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Ultra-Low Temperature Water-Gas Shift Reaction with

Supported Ionic Liquid Phase (SILP) Catalysts


Wassergas-Shift-Katalyse mit getrgerten ionischen
Flssigkeiten unter extrem milden Reaktionsbedingungen

Der Technischen Fakultt der


Friedrich-Alexander-Universitt Erlangen-Nrnberg
zur Erlangung des Grades
Doktor-Ingenieur

vorgelegt von
Diplom-Ingenieur

Sebastian Werner
aus Boppard

Erlangen 2011

Lehrstuhl fr Chemische Reaktionstechnik


Vorstand Prof. Dr. P. Wasserscheid
Egerlandstr. 3
91058 Erlangen
www.crt.cbi.uni-erlangen.de

Als Dissertation genehmigt von der Technischen Fakultt der Friedrich-AlexanderUniversitt Erlangen-Nrnberg.
Tag der Einreichung: 10.01.2011
Tag der Promotion:
Dekan
Berichterstatter:

14.03.2011
Prof. Dr.-Ing. Reinhard German
Prof. Dr. Peter Wasserscheid
Prof. Dr. Kai-Olaf Hinrichsen
Prof. Dr. Jrg Libuda

Vorsitzender:

Prof. Dr. Martin Hartmann

Die vorliegende Arbeit entstand in der Zeit von November 2007 bis November
2010 am Lehrstuhl fr Chemische Reaktionstechnik der Friedrich-AlexanderUniversitt Erlangen-Nrnberg im Rahmen des BMBF-WING Projekts "Supported Ionic Liquid Phase (SILP)-Katalysatoren" (Frderkennzeichen 03X2012H)
in Kooperation mit der Sd-Chemie AG (2007-2009). Im Rahmen des Excellenzclusters "Engineering of Advanced Materials (EAM)" der Deutschen
Forschungsgemeinschaft (DFG) wurde diese Arbeit weitergefhrt (2009-2010).
Auf Grund des internationalen Interesses wurde die englische Sprache gewhlt.

Fr meine Eltern.

Das Problem erkennen ist wichtiger als die Lsung finden, denn die genaue Darstellung
des Problems fhrt fast automatisch zur richtigen Lsung.
Albert Einstein

Danksagung
Ich mchte mich an dieser Stelle bei allen am Lehrstuhl fr Chemische Reaktionstechnik bedanken - fr kreative Atmosphre und ein schnes Arbeitsklima!
Auch wenn in den meisten Dissertationen eher frmliche Varianten der Danksagung zu finden sind, will ich diese Stelle (die ja auch fast die einzige ist, die
ich in meiner Muttersprache verfasse), dazu nutzen auch ganz persnlich und
offen zu danken.
Mein grter Dank geht an Prof. Dr. Peter Wasserscheid fr die herausfordernde Aufgabenstellung und die Betreuung dieser Arbeit. Die unschtzbaren Mglichkeiten im Bezug auf Konferenzbesuche und Kontakte - aber auch fr das
feinfhlige persnliche Coaching/Mentoring, hat mich menschlich wie fachlich
sehr viel weiter gebracht! Wenn es wirklich gebrannt hat, war immer Zeit fr ein
Gesprch oder eine prompte Antwort - auch das Korrekturlesen dieser Arbeit
mal kurz ber die Weihnachtsfeiertage ist bestimmt nicht Standard. Danke!
Dr. Marco Haumann gilt meine volle Anerkennung - ein Dr.-Ing. ehrenhalber
fr die vielen Tipps, Ideen und Hilfestellungen auch aus der ingenieurwissenschaftlichen Ecke, wre Dir meiner Meinung nach verdient - Danke Marco, das
Arbeiten mit Dir als Gruppenleiter war eine wahre Freude. Die Kaffeepausen,
lockeren Diskussionsrunden, Konferenzaktionen und auch Koch- und Grillabende mit Prof. Brinkhoffs und Dr. Fiege bleiben unvergesslich. Vermissen
werde ich selbige sowieso! Viel Erfolg Dir in Korea!
Auch Dr. Normen Szesni, Dr. Andreas Geisbauer und Dr. Richard W. Fischer
vom Industriepartner Sd-Chemie AG will ich danken. Die wirklich gute Zusammenarbeit und die fachlichen Diskussionen haben mir viele neue Einblicke
gebracht! Es ist nicht alltglich, dass man immer ein offenes Ohr bekommt und
erst recht nicht, dass sich ein Industriepartner auf so kurzen Zeitskalen auch
zu Publikationen durchringt. Ohne diese Kooperation und die externe Reflexion der erzielten Ergebnisse wre vieles nicht so schnell mglich gewesen. Ob
bei einem Bier auf der Berghtte im Kaisertal, auf einer Konferenz oder beim
Telefonat zwischen Tr und Angel. Sowohl persnlich als auch fachlich war
die Zusammenarbeit wirklich super!

Dr. Agnes Bittermann und Prof. Dr. Peter Hrter vom Lehrstuhl fr Anorganische Chemie der TU Mnchen sei fr die Synthese, Charakterisierung und
Bereitstellung der Liganden und Komplexe im Rahmen des BMBF Projekts
gedankt. Analog auch ein Dank an Dr. Marc Uerdingen von der Merck KGaA
fr anregende Diskussionen und Bereitstellung der ILs. Auch Frau Dr. Stefanie Neuendorf von der Linde AG sei fr die Wirschaftlichkeitsabschtzungen
und die Messung der Gaslslichkeiten im Rahmen des Projekts gedankt. Im
Rahmen des Excellenzclusters war vor allem die Zusammenarbeit mit der
Physikalischen Chemie, im speziellen Prof. Dr. Libuda und Marek Sobota sehr
hilfreich. Dr. Wolfgang Hieringer und Hannes Schulz von der Theoretischen
Chemie mchte ich fr aufschlussreiche Diskussionen rund um die Mechanismen der WGS danken. Auch Prof. Dr. Zenneck sei fr die Tipps in den Untiefen
der Ruthenium-Komplexe gedankt.
Danke auch den vielen Doktoranden und Diplomarbeitern am CRT - denn
das angenehme Arbeitsklima und die produktive Atmosphre hat mir stets
Motivation gegeben! Auch das faire Teamplay in wissenschaftlichen Dingen
hat Spass gemacht - auch wenn es zwischen Forschung, Lehre und Raumnot
eben ab und an Reibungspunkte gab. Besonders herausheben will ich meine Brokollegen (Nike, Subi, Karola, Steffi und Rene) sowie PS Schulz, Michi
Jakuttis und Grobi, die immer fr Diskussionen zu haben waren. Auch das
(meist weniger) erfolgreiche Kickern mit diversen Kickerpartnern hat in Motivationsminima dann fr neue Energie gesorgt :)
Als Studien- bzw. Diplomarbeiter waren Matthias Spli Schirmer, Martin
Weschta, Martin Maddin Schneider, Markus Wangler und Willi Peters direkt
oder indirekt mit dem Projekt befasst. Zusammen mit den HiWis Simon Walter, Moritz Husmann und vor allem Michael Beck wurden mir erst viele Dinge
mglich - und ich habe in der Zusammenarbeit mit Euch auch viel dazu gelernt! Danke auch fr Eure Geduld und Nachsichtigkeit! Auch die Verdienste
meines Vorgngers Tobias will ich fr die Vorarbeiten in Sachen WGS nicht
verschweigen.

Fr die kleinen und greren praktischen Hilfen mchte ich mich bei den Werkstattmitarbeitern Michael Schmacks, Achim Mannke, Julian Karl und Gerhard
Dommer bedanken - ohne Euch wre das weit schwieriger geworden! Wenn
mal wieder was nicht ging und was defekt war, dann habt ihr mit Rat und Tat
geholfen, das zeitnah irgendwie wieder in den Griff zu bekommen...
Dipl.-Ing. Florian Enzenberger, Bob Mamrak Ph.D. und Dr. Marco Haumann
mchte ich besonders fr das kritische Korrekturlesen danken.
Dem Prfungskomitee mit Prof. Dr. Hartmann, Prof. Dr. Libuda und Prof. Dr.
Hinrichsen danke ich, dass sie sich die Zeit genommen haben, dieses Dokument zu lesen und auch das Rigorosum abzunehmen.
Der allergrsste und auch tiefste Dank gilt meinen Eltern - Fr die moralische
Untersttzung, aber vor allem fr das Ermglichen des Studiums! Sicherlich
sind kistenweise Lego und die Kosmos Chemiebauksten auch daran Schuld,
dass aus mir ein Chemieingenieur wurde.
Auch meinem engeren Freundeskreis, also Basti, Alex, Julian, Martin, Uli und
den anderen Verrckten, die bei Klettern, Berg- und Skitouren sowie auf Reisen
fr den ntigen Realittsabgleich gesorgt haben, bin ich sehr dankbar...
Danke auch allen anderen, die direkt oder indirekt zum Gelingen beigetragen
haben und deren Namen hier nicht explizit genannt ist!
Mir haben die gut 4 Jahre am CRT echt einen Riesenspass gemacht!

Publications

Parts of this work have been previously published in the following publications
or presented at the conferences listed.

Patents
Werner, S., Szesni, N., Kaiser, M., Haumann, M., Fischer, R.W., Wasserscheid,
P.: Katalysatorzusammensetzung fr die Umsetzung von Kohlenmonoxid in
Gasstrmen. DE102009038690.4 (Priority 24.08.2009), WTO status pending.

Peer reviewed articles


Werner, S., Szesni, N., Kaiser, M., Fischer, R.W., Haumann M., Wasserscheid, P.: Water-Gas-Shift Reaction at ambient pressure and very low temperatures using homogenous Ruthenium based Supported Ionic Liquid Phase
(SILP) Catalysts. Chem.Cat.Chem. (2010), 2(11), 1399-1402.
Werner, S., Szesni, N., Bittermann, A., Schneider, M.J., Hrter, P., Haumann, M. Wasserscheid, P.: Very Low Temperature Water-Gas-Shift Reaction
- Screening of homogenous Supported Ionic Liquid Phase (SILP) catalysts. Applied Catalysis A (2010), 277, 70-75.
Werner, S., Schneider, M., Szesni, M., Haumann, M., Wasserscheid, P.:
Homogeneous Ruthenium-based Water-Gas Shift Catalysts via Supported Ionic
Liquid Phase (SILP) Technology at Low Temperature and Ambient Pressure.
Physical Chemistry Chemical Physics (2009), 11, 10817-10819.
Werner, S., Weiss, T., Haumann, M., Szesni, N., Wasserscheid, P.: Supported Ionic Liquid Phase (SILP) catalyzed Water-Gas-Shift Reaction. Chemie
Ingenieur Technik (2008), 9, 1259 - 1260.

Peer reviewed publications on related topics


Kim, T., Celik, F.E., Hanna, D.G., Shylesh, S., Werner, S., Bell, A.T.:
Gas-Phase Hydroformylation of Propene over Silica-Supported-PPh3 -Modified
Rhodium Catalysts. Topics in Catalysis. (In press).

ii

Publications
Werner, S., Haumann, M., Wasserscheid, P.: Ionic Liquids in Chemical
Engineering. Annual Reviews of Chemical and Biomolecular Engineering
(2010), 1, 203-230.
Haumann, M., Jakuttis, M., Werner, S., Wasserscheid, P.: Supported Ionic
Liquid Phase (SILP) Catalysed Hydroformylation of 1-Butene in a Gradient-free
Loop-Reactor. Journal of Catalysis (2009), 263, 321 - 327.

