Beruflich Dokumente
Kultur Dokumente
to Ethylene Oxide in
Microchannel Reactors
Ansgar Kursawe
Mein besonderer Dank gilt Herrn Prof. Honicke fur die hochinteres-
sante Aufgabenstellung, seine stete konstruktive Diskussionsbereit-
schaft wahrend der Erstellung der Arbeit, wertvolle Ratschlage und
Hinweise sowie fur die auergewohnliche Freiheit bei der Planung
und Durchfuhrung der Versuche. Besonders mochte ich mich fur sei-
ne Unterstutzung bezuglich des Entwurfs und des Baus der modu-
laren Reaktoren sowie der dazugehorigen mikrostrukturierten Bau-
teile mit den an einer Universitat verfugbaren Mitteln bedanken.
Ohne diese Ruckendeckung ware die schnelle und unburokratische
Umsetzung eines spontanen interdisziplinaren Entwicklungsprojek-
tes im Niemandsland zwischen Chemie und Fertigungstechnik nicht
moglich gewesen.
Diese modulare Reaktorenentwicklung und die dadurch ermoglichten
umfangreichen katalytischen Erprobungen und Erkenntnisse waren
ohne die konstruktive Mithilfe und den Erfahrungsschatz der me-
chanischen Werkstatten der TU-Chemnitz nicht moglich gewesen.
Deswegen gilt mein Dank hier stellvertretend fur alle Beteiligten
dem Werkstattleiter, Herrn Arnold.
Dem Lehrstuhl fur Fertigungstechnik und Schweitechnik und da-
mit den Herren Professor Durr, Professor Matthes sowie Dr. Pilz
danke ich fur die Anfertigung der durch Drahterosion hergestellten
mikrostrukturierten Wafer und die gewahrte unburokratische Un-
terstutzung. Den Herren Dipl.-Ing. Letsch und Dipl.-Ing. Meyer dan-
ke ich fur ihr Engagement bei Laserschweiss- und Schneidarbeiten
an Aluminiumbauteilen und diversen Dichtungsmaterialien.
Der Fa. CRI-Cataysts und damit Dr. McAteer, Dr. Rubinstein und
Herrn TeRaa danke ich fur die Bereitstellung eines kommerziellen
Ethylenoxid-Katalysators.
Diese Arbeiten wurden im Rahmen des vom BMWI geforderten AiF
Projektes Heterogen katalysierte Gasphasenoxidationen in Mikro-
reaktoren durchgefuhrt. Fur die finanzielle Unterstutzung sei an
dieser Stelle gedankt.
Fur die Anfertigung der elektronenmikroskopischen SEM Aufnah-
men sowie Hilfestellungen bei der Bewaltigung der Tucken einer
Inline-Gaschromatographie mochte ich mich besonders bei Herrn Dr.
Enrico Dietzsch bedanken. Herrn Thomas Kittel vom Otto-Schott
Institut fur Glaschemie der Universitat Jena sei fur aufschlussreiche
elektronenmikroskopische Cs-Backscatter Aufnahmen gedankt. Oh-
ne Ihre Hilfe ware eine schnelle und aussagekraftige Kontrolle der
beschichteten Wafer nur schwer moglich gewesen.
Mein besonderer Dank gilt an dieser Stelle Frau Benndorf und
Frau Wienzek fur die Betreuung der automatisiert arbeitenden Ver-
suchsanlage sowie die GC/MS Kontrolle der Kuhlfallenkondensate
und Frau Reichardt fur die Praparation dutzender Meter anodisch
oxidierter Aluminiumdrahte bzw. Wafer. Herrn Schauer danke ich
fur die Hilfestellung beim elektrischen und elektronischen Aufbau
der Versuchsanlage und sowie die erfolgreiche Eliminierung diverser
Kupferwurmer.
Nicht zuletzt bedanke ich mich bei meinen Eltern, Verwandten und
Freunden fur die moralische Unterstutzung dieser Arbeit.
Contents
1 Introduction 13
1.1 Industrial production of ethylene oxide . . . . . . . . 14
1.1.1 Wurtz-process . . . . . . . . . . . . . . . . . . 14
1.1.2 Direct oxidation process . . . . . . . . . . . . 16
1.2 Handling of ethene oxide . . . . . . . . . . . . . . . . 19
1.3 Usage of ethylene oxide . . . . . . . . . . . . . . . . 21
2 Objectives 23
3 Theory 25
3.1 Reaction mechanism of the direct oxidation process . 25
3.2 Kinetics of the ethene epoxidation . . . . . . . . . . 27
3.3 Catalyst design . . . . . . . . . . . . . . . . . . . . . 30
3.4 Reactor design and heat management . . . . . . . . 34
3.4.1 Reactor design in industrial plants . . . . . . 34
3.4.2 Laboratory and microreactor design . . . . . 41
3.4.3 Advantages of using microchannel reactors . 46
7
8 Contents
4 Results 51
4.1 Epoxidation of ethene in microchannel reactors . . . 53
4.1.1 MCR1: Bulk silver microchannel reactor . . 53
4.1.2 Silver supported on aluminum wafers:
MMCR1-5, MCR2, MCR3 . . . . . . . . . . . 62
4.1.2.1 Test of Ag/Al as a suitable, catalytic
active coating (MMCR1) . . . . . . 62
4.1.2.2 Short term aging of an Ag/Al acti-
vated microchannel reactor (MMCR2) 65
4.1.2.3 Thermal stability of an Ag/Al acti-
vated microchannel reactor (MMCR2) 69
4.1.2.4 Influence of the Ag layer thickness
on selectivity and conversion degree
(MMCR3) . . . . . . . . . . . . . . 72
4.1.2.5 Influence of the aluminum pretreat-
ment on selectivity and conversion
degree (MMCR4,MMCR5) . . . . . 76
4.1.2.6 Silver supported on anodic
preoxidized aluminum surface
(Ag/Al2 O3 /Al, MCR2) . . . . . . . 78
4.1.2.7 Silver supported on metallic Al
(Ag/Al, MCR3) . . . . . . . . . . . 83
4.1.3 Silver supported on -Al2 O3 surface . . . . . 93
4.1.3.1 Silver sputtered on ANOF prepared
-Al2 O3 surface (MMCR6) . . . . . 93
4.1.3.2 Silver sputtered on -Al2 O3 (sol-gel
coating) . . . . . . . . . . . . . . . 95
4.1.3.3 Silver impregnated on -Al2 O3 sur-
face by sol-gel coating (MMCR8) . 96
4.1.3.4 Usage of a commercial SHELL-800
Series, -Al2 O3 based EO silver
catalyst in microchannel reactors
(MMCR9, MMCR10) . . . . . . . . 104
Contents 9
5 Discussion 153
5.1 Computation of selectivity vs. conversion behavior . 154
5.1.1 Computation based on published kinetic data 154
5.1.2 Computation based on a triangular reaction
scheme . . . . . . . . . . . . . . . . . . . . . . 157
5.2 Catalytic performance of different silver coatings . . 159
5.3 Influence of the reaction conditions on catalytic per-
formance . . . . . . . . . . . . . . . . . . . . . . . . . 160
5.3.1 Impact of different oxygen concentrations . . 160
5.3.2 Impact of different ethene concentrations . . 162
5.3.3 Impact of the total pressure . . . . . . . . . . 163
5.3.4 Selectivity and conversion behavior of differ-
ent silver catalysts . . . . . . . . . . . . . . . 164
5.3.4.1 Experimental findings . . . . . . . . 164
5.3.4.2 Computations . . . . . . . . . . . . 166
5.3.5 Calculation of activation energies . . . . . . . 173
5.4 Heat effects and reaction engineering aspects . . . . 176
5.4.1 Temperature profiles and heat effects in mi-
crochannel reactors . . . . . . . . . . . . . . . 176
5.4.2 Reactor construction . . . . . . . . . . . . . . 179
5.4.3 Performance parameters of fixed-bed and mi-
crochannel reactors . . . . . . . . . . . . . . . 180
5.4.3.1 Comparison of tube type and cor-
responding microchannel reactors
(FBR1-3, MCR1-3) . . . . . . . . . 181
5.4.3.2 Comparison of reactor performance 182
6 Experimental 187
6.1 Flow apparatus . . . . . . . . . . . . . . . . . . . . . 187
Contents 11
7 Appendix 213
7.1 Chemical properties of ethylene oxide . . . . . . . . 213
7.2 Environmental effects of ethylene oxide . . . . . . . 215
7.3 Physical properties of ethylene oxide . . . . . . . . . 217
7.4 Additional figures and measurements for MCR2 . . . 218
7.5 Additional figures and measurements for MCR3 . . . 222
7.6 Additional figures and measurements for MMCR8 . 226
7.7 Additional figures and measurements for MMCR9/10 229
7.8 Additional figures and measurements for MCR2Cs . 233
12 Contents
Bibliography 239
Chapter 1
Introduction
13
14 Chapter 1. Introduction
1.1.1 Wurtz-process
Figure 1.2: Miners lamp with flame stopping 600-800 mesh sieve for use
in explosive atmospheres.
