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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
Motivation
Some Advantages commonly
attributed to micro reactors ...
 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
..
..
Source: Presentation of F. Lippert, Process Intensification @ BASF, Sep 7 - 10, 2008, Kyoto/Japan
History of Micro Process Technology
World and BASF
Publications
Patents
1. IMRET
in Frankfurt
Chairman
Dr. Jäckel BASF
Implementation of a
Heatric PCHE
as compact heat exchanger
Start of Operation
of a Heatric PCHE
as reactor for
fine chemicals
400
300
200
Dr. Wörz (BASF)
starts cooperation
with IMM (Prof. Ehrfeld)
and FZK (Prof. Schubert)
Fast liquid phase reactions,
Oxy-dehydrogenation
Start of SOLEMIO
a BMBF founded project
Focus on
wall coated micro reactors
BMBF-Project
µ.Pro.Chem
BASF, Degussa,
IMM, BAM,
TU-Chemnitz
Bringing µ-reactors
into technical scale
2008
2006
2004
2002
2000
1998
1996
1994
1992
1990
100
0
EU-Projekt
F³-Factory
BASF, Bayer, Evonik,
KIT, Astra Zeneca….
Development of
modular continuous plant
Outline
1 µ-Process-Technology @ BASF
2 Lessons learnt and bad luck
3 Applications and outlook
Heat exchanger, Reactor, Evaporator
Dehydrogenation (heterogeneous gas phase)
Strong exothermic heterogeneous gas phase reaction:
Q: heat flow
P: mass flow
Q
P
Laboratory
reactor
S = 90%
d: 50 mm
former
plant reactor
S = 45 %
d > 1m
T = 550 °C
Laboratory
microreactor
S = 96%
T: 390 °C
Quelle: O.Wörz et al., Microreactors a new efficient tool for reactor development, Cem. Eng. Technol 24, 2 (2001) 138-143
current plant reactor
S = 80-85%
d: 3m
Tmax = 450°C
Hot spot: 60 °C
Dehydrogenation
Cooling channels
500 h
10 Vol.-% O2
450 °C
Source: IMVT of KIT
 Pilot plant operation

Silver micro reactor become leaky

Structural failure

Catalytically active material is not
suitable as construction material
Cyclohexane Oxidation (gas – liquid phase)
BMBF Förderkennzeichen 16SV1992
 Large scale industrial processes:
OH
+ O2
OOH
+ H2O
O
 T < 180 °C / p < 20 bar /  = 15 - 60 min
 Cyclohexane conversion only < 6 %
 Selectivity: 70 - 90 %
Expectations in using a microreactor
 high mass and heat transfer
 increasing selectivity and/or conversion
 lowering reaction volume
Source: Presentation of R. Böhling, µ.pro.chem,
ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
Results of µ-experiments
Uncatalyzed cyclohexane oxidation in capillary tubes
D = 0.25-2.1 mm / p = 40-60 bar / conversion of cyclohexane 5 %
 Space-time-yield of up to 10 t/m3·h achieved, impact of wall eliminated
but: Selectivity decreases at higher temperatures  project terminated
Source: Presentation of R. Böhling, µ.pro.chem, ACHEMA Kongress 2009, 12 -13 May, Frankfurt am Main
Mercaptoethanol (MCE) from EO and H2S
BMBF Förderkennzeichen 16SV1992
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 ?
Lab results
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
Flow chart pilot plant at EVONIK site Hanau-Wolfgang
EO; H2S; N2
Mixing zone
Mingatec only
H2S
EO
Mixer
µ-Reactor
(CSTR)
25 °C
MCE
1.
Sambay
2.