Conference contributions
Werner, S., Szesni, M., Haumann, R.W. Fischer, M., Wasserscheid, P.:
Supported Ionic Liquid Phase (SILP) Catalysts for the Water-Gas-Shift Reaction
at Ambient Pressure and Very Low Temperature. Presentation at AIChE
Annual Meeting, Salt Lake City (2010).
Werner, S., Szesni, M., Haumann, M., Wasserscheid, P.: Supported Ionic
Liquid Phase (SILP) Catalysts for the Water-Gas-Shift Reaction at Ambient
Pressure and Very Low Temperature. Presentation at Process.NET Jahrestagung (2010).
Werner, S., Schneider, M., Szesni, M., Haumann, M., Wasserscheid, P.:
Supported Ionic Liquid Phase (SILP) Catalysts for the Water-Gas-Shift Reaction at Ambient Pressure and Very Low Temperature. Presentation at EUCHEM2010, Bamberg (2010).
Werner, S., Schneider, M., Szesni, M., Haumann, M., Wasserscheid, P.:
Supported Ionic Liquid Phase (SILP) Catalysts for the Water-Gas-Shift Reaction
at Ambient Pressure and Very Low Temperature. Presentation at 43rd Annual
Conference of the German Catalysis Society, Weimar (2010).
Werner, S., Haumann, M., Szesni, N. Wasserscheid, P.: Supported Ionic Liquid Phase (SILP) Catalysts for Ambient Pressure and Low Temperature WaterGas-Shift Reaction. Presentation at AIChE Annual Meeting, Nashville
(2009).
Werner, S., Szesni, N., Haumann, M., Wasserscheid, P.: Exceptionally
High Activity of Homogeneous, Ruthenium-based Water-Gas-Shift Catalyst

Publications

iii

via Supported Ionic Liquid Phase (SILP) Technology. Presentation at World


Congress of Chemical Engineering 8, Montreal (2009).
Werner, S., Jakuttis, M., Haumann, M., Wasserscheid, P.: Application of a
gas-phase loop reactor (Berty) for supported ionic liquid phase (SILP) catalysed
continuous reactions. Presentation at Achema 2009, Frankfurt (2009).
Werner, S., Szesni, N., Haumann, M., Wasserscheid, P.: Low temperature
Homogenous Water-Gas-Shift Reaction using Supported Ionic Liquid Phase
(SILP) Catalysts. Poster at 42nd Annual Conference of the German Catalysis Society, Weimar (2009).

Contents

1 Introduction

2 Basics & Background

2.1

Water-Gas-Shift Reaction . . . . . . . . . . . . . . . . . . . . . . .

2.1.1

Thermodynamics & Kinetics . . . . . . . . . . . . . . . .

2.1.2

Industrial catalysts . . . . . . . . . . . . . . . . . . . . . .

2.1.2.1

Reaction mechanisms . . . . . . . . . . . . . . .

2.1.2.2

Novel developments . . . . . . . . . . . . . . .

10

2.1.3

Homogeneous catalysts . . . . . . . . . . . . . . . . . . .

13

2.1.4

Base catalyzed homogeneous systems . . . . . . . . . . .

13

2.1.5

Homogeneous transition metal catalysts

. . . . . . . . .

16

2.1.5.1

Pettit group . . . . . . . . . . . . . . . . . . . . .

17

2.1.5.2

Ford group . . . . . . . . . . . . . . . . . . . . .

19

2.1.5.3

Laine group . . . . . . . . . . . . . . . . . . . . .

21

2.1.5.4

Cole-Hamilton & Tanaka . . . . . . . . . . . . .

22

2.1.5.5

Pardey group . . . . . . . . . . . . . . . . . . . .

24

2.1.5.6

Fachinetti group . . . . . . . . . . . . . . . . . .

24

2.1.5.7

Other contributions to homogeneous WGS from


other groups . . . . . . . . . . . . . . . . . . . .

25

Immobilization of homogeneous WGS catalysts . . . . .

26

2.1.6.1

Pakkannen, Luukkanen & Haukka . . . . . . .

27

Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

29

2.2.1

History and current state . . . . . . . . . . . . . . . . . .

29

2.2.2

Physicochemical properties . . . . . . . . . . . . . . . . .

31

2.2.3

Solubilities in Ionic Liquids . . . . . . . . . . . . . . . . .

34

2.2.3.1

Carbon monoxide . . . . . . . . . . . . . . . . .

35

2.2.3.2

Water . . . . . . . . . . . . . . . . . . . . . . . .

36

2.2.3.3

Hydrogen . . . . . . . . . . . . . . . . . . . . . .

38

2.2.3.4

Carbon dioxide . . . . . . . . . . . . . . . . . . .

39

Immobilization of homogeneous catalysts . . . . . . . . . . . . .

40

2.3.1

Multi-phase catalysis . . . . . . . . . . . . . . . . . . . . .

42

2.3.2

Supported catalysts . . . . . . . . . . . . . . . . . . . . . .

43

2.3.3

Supported Ionic Liquid Phase (SILP) catalysis . . . . . .

44

2.1.6
2.2

2.3

iv

Contents

3 Experimental
3.1

48

Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

48

3.1.1

Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . .

48

3.1.2

Homogeneous catalysts . . . . . . . . . . . . . . . . . . .

48

3.1.3

Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . .

54

3.1.4

Additives . . . . . . . . . . . . . . . . . . . . . . . . . . .

55

3.1.5

Support materials . . . . . . . . . . . . . . . . . . . . . . .

56

3.2

SILP catalyst preparation . . . . . . . . . . . . . . . . . . . . . . .

56

3.3

Continuous test-rig . . . . . . . . . . . . . . . . . . . . . . . . . .

58

3.3.1

Dosing of substrates . . . . . . . . . . . . . . . . . . . . .

61

3.3.2

Analytics / Gas chromatography . . . . . . . . . . . . . .

61

Calculation procedures . . . . . . . . . . . . . . . . . . . . . . . .

63

3.4.1

Degree of conversion . . . . . . . . . . . . . . . . . . . . .

63

3.4.2

Turn over frequency, rate of reaction and turn over number 64

3.4.3

Space-time yield . . . . . . . . . . . . . . . . . . . . . . .

65

3.4.4

Gas hourly space velocity . . . . . . . . . . . . . . . . . .

66

Catalyst testing procedure . . . . . . . . . . . . . . . . . . . . . .

66

3.5.1

Work protocol . . . . . . . . . . . . . . . . . . . . . . . . .

66

3.5.2

Determination of effective kinetic parameters . . . . . . .

67

3.5.3

Reproducibility and error estimation . . . . . . . . . . . .

69

3.4

3.5

4 Results and Discussion


4.1

4.2

4.3

70

Benchmarking of the experimental setup . . . . . . . . . . . . .

71

4.1.1

Reproducibility . . . . . . . . . . . . . . . . . . . . . . . .

71

4.1.2

Blank tests . . . . . . . . . . . . . . . . . . . . . . . . . . .

72

Reference measurements . . . . . . . . . . . . . . . . . . . . . . .

74

4.2.1

Commercial ShiftMax 240 . . . . . . . . . . . . . . . . . .

74

4.2.2

Supported gold nano particle LTS catalysts . . . . . . . .

77

Screening of Precursors . . . . . . . . . . . . . . . . . . . . . . . .

78

4.3.1

Literature-known precursors . . . . . . . . . . . . . . . .

79

4.3.2

Transition metal chlorides . . . . . . . . . . . . . . . . . .

81

4.3.3

Transition metal carbonyls . . . . . . . . . . . . . . . . . .

83

4.3.4

Catalysts with bipyridine ligands . . . . . . . . . . . . . .

84

4.3.5

Novel catalyst systems . . . . . . . . . . . . . . . . . . . .

86

vi

Contents

4.4

4.5

4.3.6

Gas-phase stripping of volatile catalyst compounds . . .

89

4.3.7

General trends . . . . . . . . . . . . . . . . . . . . . . . .

93

Optimizations of catalyst systems . . . . . . . . . . . . . . . . . .

94

4.4.1

Variation of the support material . . . . . . . . . . . . . .

95

4.4.2

Addition of organic bases . . . . . . . . . . . . . . . . . .

99

4.4.3

Variation of ionic liquid loading . . . . . . . . . . . . . . 105

4.4.4

Variation of metal loading . . . . . . . . . . . . . . . . . . 109

4.4.5

Variation of the ionic liquid . . . . . . . . . . . . . . . . . 111

4.4.6

Optimization of the induction period . . . . . . . . . . . 115

4.4.7

Combination of beneficial trends . . . . . . . . . . . . . . 118

Application specific characterization . . . . . . . . . . . . . . . . 122


4.5.1

Restart behavior & condensation tolerance . . . . . . . . 122

4.5.2

Self-healing behavior . . . . . . . . . . . . . . . . . . . . . 124

4.5.3

Long-term investigations . . . . . . . . . . . . . . . . . . 126

4.5.4

Use of technical support materials . . . . . . . . . . . . . 128

4.5.5

Elevated pressure influence . . . . . . . . . . . . . . . . . 133

4.5.6

Synthesis gas tests . . . . . . . . . . . . . . . . . . . . . . 137

5 Summary

144

5.1

Summary / Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . 144

5.2

Zusammenfassung / Kurzfassung . . . . . . . . . . . . . . . . . . 148

Appendix
A

Calibration curves . . . . . . . . . . . . . . . . . . . . . . . . . . .

A.1

Mass flow controller - carbon monoxide . . . . . . . . . .

A.2

Mass flow controller - carbon dioxide . . . . . . . . . . .

A.3

Mass flow controller - nitrogen . . . . . . . . . . . . . . .

II

A.4

Micro Gas chromatograph . . . . . . . . . . . . . . . . . .

III

Acronyms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

IV

Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

IV

List of Schemes . . . . . . . . . . . . . . . . . . . . . . . . . . . .

VI

List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

VI

List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

IX

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XXVI

1 Introduction
For mobile applications, such as transportation, fossil fuels are currently the
state of the art - and emissions from those are expected to grow rapidly [1] . Fuel
cells that operate with hydrogen and air at low temperatures and pressures
such as proton-exchange fuel cells (PEMFCs) are a promising alternative for
decentralized mobile applications [2] . As hydrogen storage and transportation
is technically challenging, liquid-fuel processing / reforming for on-board hydrogen production appears as an attractive technology [3] . However typical
reformers do not produce hydrogen in a fully selective manner. The most
prominent by-product is carbon monoxide (1-10 vol%), which adsorbs at a
PEMFCs platinum electrode as a catalyst poison [2] . In technical operations,
where low carbon monoxide content is crucial (e.g. Haber-Bosch process) the
well-known water-gas shift (WGS) reaction, namely the exothermic reaction of
carbon monoxide with water towards carbon dioxide and hydrogen, is applied,
which is depicted in Scheme 1.1 [4] .