H O
Cl2 + 2OH
2
Cl + ClO + H2 O
ClO + C2 H4 + H2 O Cl CH2 CH2 O + OH
2 Cl CH2 CH2 OH + CaO 2 C2 H4 O + CaCl2 + H2 O
Cl2 + C2 H4 C2 H4 Cl2
HCl + C2 H4 C2 H3 Cl
C2 H4 O + H2 O HOCH2 CH2 OH
oxide. Thus, ethene is better utilized than in the air based process,
although an additional air separation unit for oxygen enrichment is
required. Despite the higher investment costs, nowadays the oxygen
based process is the only one left.
1.2. Handling of ethene oxide 19
product usage / %
ethylene glycols 55
polyglycols 4
ethanolamines 7
glycol ethers 12
surface active agents 12
polyols 4
other 6
and TEG are used for gas treatment as absorbent and TEG is
furthermore needed for production of cellophane. PEG is used
in the cosmetic and pharmaceutical industry as base material for
carrying the active ingredients [10].
Ethanolamines, which are also widely used in pharmaceutical
and cosmetic products are obtained by the reaction of ethylene oxide
and ammonia:
Those ethers are mainly used as solvents, detergents, brake fluid and
extracting agent for SO2 , H2 S, CO2 and mercaptanes from natural
gas. Minor amounts of ethylene oxide are directly used as sterilizing
agent in hospitals and the food industry [12, 14] (see Appendix, page
215 for toxicity and environmental data) .
Chapter 2
Objectives
23
24 Chapter 2. Objectives
25
26 Chapter 3. Theory
6 O2 + 6 Ag 6 (Ag O2 )
3 O2 + 6 Ag 6 (Ag O)
6 (Ag O2 ) + 6 C2 H4 6 C2 H4 O + 6 (Ag O)
6 (Ag O) + C2 H4 2 CO2 + 2 H2 O + 6 Ag
7 C2 H4 + 6 O2,ads 6 C2 H4 O + 2 CO2 + 2 H2 O
6 N2 O + 6 Ag 6 (Ag O) + 6 N2
6 (Ag O) + C2 H4 2 CO2 + 2 H2 O + 6 Ag
oxygen partial pressure than the rate of the total oxidation. There-
fore, higher oxygen partial pressures improve the degree of conver-
sion as well as the selectivity to ethylene oxide Contrary, Borman &
Westerterp [29] found in more recent investigations, that there is no
difference in the reaction rate whether 7% or 12% oxygen are used,
applying 1% C2 H4 in the feed.
Furthermore, the reaction rate of ethene to ethylene oxide on
the one hand and to carbon dioxide on the other increase nearly
simultaneously with increasing ethene partial pressure, showing a
maximum in both reaction rates [8]. After passing the maximum,
the reaction rate of the total oxidation drops faster the rate of the
epoxidation, suggesting increased selectivities with increasing ethene
partial pressures. Similar observations were made by Khasin [30]
as well as Cant & Hall [28]. Again contrary, Borman & Westerterp
found, that the selectivity to ethylene oxide decreases with increasing
ethene partial pressure [29].
There is also little common agreement about the influence of
the reaction products on selectivity and conversion degree, although
many authors (but not all) agree, that in absence of chlorine com-
pounds, carbon dioxide enhances selectivity and decreases the overall
reaction rate [31, 32]. In order to get a brief insight of the influence of
C2 H4 and O2 partial pressures on selectivity and conversion degree,
a kinetic model had to be adapted. Recently, a Dutch research group
performed extensive investigations [63, 64] and published a kinetic
model [29, 31], which was derived from experiments with a tube-type
(single pass) and a Berty / Bobo reactor (internal gas recirculation)
using a commercial ethylene oxide catalyst based on Ag/-Al2 O3 .
The authors tested four different kinetic models, generally assuming
Table 3.1: Kinetic constants for the selective oxidation and to-
tal combustion of ethene for a Berty- and tubular-type reac-
tor [31]
18,0
17,5
lg rC H O / a.u.
17,0
4
2
Ag/Al 2O3
16,5 Ag/SiO 2
Ag powder
16,0
0 20 40 60 80 100 1000
particle diameter / nm
510
400
504
476
499
300
axial position / mm
488 482
493
temperature / K
493 488
200 504
499 482
100 476
471
476 471
0 465
0 5 10 15 20 25
radial position / mm
475 50
42
470
33 42
465 17 25
wall temperature / K
33
460
temperature / K
455 8 25
450
17
445 8
8
440
435 0
0 100 200 300 400
axial position / mm
Figure 3.4: Axial reactor temperature rise (at r=0 mm) within an
industry-like reactor tube as a function of the adjusted wall tempera-
ture [62]. Reaction conditions: GHSV=0.82 kg/m2 s, c(C2 H4 )=0.5% in
air, p=0.5 MPa.
120
100
temperature rise / K
heat production / W
80
10
60
40
heat production
20 calculated adiabatic temperature rise
measured temperature rise
1
430 440 450 460 470 480
wall temperature / K
505
250
475 500
470 475
200 495
temperature / K
490
flow rate / l/min
150 480
485
480
100
485 475
495
50 490 500 470
20 465
0 100 200 300 400
axial position / mm
120 70
110 60
100 50
heat production / W
(Tmax-TWall) / K
90 40
80 30
70 20
heat production
60 10
calculated adiabatic temperature rise
measured temperature rise
50 0
0 50 100 150 200 250
0,9 540
520
490 530
0,8
ethene concentration / vol%
510 520
0,7
temperature / K
500 510
0,6
500
0,5
490
0,4
480
0,3 480
470 470
470
0,2 460
0 100 200 300 400
axial position / mm
The highest absolute heat production of 163 Watt within this reactor
was obtained at a wall temperature of 465K, 22% conversion degree,
64% selectivity and a mass flow rate of 2.51 kg/m2 s. Therefore,
the highest volume specific heat production rate was 144 kW/m3
catalyst. At this point, the authors pointed out the reactor was
operated very close to a runaway.
3.4. Reactor design and heat management 41
dT
Q = A (3.4)
dx
Therefore, the higher the heat conductivity , the higher the heat
exchange area A and the lower the distance x, the lower is the result-
ing temperature gradient T for a given heat flux Q. A thin coating
with only a few microns will not cause a major heat transfer resis-
tance between the presumably ceramic like coating to the metal core
of the reactor. Furthermore, the metallic framework provides a su-
perb heat conductivity, which is typically one dimension higher than
that of a ceramic frame. For example, the heat transfer coefficient
of glass is in the range of to 1 W/mK, ceramic frames such as -
Al2 O3 exhibit 25 W/mK, whereas metals like steel, aluminum and
silver have heat transfer coefficients of 70 to 400 W/mK [66]. And
3.4. Reactor design and heat management 43
ide (utilizing hydrogen from the carrier gas) in order to make them
visible in the sensitive flame ionization detector [70]. Another ex-
ample is the application of microreactors and microchannel reactors
in screening devices for rapid discovery and evaluation of catalysts.
