - 10, 2008, Kyoto/Japan
Outline
1 µ-Process-Technology @ BASF
history and motivation
2 Lessons learnt and bad luck
Deydrogenation, Mercaptoethanol,
Cyclohexane Oxidation
3 Applications and outlook
Heat exchanger, Reactor, Evaporator
Micro Process Technology
Strong exothermic heterogeneous gas phase reaction:
Quelle: O.Wörz et al., Microreactors a new efficient tool for reactor development, Cem. Eng. Technol 24, 2 (2001) 138-143
Dehydrogenation (heterogeneous gas phase)
Laboratory
microreactor
S = 96%
T: 390 °C
Q
P
Laboratory
reactor
S = 90%
d: 50 mm
current plant reactor
S = 80-85%
d: 3m
Tmax = 450°C
Hot spot: 60 °C
former
plant reactor
S = 45 %
d > 1m
T = 550 °C
Q: heat flow
P: mass flow
Pilot plant operation
Silver micro reactor become leaky
Structural failure
Catalytically active material is not
suitable as construction material
Source: IMVT of KIT
500 h
10 Vol.-% O2
450 °C
Dehydrogenation
Source: Presentation of F. Lippert, Process Intensification @ BASF, Sep 7 - 10, 2008, Kyoto/Japan
Cooling channels
Micro Process Technology
Cyclohexane Oxidation (gas – liquid phase)
Micro Process Technology
OOH + O2
OH
O
+ H2O
BMBF Förderkennzeichen 16SV1992
Large scale industrial processes:
T < 180 °C / p < 20 bar / = 15 - 60 min
Cyclohexane conversion only < 6 %
Selectivity: 70 - 90 %
Source: Presentation of R. Böhling, µ.pro.chem,
ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
Expectations in using a microreactor
high mass and heat transfer
increasing selectivity and/or conversion
lowering reaction volume
Space-time-yield of up to 10 t/m3·h achieved, impact of wall eliminated
but: Selectivity decreases at higher temperatures project terminated
Results of µ-experiments
Micro Process Technology
Cyclohexane Oxidation
Uncatalyzed cyclohexane oxidation in capillary tubes D = 0.25-2.1 mm / p = 40-60 bar / conversion of cyclohexane 5 %
Source: Presentation of R. Böhling, µ.pro.chem, ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
Existing BASF Process
Long residence time (>> 1 h)
Low temperature and low pressure
Byproduct TDG (up to 20 %), TDG is essential as catalyst
highly exothermic gas-liquid reaction
Potential for micro reactor ?
Mercaptoethanol (MCE) from EO and H2S
Micro Process Technology
Source: Presentation of R. Böhling, µ.pro.chem, ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
BMBF Förderkennzeichen 16SV1992
Mercaptoethanol (MCE) from EO and H2S
Micro Process Technology
Lab results with several µ-reactors
(T = 110-140 °C / p = 30-90 bar / = 2 min)
- Capillary tubes (d<1 mm)
- Parallel channel structure (IMM)
- Mingatec reactor
STY up to 16 t/m3h achieved
high selectivity only in liquid phase
Selectivity up to 95 % achieved
Pilot plant tests planned
Source: Presentation of R. Böhling, µ.pro.chem, ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
Lab results
Flow chart pilot plant at EVONIK site Hanau-Wolfgang
Micro Process Technology
Mercaptoethanol (MCE) from EO and H2S
H2S
EO
TDG
EO; H2S; N2 MCE
N2
Mixer (CSTR)
25 °C
1.
Sambay
1 bar
µ-Reactor 2.