H2 O + CO H2 + CO2

HR = 41.2 kJ mol1

Scheme 1.1: The water-gas shift reaction

Besides reducing the CO content, this reaction also includes a favorable hydrogen enrichment which also enhances the overall energetic efficiency. Because
of the exothermic nature of the WGSR, highest equilibrium conversions are
achieved at lowest temperatures [5] .
State of the art heterogeneous WGS catalysis is performed in a combination
of high temperature (HTS, Fe2 O3 /Cr2 O3 , 450 C / 30 bar) and low temperature
(LTS, CuO/ZnO/Al2 O3 , 200 C) shift, reducing the CO level to 0.1 - 0.3 wt% [6] .
This level is too high for most direct applications of the obtained hydrogen
and therefore additional purification steps (selective oxidation, methanation,
adsorption) are required [7] . Therefore a strong urge exists to develop catalysts
that reduce the CO content in the reformer gas stream in one step down to an
acceptable low level. To reduce the equilibrium CO level in the exothermic
WGS reaction, catalysts are required that efficiently operate at temperatures
below 180 C (ultra low temperature shift, ULTS). This goal that could never be

Introduction

achieved so far with known commercial heterogeneous catalysts. But as lower


temperatures also lower the rate of reaction, highly active and stable ultralow temperature catalysts are needed. Unlike current industrial operations,
lower operating pressures (atmospheric pressure up to 5 bars) are favorable
for mobile applications. Other requirements such as fast restart behavior and
tolerance against sulfur and chlorine are also not met by commercial systems
currently available [2] .
Whilst robust high-temperature shift (HTS) catalysts based on iron and chromium operate at temperatures above 350 C to tolerate the gas-phase impurities
such as sulfur components, the low-temperature shift (LTS) catalysts that show
good activities even below 200 C cannot withstand those poisons. Both commercial systems need a time-intense activation process in reducing atmosphere.
Activated WGS catalysts show pyrophoric behavior and additionally, these catalysts have poor restart behavior and are sensible to condensation that might
arise during shutdown cycles [8] . Intense research has been carried out to circumvent these limitations and create cheap, stable and active catalysts for the
low temperature water-gas shift reaction. Latest developments on heterogeneous systems include several noble metals such as gold, platinum or rhodium
supported on oxide materials that are promising for those applications [9] .
A promising alternative to heterogeneous WGS catalysts is the clever application of homogeneous transition metal complexes in multiphase systems.
Mainly liquid-gas multiphase-systems operating in batch-mode have been
published. Intensive studies on ruthenium based systems in batch operation mode at elevated pressures have been carried out by the group of Ford,
whereas the group of Pettit investigated different transition metals such as
rhodium, osmium and iridium in batch mode at 25 bar [5,1014] . Investigations
in a continuous mode are favorable, because a single experiment can reveal
activation behavior, activity and stability of the catalyst. However, moderate
activities, the requirement for high total pressures (typically 25 bar) and catalyst recycling problems have been major drawbacks of these systems.
Several approaches to immobilize catalytically active complexes on a porous

3
support have been developed [15] . In all cases these immobilization strategies try to circumvent some substantial drawbacks of homogenous catalysis,
namely the separation of catalyst and products. In recent years, our research
group in Erlangen and other groups have established the so-called Supported
Ionic Liquid Phase (SILP) concept as very efficient catalyst immobilization technique [1618] . In SILP systems a thin film of an Ionic Liquid, containing the
homogeneously dissolved catalyst, is dispersed on a porous support. Because
of the very low vapor pressure of the ionic liquid in the range of 108 Pa no
stripping of the liquid phase is to be expected [19] . Various publications show
an enhancing effect on activity when using ionic liquids in homogenous catalysis [20] . Our work-group in Erlangen and other groups around the world successfully applied the SILP concept to both slurry and gas-phase reactions [2126] .
In this work the application of the Supported Ionic Liquid Phase methodology
to the water-gas-shift reaction will be investigated in detail. Aim of this work
was the development of a novel class of water-gas shift catalysts tackling with
the above mentioned problems of state-of-the art industrial WGS catalysts.
Beginning with an intense study on the activity of various homogeneous transition metal complexes, a system optimization was carried out, in order to
achieve a highly active, selective and stable catalyst applicable to the desired
reaction conditions. Systematic variation of influencing system parameters,
such as catalyst precursor, ionic liquid, support material and the inherent parameters such as loadings, properties (e.g. acidity/basicity) and preparation
methodology was carried out. In order to evaluate the feasibility of the newly
developed catalysts, tests to confirm restart ability and long-term operation
were conducted. The newly developed catalyst are also characterized in terms
of effective partial reaction orders and activation energies by standard reaction
engineering procedure. In a final set of experiments, behavior at real synthesis
gas conditions was tested, to evaluate the potential for industrial operations.

2 Basics & Background


2.1 Water-Gas-Shift Reaction
Water-Gas Shift refers to the slightly exothermic reaction of carbon monoxide
and water forming carbon dioxide and hydrogen as depicted in Scheme 2.1.

H2 O + CO H2 + CO2

HR = 41.2 kJ mol1

G = 28.6 kJ mol1

Scheme 2.1: The water-gas shift reaction

WGS reaction was first reported in 1888 and became popular as part of the
Haber-Bosch process. Because of its importance several reviews were published that summarize this field of research in a comprehensive manner, such
as the ones by Newsome in 1980 [27] , Jacobs in 2007 [6] and Ratnasamy in 2009 [7] .
The industrial importance of the reaction in the production and purification of
hydrogen for various intermediate bulk chemicals is also worth mentioning [28] .
WGS is closely linked to current efforts in utilization of biomass and use in PEM
fuel-cells as depicted in Figure 2.1.
Biomass

High Temp
Fuel Cell

Gasification
Solid Fuel
Liquid Fuel
Desulfurization

Reforming

Natural Gas
Synthesis Gas
H2/CO ~ 2

FischerTropsch

MeOH / DME

Others

Haber-Bosch
Ammonia

HT/LT WaterGas-Shift

CO Clean-Up
(PSA, PROX)

ULT WaterGas-Shift

Low Temp
Fuel Cell

Hydrogen
storage

Figure 2.1: Pathways from resources towards hydrogen-consuming processes involving water-gas shift including a possible ultra-low temperature shift.

There are several ways to produce hydrogen from different feedstocks. Depending on their CO content and tolerance of catalysts against it, different

2.1 Water-Gas-Shift Reaction

specialized processes have been developed. Especially for highly pure hydrogen which is needed in low temperature fuel cells, the conventional two-step
WGS processes that have been established for Haber-Bosch, are not sufficient.
In this case either preferential oxidation (PROX) or pressure swing adsorption
(PSA) are applied to further purify the hydrogen from conventional WGSreactor systems. Possibly these processes can be integrated or even replaced
by an ultra-low temperature water-gas shift reaction step.
2.1.1 Thermodynamics & Kinetics
Being moderately exothermic with HR = 41.2 kJ mol1 , WGS is an equilibrium limited reaction with higher conversions at lower temperatures. The
equilibrium constant Kp is severely influenced by temperature, as a correlation
(2.1) of Newsome et al. clearly illustrates [27] .
Kp =



pH2 pCO2
4577.8
= exp
4.331
pCO pH2 O
T

(2.1)

At elevated temperature Kp (T = 400 C) = 11.8 while Kp (T = 200 C) = 228


resulting in the fact that the CO content at equilibrium can be 20 times lower
at 200 C than at 400 C. To increase hydrogen production and reduce carbon
monoxide content, lower reaction temperatures are favorable.
Additionally, the ratio of pH2 O /pCO , or in other words the steam to gas ratio,
clearly influences the equilibrium. With more water present, the equilibrium
is shifted towards the products, resulting in lower CO concentrations. Especially at elevated temperatures, this effect has tremendous impact on the WGS
equilibrium. Expressed by the degree of conversion with respect to CO (XCO ),
this can be seen from Figure 2.2. However a higher steam-to-gas ratio is disfavorable because of condensation issues (dewpoint) and cost for the steam, so
that a classical engineering cost and design optimization problem arises.
However, in order to maintain the necessary reaction rates, higher temperatures are often required. In this case, the optimization focus is smaller reactor
volume, so that a minimized cost expressed by maximum space-time yield is
achieved. Hence an ideal condition for the industrial water-gas shift reaction
would be the use of a catalyst active enough to operate at low temperatures,
so that space-time yield is high and equilibrium is favorable.

Basics & Background

1,0

0,8

CO

0,6

0,4

0,2

0,0
0
100

4,0
3,5

200

3,0

300

2,5
400

2,0
1,5

500

/ p

1,0

600

0,5

2O

700

Figure 2.2: Equilibrium conversion of the Water-Gas Shift reaction at various pH2 O /pCO
and T for ptotal = 1bar (pCO = 0.1, pH2 O = 0.05 . . . 0.4bar, balance nitrogen).
Calculation using Aspen 2006.3 with equilibrium constants from Laine
et al. [5]

Reaction total pressure has a low effect on the equilibrium of the shift reaction,
since the number of moles of material in the shift reaction does not change
during reaction. Several authors claim, that at highly elevated pressures formation of carbon adducts such as higher alkanes is favored due to Le Chatelier
principle [6] .
Of course the rate of reaction decreases severely when approaching the equilibrium, thus in technical WGS setups, low gas hourly space velocities (GHSV,
N

m3gas m3
h1 ) values would be needed. Instead of that, this thermodynamic
catalyst

issue is practically tackled by using two or more catalytic beds, where heat is
removed intermediately, as depicted in Figure 2.3. First, a high-temperature
shift reaction operating at around T = 450 C reduces the CO content down to

2.1 Water-Gas-Shift Reaction

about xCO = 5 mol% at short contact times, using the very high rate of reaction
at these elevated temperatures. In a second step, the so-called low-temperature
~10 vol% CO

HTS

LTS

~3 vol% CO

~0.3 vol% CO

Raw gas
Process
Steam
300-500C

180-270C

Fe2O3/Cr2O3

CuO/ZnO/Al2O3

Figure 2.3: The two step industrial water-gas shift setup.

shift, which typically operates around T = 200 . . . 250 C reduces the CO content further to almost equilibrium level (0.3 mol%), whereas the rate of reaction
slows down. This setup is the result of a cost-optimization where final CO
content and resulting reactor volumes where evaluated.
In a recent review of Smith et al. a detailed summary of kinetic rate expressions
for the Water-Gas shift reaction is given, which covers both low and high
temperature shift [29] .
2.1.2 Industrial catalysts
A modern two-stage WGS converter system reduces the CO concentration to
about 0.3 mol% from the high level of 10 50 mol% obtained in the outlet of the
reformer.
Currently, there are four basic types of commercial WGS catalysts. First, Iron
oxide or Fe Cr mixed oxide catalysts promote WGS in the 350 . . . 450 C range
and for this reason are called high-temperature shift catalysts (HTS). For improvement of methane conversion (natural gas is used as feedstock), MgO or
ZnO possessing good sulfur resistance and mechanical strength are added in
HTS catalysts [7] .
The second type of WGS catalysts are mixed copper-zinc oxides which promote
WGS in the 190 . . . 250 C range, thus referred as low-temperature shift (LTS)
catalysts. This catalyst system has been developed in the 1960s because of
the fact that HTS catalysts showed high final CO contents due to equilibrium
limitations [27] . A typical LTS catalyst developed by ICI comprises 30 wt% CuO,

Basics & Background

45 wt% ZnO and 13 wt% Al2 O3 , which is similar to a LTS catalyst of Sd-Chemie
AG, which is consisting of 57 wt% CuO, 31 wt% ZnO and 11 wt% Al2 O3 - in
both cases, the remaining percentage is an undisclosed mixture of promoting
additives. This catalyst is prone to poisoning by sulfur traces due to formation
of stable copper sulfides that leads to rapid deactivation [4] . LTS catalysts have
been optimized to minimize by-product formation such as C1 C3 alkanes &
alcohols and aldehydes / ketones by addition of rare-earth metal traces.
The third type of catalysts includes sulfur-tolerant materials which have as active phase cobalt and molybdenum sulfides. Molybdenum is usually dispersed
onto the metal oxide support used, such as Al2 O3 , MgO, ZnO, Mg-aluminate,
Zn-aluminate, etc. [7] . Due to the fact that these catalysts can be potentially
used in sulfur containing sour-gas streams, they are called sour gas-shift catalysts. Their industrial use however is rather limited. Sour-gas shift catalysts
are only used in specific environments, where the other systems suffer from
severe disadvantages and cannot take advantage of higher activity.
A fourth type are the nowadays obsoleted medium-temperature shift catalysts,
that are modified low-temperature catalysts that operate at slightly higher
temperatures of 500 . . . 575 K.
Besides the above mentioned types of industrial catalysts, a series of precious
metal-containing catalysts have been also used in specific cases. These systems
employ mostly Gold or Platinum as active phase and are limited to smaller
scale.
2.1.2.1 Reaction mechanisms
Despite extensive kinetic studies by various groups, the exact reaction mechanism remains unsettled. Generally, two mechanisms have been discussed. On
one hand the regenerative or redox mechanism, on the other hand the associate /
carboxyl or formate mechanism [7] . For the high temperature shift, most authors
use the redox mechanism for their kinetic investigations, whereas for the low
temperature shift, both mechanisms are discussed.
The mechanisms are summarized in Scheme 2.2.
The redox mechanism involves CO oxidation by surface-adsorbed atomic O [7] .
Oxygen itself can be obtained by two-step water dissociation or by a disproportionation of OH. In this case the hydroxide is formed by hydrogen abstraction