In order to keep the effort for synthesizing huge numbers of catalyst
samples low, microchannel reactor have successfully been utilized for
suchlike systems (Fig. 3.13) [69, 71].
Another interesting feature of a microchannel reactor is its suit-
ability for handling explosive mixtures. Recently, the oxidation of
hydrogen was performed in a 1 cm3 microchannel reactor (Fig. 3.12)
providing a crossflow cooling and having a microchannel cross sec-
tion of 140 x 200 m2 [67]. In this reactor, a stoichiometric mix-
ture of undiluted H2 and O2 was converted neither with runaway
nor explosion. The authors reported, that the microchannels are
smaller than the quenching distance of hydrogen, which is reported
to be 1 mm in capillary tubes. Therefore, possible explosions are
quenched immediately in the narrow channels of the reactor.
1,0
0,8
degree of conversion
0,6
0,4
0,2
0,0
0 1 2 3 4 5
time / min
Figure 3.15: Photo of a 30 t per year pilot plant system for pigment
synthesis [89].
Chapter 4
Results
51
52 Chapter 4. Results
Table 4.1: Overview of the investigated microchannel & fixed bed re-
actors and their main purpose. MCR = MicroChannelReactor, MMCR
= Modular MicroChannelReactor
Denomination Purpose
MCR1 Benchmark reactor using bulk silver
Vreactor,geometric
= (4.1)
VSTP
0,016 0,8
0,014 0,7
0,012 0,6
0,010 0,5
0,008 0,4
0,006 0,3
0,004 0,2
0,002 0,1
0,000 0,0
0 5 10 15 20 25 30 35
time on stream / h
0,65
0,60 523K
543K
0,55
0,50
degree of conversion
543K
0,10
523K
0,05
503K
0,00
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
0,62
0,5
0,60
0,58
0,3
0,56
0,1
0,52
0,0
0 10 20 30 40 50 60 70
C H concentration / %
2 4
0,60
503K
0,58 523K
543K
selectivity to ethylene oxide
0,56
0,54
0,52
0,50
0,48
0,46
0,15 0,20 0,25 0,30 0,35 0,40 0,45 0,50 0,55 0,60
degree of conversion
0,64
0,62 503K
0,60 523K
543K
selectivity to ethylene oxide
0,58
0,56
0,54
0,52
0,50
0,48
0,46
0,44
0,42
0,40
0,05 0,10 0,15 0,20 0,25 0,30 0,35
degree of conversion
/ K
1400
ad
heat production / W
T
1200
800
600
1
400
200
0 0
selectivity to ethylene oxide
0,65
0,60
0,55
0,50
0,45
0,40
0,00 0,05 0,10 0,15 0,20 0,25 0,30 0,35
degree of conversion
0 5 10 15 20
0,58
0,56
0,54
0,30
degree of conversion
0,25
0,20
0,15
0,0 0,5 1,0 1,5 2,0
pressure / MPa
0,62
0,60
0,58
0,56
degree of conversion
0,10
0,05
0,00
480 490 500 510 520 530 540
reactor temperature / K
0,45 0,65
0,40
0,35 0,60
0,30
0,25 0,55
0,20
0,15 0,50
0 2 4 6
210
ratio EO / acetaldehyde
concentration
200
190
180
0,004
selectivity to acetaldehyde
conc. / %
0,025
0,020
acetaldehyde
0,015 0,002
0,010
0,005
0,000 0,000
0 1 2 3 4 5 6
/ s (STP)
Figure 4.11: REM surface picture of the 200 nm silver coated (PVD)
modular microchannel reactor MMCR1 before (a) and after (b) use.
first run
second run
0,72
selectivity to ethylene oxide
0,70
0,68
degree of conversion
sion after the first run. Each experiment took about 12 hours. Small
amounts of acetaldehyde were detected only at high conversion de-
grees and the concentration ratio of EO to acetaldehyde was close
to 600, resulting in selectivities close to 0.1%.
Internal repeatability test: Nearly any experiment in the
present work was performed such, that the data point with the high-
est flow rate was repeated at the end of each run. Thus, the run was
started with the highest available flow rate and the flow rate step-
wise lowered until the lowest flow rate was reached. Eventually, the
first data point at the highest flow rate was adjusted again to check
for a potential deviation by a not fully stabilized / aged catalyst.
If this check for repeatability was unsuccessful, the whole run was
performed again. Each run took approximately 12 hours, therefore
this procedure ensured a short term repeatability.
4.1. Epoxidation of ethene in microchannel reactors 69
0,6
0,5
0,8
degree of conversion
0,6
0,4
0,2
0,0
440 460 480 500 520 540 560 580 600 620 640
reactor temperature / K
ratio EO/acetaldehyde
600
concentration
400
200
0
conc. of acetaldehyde / %
0,08
0,06
0,04
0,02
0,00
440 460 480 500 520 540 560 580 600 620 640
T/K
0,72
0,70
0,68
0,66
0,64
first run
second run
after high
0,62
temperature exp.
degree of conversion
0,60
0,55
0,50
selectivity to ethylene oxide
0,45
0,40
0,35
0,30
degree of conversion
0,030
50 nm Ag
Figure 4.17: Concentration
concentration of acetaldehyde / %
0,000
0,65
0,60
b tion of the conversion degree
(attained by residence time
0,55 variation) for the Ag/Al mi-
crochannel reactor MMCR3
a
(1400 nm Ag). Unstructured
0,50
backside of wafers (a) with-
out coating (b) with 400 nm
0,45 Ag sputter coating. Reaction
uncoated unstructured side conditions: 20% C2 H4 in O2 ,
400 nm Ag on unstructured side
p= 0.3 MPa, T= 523 K.
0,40
0,1 0,2 0,3 0,4
degree of conversion
0,52
selectivity to ethylene oxide
0,50
0,48
0,46
0,44
degree of conversion
0,15
0,10
0,05
MMCR4: Ag on unmodified Al surface
residence time / ms
0,70
0,68
selectivity to ethylene oxide
0,66
463K
0,64
483K
0,62
0,60
503K
0,58
0,56
degree of conversion
0,68
463K
0,66
selectivity to ethylene oxide
0,64
483K
0,62
0,60
0,58 503K
0,56
0,54
0,52
0,50
0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40
degree of conversion
0,70
0,65
0,60
0,55
degree of conversion
0,15
0,10
0,05
0,00
430 440 450 460 470 480 490 500 510
reactor temperature / K
0,66
fresh catalyst
aged catalyst
selectivity to ethylene oxide
0,64
0,62
0,60
0,58
0,56
degree of conversion
tion was always below 0.004 vol% and thus, below the detection limit
of the online gas chromatograph for this component.
0,68
483K
selectivity to ethylene oxide
0,66
503K
0,64
0,62
0,60 523K
0,58
0,56
0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45 0,50 0,55
degree of conversion
0,70
503K
0,66
0,64
523K
0,62
0,60
degree of conversion
0,53
0,52 4% C 2H 4
0,51
selectivity to ethylene oxide
0,50 20% C 2H 4
0,49
0,48
0,47 40% C 2H 4
0,46
0,45
0,44
0,43
0,42 60% C 2H 4
degree of conversion
40% C H
2 4
7
EO concentration / %
6 60% C H
2 4
20% C H
2 4
5
4% C H
2 4
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4
residence time / s
0,55
0,50
selectivity to ethylene oxide
0,45
0,40
0,35
0,30
0,25
0,20
degree of conversion
0,64
0,62
0,60
0,58
degree of conversion
0,20
0,15
0,10
0,05
reactor temperature / K
0,70
selectivity to ethylene oxide
0,65
0,60
0,55
0,25
degree of conversion
0,20
0,15
0,10
0,05
0,00
450 460 470 480 490 500 510 520 530
reactor temperature / K
0,66
increasing TOS
first experiment
0,64
selectivity to ethylene oxide
0,62
0,58
0,56
0,54
0,52
0,50
0,48
0,46
0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45 0,50 0,55 0,60 0,65
degree of conversion
adjusted. Therefore, the very first and the very last data point in
each experiment refers to the same residence time. The results of
those experiments are shown in figure 4.31.