Sambay
1 bar
vacuum
N2
recycle TDG
TDG
TDG
Pilot plant (start up III/07 at Evonik site Hanau-Wolfgang)
Front view (work-up section on back side)
IMM
reactor
Exchangeable
microstructured
reaction module
Mingatec
reactor
µ-Reactors tested in pilot plant
 Heatric-type
 IMM – type
Lab reactor 3 ml reactor volume
Pilot reactor 90 ml (30 fold stack)
Enlarged view: cut through
the (BASF) reactor stack
Major step during
manufacturing:
brazing of the wet
chemically etched plates
 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)
 130 ml pilot reactor
(4 channels / 1.0 mm)
Pilot plant results
MCE-Pilotanlage
110°C / 80 bar( 1,3 mol/mol H2S/EO)
100
 During start-up period:
98
 STY of up to 16 t/m3h
confirmed
Sel. %
96
94
92
90
 Sel. 90-94 % at EO
conversion of
> 95 % achieved
88
86
84
70
75
80
85
90
95
100
Conversion %
Mingatec Labor
Mingatec 100 ml
Heatric II
IMM
Mingatec (+TDG)
Kinetic
mmlab
Rohr
Kinetic 11mm
tube
Results
recycle TDG
**A-Reactor
* fresh TDG
**B-Reactor
 With closed TDG-recycle:
 Fast plugging of all micro reactors
 Decrease in reactor performance
* fresh TDG from the Lu-site BASF plant
synthesis by addition of MCE and EO
** A and B-Reactor are two identical Heatric PCHE
Results
Heatric A-Reactor
running with recycle TDG
Heatric B-Reactor
running with fresh TDG
IMM Reactor
running with recycle TDG
scrubbing solutions after operation
 Instable process due to oligomer formation
 Continuous process only with additional TDG-work-up feasible
Alkane Nitration (hom. gas phase)
State of the art:
DOW process with an adiabatic multi stage reactor with
HNO3 feeding between the stages – operation up to 400°C
 broad product spectrum with nitromethane, nitroethane, 1- and 2- nitropropane......
 Low conversion with the need of propane recycle
 2-nitropropane selectivity around 25 - 30 %
Target:
> 50% propane selectivity, nearly full conversion to avoid the propane recycle
Idea:
Using a micro reactor to ensure isothermal conditions for shifting product
mix to the kinetically preferred 2-nitropropan
Gas-Phase Alkane Nitration
Background
Challenge:
Optimum reaction condition are in an explosive regime and elevated pressure range.
Quenching distance for stochiom.
Dependency of quenching distance and pressure
combustible air mixture
Quench
distance
[mm]
Gas componente
→
Hydrogen
0,58
Methane
2,03
Ethylenoxide
1,17
Acetylene
0,64
Methanol
1,50
Micro structure can not avoid explosion – a multiplication factor for pressure rise in case
of explosion of around 50 is taken into account
Challenge
→
Using an inherent safe reactor concept with pressure resistant > 500 bar and
do not forget all other parts with reaction mixture inside must also pressure resistant > 500 bar
– for example
Lab scale down:
HEATRIC heat exchangers
60 m capillary inside a hot air oven
Results
 Gas-phase nitration under thermal
control is within micro structured
devices feasible
 for high selectivity inter stage feeding
of O2 is necessary to suppress side
reaction of O2
 High temperature leads to the
thermodynamically preferred products
 Avoid explosive liquid phase - strictly
Results
Reactor concept: Cascade of Heatric heat exchangers with O2 feeding between them
100 bar
280 °C
110 bar
270 °C
280 °C
25 °C
55 °C
285 °C
Project status:
311 °C
Stopped due to decrease of marked scenario from several thousends to
some hundred tons per year
Bi-phasic Substitution (liquid-liquid phase)
Corning reactor
State of the art:
Batch process with a complex temperature management
Target:
Increasing selectivity, saving cooling costs and
reducing toxic hold up
Idea:
Using a Corning micro reactor to ensure isothermal
conditions and good mixing to get a stable emulsion
during the operation
Bi-phasic Substitution
Corning reactor
Temperature profiles
batch
Results:
 Stable emulsion formed
inside Corning - fast phase
separation at Corning
outlet
 Residence time < 1min
feasible
Corning lab plant
 Temperature 60°C higher
than batch
 Selectivity comparable to
batch process
 Saving of cooling shown
Project status:
Stopped - investment due to capital costs uneconomically
conti Corning
Glucose Dehydration (super critical phase)
OH
HO
HO
O
OH
O
H2O
OH
OH
p = 400 bar
T ~ 450°C
HO
O
Zeit < 1sec
C1 ID: 250 µm Heating rate: 10000 - 100000 K/sec
Heating time: 3 – 30 ms
C2 ID: 800 µm Reaction tube
W3 ID: 800 µm
Cooling rate
2000 - 10000 K/sec
Heat transfer coefficient: 9000 – 27000 W/m²/K
Quelle: Alois Kindler BASF SE, GCN
Glucose Dehydration (super critical phase)
Results
 Dehydration of glucose under
super critical conditions is
feasible without formation of
brown colored waste
70
Yield DHD in mol%
60
50
40
 An extremly short residence time
avoids plugging of the reactor
30
20
10
0
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
VWZ_nom in s (rho=0,4)
450 °C - 5% Glucose
425°C - 5% Glucose
475°C - 10% Glucose
450°C - 10 % Glucose
Project stopped
425°C - 10% Glucose
 work up is uneconomically
 Lack of demand for DHD
Outline
1 µ-Process-Technology @ BASF
2 Lessons learnt
Cyclohexane Oxidation, Propane Nitration…..