2.1 Water-Gas-Shift Reaction

Redox mechanism

Formate mechanism

CO + CO

CO + CO

H2 O + H2 O

H2 O + H2 O

H2 O + H +OH

H2 O + H +OH

OH + O +H

CO +OH COOH +

OH +OH H2O +O COOH + CO2 +H


CO +O CO2 +

COOH +OH CO2 +H2 O

CO2 CO2 +

CO2 CO2 +

H +H H2 + 2

H +H H2 + 2

Scheme 2.2: The redox and formate mechanism of heterogeneous water-gas shift.
refers to an unoccupied active site, whereas indicates an absorbed
species. Adapted from [30]

from water [31] . Currently the redox mechanism seems to be the most accepted
one, however spectroscopic measurements provide evidence to the existence
of an absorbed formate species which is not properly explained by this mechanism [32,33] .
Contrasting to that the associative mechanism is discussed. In this reaction
pathway adsorbed surface species form a surface intermediate that is subject
to subsequent decomposition into carbon dioxide and hydrogen. The exact
nature of the intermediate is still under discussion. Whereas Grenoble et al.
proposed formic acid as intermediate [34] , Rhodes et al. identified a surface
formate species [35] . Ovesen et al. proposed a micro-kinetic redox model [31] in
1992, which was later revised to a formate involving model [36] . Their microkinetic studies identified water dissociation as the rate determining step, which
links directly to the basicity of the system.
Gokhale et al. proposed that a surface formate species is the key intermediate for this pathway. They proposed the so-called formate mechanism. It involves interaction between CO molecule and a surface formate species HCOO.
This formate is believed to decompose into the reaction products CO2 and H2
that desorb independently [30] . The formate itself is formed by the reaction
of adsorbed CO and OH. Both kinetic measurements and quantum-chemical
methods underline the possibility of this reaction pathway.
Further insight into water gas shift mechanisms are provided in reviews of

10

Basics & Background

Jacobs [6] and Smith et al. [29] .


2.1.2.2 Novel developments
In parallel to the optimization of the existing catalyst types, new types of
heterogeneous WGS catalysts have been developed. During the last decade,
novel developments focused on two major fields: nano-particular precious
metal clusters and mixed metal / rare earth materials. In addition to these
novel developments improvement of existing copper based catalysts by tuning activity and selectivity has been achieved. For these specific aspects, one
should consider recent reviews by Hinrichsen and Jacobs [6,28] .
In 2003 Tanaka et al. published a comprehensive study on the performance
of mixed copper oxides. CuAl2 O4 and CuMn2 O4 gave higher specific rates
of CO conversion than classical Cu/ZnO/Al2 O3 under the same conditions [37] .
Although WGS activity emerged from reduction of the mixed oxides, hightemperature reduction gave rise to the sintering of Cu. CuAl2 O4 showed low
WGS activity at lower temperatures and additionally low selectivity was found.
A CuMn2 O4 catalyst reached high WGS activity around 225 C, comparable to
conventional Cu/ZnO/Al2 O3. The authors claim that the CuMn2 O4 catalyst
could be a promising candidate for CO preferential oxidation of reformed fuels.
Also the work of Guo et al. is basically aiming on reformed fuels, especially
the fact, that this application requires frequent shut-down/start-up cycles [8] .
In a comparison of Cu/ZnO and Cu/ZnO/Al2 O3 catalysts, the Cu/ZnO catalyst
exhibited comparable activity to the conventional catalyst, but better stability
in shut-down/startup cycle. Since the Cu/ZnO system had significantly less
copper surface area and larger copper domains, the authors suggest, that the
Cu/ZnO interface sites directly participate in the reaction. Deactivation of the
Cu/ZnO/Al2 O3 catalyst was attributed to formation of carbonate species during shut-down rather than sintering of the copper crystallites. It is suspected,
that the catalyst without alumina is more stable, because the formation of carbonates is cause by alumina presence. So a future WGS catalyst for fuel cell
applications should use another oxide support.

2.1 Water-Gas-Shift Reaction

11

Tanaka tested a combination of platinum nanoparticles on several support materials (Al2 O3 , SiO2 , ZrO2 , Nb2 O5 and TiO2 ) and modifications thereof with
alkali metals [38] . It turned out, that potassium addition on an alumina support
had a promising impact on performance, whereas sodium, lithium, rubidium
and cesium had less impact.
The role of promotors was focus of a comprehensive study by Jacobs et al. [39] .
These authors combined several metal with ceria (CeO2 ) supports and conducted catalytic experiments and XANES measurements. Performance of the
catalyst was in the order of Pt > Ni > Fe > Au > Co, which is strongly related
to the surface formate concentration that seemed to be crucial.
Thinon et al. screened 20 bi-functional WGS catalysts as depicted in Figure 2.4 [40] .
Bi-functional means, that both reducible support and metal add activity. In
their study Rh and Ru based catalysts produced significant amounts of methane.
Pt/CeO2 /Al2 O3 and Pt/TiO2 were found to be the most active catalysts for
the high temperature water-gas shift while gold and copper catalysts showed
promising results for low temperature applications. But these systems still
require testing at lower CO partial pressures.
Sandoval et al. tested gold nanoparticles on reducible(TiO2 and CeO2 ) and
non-reducible oxides (Al2 O3 and SiO2 ) with comparable gold particle size (2.53.5 nm) as catalysts in the WGS reaction [41] . The Au/CeO2 catalyst showed an
enhanced reduction potential at low-temperatures as evidenced by the H/Au
ratio. Lowest reduction temperature was observed for gold in the Au/TiO2
catalyst. When supported on TiO2 and CeO2 , the activity of gold nanoparticles
was much higher than the one observed when supported on Al2 O3 and SiO2 ,
where catalysts were practically inactive.
The PhD thesis of Leppelt focused on water-gas shift reaction over gold
nanoparticles supported on ceria and titania [42] . DRIFTS studies showed, that
surface species are mainly carbonates and formates again. Activation energy
was determined to 40 kJ mol1 and partial reaction orders to 0.5 for the sub

Also called methanoate and refers to a simple carboxylate CHOO anion.

12

Basics & Background

Figure 2.4: Performance of bi-functional water gas shift catalysts at 300 C with a reformate mixture (100 mlN mil1 , 10% CO, 10% CO2 , 20% H2 O, 30% H2 and
30% Ar) and pure reactant mixture (100 mlN mil1 , 10% CO, 20% H2 O and
70% Ar). [40] .

strates CO and H2 O. 0.5 was determined as reaction order for H2 and CO2 .
Interestingly, the amount of oxidized ceria and gold species was always found
to be 22% for ceria and 10% for gold independent of gold loadings. CO is
adsorbing not only on gold, but also on ceria, forming a formate intermediate,
that is decomposed at active centers later on in the cycle.
Recently Mendes et al. published a comprehensive study on the same catalyst
systems as used by Leppelt, but tested at real syngas conditions and compared
those to a commercial BASF low temperature WGS catalyst [9] . It was found
that the presence of reaction products in the feed stream had a higher negative effect on CO conversion for Cu-based catalysts when compared with the
gold-based ones. Under reformate conditions (4.74% CO, 35.39% H2 O, 28.46%

2.1 Water-Gas-Shift Reaction

13

H2 , 10.06% CO2 , balance N2 ), the Au/CeO2 sample was the most active, especially in the range of 150 . . . 200 C. It was suspected that activity of gold/ceria
indicates that the support plays an important role in this reaction. The commercial CuO/ZnO/Al2 O3 catalyst showed the best relation of activity/stability.
In agreement with previous studies, it was found that the CO concentration
present in the reactor feed greatly affects the activity of all catalysts tested.
Depending on the reaction temperature, this effect is negative or positive in
terms of the catalysts performance. Interestingly for the gold/titania catalyst
no positive effect on conversion was found when water partial pressure was
increased, which is rather untypical for WGS catalysts.
2.1.3 Homogeneous catalysts
The application of homogeneous catalysts for the water-gas shift reaction has
been studied for almost a century. Work in this field is summarized by extensive
reviews of Newsome [27] , Ford [11] , Laine and Crawford [5] and recently Jacobs
and Davis [6] .
The work in homogeneous WGS research can be classified into four main fields,
namely
1. Early work on base catalyzed systems,
2. Transition metal carbonyls in aqueous solution of organic bases,
3. Base-modified transition metal carbonyls with pyridines and phenanthroline ligands,
4. Immobilization of ruthenium catalysts.
2.1.4 Base catalyzed homogeneous systems
Early research on homogeneous water-gas shift started with base catalyzed
systems. As early as 1943, Yoneda and coworkers reported on the homogeneous water-gas shift in an aqueous solution of potassium bicarbonate [43] .
Their proposed mechanism involved the formation of a formate species via
bicarbonate reaction releasing CO2 . The formate species then reacts with water which regenerates the bicarbonate and produces hydrogen as depicted in
Scheme 2.3.

14

Basics & Background

KHCO3 + H2O K+ + HCO3


HCO3 + CO HCOO + CO2
HCOO + H2O HCO3 + H2
Scheme 2.3: Proposed base-catalysed WGS reaction scheme by Yoneda [43]

However, this system was operated under rather harsh conditions: 250325 C
and about 150 bar.
The approach of Royen and Ehrhard to support the above mentioned catalyst
system on charcoal yielded mediocre success [44] . Their experiments led to the
conclusion, that formic acid was possibly involved, whereas bicarbonate was
not, as depicted in Scheme 2.4.

K2 CO3 + H2 O 2 KOH + CO2


2 KOH + 2 CO 2 HCOOK
2 HCOOK + 2 CO 2 KOH + 2 HCOO2H
2 HCOOH 2 H2 + 2 CO2
2 KOH + CO2 K2 CO3 + H2 O
Scheme 2.4: Proposed base-catalyzed WGS reaction scheme by Royen [44] .

The experiments were carried out at around 150 to 250 C and elevated pressures. Again, a formate species, in this case formic acid, was proposed to be a
key intermediate.
Another batch tank reactor study involving base catalysts was reported by
Elliot and coworkers in the 1980s [4547] . These extensive experiments employed
various basic metal salt catalysts in aqueous solution at 200 to 400 C and around
35 bar. In a first report, 15 carbonate salts, 17 sodium salts and 6 potassium
salts were tested to evaluate cation and anion effects [45] . Several alkali metal

2.1 Water-Gas-Shift Reaction

15

salts and some transition metal salts showed more active catalysts than similar
alkaline earth compounds. But in general most of the alkali compounds can
act as catalysts (or generate a catalytic species in situ) for the water-gas shift
reaction in a pressurized aqueous system. The studies on mechanisms agreed
with the investigations of Royen and Erhard, but partially disagreed with
Yonedas work as depicted in Scheme 2.5 [46] .

Na2 CO3 + H2 O 2 Na+ + CO2


3

CO2
3 + 2 H2 O 2 OH + H2 CO3

H2 CO3 CO2 + H2 O
2 CO + 2 OH 2 HCOO
2 HCOO CO2
3 + H2 CO
H2 CO H2 + CO

Scheme 2.5: Proposed base-catalysed WGS reaction scheme by Elliott [46] .