With the fresh catalyst, the selectivity decreased with increas-
ing reactor temperature from a range of initially 66.1% to 59.7%
at conversion degrees of 11.7% and 26.0%, respectively (see Fig.
4.25). With increasing time on stream, including some experiments
at very high reactor temperatures, the selectivity dropped to a range
of 55.8% to 46.2% at higher conversion degrees of 22.3% to 60.4%,
respectively. Therefore, the conversion degree nearly doubled as a re-
sult of aging of this catalyst, whereas the selectivity to EO decreased
by 10.3% (abs.). Furthermore, the shape of the X/S curves changed.
Although the selectivity of the fresh catalyst was higher than that
of the aged one, the selectivity of the fresh dropped sharply at con-
version degrees of about 20 - 25%. In contrast, the aged catalyst
showed no remarkable dependence of the selectivity on conversion
degree within that range.
92 Chapter 4. Results
0,016
0,6
0,014
degree of conversion
0,012
0,010
0,5
0,008
0,006
0,4
0,004
0,002
0 5 10 15
time on stream / h
At this point, the experiment was stopped. Despite the low conver-
sion degree and low EO selectivity, small amounts of acetaldehyde
(0.002 to 0.004%) were observed within the first five hours of oper-
ation. Due to these disappointing results, this coating method was
not further investigated.
0,07 0,7
0,06 0,6
0,04 0,4
0,03 0,3
0,02 0,2
0,01 0,1
0,00 0,0
/ s
0,30
Figure 4.34: Selectivity to
ethylene oxide as a func-
selectivity to ethylene oxide
0,25
tion of the conversion degree
0,20 (attained by residence time
variation) for the Ag/-
0,15 Al2 O3 microchannel reac-
0,10
tor MMCR8 (impregnated
once). Reaction condi-
0,05 tions: 20% C2 H4 in O2 ,
p= 0.3 MPa, T= 523 K.
0,00
0,55
0,50
selectivity to ethylene oxide
0,45
0,40
0,35
483K 503K
0,30
0,25
0,20
0,15
0,10
0,0 0,1 0,2 0,3 0,4 0,5 0,6
degree of conversion
0,50
0,45
selectivity to ethylene oxide
0,40
40% C2H4
0,35
60% C2H4
0,30
0,25
0,20
0,15
20% C2H4
0,10
0,05
4% C2H4
0,00
0,0 0,2 0,4 0,6 0,8 1,0
degree of conversion
60% C H
2 4
3
20% C H
2 4
4% C H
2 4
/ s
0,58
0,56
0,54
0,52
0,50
degree of conversion
0,06
0,04
0,02
0,00
460 470 480 490 500 510
reactor temperature / K
0,60
= 240 ms
0,55
selectivity to ethylene oxide
0,50
C H concentrations
2 4
0,40
0,35
0,30
0,25
0,20
fresh,
0,15
after preparation
0,10
degree of conversion
tial pressure was lowered from 20% to 8.8% in order to apply oxygen
conditions, which are comparable to industrially used reaction con-
ditions. It will be shown later (see chapter 4.4) that MMCR10 using
the new modular microchannel reactor type II design having low post
catalytic volumes performed better than the traditional modular mi-
crochannel reactor type I. Therefore, after activation four of the six
wafers were mounted in the new modular reactor type II (MMCR10)
and all further examinations in this part refer to MMCR10 and the
newer construction type of the microchannel reactor.
483K
0,55
selectivity to ethylene oxide
0,50 503K
0,45
523K
0,40
0,35
0,30
543K
degree of conversion
0,65
0,55
503K
0,50
0,45
523K
0,40
0,35 543K
0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45 0,50
degree of conversion
0,6
0,5
degree of conversion
0,15
0,10
0,05
0,7
20% O 2 80% O 2
0,6
0,5
0,4
0,06
0,05
degree of conversion
0,04
0,03
0,02
0,01
0 10 20 30
time on stream / h
0,54
0,52
0,50
0,48
0,46
0,0 0,2 0,4 0,6 0,8 1,0
degree of conversion
0,70
0,65
0,60
0,20
degree of conversion
0,15
0,10
0,7
0,6
0,5
unpromoted
0,4 130 ppm NO2
degree of conversion
0,3
0,2
0,1
0,0
degree of conversion
selectivity to EO Figure 4.47: Degree of
0,6
conversion and selectivity
to ethylene oxide of the
0,5
Ag/Al microchannel reactor
MMCR12 at NO2 -free con-
0,4
trol experiments. Reaction
conditions: 20% C2 H4 in
0,3 O2 , p= 0.3 MPa, T= 503 K,
= 1.0 s.
0,2
0,1
0,0
inital state after NO 2 treat- after NO 2 treat-
ment (low conc.) ment (high conc.)
0,76
Exp.1: unprom.
0,74
Exp.2: NO (130 ppm) prom.
2
0,72
Exp.3: Cs modified
0,66
0,64
0,62
0,60
0,58
0,56
0,54
0,52
0,50
0,48
degree of conversion
463K
selectivity to ethylene oxide
0,66
483K
0,64
0,62
503K
0,60
0,2 0,3 0,4 0,5 0,6 0,7 0,8
degree of conversion
0,70 463K
selectivity to ethylene oxide
0,69
483K
0,68
0,67
0,66
503K
0,65
0,64
0,63
0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45
degree of conversion
0,80
0,75
0,70
0,65
0,60
degree of conversion
0,20
0,15
0,10
0,05
0,00
430 440 450 460 470 480 490 500 510
reactor temperature / K
0,75
FB R 1a, 523K
0,70
selectivity to ethylene oxide
FBR 1a, 543K
0,65
0,60
MCR 1, 523K
0,55
0,45
0,40
degree of conversion
0,55
543K
0,50
0,45
0,40
selectivity to ethylene oxide
0,55
0,50
523K
0,45
543K
0,40
0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45
degree of converion
The sputter and PVD coated aluminum wafers used in the mi-
crochannel reactors MCR2 (Ag/Al2 O3 /Al) and MCR3 (Ag/Al) were
investigated in a fixed bed reactor by coating and treating thin alu-
minum coil material in the same way, the microstructured wafers
were treated. Therefore, two different aluminum supported silver
catalysts were investigated in a fixed bed reactor.
The Ag/Al2 O3 /Al catalytic system used in the microchannel
reactor MCR2 was transferred into a fixed bed reactor by treating a
0.1 mm Al foil (AlMg3) in the same way, the microstructured wafers
were treated. According to the preparation of MCR2, the foils were
anodically oxidized first and then subsequently coated with 800 nm
silver by sputtering. Therefore, the catalytic active surface and the
surface area should be the same. The geometric surface area of this
catalyst denominated FBR2 was 340 cm2 and therefore the same as
in MCR2.
In order to attain better comparability and to exclude aging
effects, an experiment with the fresh microchannel reactor, having
nearly the same initial degree of conversion was chosen as refer-
ence. This time, very similar selectivities and conversion degrees
were obtained, as shown in figure 4.55 and 4.56. Using 20% ethene
in oxygen and a reactor temperature of 503 K, the selectivity was
initially 64.8% at a conversion degree of 11.4%. With increasing de-
gree of conversion, the selectivity decreased nearly steadily to 55.2%
128 Chapter 4. Results
0,66
MC R2
0,62
0,60
0,58
0,56
FBR2
0,54
degree of conversion
0,68
0,66
MC R2
selectivity to ethylene oxide
0,64
0,62
0,60
FBR2
0,58
0,56
0,54
0,52
0,50
0,30 0,35 0,40 0,45 0,50 0,55 0,60 0,65 0,70 0,75
degree of conversion
aluminum foil was 340 cm2 and therefore the same as the total
geometric surface area of MCR3. The selectivity / conversion
behavior of this Ag/Al coating in a fixed bed (FBR3), as well as in
the microchannel reactor MCR3 is depicted in figure 4.57.