3 Applications and Conclusion
Heat exchange, Evaporation, Reaction, Mixing
Heat exchange
Heatric heat exchanger at BASF plant
Source:http://www.heatric.com/index.html
Located on 3rd deck of the plant
Compact design – small footprint
Source: Presentation of R. Böhling / S.Schirrmeister Micro Process Technology, April 25,—April 27 2008, German-American Frontiers of Engineering Symposium Irvine, California
Heat exchange
Micro reactor fouling
Parameter
Design
Actual
Flow (t/h)
526
526
T hot (°C)
131.0  42.9
131.0  46.5
P (bar)
1.5
1.9
Flow (t/h)
555
555
37.9  120.2
38.4  117.5
P (bar)
1.5
1.8
Heat Duty (MW)
52.8
49.2
T cool (°C)
 Heatric heat exchanger in
operation at BASF since 2002
 Decreasing performance
after 2 ½ years
Heat exchange
Gas puffing for cleaning of Heatric PCHE
Heat exchange
Gas puffing for cleaning of Heatric PCHE
View into feed header
Offsite gas puffing
(Heatric)
Debris from gas puffing
Evaporation
Background
Evaporation with technical evaporator leads to
Decomposition
Content of decomposition gases
in the exhaust vapor [Vol.-%]
within the miniplant evaporator at
different pressure
35
 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
30
25
 high cost for vacuum pumps and electrical
power supply
20
15
10
5
0
0
200
400
Pressure [mbar]
600
used tube bundle of a technical evaporator
Evaporation
Micro vs. macro
Evaporation at lab with a micro evaporator compared to a discontinuous
distillation at atmospheric pressure
Temperature of
exhaust vapor
[°C]
Decomposition
fraction
[%]
8 cm³ KIT-Cube
discont. lab
distillation*
225
198
< 0,5
50,5
* Source: Dr. Achhammer BASF SE
 Nearly no decomposition with a micro evaporator
 Up to 50 % decomposition with usual lab equipment
Evaporation
KIT micro evaporator
 The micro evaporator (1 cm³ KITCube) operates at 1,2 - 2,6 bar up to
more than 1000 h without plugging
1 cm³ “KIT-Cube”
capacity: 1 kg/h
channel wide: 200 µm
channel length: 1,4 cm
 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
Source: FZK
Lab plant with a
sectional view of the
used micro evaporator
capacity: 5 kg/h
Evaporation
Micro vs. macro
 Characteristic data for micro and technical evaporators
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
 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.
Reaction
Smale scale production
BASF operates two Heatric microreactors at its
Ludwigshafen site
 One to produce samples of up to about 20 kilograms
 One can manufacture quantities ranging from 1 to 50
tons for market launches of new products
 The microreactors are used for reactions that require
high pressure, high temperatures or/and are strong
exothermic
 The continuous mode of operation and the short
reactor residence time of the reaction media ensure
end products of consistently high quality
Source: http://www.basf.de/en/pharma/inside/2010-09/microreactors.htm
Mixing
Large scale production - BASILTM
nucleophilic
catalysis/
Ionic liquid
> 8 x 103
space time yield
8 kg m-3 h-1
batch process
stirred vessel
space time yield
69000 kg m-3 h-1
continuous process
jet reactor
Source: http://www.dechema.de/dechema_media/Downloads/fachsektionen/FS_PI/Workshop_2006_05_29-p-1798/Strohrmann_M_Prozessintensivierung_in_der_BASF.pdf
Conclusions
 Micro reactors are versatile
lab devices
 Refrain from improper
generalizations
 Operation in explosive regime
needs careful consideration
 Corrosion, fouling and scale up pose
severe problems for production
applications
 BASF already uses micro devices
and explores further applications
Thank you for your attention

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