In a follow up study, a continuous stirred tank was employed yielding around


300 l mol1h1 [47] .
In the work of Schuchard and Sousa, sodium hydroxide, formate and carbonate
catalysts were employed at 200 to 350 C and 70 bar [48] . Their ex-situ IR studies
identified always small traces of oxalates and mainly formates. This yielded in
their proposed mechanism that involves a oxalate species (HC2 O4 ) as depicted
in Scheme 2.6.
In summary, all base-catalyzed WGS systems lack proof of economic feasibility
and are far off desirable process conditions, because they use high temperatures
and pressures. Additionally, corrosivity issues arise, that create a requirement
TM

for costly Hastelloy

equipment. Note, that base catalyzed WGS reaction

requires the same harsh temperature conditions as traditional heterogenous


catalysts. Interestingly in direct connection to heterogeneous catalysts the
existence of a formate species is also discussed.

16

Basics & Background

Na2CO3 + H2O 2 Na+ + CO2


3

CO2
3 + 2 H2 O 2 OH + H2 CO3

H2 CO3 CO2 + H2 O
CO2 + OH HCO3
HCO3 + CO HC2 O4
HC2 O4 HCOO + CO2
HCOO + H2O H2 + HCO3

Scheme 2.6: Proposed base-WGS catalyzed reaction scheme by Schuchard [48] .

2.1.5 Homogeneous transition metal catalysts


Since first approaches in the late 1970s, several groups worked on homogeneous transition metal catalysts that are active in the water-gas shift reaction.
The most comprehensive and updated summary of that work is provided in a
review of Jacobs and Davis in 2007, who evaluated more than 170 references [6] .
Out of these, this work lists some selected studies that represents milestones
in the development of homogeneous WGS catalysis.
Usage of metal carbonyls as catalysts in the low temperature water-gas shift
reaction was a main driver in this first phase in research starting in the late
1970s. The first application of water-gas shift reaction by metal carbonyls was
carried out by Kang in the Pettit group [49] , that utilized the poisonous Fe(CO)5 .
Work in the field of homogeneous water-gas shift was mainly driven by the
groups that are mentioned in section 2.1.5.1 to 2.1.5.7. Generally spoken, the
reaction can be either carried out in acidic or basic environment, whereas, in
agreement with studies of heterogeneous catalysts, basic milieu is preferred.
Proposed mechanisms favor an associative mechanism that involves addition
of a solute gas-phase species towards an intermediate complex that is subject
to decomposition into the reaction products namely carbon dioxide and hydrogen [6] . An aqueous environment is preferred in most applications, whereas the
addition of bases to these solutions was intensely discussed. The low solubility

2.1 Water-Gas-Shift Reaction

17

of carbon monoxide in water requires high operating pressures to achieve at


least moderate activities.
2.1.5.1 Pettit group - metal carbonyls in aqueous trimethylamine
solutions
In the group of Pettit, several studies on metal carbonyl systems were conducted. They used elevated pressures (p 25 bar) and applied an aqueous
solution of basic trimethylamine, whereas different temperatures in the range
of 100 to 180 C were used as listed in Table 2.1. Interestingly the ruthenium
Table 2.1: WGS Activity of metal carbonyl systems reported by Pettit et al. [10] . Conditions: 0.05 mmol of catalyst in a 300 ml stirred autoclave containing 22 ml of
25 % aqueous trimethylamine, 78 ml of THF, and 350 psi 25 bar of CO

Compound

TOF / molH2 molcat h1

T / C

Fe(CO)5

0.5

110

Rh6 (CO)16

170

125

Ru3 (CO)1 2

330

100

H4 Ru4 (CO)12

340

100

Os3 (CO)12

27

180

H2 Os3 (CO)12

2.7

180

H4 Os4 (CO)12

40

180

Ir4 (CO)12

30

125

(Bu4 N)[Pt3 (CO)6 ]5

70

125

carbonyls were found to be significantly more active than iridium, osmium


and platinum analogues. The activity reached for triruthenium dodecacarbonyl is still one of the highest ever reported in homogeneous WGS. Based
on infrared studies of iron carbonyl systems, they postulated a mechanism for
the water-gas shift reaction that involves addition of a hydroxide anion as rate
determining step. A follow-up study focused on the effect of basicity of this
catalysts activity, in order to prove this hypothesis. In this case several organic
bases were screened by Slegeir et al. in a stirred tank reactor setup, revealing
that the activity of the Ru3 (CO)12 catalyst system is highest, when bases such
as NMe3 (TOF = 547 h1 ), N methylpyrrolidone (TOF = 240 h1 ) or NHMe2

18

Basics & Background

CO

Fe(CO)4

H2
H2Fe(CO)4

Fe(CO)5
OH-

OH-

HFe(CO)4H2O

CO2

Scheme 2.7: Proposed WGS catalyzed reaction scheme for iron carbonyl [10]

(TOF = 220 h1 ) are used [50] . Use of pure water (TOF = 0.5 h1) significantly
reduced the activity. The key issue of selecting a base for WGS is, that it must
be mild enough to be regenerable from its carbonate salt at low temperatures.
Otherwise, the CO2 generated would essentially block the catalysis by converting the base into the carbonate salt. Thus, an underlying requirement for the
metal carbonyl catalyst was that it must be capable of being converted to a
metal hydride species by attack of a weak base [6] .

Ru3 (CO)13 + 3 CO 3 Ru(CO)5

Activation step

Ru(CO)5 + NMe3 (CO)4 Ru(CO)NMe3


(CO)4 Ru(CO)NMe3 + H2 O (CO)4 RuH + CO2 + Me3 NH+
(CO)4 RuH + H2 O (CO)4 RuH2 + OH
Me3 NH+ + OH NMe3 + H2O
(CO)4 RuH2 Ru(CO)4 + H2
Ru(CO)4 + CO Ru(CO)5
Scheme 2.8: Proposed WGS catalyzed reaction scheme for triruthenium dodecacarbonyl [50]

A mechanistic study of Slegeir et al. on Ru3 (CO)12 systems revealed intermediates similar to those from the iron carbonyl catalyst as proposed in Scheme 2.7
- most interestingly the normalized reaction rate was found to be almost equal

2.1 Water-Gas-Shift Reaction

19

when Ru3 (CO)12 , H4 Ru4 (CO)12 or H2 Ru4 (CO)13 were applied as precursors [50] .
This work led to a mechanism that is shown in Scheme 2.8. One key step is the
nucleophilic attack of the amine to the activated ruthenium complex
2.1.5.2 Ford group - ruthenium carbonyls and their nucleophilic
activation
In the group of Ford, Hieber-base reactions of different transition metals in
groups VIIb and VIIIb were investigated [11,51,52] . In this type of reaction a metal
carbonyl reacts with a hydroxide ion in a nucleophilic attack at the carbonyl
carbon atom forming a metal hydride [53,54] . This step is then followed by
deprotonation of the hydride so that the metal center is reduced by two units.
So this type of reaction basically involves main steps of a water-gas shift, which
raised their interest. The group focused on ruthenium in alkaline solutions and
conducted mechanistic studies. Catalytic activities of the investigated systems
are summarized in Table 2.2.
Table 2.2: WGS activity of metal carbonyls reported by Ford [11,51,52] .

Conditions:

0.02 mmol of catalyst in a 100 ml glass cylinder containing the catalyst solutions prepared from 0.04 mmol of complex, 2 mmol of KOH (0.6 M), 0.02 mol
of H2 O and 3 ml of 2-ethoxyethanol at pCO = 0.9bar and T = 100 C

Compound

TOF / molH2 molcat h1

H2 FeRu3 (CO)13

0.43

Ir4 (CO)12

0.23

H2 Ru4 (CO)12

0.18

H4 Ru4 (CO)12

0.15

Ru3 (CO)12

0.12

Ru6 C(CO)17

0.06

Fe(CO)5

0.04

Rh6 (CO)16

0.03

H3 Re3 (CO)12

0.01

Re2 (CO)10

0.00

First, in analogy to the cycle proposed by Pettit (Scheme 2.7), a slightly modified reaction mechanism that involved a carboxyl species, was established

20

Basics & Background

(Scheme 2.9). But in low pressure experiments at around p = 1 bar it was


found, that water-gas shift using Ru3 (CO)12 is first order with respect to CO
and Ru. In Scheme 2.9 it is less likely, that addition of CO to the Ru3 (CO)11 is
a rate limiting step, because the ruthenium center is not coordinatively saturated. From studies of Hieber, it is known that activation of transition metal
complexes with bases is generally also a rapid reaction. This leads to the conclusion, that the elimination of H2 from the intermediate complex would be the
rate determining step [55] .

Ru3 (CO)11 + CO Ru3 (CO)12


Ru3 (CO)12 + OH [Ru3 (CO)11 (COOH)]
Ru3 (CO)11 (COOH) + H2 O HRu3 (CO)11 (COOH)H + OH
HRu3 (CO)11 (COOH) H2 Ru3 (CO)11 + CO2
H2 Ru( CO)11 H2 + Ru3 (CO)11

Scheme 2.9: Proposed WGS catalyzed reaction scheme for ruthenium carbonyl [51]

In order to get consistent with the data, a new updated reaction mechanism has
been proposed, that involved the formation of an anion [H2 Ru4 (CO)12 (COOH)]
cluster, which involves addition of CO and elimination of H2 in one single
step. But in subsequent IR studies, a trinuclear [HRu3 (CO)11 ] was found,
so that another hypothesis was reported. Additionally, a [H2 Ru4 (CO)12 ] was
detected leading to an analogous tetranuclear cycle. Scheme 2.10 illustrates
the proposed trinuclear cycle.
The hypothesis, that a COOR carboxyl intermediate was involved, was investigated in follow-up work, where several carboxylic adducts of the general type
Ru3 (CO)11 (COOR) where reported after exposure of Ru3 (CO)12 to nucleophiles
like CHO or OH [56] . All these investigations did not clearly reveal the exact
nature of the catalytic cycle, but most likely a carboxylic species is involved [57] .
In further studies, co-workers of Ford also investigated acidic water-gas shift
in detail - but as activities were far lower than in the base case, this work is not
discussed here [12] .

2.1 Water-Gas-Shift Reaction

21

Ru3 (CO)12 + OH [HRu3 (CO)11 ] + CO2


[HRu3 (CO)11 ] + H2O H2 Ru3 (CO)11 + OH
H2 Ru3 (CO)11 + CO Ru3 (CO)12

Scheme 2.10: Revised WGS reaction scheme for ruthenium carbonyls [11]

2.1.5.3 Laine group - identification of intermediates in WGS chemistry


Work of Laine on the homogeneous water-gas shift reaction actually started as
part of the Ford group. It is a logical follow-up to the initial steps that were
carried out in the Ford group at Santa Barbara [52,55] .
With in-situ IR work on the intermediates in the ruthenium-carbonyl catalyzed water gas shift a possible involvement of formic acid or formate was
discussed [55] . Also the occurrence of polymeric ruthenium clusters was reported [58] . In follow-up work on different reactions, that also involved CO
activation, similar intermediates were found [59] .
In a review in 1984, a variety of possible reaction pathways is intensely discussed. The review concludes, that mechanisms involving formate are the
most probable ones [60] . It also mentions the fact, that slightly alkaline systems
involving amines showed a better activity than ones involving strong bases.
However the question, why strong bases slow down the reactivity whilst OH
is involved in the catalytic cycle remains under debate. It was found that Rh,
Os, Ir and Ru strongly interact with tertiary amines, so the authors concluded,
that amine-metal complexes have a beneficial role in the WGS chemistry [6,59,61] .
As catalytic experiments showed before, the activity of these systems diverge
by several orders of magnitude, with the ranking Ru Rh > Ir > Os [5,60] .
The most comprehensive list of the WGS mechanisms proposed until 1988
was compiled by Laine and Crawford and presented in their review [5] . In
general, for basic ruthenium carbonyl catalyzed water gas shift reaction most
evidence leads to the existence of a metallo-carboxylic intermediate [5] . But
several key questions regarding base-promoted WGS are yet not answered.