At low conversion degrees, 60.9% selectivity at a conversion de-
gree of 14.5% was observed for FBR3. With increasing conversion
degree, the selectivity increased slightly with increasing degree of
conversion to 62.9% at a conversion degree of 44.4%. In order to
attain better comparability and to exclude aging effects, an experi-
ment with the fresh microchannel reactor MCR3, having nearly the
same initial degree of conversion was chosen. Initially, a selectivity of
62% at a conversion degree of 14.1% was observed. With increasing
degree of conversion, the selectivity decreased to 57.4% at a conver-
sion degree of 40.1%. Therefore, the microchannel MCR3 showed
initially a higher selectivity, but a very different selectivity / con-
0,64
FB R 3
selectivity to ethylene oxide
0,62
0,60
MCR 3
0,58
0,56
degree of conversion
Figure 4.57: Selectivity to ethylene oxide of the Ag/Al fixed bed reac-
tor FBR3 and the corresponding microchannel reactor MCR3 as a func-
tion of the conversion degree. Reaction conditions: 20% C2 H4 in O2 ,
p= 0.3 MPa, T=523 K.
4.2. Epoxidation in traditional tube-type fixed bed reactors 131
0,64
catalyst after accidental
treatment with 60% C2H4 in O2
0,63
selectivity to ethylene oxide
0,62
0,61
0,60
0,58
0,00 0,02 0,04 0,06 0,08 0,10 0,12 0,14
degree of conversion
483K 503K
selectivity to ethylene oxide 0,64
0,62
523K
0,60
0,58
0,56
0,54
0,00 0,05 0,10 0,15 0,20
degree of conversion
5.6% (abs.). After each GHSV variation, the reactor was switched
from minimum throughput (highest conversion degree, lowest heat
production rate) to maximum throughput (lowest conversion degree,
highest heat production rate) to check for potential deactivation. On
this occasion, the reactor had a runaway followed by an explosion of
the C2 H4 / O2 mixture in the cooling traps - directly after switching
between the two flow rates in the last experiment at 523 K. At this
point, the experiments with the fixed bed catalyst were stopped.
MMCR10, 483K
0,62
FBR4, 483K
MMCR10, 503K
selectivity to ethylene oxide
FBR4, 503K
0,60
0,58
0,56
0,54
0,52
degree of conversion
566 O
2
20% 2H4 C in O
2
564
T/K
562
560
1,0
0,5
0,0
T / K
-0,5
-1,0
-1,5
-2,0
0 10 20 30 40 50
pos o
iti n in the wafer stack / mm
inlet = 0 , ou
mm tlet = 50 mm
heating device was used as reference. The heating device always adjusted this
point in the middle of the reactor to the setpoint temperature
138 Chapter 4. Results
800
600
/K
400
ad
T
200
10
5
P/W
stack inlet
l=0 mm
-2,0
0,5
-0,5 0 -1,0
-0,5
as flow
ection
T / K
0
0
dir
g
0,5
2,0
l=50 mm
T / K
attained, but the total heat production was comparably low. Con-
trary, at high flow rates, low conversion degrees at low adiabatic
temperature rises were attained, but the highest heat production
was observed. The dependence of the calculated adiabatic temper-
ature rise and the heat production on the flow rate is depicted in
figure 4.65.
2500
2000
Tad / K
1500
1000
500
15
10
P/W
0
0 200 400 600 800 1000 1200
flow rate / ml/min (STP)
stack inlet
l=0 mm
-3,0
-2,0
1,0
-1,0
as flow
ection
T / K
0 0
dir
g
-1,0
1,0
2,0
-2,0
3,0
l=50 mm
l
f ow r ate / ml/min (STP)
stack inlet
l=0 mm
-2,0
-1,0
2,0
0
flow
direction
T / K
1,0
gas
1,0
2,0
-1,0
3,0
4,0
stack outlet 0 10 20 30 40 50 60
l=50 mm
C H concentration / %
2 4
stack inlet
l=0 mm
-2,0
-1,0
2,0
0
flow
direction
T / K
1,0
gas
1,0
2,0
-1,0
3,0
4,0
stack outlet 0 10 20 30 40 50 60
l=50 mm
C H concentration / %
2 4
30
25
20
reactor inlet middle of reactor
T / K
15
10
0
reactor outlet
0 5 10 15 20 25 30 35 40 45 50 55
time / min
to precisely 563 K.
The opposite effect was observed when the reaction mixture
of 20% C2 H4 was switched to 100% oxygen. Therefore, no more
heat was produced by the reaction and the heated sheathing cooled
down for a short time before the temperature controller increased
the electric power compensating the sudden loss of heat. The results
of this experiment are depicted in figure 4.70. This time, the reactor
temperature decreased rapidly as ethylene was removed from the
feed. At t= 3 min, the reactor temperature at the inlet was down
by 21K, the temperature in the middle of the reactor was down by
19 K and at the end of the reactor, the temperature was down by
14.5 K. After approximately one hour, the reference temperature
was back to 563 K and the temperature controller had successfully
finished its adaption to the new thermal properties of the device.
Applying lower reactor temperatures and therefore, lower heat
production rates, those dynamic temperature gradients of the reac-
reactor outlet
-5
T / K
-10
-15
0 5 10 15 20 25 30 35
time / min
0 10 20 30
time / min
0 10 20
time / min
4.4. Design aspects of modular microchannel reactors 149
0,62
MMCR10
0,60
Type II
selectivity to ethylene oxide
0,58
0,56
0,54
MMCR9
0,52
Type I
0,50
0,48
0,46
0,54
MMCR 15
selectivity to ethylene oxide
Type II
0,52
0,50
MMCR 14
0,48 Type I
0,46
0,44
0,42
This chapter is divided into four parts. In the first part as a phase-
in for the experimental results, selectivity vs. conversion curves are
computed from published kinetic parameters to allow a re-evaluation
of the obtained results and their consistency with published data.
In the second part, the general catalytic performance of different
silver coatings is summarized.
In the third part, the influence of the reaction conditions on
the catalytic performance of the best coating methods is discussed.
The performance and catalytic properties of different coatings will
be compared, applying ethylene/oxygen concentrations within the
explosion range to reach high degrees of conversion and therefore,
challenging reaction conditions.
In the fourth part of the discussion, reaction engineering aspects
are addressed, with a main focus on reactor and wafer construction.
153
154 Chapter 5. Discussion
0,05 0,35
0,014 0,65
conversion degree
0,010 0,55
0,03 0,25
0,008 0,50
0,004 0,40
0,01 0,15
0,002 0,35
Berty-reactor tubular-reactor
0,000 0,30 0,00 0,10
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
0,10 0,12
0,32
0,09 0,55
0,10
0,08
conversion degree
0,08
0,06
0,24
0,20
0,04
0,04
0,03 0,40
0,16
0,02
0,02
0,01 0,35
tubular-reactor 0,12
Berty-reactor
0,00 0,00
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
0,55
0,50
selectivity to ethene oxide
0,40
0,35
0,30
0,25
tubular reactor
0,20
s
conver ion degree
C2H4O
k2 k3
k1
C2H4 CO2 + H2O
3. The Dutch group [31, 32] assumed a first order reaction for the
consecutive combustion of ethylene oxide
158 Chapter 5. Discussion
k2/k3=10.0
0,50
5.0
0,45
0,40 3.3
0,35
2.0
Selectivity to EO
0,30
1.0
0,25
0.5
0,20
0,15
0,10
0,05
0,00
D egree of Conversion
Figure 5.5: Selectivity vs. conversion plot for the reaction scheme de-
rived from Fig. 5.4 assuming a first order power law kinetic, a ratio of
k1
k2
= 1 and k2
k3
of 10, 5, 3.3, 2, 1 and 0.5 for the rates of the consecutive
combustion.
cA
= k1 cA k2 cA (5.1)
t
cB
= k2 cA k3 cB (5.2)
t
cC
= k1 cA + k3 cB (5.3)
t
It can be clearly seen (Fig. 5.5), even high rates for the subsequent
combustion of ethylene oxide still allow high selectivities for the in-
termediate product ethylene oxide. As a matter of fact, this simple
model can neither explain any increase in selectivity with increas-
ing degree of conversion, nor it allows any change in the selectivity
/ conversion curve caused by different concentrations of a reactant
A. All reaction rates follow a first order and thus, their conversion
degree is only a function of the residence time. A dependence on
5.2. Catalytic performance of different silver coatings 159
1. The higher the reactor temperature, the higher the gain in con-
version degree as soon as the oxygen concentration is increased
(e.g. Fig. 4.2, 7.2, 7.6, 7.9, 7.13). Generally, improvements of
the conversion degree by several hundred percent in compari-
son to the typical 8-9% O2 have been observed.