Sambay
vacuum
recycle TDG
Mixing zone
Mingatec only
TDG
Source: Presentation of R. Böhling, µ.pro.chem, ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
IMM
reactor
Mingatec
reactor
Front view (work-up section on back side)
Exchangeable
microstructured
reaction module
Pilot plant (start up III/07 at Evonik site Hanau-Wolfgang)
Micro Process Technology
Mercaptoethanol (MCE) from EO and H2S
Source: Presentation of R. Böhling, µ.pro.chem, ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
µ-Reactors tested in pilot plant
Micro Process Technology
Mingatec-reactor (Miprova®, 2 types)
20 ml lab. reactor
(1 channel / 1,7 x 12 mm / 3 x 0,5 mm N comb layers)
100 ml pilot reactor
(12 channels / 1,2 x 12 mm / 2 x 0,5 mm N comb layers)
Located on 3rd deck of the plant Compact design – small footprint
Micro Process Technology
Heatric heat exchanger at BASF plant
Source: Presentation of R. Böhling / S.Schirrmeister Micro Process Technology, April 25,—April 27 2008, German-American Frontiers of Engineering Symposium Irvine, California
Source:http://www.heatric.com/index.html
49.2 52.8 Heat Duty (MW)
1.8 1.5 P (bar)
38.4 117.5 37.9 120.2 T cool (°C)
555 555 Flow (t/h)
1.9 1.5 P (bar)
131.0 46.5 131.0 42.9 T hot (°C)
526 526 Flow (t/h)
Actual Design Parameter
Heatric heat exchanger in
operation at BASF since 2002
Decreasing performance
after 2 ½ years
Micro reactor fouling
Heat exchange
Source: Presentation of R. Böhling / S.Schirrmeister Micro Process Technology, April 25,—April 27 2008, German-American Frontiers of Engineering Symposium Irvine, California
Micro Process Technology
Gas puffing for cleaning of Heatric PCHE
Heat exchange
Source: Presentation of R. Böhling / S.Schirrmeister Micro Process Technology, April 25,—April 27 2008, German-American Frontiers of Engineering Symposium Irvine, California
Micro Process Technology
Offsite gas puffing
(Heatric)
View into feed header
Debris from gas puffing
Source: Presentation of R. Böhling / S.Schirrmeister Micro Process Technology, April 25,—April 27 2008, German-American Frontiers of Engineering Symposium Irvine, California
Gas puffing for cleaning of Heatric PCHE
Heat exchange
Micro Process Technology
Decomposition
within the miniplant evaporator at
different pressure
0
5
10
15
20
25
30
35
0 200 400 600
Pressure [mbar]
Co
nte
nt o
f d
eco
mp
ositio
n g
ase
s
in th
e e
xh
au
st va
po
r [V
ol.-%
]
Background
Evaporation
Micro Process Technology
Evaporation with technical evaporator leads to
a brown colored waste stream and
could plug the evaporator even under vacuum conditions at 100 - 200 mbar
increasing pressure and temperature leads to non selective starting material cleavage
high cost for vacuum pumps and electrical power supply
used tube bundle of a technical evaporator
8 cm³ KIT-Cube discont. lab
distillation*
Temperature of
exhaust vapor
[°C] 225 198
Decomposition
fraction
[%] < 0,5 50,5
Evaporation at lab with a micro evaporator compared to a discontinuous
distillation at atmospheric pressure
Nearly no decomposition with a micro evaporator
Up to 50 % decomposition with usual lab equipment
* Source: Dr. Achhammer BASF SE
Micro vs. macro
Evaporation
Micro Process Technology
The micro evaporator (1 cm³ KIT-Cube) operates at 1,2 - 2,6 bar up to more than 1000 h without plugging
Lab tests (8 cm³ “KIT-Cube”) with cycles of evaporation and condensation showed no formation of colored byproducts
fresh
starting
material
16-fold
evaporated ↔
condensed
1 cm³ “KIT-Cube”
capacity: 1 kg/h
channel wide: 200 µm
channel length: 1,4 cm
Lab plant with a
sectional view of the
used micro evaporator
capacity: 5 kg/h
Source: FZK
KIT micro evaporator
Evaporation
Micro Process Technology
The heat transfer coefficient is only secondary for the feed material
decomposition within a technical evaporator
The crucial point is the residence time. In a micro evaporator it is less than
one thousandth compare to a technical evaporator.
1 cm³ KIT-Cube 10 l KIT-Cube tech.
evaporator
tube length cm 1,4 12 200
hyd. diameter mm 0,15 0,15 21
heat trans. coefficient W/(m²K) 4600 4600 300
Heat power kW 0,05 1000 1000
residence time sec 0,1 0,1 700
Characteristic data for micro and technical evaporators