22

Basics & Background

The involvement of mono- and binuclear species into a catalytic cycle remains
unclear. However the question remains open, which species is responsible for
the H2 elimination.
2.1.5.4 Cole-Hamilton & Tanaka - Pyridine modified ruthenium systems
The work of Cole-Hamilton was inspired by the fact, that the pyridine modified ruthenium complexes are active in WGS catalysis [11,62,63] . These authors
started working on photo-catalyzed WGS to obtain a more active catalyst. This
was based on the fact, that an active catalyst needs a "Janus-face" nature [64,65] :
It needs to be electrophilic to allow the attack of a hydroxide anion followed
by protonation of an hydrido intermediate. Additionally, it needs to be nucleophilic to ease the reductive elimination that leads to formation of hydrogen.
In their case, they used light to speed up the hydrogen elimination from an
electrophilic [RuClH2 (bipy)2 ]+ complex. Their proposed catalytic cyclic is depicted in Scheme 2.11. The effect of pH value was also studied in detail,

H2O
[RuL2(H2O)Cl]+

RuL2Cl2
ClH2
[RuL2ClH2]+
H+

H2O
CO
+
[RuL2Cl]

H+

CO

[RuL2(CO)Cl]+
OHOH-

[RuL2ClH]
CO2
[RuL2Cl(COOH)]

L = bipy

Scheme 2.11: Proposed scheme for the photo-catalyzed water-gas shift reaction using
ruthenium bipyridines [64] .

revealing that pH 9 gives the highest hydrogen production rate, with a


TOF 20h1 at 160 C and p = 1 bar. Activation energies were reported to be
EA = 35.3 kJ mol1 , which is clearly lower than activation energies previously

2.1 Water-Gas-Shift Reaction

23

reported (EA 80..110 kJ mol1 ). This was attributed to the fact, that the illumination shifted the rate determining step from the H2-elimination towards the
CO addition.
In contrast to that, Tanaka et al. found the same system active without irradiation [66] . The proposed mechanism in this case involves a H3 O+ species in a
highly alkaline environment, which is quite debatable.
The work of Mahajan et al. showed a TOF of about 3 h1 for [Ru(bipy)2 ]+ at
90 C, 1 bar in alcohol/water mixtures [67] .
Ishida et al. also performed studies on ruthenium bipyridine systems. Using spectroscopical methods they found possible intermediates of the WGS
with [RuCl(CO)(bipy)+] . This was possible by comparison of infrared spectra
obtained in experiments to the ones of separately prepared intermediate complexes. Based on this data, a new mechanism was proposed, that involves
again a carboxylic species as depicted in Scheme 2.12. The nucleophilic at-

CO
RuL2Cl2
ClH2
H3O

[RuL2(CO)Cl]+
CO
Cl
[RuL2(CO)(H2O)]
OHH+

[RuL2(CO)H]+

2+

CO
H2O

H2O

[RuL2(CO)(OH)]+

CO2

[RuL2(CO)2]2+
OHOH-

[RuL2(CO)(COOH)]+
OHH+

L = bipy

H2O

[RuL2(CO)(COO-)]+
Scheme 2.12: Proposed scheme for the water-gas shift reaction using ruthenium
bipyridines [68] .

tack of OH to one of the coordinated CO of [Ru(bipy)2 (CO)2 ]2+ at pH 8.0 9.0

24

Basics & Background

forms [Ru(bipy)2 (CO)(COOH)]+ , which undergoes a decarboxylation to give


[Ru(bipy)2 (CO)H]+ . This pathway is supported by the species found in the
catalytic system.
2.1.5.5 Pardey group - Rhodium amine systems
The work of the Pardey group is also closely related to the Ford group, as
Pardey got his PhD with Ford as primary advisor.
Starting with rhodium complexes in aqueous pyridine [13] or picoline [14] solutions for water-gas shift applications, the work shifted to investigations on
cationic rhodium complexes [6971] . In general, activities are orders of magnitude lower than in previously mentioned ruthenium cases. So the group looked
for other possibilities and investigated homogeneous WGS with Re2 (CO)12 [72] ,
CuCl2 [73] and iridium [74] - but all these attempts resulted in mediocre activities.
In order to follow up the previous rhodium work, mechanistic studies were carried out [7577] . Additionally, a heterogenization of the cis-[Rh(CO)2 (amine)2 ]PF6
on polyvinylpyridine was carried out [78] . This catalyst showed a rather low
turn-over frequency of 8.9 molH2 d1 . These low activities which are given per
day lead to the conclusion that rhodium seems not to be the right metal center
for water gas shift catalysis. Later work of the Pardey group on ruthenium
bipyridine systems confirmed results previously mentioned, but revealed no
new insights [79] .
2.1.5.6 Fachinetti group - Acid co-catalyzed WGS with Rh and Ru
Fachinetti carried out work on either rhodium or ruthenium systems. The work
in the rhodium case was carried out in the exact same way as the Pardey group
- rhodium precursors in pyridine/water solutions [80] . Their batch experiments
revealed, that the reaction seemed to be inhibited by chloride ions Cl from
the RhCl3 precursor, as the activity dropped as soon as the water content was
reaching about 5 %.
In a follow-up publication, the authors focused on identification of intermediates in ruthenium based water-gas shift starting from Ru3 (CO)12 in acidic
aqueous solution. Acidity was maintained by adding CF3 COOH to water. Using IR and NMR techniques, the existences of Ru2 [ 2 OC(CF3 )O]2 (CO)6

2.1 Water-Gas-Shift Reaction

25

and fac-[Ru(CF3 COO)3 (CO)3 ] in solution was found [81] . It was suspected,
that the precursor and these two newly found species are all involved in the
catalytic process as depicted in Scheme 2.13.
1

/2 H2

HL

/ 3 [Ru3(CO) 12]

Ru2L2(CO) 6
L-, CO

/ 2 H2, CO2, HL, L-

H2O

[RuL3(CO) 3]L = CF3COO

Scheme 2.13: Reaction scheme suggestion by Fachinetti et al. for the acidic water-gas
shift reaction for Ru3 (CO)12 [81] .

Ru(0) from the carbonyl is oxidized by H+ to Ru(I), which is subsequently


disproportionating to Ru(0) and Ru(II). The Ru(II) species is then prone to a
nucleophilic attack of water. Again, as mentioned by other groups, a metallocarboxylic acid intermediate is formed, that decomposes into a Ru(I) species
while liberating H2 and CO2 .
2.1.5.7 Other contributions to homogeneous WGS from other groups
Also various other groups contributed to homogeneously-catalyzed water gas
shift reaction. Their findings will be highlighted here. The before mentioned
review of Jacobs et al. cover details to much greater extent [6] .
In 1981, Doi and co-workers applied plain RuCl3 for water-gas shift reaction [82] .
This approach is contrasting the application of carbonyl complexes used by
most other groups, as mentioned before. The level of activity reached in an
aqueous solution of KOH/water was 8.5 molH2 molRu d 1 = 0.25 molH2 molRu h 1 at
90 o C and 0.9 bar of CO. Again the existence of a formate intermediate was
suggested. A partial confirmation was performed by decomposition studies of
sodium formate.

26

Basics & Background

The work of Khan on Ru(EDTA)-complexes in the water gas shift reaction revealed the formation of formic acid and formaldehyde [83] . Experiments were
conducted at 7 34 bar and 40 80 o C in water. Interestingly, the formation
of formic acid and formaldehyde formation were found to be both first order
with respect to CO and catalyst concentration. The apparent activation energy
was determined to be 67 kJ mol1 for formaldehyde and 135 kJ mol1 for formic
acid production. Also the authors proposed a mechanism which is similar to
previous reports by Ford et al.
Pakkanen reported on synergistic effects of mixed metal carbonyls containing
ruthenium and iron in WGS catalysis [84] . Solutions of iron and ruthenium
carbonyls or mixed ruthenium/iron carbonyls showed an enhanced activity of
about two orders of magnitude higher compared to the pure carbonyls. Other
combinations such as Fe-Co, Fe-Rh, Ru-Co, Co-Rh, Co-Ir and Rh-Ir mixed
carbonyls did not show any significant improvement.
2.1.6 Immobilization of homogeneous WGS catalysts
Attempts to immobilize water-gas-shift catalysts have been reported since the
early 1980s. Doi et al. reported on ruthenium carbonyl complexes linked via
phosphorous ligands to silica supports [85] .
Activity reported for a Ru(CO)4 (PPh2 C2 H4 Silica) was 11.2 molH2 molRu d1 at
150 C at low pressure in a closed circulating glass reactor (absolute reaction
pressure is not provided). An immobilized H4 Ru4 (CO)8 (PPh2 C2 H4 Silica) catalyst in comparison showed an activity, that was an order of magnitude lower.
Roberto et al. tried to immobilize RuCl3 -hydrate on silica and identified species
by means of infrared spectroscopy [86] .

They observed the formation of a

silica-bound tricarbonyl species [Ru(CO)X Cl2 (HO Silica)2 ] (with x = 2 for


temperatures < 50 C and x = 3 for T > 100 C) under carbon monoxide atmosphere. Most interestingly an extraction with acetone and recrystallization led
to the formation of [Ru(CO)3 Cl2 ]2 , which has a high sublimation tendency at
T = 180 C. The authors also started to physisorb [Ru(CO)3 Cl2 ]2 on silica, which
led to the appearance of [Ru2 (CO)6 Cl4 (H2 O)] on the surface in a H2 O / CO environment. Although these authors did not perform catalytic measurements for

2.1 Water-Gas-Shift Reaction

27

the WGS reaction, the transformation of RuCl3 towards carbonyl dimers was a
new insight.
Verdonck and coworkers investigated Ru(NH3 )6 Cl3 heterogenized in faujasitetype zeolites. Their heterogenized catalyst showed a TOF of 0.765 molH2 molRu h1
at 120 C [87] .
2.1.6.1 Pakkannen, Luukkanen & Haukka - Ruthenium pyridindes on
silica
Pakkanen and coworkers heterogenized Ru3 (CO)12 by sublimation onto silica
and alumina, which was later treated by pyridines [88,89] . Triruthenium dodecacarbonyl has been proven to be active in homogeneous WGS systems.
The compounds is volatile, so chemical vapor deposition was used for catalyst preparation using three different methods [10,50] . In preparation method
A, Ru3 (CO)12 was physisorbed onto the support surfaces, mixed with 2,2bipyridine, and evacuated at 100 C for 72 hours. In method B, Ru3 (CO)12
was chemisorbed onto the support at 120 145 C prior to mixing with bipyridine. Method C involved chemisorption onto the support first and bipyridine
dry-mixing afterwards.
The samples were tested at WGS conditions using pCO = 7 bar, pH2 O = 2.7
4.8 bar, T = 150 C with a flow rate of 10 100 cm3min1 . Table 2.3 shows the
WGS activity of the catalysts prepared by the different methods. Catalyst systems show high WGS activity, however, an influence of preparation methods,
support or catalyst loading can hardly extracted from the data, particularly due
to the lack of detailed information on the applied WGS reaction conditions.
In the following years, the same group focused on synthesis and characterization of ruthenium-carbonyl-pyridine complexes that were suspected to form insitu when Ru3 (CO)12 and pyridine were kept in WGS reaction conditions [90,91] .
Follow-up studies also immobilized the obtained [Ru(bipy)(CO)2 Cl2 ] complexes
on silica [92,93] . Again, specific residence times and other reaction conditions
were not reported, but published turn-over-frequencies are quite high, reaching a maximum of > 500 h1 [91] . The studies of Luukkanen [93] and the one of
Haukka [92] show a strong overlap. Influence of an activation of those catalysts
by Na2CO3 and NaOH was also tested. The carbonate additive turned out to
be more suitable than the strong base, producing the highest activities.

28

Basics & Background

Table 2.3: WGS activity of supported Ru3 (CO)12 / 2,2-bipyridine [89] . Conditions: pCO =
7bar, pH O = 2.7 . . . 4.8 bar, V total = 10 . . . 100 ml min1 and T = 150 C. Exact
2

conditions were not listed. Preparation method as described in text.