5,0 5,0
STY / mol/ms
STY / mol/ms
4,0 4,0
3,0 3,0
In order to evaluate the different coating methods applied for the mi-
crochannel reactors, the selectivity / conversion behavior of the fresh
catalysts was used as criterion, applying a temperature of 503 K,
20% ethene in oxygen and a pressure of 0.3 MPa. The results are
shown in figure 5.7, with the data points originating from figures
4.5, 4.21, 4.25, 4.35, 4.41 and 4.51. The selectivities were in a range
of nearly 70% down to 15% and conversion degrees up to 62%. The
highest selectivities were observed for the fresh Ag/Al microchannel
reactor MCR3 and the Cs modified reactor MCR2Cs. The lowest
selectivities were observed for the Ag/-Al2 O3 -microchannel reactor
MMCR8 having selectivities slightly above 50%. The lowest conver-
sion degrees were observed for the bulk-silver reactor MCR1 and the
0,7
0,6
selectivity to ethylene oxide
0,5
0,4
MCR1 (Bulk-Ag)
0,3 MCR2 (Ag/Al O /Al)
2 3
degree of conversion
Ag/Al reactor MCR3, although the latter gained a some activity and
lost selectivity with increasing time on stream (see Fig. 4.31). This
aging effect makes it difficult to compare the Ag/Al based catalysts
MCR2 and MCR3 with each other, because the catalytic proper-
ties depend on the time on stream and treatment of the reactor.
It showed, that the selectivity as well as the conversion degree was
initially constant for hours, as long as the flow rate was kept con-
stant. As soon as the flow rate was decreased and thus, the degree of
conversion increased, selectivity was irreversibly lost (see Fig. 4.12,
page 68). Probably, the reaction by-product water is responsible for
this effect. It is known, that aluminum surfaces are sensitive toward
steam, especially at higher temperatures.
All microchannel reactors had in common, that the selectivity
was nearly independent from the degree of conversion as long as
the degree of conversion was kept low. This initially flat selectiv-
ity/ conversion curve indicates an initially similar reaction order of
the partial and the total oxidation reaction as long as simple tri-
angular scheme (Fig. 5.4) is assumed. Therefore, with increasing
reaction progress and decreasing ethylene concentrations, the ratio
of both rates stays similar. With further progress, remarkable selec-
tivity losses are observed. One of the highest degrees of conversion
applying 20% C2 H4 in O2 of 62.4% was observed for the unpromoted
and unmodified Ag/-Al2 O3 catalyst MMCR8 as depicted in figure
4.35.
It can be clearly seen, the self made Ag/-Al2 O3 microchannel
reactor MMCR8 exhibited slightly lower selectivities at the same
degree of conversion than the commercial made Shell 800 Series
Catalyst in the microchannel reactor MMCR10. Concerning the
space time yield, this commercial catalyst is even inferior. At a
conversion degree of 8.1%, a reactor temperature of 503 K and a
pressure of 0.3 MPa, the Shell 800 Series Catalyst in the mi-
crochannel reactor MMCR10 yielded 2.12 mol/m3 s EO, whereas a
space-time-yield of 12.45 mol/m3 s EO was calculated for MMCR8,
adjusting the same pressure, temperature and conversion degree. It
cannot be excluded, that the SHELL catalyst performs better in
presence of chlorine containing modifiers, for which it was intention-
ally designed.
Decreasing selectivities with increasing degree of conversion
166 Chapter 5. Discussion
5.3.4.2 Computations
cA1
= k1 cA1 cA2 k2 cA1 cA2 (5.5)
t
cB
= k2 cA1 cA2 k3 cA2 cB 2 (5.6)
t
cC
= k1 cA1 cA2 + k3 cA2 cB 2 (5.7)
t
In this approach the decomposition rate is proportional the
second power of the ethylene oxide concentration.
cA1
= k1 cA1 cA2 k2 cA1 cA2 (5.8)
t
cB
= k2 cA1 cA2 k3 cB cC cA2 (5.9)
t
cC
= k1 cA1 cA2 + k3 cB cC cA2 (5.10)
t
1 see e.g. Fig. 4.36, p.99
168 Chapter 5. Discussion
0,6
0,5
selectivity to ethylene oxide
0,4
0,3
calc. / exp. data
0,2 / 4% 2H4
C
/ 20% 2H4 C
40% 2H4
0,1
/ C
/ 60% 2H4 C
bal. O
2
0,0
0,0 0,2 0,4 0,6 0,8 1,0
s
degree of conver ion
0,6
0,5
selectivity to ethylene oxide
0,4
0,3
calc. / exp. data
0,2 / 4% 2H4
C
/ 20% 2H4
C
/ 60% 2H4
C
0,0 2
bal. O
b 2
al. O
0,4
0,3
0,2
0,1
0,0
0,0 0,2 0,4 0,6 0,8 1,0
degree of conver ion s
calculated
selectivity to ethylene oxide
0,5
0,4
experimental data
0,3
0,2
0,3
degree of conversion
experimental data
0,2
calculated
0,1
0,0
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
-13
Epoxidation -13,0 Epoxidation
Ea = 60.3 kJ/mol Ea = 58.8 kJ/mol
+/- 1.4 kJ/mol (95%)
-14 -13,5 +/- 1.1 kJ/mol (95%)
-14,0
ln(r) / a.u.
ln(r) / a.u.
-15
-14,5
Total Combustion
Ea = 76.5 kJ/mol -15,0 Total Combustion
+/- 1.7 kJ/mol (95%)
-16 Ea = 73.4 kJ/mol
-15,5 +/- 1.2 kJ/mol (95%)
-17 -16,0
2 3 MCR3 - Ag/Al
-14,5 -15,0
ln(r) / a.u.
ln(r) / a.u.
-15,0
-15,5
Total Combustion Total Combustion
Ea = 76.8 kJ/mol
-15,5 Ea = 73.3 kJ/mol +/- 0.8 kJ/mol (95%)
+/- 1.5 kJ/mol (95%)
-16,0
MCR1 - bulk Ag MMCR8 - Ag/ -Al O
-16,0 2 3
-13 -12,0
Epoxidation
Epoxidation
E = 49.1 kJ/mol
a
E = 59.6 kJ/mol
a
+/- 4.0 kJ/mol (95%)
+/- 0.8 kJ/mol (95%)
-14
-12,5
ln(r) / a.u.
ln(r) / a.u.
-15
-13,0
Total Combustion
-16 Total Combustion
E = 73.0 kJ/mol
E = 71.4 kJ/mol a
a
-1
1/T / K
-1
1/T / K
from the initial silver sputtering. Due to the color of bare aluminum
and silver, such an incident would be unnoticed during preparation.
Such an issue could furthermore explain the lower than anticipated
selectivity of this catalyst (MMCR12, only 55% at 503 K instead of
approx. 60% as anticipated and suggested by the MCR2 and MCR3
results). Exposing the reaction mixture to large areas of bare alu-
mina, selectivity losses caused by isomerization / combustion are
likely. With Cs decreasing the acidity and number of Al2 O3 -sites,
a selectivity gain of 18% and peak selectivities close to 70% were
observed (Fig. 4.48). Contrary, the treatment of MCR2 with Cs
resulted in selectivities of 66% in comparison of initially observed
60% (Fig. 4.21). Therefore, the MCR2 catalyst gained only 6% by
this Cs-treatment but both catalysts reached nearly the same level.
Therefore, an alkali-treatment seems to lower the total oxidation ac-
tivity of Lewis acidic sites on Al2 O3 such that both types of reactors
and catalysts reached a similar performance level despite MMCR12
had a (likely) defect of its coating. The degree of conversion was
176 Chapter 5. Discussion
been investigated. The most important finding was, that the hot-
spot temperature is strongly correlated with the conversion degree
and not with absolute heat production of the reactor. Increased wall
temperature as well as increased hydrocarbon concentration resulted
in higher hot-spot temperatures.
As shown in chapter 4.3 (see p.136ff), similar investigations were
performed for the microchannel reactor MCR3.
Applying only O2 gas flow in absence of C2 H4 , a temperature
profile had to be noted along the reactor axis as shown in figure
4.62. This is likely caused by the outer electric heating device, which
seems to show a non uniform heat distribution although it was made
of aluminum because of its high heat conductivity. Nevertheless,
there must be a contact area between the reactors housing and the
heating device with its cartridges and minor differences in local heat
conductivities caused by non uniform clearance between the two
devices may result in small but measurable heat transfer issues.
After switching to an ethylene/oxygen mixture, the tempera-
ture profile changed slightly. The difference between the maximum
and minimum temperature in absence of a reaction was approx-
imately 3.8 K, with this highly exothermic reaction the gradient
increased to 6.1 K. Furthermore, it was observed that in presence
of an exothermic reaction, the temperature at the reactor inlet in-
creased and the temperature at the outlet decreased. This can be
understood, as soon as the behavior of electrical heating support
is taken into account. The reactor temperature is measured by a
thermocouple located in the middle of the reactor and a self opti-
mizing PID controller adjusts the electrical energy in the heating
cartridges in a way that the temperature at this point is exactly as
adjusted. In presence of an exothermic reaction, fewer electrical en-
ergy is required to keep the reactor on temperature and the gradient
caused by the exothermic chemistry evolves. The reactors inlet with
the highest reaction rate may be therefore slightly hotter than be-
fore and the reactors outlet with a lower reaction rate gets slightly
cooler. Nevertheless, this gradient of 6K at the most is despite the
high heat production per reactor volume by far lower than that of
the industrial reactor tube, having gradients of up to 50 K.
In order to compare microchannel with fixed bed reactors, the
gradient across the reactor is therefore used to characterize the mi-
178 Chapter 5. Discussion
crochannel reactors MMCR type I and type II (see Fig. 4.73). The
reactor type II is designed for a low diffusor volume, providing very
low residence times in the post catalytic zone. This type proved
to be more selective (by 5%) when compared to the older MMCR
type I with its large diffusors using the same flow rate in both
devices. Therefore, post catalytic total oxidation of ethylene oxide
has to be assumed in every single reactor having large diffusors.
Similar observations were found by co-workers [86]. Cs salts seem
to suppress even total oxidation activity of stainless steel diffusors.
When comparing the selectivity/conversion curves for MCR2 and
MCR2Cs (Fig. 4.21 and 4.51), the previously observed crossover
between curves for 483 K and 503 K is surprisingly missing after Cs
treatment.
The modular reactor type II showed much higher temperature
gradients due to its construction and especially at the bottom of
the device with its attached heating cartridge. In comparison to the
MMCR type I with its heating device enclosing the whole reactor
housing, temperature gradients of several Kelvin are unnecessarily
high. In order to decrease the temperature gradients it would be
advisable to attach a second heating device to the reactor, preferably
on the top side. Therefore, the wafers would be heated from the top
and bottom simultaneously. Such an improvement would result in
a reactor having low temperature gradients and a low post-catalytic
volume at the same time. Thus, the advantages of both modular
reactor designs could be combined in a single device if these reactors
types are used in further investigations.
187
188 Chapter 6. Experimental
C2H4
CH4
O2
1
K3
K2
K1
V4
V5
0 C
- 78 C
- 78 C
V3
V1
V2
Q
Q
GC
IR
3
2
off-gas
off-gas
6.1.2 Analytics
The first stream passed some cooling traps to remove volatile com-
pounds such as water and is analyzed online by a Fisher Rosemount
IR regarding its CO2 level. This instrument was also capable of an-
alyzing CO by IR but CO was practically never observed. Instead,
a minor cross sensitivity towards C2 H4 had to be noted.
The condensed (liquid) products collected in the ice traps were
analyzed by a Shimadzu QP-5000 GC/MS and consisted mostly of
water. Besides the main product ethylene oxide, others as acetalde-
hyde, 1.4-dioxane (cyclic dimer of EO), ethylene glycol (EO+H2 O),
acetic acid, formic acid, formalin and formic acid methyl/ethyl ester
have been found in traces. It is likely that most of these components
were formed by side-reactions within the trap.
The second stream was directly fed by an automatic 10-port-
valve having two independent injection loops into a Chrompack CP-
9001 GC equipped with two columns. Both were operated using
Helium as carrier gas. The first column is a Chrompack Silicaplot
column1 and performs the separation of the hydrocarbons including
the separation of methane, ethylene, ethylene oxide and acetalde-
hyde. This column is equipped with a FID2 . The second column
is a Chrompack Poraplot-Q column3 equipped with a TCD4 . This
column is used for the separation of ethene, oxygen and methane.
Water was hardly detectable, because the very broad peak shape did
not allow a sufficient integration / accuracy. Furthermore, its pos-
sible to use this column for the additional quantification of carbon
dioxide to double check this result with the attached IR-photometer.
This method allowed the quantification even at high CO2 concen-
trations above 5%, leaving the metering range of the IR. Therefore,
ethene and methane are analyzed on both columns, CO2 on the
Poraplot- and ethylene oxide and acetaldehyde on the Silicaplot-
column. An example chromatogram is depicted in figure 6.2. The
ability to measure the concentration of the most abundant species
on two independent columns avoids problems caused by statistical
analysis effects. Furthermore, the ability to quantify ethene, ethy-
1 30 m x 0.32 mm, dF= 4 m, column pressure 120 kPa, splitflow 8.4 ml/min
2 Flame ionization Detector
3 30 m x 0.32 mm, dF= 10 m, column pressure 83 kPa, splitflow 15.1 ml/min
4 Thermal Conductivity Detector
190 Chapter 6. Experimental
lene oxide and carbon dioxide as the main carbon containing species
allows to cross-check the results for a good mass balance. This check
was done automatically by a small program, analyzing the logbook
of the GC.
Both GC-detectors as well as the IR were calibrated using
ethene (2.7), oxygen (3.5) and methane (4.0). The calibration for
ethylene oxide and CO (IR only) as well as CO2 was performed
using certified gas-mixtures supplied by Messer-Griesheim.
Selectivities and conversion degrees were automatically calcu-
lated from the GC results making use of the additional CO2 level
measured by IR. It has to be noted, that the calculation of the
selectivity as well as conversion degree are based on the amount
120
1
100 Silicaplot [FID]
Signal / a.u.
80
60
2
40
20
0 2 4 6 8 10 12 14
t/ min
3
400 Poraplot Q [TCD]
300
Signal / a.u.
200
4 5 6
100
0 2 4 6 8 10 12 14
t/min
In this section, the reactor design of the four used types of labo-
ratory reactors is described. Generally, all reactors were made of
stainless steel to allow a guaranteed pressure resistance of 2.5 MPa.
All sealings were made of copper, the reactor material was stainless
steel type 1.4571.
a b
are attached to the stack on each side. A wafer in the middle of the
stack with drillings for thermocouples is provided. Such a reactor is
depicted in figure 6.4.
The heating was performed by resistance wire coiled around the
reactor and insulated by glass fiber tissue (early experiments), later
with an aluminum shell encapsulating the cylinder and providing
sufficient wall thickness of 10mm for four 6.35 mm heating cartridges
having each 50 W electrical power.
This type of reactor has several advantages:
low weight: due to the absence of any fittings, the wall thick-
ness of the housing-material is low compared to the construc-
tions described in the following sections and therefore, the
heat-up and cool down cycle times are very short.
Due to the nature of this construction, there are also some disad-
vantages:
194 Chapter 6. Experimental
hand, the residence time on the catalytic surface for the stream still
passing the catalyst section is higher than estimated.