Preparation

Support

TOF / molH2 molRu h1

XCO

2 1

0.4

2 1

104.2

98

2 1

21.1

2 1

SiO2 400 m g

38.1

18

SiO2 400 m2 g1

44.4

2 1

SiO2 400 m g

65.3

30

SiO2 500 m2 g1

73.8

48

2 1

SiO2 500 m g

81.2

36

SiO2 500 m2 g1

Subl, Ru3 (CO)12


Impregnation
B

SiO2 400 m g

SiO2 400 m g

SiO2 500 m g

84.0

58

2 1

Al2 O3 155 m g

139.0

40

Al2 O3 155 m2 g1

147.1

60

2 1

Al2 O3 155 m g

157.4

66

SiO2 400 m2 g1

158.3

64

2 1

Al2 O3 155 m g

164.9

72

SiO2 400 m2 g1

191.7

98

2 1

Al2 O3 155 m g

224.8

74

SiO2 400 m2 g1

233.3

84

2 1

270.8

72

SiO2 400 m g

Heterogenization of catalyst system onto a support has been shown to give


highly active WGS catalysts with various advantages such as the potential
use in continuous gas-phase applications. Yet, these heterogeneous systems
lack of the advantages of homogeneous catalysis, such as uniform nature of
the catalytic centre and the possibility to use them at low temperature WGS
conditions.
In the present work, a new concept for supported homogeneous WGS catalysts
is demonstrated using ionic liquids as solvent in so-called Supported Ionic
Liquid Phase (SILP) concept. Ionic liquids and their use for SILP-catalysis are
introduced below.

2.2 Ionic liquids

29

2.2 Ionic liquids


Ionic liquids are a new class of materials, that were defined to consist completely of ions and to have a melting point of Tm < 100 C [94,95] . Generally, salts
in liquid state are called molten salts, so one could expect analogies between
molten salts and ionic liquids.
Ionic liquids and molten salts are both polar solvents and commonly have a
very low vapor pressure in the range of pvap 108 Pa when used below their
decomposition temperatures [19] . Molten salts however are commonly highmelting and very corrosive, whereas ionic liquids are liquid at low and even
ambient temperature and have generally a lower viscosity than molten salts [96] .
Whereas molten salts are mostly consisting of combinations of inorganic cations
and anions, ionic liquids consist mostly of organic cations and a variety of
anions [97] . Size differences and asymmetrical packing of inorganic and organic
ions leads to reduced melting points, due to lower intermolecular forces and
better delocalization of charges [96,98] .
The possibility of combining cation and anion offers the feature of tunable
physicochemical properties, such as viscosity, coordination strength, acidity
and solubility, which creates a substantial advantage over conventional molten
salts and other solvents [99] . Especially low vapor pressure, low coordination
strength, large electrochemical window, a thermal stability up to Tdecomp
300 C and the solubility of transition metal catalysts lead to a high attractivity
of ionic liquids with regard to their use in organometallic catalysis [100] .
Some typical cations and anions forming in ionic liquids are depicted in
Figure 2.5.
2.2.1 History and current state
As early as 1914, Sudgen et al. reported on [EtNH3 ][NO3 ] as a room-temperature
molten salt - today, this compound would have been possibly referred to as
ionic liquid [97,101] . But significant interest in both academia and industry was
not created, because a real use was not found for those materials at this time.
Chloroaluminates, that were discovered in the 1940s did not change the state of
low-temperature molten salts as laboratory curiosities without broader use [102] .
Because of their high sensibility towards water, which leads to instantaneous

30

Basics & Background


+

R1
R2

R3

Cl

F 3C

R'

Cl
Cl

R3

R4

Al
Cl

R4

R2

R1

CF3

SO3 -

Figure 2.5: Typical ionic liquid anions (top row) and cations (bottom row) and their typical abbreviation. a) alkylpyridinium([R4 Pyr]+ ), b) tetraalkylphosphonium
([R4 P]+ ), c) tetraalkylammonium ([R4 N]+ ), d) dialkylimiadzolium ([RR IM]+
or [Cn Cm IM]+ ), e) tetrachloroaluminat ([AlCl4 ] ), f) tetrafluoroborat
([BF4 ] ), g) bis(trifluoromethylsulfonyl)imide (NT f2 or BTA), h) alkylsulfat
(ROSO3 )

decomposition to Al2 O3 , the use of chloroaluminate melts was limited to special


applications in military and electrochemistry.
In the 1960s tetrahexylammoniumbenzoate room-temperature ionic liquids
were discovered [103] , whereas Osteryoung and Wilkes performed intense research on chloroaluminates [104] . Catalysis in molten salts was considered to be
difficult because of limitations due to corrosivity and separations [105] . However, research in the groups of Seddon in Belfast and Wilkes in the US during
the 1980s on the applications of ionic liquids, especially in catalysis, created
growing interest in the scientific community [106,107] .
When ionic liquids with better stability towards water, like ammonium and
sulfonium tetrafluoroborates [BF4 ] were published, systematic studies began [108] . Although these fluorine containing ionic liquids tend to formation
of toxic and corrosive HF, these first-generation ionic liquids are still in use in
several groups. A breakthrough was the report of Wilkes on hydrolytically
stable ionic liquids based on alkyl-imidazolium cations [109] . In the following
decade, groups of Seddon and Chauvin reported on ionic liquids, and several
other groups started working with catalysis in ionic liquids [110112] .
Because of their low vapor-pressure that is advantageous for the use as process
solvent, ionic liquids got the term green solvents [113116] . A major breakthrough

2.2 Ionic liquids

31

was the discovery of halogen-free ionic liquids by van Hal in the group of
Wasserscheid - which lead more in the way of green chemistry [117] . Catalysis in
ionic liquids was reviewed in detail by Seddon [118] , Dupont [119] , Welton [95,100] ,
Wasserscheid [94,99] , Cole-Hamilton [120] and recently by Olivier-Bourbigou [98] .
Before the report of Earle et al. in 2006, ionic liquids were considered to have no
vapor pressure at all - but it was demonstrated, that at certain conditions ionic
liquids even can be distilled [121] . Later on, even vapor pressure measurements
were published [19] .
In general, since 2000, the interest in ionic liquids raised tremendously - resulting in a huge increase in publications [96] . Publications and applications
not only focus on reaction media, but also on various other fields of chemical engineering, such as separation science (e.g. as entrainers, extracting
phase), electrochemistry (e.g. as electrolytes in batteries or solar cells), process
machinery (e.g. as lubricant or process fluid) or semiconductor fabrication.
Additionally, elementary understanding on ionic liquids is fostered by work in
physical or theoretical chemistry, whereas the data basis of thermodynamical
and physicochemical data is growing rapidly.
2.2.2 Physicochemical properties
As mentioned beforehand, ionic liquids offer the feature of tunable properties
by variation of their anion / cation combination. Table 2.4 illustrates typical
boundaries for practically relevant properties of ionic liquids.
However properties cannot be changed completely independently in some
cases. Changing the anion from Cl to [NT f2] influences e.g. water miscibility,
corrosivity and viscosity. This results in a trade-off between different important
factors, so that one has to focus on a specific property as a primary objective.
Additionally, other properties are directly linked to those listed: For example,
a lower viscosity results in higher diffusion coefficients, ion mobility and thus
electrical conductivity. In addition to the properties listed in Table 2.4, factors such as coordination strength, electrochemical window and even vapor
pressure are worth mentioning. So one has to keep in mind, that properties
are tunable, but one change in structure might result in more than one altered
property. Due to their tunable properties ionic liquids are sometimes referred
as "designer"-solvents [113,116] .

32

Basics & Background

Table 2.4: Typical property ranges of ionic liquids. Modified from own publication [99]
and references therein.
Property
d

Thermal stability
Melting point

Lower limit

Typical range

Upper limit

[EMIM][OAc]
180 C

200 C 280 C

[EMIM][NT f2 ]
300 C

[EMIM]Cl
AlCl3
ab

0 C 60 C

100 C by definition

=1:2

96 C
c

Density

Viscosityc

[HMpyr][N(CN)2 ] 1.1 1.6 g cm3


0.92 g cm3
[EMIM]Cl
AlCl3

=1:2

[EMIM]Br
AlBr3

2.2 g cm

=1:2
3

40 800 mPa s

[BMIM]Clc
40.89 Pa s

14 mPa s
Surface tension

[C12 MIM][PF6 ]
23.6 mN m1

30 50 mN m1

[MMIM][MeSO4 ]
59.8 mN m1

Heat capacity

[BMIM][MeSO4 ]

300 400 J mol1 K1

[OMIM][NT f2 ]

Water miscibility

247 J mol K
[NT f2 ] ,

many ILs do mix with wa-

654 J mol1 K1
[RSO3 ] , [RSO4 ] ,

[P(C2 F5 )3 F3 ]

Hydrolytic
stability

[BF4], [PF6]

Base stability

[Al2 Cl7 ] ,

Corrosion

Toxicity

ter but also can be extracted from water

[R2 PO4 ]

heterocyclic cations can


hydrolyze under extreme

[NT f2 ] , [OT f ] ,
[CH3 SO3 ]

conditions
all 1,3-dialkylimidazoli-

[PR4 ]+ , [OAc]

[HSO4 ]

um ILs are subject to deprotonation

[NT f2 ] ,
[OT f ]

most ILs are corrosive versus Cue

[cholinium][OAc] often increasing toxicity

Cl , HF formed
from [MFx ]
hydrolysis
[EMIM][CN]

for aquatic systems with


Price

[HNR3 ][HSO4 ]
3 e kg

increasing lipophilicity
25 250 ekg1

[BMMIM][NT f2 ]
1.000 e kg1

a Glass

b Supercooled.
transition temperature.
c At room temperature.
d TGA experiments at 10 K min1 .
e Additives available.
f Estimation made for a production scale of 1000 kg and for a purity > 98 %.

The possibility of altering properties by different anion / cation combination creates the need of prediction of those properties [122] . In this context
the availability of a-priori methods gain importance [123] . Most notably the

2.2 Ionic liquids

33

COSMO-RS method [124] has been applied to predict chemo-thermodynamical


data such as activity coefficients or vapor-liquid equilibria of IL-hydrocarbon
mixtures [125,126] . It is worth mentioning, that values predicted by COSMO-RS
represent actual trends quite well, whereas experimental and calculated values
do not match exactly in most cases.
Besides these first results in prediction of data very few approaches have been
successfully accomplished.
In order to predict data, correlations derived from actual measurements where
cation or anion are varied in series, e.g. varying the length of the alkyl chains
of a imidazolium heterocycle, tend to be state of technology. These ab-initio
extrapolation techniques are also predicting just trends, not actual values.
For this work, the following physicochemical properties are especially important, to achieve an optimum in catalyst activity:
Low viscosity at reaction conditions resulting in good transport properties
Good solubility for substrates (carbon monoxide and water)
Low solubility for products (carbon dioxide and hydrogen)
Hydrolytic & base stability at operation conditions
Immobilization & solubility of catalyst complex
Low price & ecotoxicity
Ionic liquids have been reported to display stability problems under basic
conditions. In case of imidazolium based ionic liquids, this is related to the
formation of carbenes by abstraction of the most acidic C2 H proton [119] .
Additionally, Hofmann-elimination can occur in case of ammonium based
ionic liquids. There are two possibilities to tackle these issue: Usage of ionic
liquids that are not subject to carbene formation and Hofmann-elimination
(e.g. phosphonium) or imidazolium based ionic liquids with C2 -methylated
imidazolium heterocycle [96] .