In order to improve the situation, the application of additional
aluminum foils as an additional gasket was tested. These gaskets
were applied to increase the pressure drop in the bypass pathway
(i.e. between the inner housing and the diffusors). These gaskets
decreased the bypass-flow a bit, but it proved impossible to suppress
it completely.
This drawback combined with the problem of total oxidation
(most likely in the diffusors, see p. 179), a different design of a
modular microchannel reactor was built and tested.
4. The heating plate. This plate located at the bottom of the de-
vice contained a heating cartridge having a maximum power of
6.2. Reactor design 199
Figure 6.7: Modular microchannel reactor MMCR type II. (1) cover
plate, (2) copper gasket, (3) reactor plate, (4) heating plate. Photo with-
out insulation.
200 Chapter 6. Experimental
ered. And finally, the availability of the WEDM machine was limited
and therefore, a different method had to be tested.
One of the less expensive production methods is the milling
process and CNC machines are widely spread. Therefore, 19 par-
allel side milling cutters were precisely mounted on the same arbor
(fig. 6.10). Each cutter had a width of 250 m and was separated
from its neighbors by a thin ring washer of approximately 200 m.
Now, a thin aluminum sheet of 250 x 100 x 0.5 mm was fixed on the
CNC machines work space by a vacuum table. The CNC machine
was now operated in a way, that the parallel mill cuts had a depth of
250-300 m (fig. 6.11). Without further optimization, one 200 mm
millcut took approximately 5 minutes and a whole sheet with four
to five of these millcuts was made within an hour. Using precision
206 Chapter 6. Experimental
Figure 6.11: Sheet with the parallel mill cuts of each 19 channels by use
of the parallel multiple milling method. Resulting channel geometry: 300
x 300 m2 , channel length up to 200 mm possible.
laser cutting, single wafers were made from this sheet. One of these
sheets yielded up to 20 single wafers. After degreasing in acetone
followed by chemical deburring for 30 s in 10 wt% NaOH, the wafers
were ready for use.
dized aluminum was poor and hard to measure due to absence of the
target product ethylene oxide (< 0.002Vol%). Using H2 SO4 as elec-
trolyte, in most cases only CO2 was observed. Using H3 PO4 , nearly
no activity was left accompanied by a not detectable ethylene oxide
formation. Only using 1.5% Oxalic Acid as electrolyte, noteworthy
amounts of ethylene oxide were observed only when large amounts of
silver were immobilized. The immobilization of these amounts was
6.4. Catalyst preparation and coating procedures 209
Combustion
5
C2 H 4 O + O2 2 CO2 + 2 H2 O
2
The combustion is highly exothermic and yields -1210 kJ/mol
or -27469 kJ/kg. The lowest flammability limit is 2.6% in Air.
Even solutions of ethylene oxide in water support combustion
for concentrations above 5 wt%. Therefore, a dilution of 1:100
is necessary if ethylene oxide has to be removed by water [12].
Decomposition
213
214 Chapter 7. Appendix
C2 H4 O CO + CH4
The reaction yields 3051 kJ/kg (134 kJ/mol), causing a
pressure rise in closed systems. This decomposition reaction
is known to proceed explosively under certain circumstances.
TNT for example has a maximum decomposition energy of
4600 kJ/kg [96].
Disproportionation
6 C 2 H4 O 5 C2 H4 + 2 CO2 + 2 H2 O
C2 H 4 O CO + CH4
2 C 2 H4 O 2 CO + C2 H4 + 2 H2
2 C 2 H4 O 2 CO + C2 H6 + H2
Isomerisation
C2 H4 O CH3 CHO
Ethylene oxide can be isomerized to acetaldehyde, yielding a
reaction enthalpy of 2621 kJ/kg (115 kJ/mol). This reaction
is normally performed by use of acidic and / or high surface
materials, such as Al2 O3 , SiO2 , iron oxides or phosphoric
acid [92].
Polymerisation
0,7
0,6
0,10
degree of conversion
0,08
0,06
0,04
0,02
0,00
00 24 48 72 96 120 144 168
time on stream / h
483K
0,6
503K
0,5
0,20 503K
degree of conversion
0,15
483K
0,10
0,05 463K
0,00
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
463K
0,64
0,62
503K
0,60
0,58
0,8
0,6
degree of conversion
0,4
0,2
503K
463K
0,0
0 10 20 30 40
ethene concentration / %
0 2 4 6 8
selectivity to ethylene oxide
0,65
0,60
0,55
0,50
0,18
degree of conversion
0,16
0,14
0,12
0,10
0,0 0,2 0,4 0,6 0,8 1,0
pressure / MPa
0,8
0,6
503K 523K
20% C 2 H4 in 20% O 2
degree of conversion
0,05
523K
20% C 2 H4
0,00 in 80% O 2
0 10 20 30 40 50 60 70 80 90 100 110
TOS / h
483K
0,60
503K
0,55 523K
0,50
0,45
523K
0,20
degree of conversion
0,15
503K
0,10
0,05 483K
0,00
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
483K
0,70
523K
0,65
0,60
0,5
degree of conversion
0,4
0,3
0,2
0,1 523K
483K
0,0
0 10 20 30 40
ethene concentration / %
0,64
0,62
0,60
0,58
0,56
degree of conversion
0,150
0,125
0,100
0,075
pressure / MPa
0,5 483K
503K
0,4
0,3
0,35 503K
degree of conversion
0,30
0,25
0,20 483K
0,15
0,10
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
0,54
483K
0,52
0,50
503K
0,48
503K
0,3
degree of conversion
0,2
483K
0,1
0,0
0 10 20 30 40 50 60
ethene concentration / %
0.55 483K
0.50
503K
0.45
0.25
503K
degree of conversion
0.20
0.15
483K
0.10
pressure / MPa
0,035
0,030 0,60
0,025
0,020 0,55
0,015
0,010 0,50
0,005
0,000 0,45
0 5 10 15 20 25
time on stream / h
0,6
483K
selectivity to ethylene oxide 503K
0,5 523K
543K
0,4
0,3
543K
0,15
degree of conversion
523K
0,10
503K
0,05 483K
0,00
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
0,60
483K
0,50
0,45
0,4
degree of conversion
0,3
0,2
0,1 503K
483K
0,0
0 5 10 15 20
ethene concentration / %
0,60
0,50
0,070
degree of conversion
0,065
0,060
0,055
0,050
0,0 0,5 1,0 1,5 2,0
total pressure / MPa
0,80
0,75
0,70
0,15
degree of conversion
0,10
0,05
0,00
0 10 20 30 40 50
time on stream / h
0,70
selectivity to ethylene oxide
463K
0,65
483K
0,60
503K
0,55
503K
degree of conversion
0,15
483K
0,10
463K
0,05
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
0,70 463K
503K
0,65
0,60
0,55
0,7
0,6
degree of conversion
0,5
0,4
0,3
0,2
503K
0,1
463K
0,0
0 10 20 30
ethene concentration / %
0,80
0,75
0,70
0,65
0,60
degree of conversion
0,20
0,15
0,10
0,05
0,00
430 440 450 460 470 480 490 500 510
reactor temperature / K
0,60
0,55
0,50
0,06
degree of conversion
0,04
0,02
0,00
0 10 20 30 40 50 60 70 80 90
oxygen concentration / %
0,60
0,55
0,50
0,30
0,25
degree of conversion
0,20
0,15
0,10
0,05
0 5 10 15 20
ethene concentration / %
239
240 Bibliography
[14] Sterigenics Food Safety, 344 Bonnie Circle, Corona, CA: Online:
http://www.sterigenics.com
Geburtstag 25.4.1971
Geburtsort Essen
Eltern Hildegard und Hans-Theo Kursawe
Familienstand ledig
Nationalitat deutsch
Berufserfahrung
Siemens AG seit 05/2007
CPC-Systems GmbH 02/2002 bis 05/2007
Ausbildung
Promotion Experimenteller Teil 10/1996 - 01/2002
Technische Universitat Chemnitz