34

Basics & Background

2.2.3 Solubilities in Ionic Liquids

In order to use a catalyst phase efficiently, it should homogeneously dissolve the


catalyst and also provide good solubility for the substrates. Catalyst solubility
is not a strong concern for transition metal catalysis in ionic liquids. Many
transition metal complexes are polarizable enough to be soluble in most ionic
liquids in the ppm ranges that are required for catalysis applications [96] . In
other solvents a special ligand design is needed to overcome this limitation,
e.g. poly-tails for scCO2 . For ionic liquids this specific kind of ligand design
is usually not necessary to get catalyst complexes dissolved in sufficiently
high concentration. However, dissolving a solid, crystalline complex in an
often relatively viscous ionic liquid can be slow due to restricted mass transfer.
The dissolution can be speeded up by either increasing the exchange surface
(ultrasonic bath) or by lowering the ionic liquids viscosity. The latter is easily
achieved by adding small amounts of a volatile organic solvent that dissolves
both the catalyst complex and the ionic liquid. As soon as the solution is
homogeneous the volatile solvent is then removed in vacuo.
Another, more important point when talking about solubilities in ionic liquids
is the substrate and the product solubility. Usually, the rate of a catalytic
reaction depends on the concentration of the substrates in a positive order.
Thus, a high concentration of the feedstock in the catalyst phase is desired. In
multi-phasic catalysis the available substrate concentration depends on both
the thermodynamic equilibrium solubility of the reactant in the ionic liquid
and on the mass transfer rate of the reactant into the ionic reaction medium.
So a complex interplay of kinetics and thermodynamics is occurring. In case of
the WGSR the solubility of the gases carbon monoxide, water, carbon dioxide
and hydrogen in the ionic liquid is important. An ionic liquid that combines
a high solubility of the feedstock molecules carbon monoxide and water and a
low solubility of carbon dioxide and hydrogen would favor the product side of
the WGSR equilibrium and therewith improve the hydrogen yield. In general,
gas solubilities are measured at constant temperature as a function of pressure.
For most liquids, solubility of many gases is quite low and can be adequately
described at ambient pressure or below by the Henry law. Typically, the Henry

2.2 Ionic liquids

35

coefficient can be expressed as follows.


KH (T, p) = lim

x1 0

f1L
x1

p1
x1 0 x1

= lim

(2.2)

For low pressures the partial pressure pi instead of the fugacity fi can be used
for the calculation. The Henrys law constant can be determined experimentally
from the limiting slope of the solubility as a function of pressure. A large Henry
constant indicates low gas solubility, whereas a small Henry law constant
constitutes a high gas solubility. Solubility can be determined by different
techniques which are described elsewhere [127,128] .
The Henry constant offers a measure to compare gas solubilities in different
ionic liquids. Anthony et al. investigated gas solubilities in ionic liquids and
discovered that gases with a large dipole moment (e.g. water) or quadrupole
moment (e.g. CO2 ), as well as those with the opportunity for specific interactions (e.g. hydrogen bonding) have the highest solubilities in ionic liquids,
whereas the solubilities of non-polar gases correlate well with their polarizabilities [129] . In the following, the solubilities of the gases involved in the WGSR
are discussed.
2.2.3.1 Carbon monoxide
Carbon monoxide solubility has been studied for a large number of ionic liquids [129131] . According to Ohlin et al. the solubility of carbon monoxide is
strongly dependent upon the nature of the ionic liquid, presumably due to the
presence of a dipole moment, and high polarizability [130] . Ohlin investigated
CO solubility in a number of ionic liquids and found the highest solubilities in
imidazolium-based ionic liquids. The solubility of carbon monoxide increases
according to his data in the series [BF4 ] < [PF6 ] < [SbF6 ] < [CF3 CO2 ] <
[NT f2 ] . This coincides with an increase in the size of the anion, and a decrease
in interactions between anion and carbon monoxide

[131]

. From the series

of [NT f2] and [BF4 ] ionic liquids additional trends are apparent. Solubility

increases with the chain length of the alkyl substituent in the ionic liquids
cation. This trend is shown in Figure 2.6 for the anions [BF4 ] and [NT f2] .

A interaction refers to anti-binding, non-covalent interaction, that involves an electronrich -system and a (polarizable) molecule. It is similar to an electrostatic interaction where
a negative region interacts with another one.

36

Basics & Background

8000
[RMIM][NTf ]
2

[RMIM][BF ]
4

[RMMIM][NTf ]
2

4000

/ bar

6000

2000

4
alkyl chain length

n (R = CnH

n+1

Figure 2.6: Effect of alkyl chain length in [RMIM] ionic liquids with different anions.
Data from Ohlin [130] .

Additionally, solubility of carbon monoxide decreases when the alkyl group


is replaced by a benzyl group. This also corresponds to an increase in
interactions, which generally leads to a decrease in CO solubility. Kumelan
et al. [131] also investigated carbon monoxide solubility in [BMIM][PF6 ] and
found a Henry constant of 552 bar at 293.2 K which differs by a substantial
amount from the result of Ohlin et al. [130] , but yields very good agreement
with a model study by Hayden and OConnell [132] . However, all studies show
the same trend: Highest CO solubilities are found for imidazolium based ionic
liquids with long chain length of the alkyl substituent, which makes these ionic
liquids favorable for the use in WGSR.

2.2.3.2 Water
Many ionic liquids are hygroscopic and can absorb large quantities of water.
Water-gas shift reaction requires solubility of water vapor.

2.2 Ionic liquids

37

Seddon and coworkers investigated the solubility of ionic liquids in water,


which is strongly correlated with the anion present in the ionic liquid [133] . This
offers the opportunity to determine trends for the solubility of water vapor in
ionic liquids. Water soluble ionic liquids exhibit strong interactions between
water and especially their anion, so that one should expect also a high solubility
for water vapor.
Seddon indicated that all halide-, ethanoate-, nitrate- and trifluoroacetatebased ionic liquids are fully water miscible, whereas all [RMIM][PF6 ] and
[RMIM][NT f2 ] are insoluble in water and show a miscibility gap. Depending
on the alkyl chain length on the cation [RMIM][BF4 ] and [RMIM][OT f ] are
either fully miscible with water (e.g., [EMIM][BF4 ] and [BMIM][BF4 ]) or form
biphasic systems (e.g. [Cn MIM][BF4 ], n > 4). Thus, the anion has a primary
effect on water miscibility and the cation a secondary.
Solubility measurements of water vapor in ionic liquids were carried out by
Anthony et al. [134] and Cammarata and coworkers [135] . Anthony measured
the solubility of water vapor in three ionic liquids resulting KH,[OMIM][BF4 ] =
0.055 bar, KH,[BMIM][PF6 ] = 0.17 bar, and KH,[OMIM][PF6 ] = 0.2 bar.
Although the small values for KH indicate high solubility of water vapor in
the ionic liquids, a strong effect of the cation can be observed. [BF4 ] as anion
shows significantly higher water vapor solubility than [PF6 ] . This was related
to the smaller van der Waals volume of the [BF4 ] resulting in a higher charge
density. However, both anions [BF4 ] as well as [PF6 ] are well known to be
hydrolysis instable and relatively hydrophobic [136] .
Increasing the length of the side chain increases hydrophobicity and consequently leads to a lower water solubility, though this effect is relatively small.
Cammarata et al. measured the state of water in ionic liquids with a [BMIM]+
cation and various anions for example [PF6 ] , [BF4 ] and [OT f ] . The strength
of hydrogen-bonding between the anion and the water molecules was found
to be most important for the water solubility in ionic liquids. The anion [PF6 ]
was shown to have the weakest H-bonding interactions, while [CH3 CO2 ] has
the strongest. According to the study the strength of the H-bonding interaction
appears to be in direct correlation with the water solubility in the ionic liquid.
The results of Anthony [134] and Cammarata [135] correlate well with the solubility behavior described by the above mentioned data from Seddon [136] . Note

38

Basics & Background

that for the WGS reaction and the SILP-system the ionic liquid should not to be
too hygroscopic, to avoid washing off the catalyst from the support material.
According to the results of Seddon and Cammarata the use [Cn MIM][OT f ]
with 2 n 4 would be reasonable.
2.2.3.3 Hydrogen
For the application of ionic liquids as solvents in the homogeneous WGSR
low hydrogen solubility is desired due to a shift of the equilibrium towards the
products. Hydrogen solubility is similar to or even lower than the one of carbon
monoxide for the ILs where carbon monoxide solubility data are available.
Dyson et al. used NMR spectroscopy to measure hydrogen solubility in a wide
variety of ionic liquids, the majority of which were imidazolium-based ionic
liquids [137] . At atmospheric pressure the dissolved hydrogen concentrations
were lower than the detection limit of the NMR method and it was only on
increasing the pressure to 100 bar that the peak corresponding to hydrogen
could be clearly resolved and integrated relative to the solvent peaks. The
concentration of hydrogen that dissolves in the investigated ionic liquids is
very low, much lower than for molecular organic solvents, and is in the same
range as for water.
The hydrogen solubility and Henry constants for the ionic liquids at 1 bar, 20 C
are generally in a range of KH = 3800..6500 bar, with lowest values for less coordinating anions, such as [NT f2]. Berger et al. reported on the conversion and
enantioselectivity of a hydrogenation reaction in the ionic liquids [BMIM][BF4 ]
and [BMIM][PF6 ] and showed that hydrogen is four times more soluble in
the tetrafluoroborate than in the hexafluorophosphate [138] . This also showed
a significant effect in terms of higher conversion and enantiomeric excess for
the [BF4 ] containing ionic liquid. Furthermore Kumelan et al. determined the
hydrogen solubility in the ionic liquid [BMIM][CH3 SO4 ] and noticed increasing
gas solubility with increasing temperature [139] . The Henry constants investigated in the above mentioned studies ranged from 700 to 7200 bar. Therefore
the solubility of hydrogen in the ionic liquids investigated is rather low which
is exactly what is needed for the use as solvent in the WGS reaction. It has been
shown by Solinas et al. that H2 solubility increases in the presence of CO2 at high
pressures [140] . Solinas investigated the hydrogen solubility in [EMIM][NT f2 ]

2.2 Ionic liquids

39

by using high-pressure NMR spectroscopy. At 30 bar H2 the characteristic


signal of hydrogen could not be detected. When adding carbon dioxide with
a pressure of 120 bar at a constant partial pressure for hydrogen of 30 bar, the
solubility of hydrogen increased dramatically. The characteristic NMR-signal
revealed a solubility similar to the hydrogen solubility in common organic
solvents and two orders of magnitude higher than in common ionic liquids.
This enhancement effect was explained by the excellent solubility properties
of carbon dioxide in ionic liquids and its miscibility with hydrogen in all
proportions [141,142] . The solubility enhancement effect of carbon dioxide was
observed by Hert et al. for oxygen and methane as well [143] .
Additionally, to these thermodynamic considerations, a kinetic implication is
also important. It is known, that the viscosity of ionic liquids decreases as a
function of carbon dioxide pressure, which leads to enhanced mass transfer in
the IL phase.
2.2.3.4 Carbon dioxide
Carbon dioxide has one of the highest solubilities in ILs and the solubility is
generally even higher than in conventional solvents. Anthony and coworkers investigated gas solubilities of different gases including carbon dioxide in
ionic liquids [142] . They found a rather strong dependence of CO2 solubility depending on the anion present in the ionic liquid. Solubility measurements for
CO2 were carried out at 298 K in the ionic liquids [BMIM][PF6 ], [BMIM][BF4 ],
[BMIM][NT f2 ], [MB3 N][NT f2] and [BMPy][NT f2]. Temperature-dependence
was also studied and the solubility was found to decrease with increasing temperature. Henry constants differ little for carbon dioxide in [PF6 ] and [BF4 ]
whereas the [NT f2 ] containing ionic liquids exhibit a significantly higher CO2
solubility.
This was explained by the larger size of the [NT f2 ] anion, accordingly the
stronger non-specific van der Waals interactions and the potentially stronger
interactions between the partial positive charge on the carbon of CO2 and the
partial negative on the fluorine atoms. The [NT f2] containing ionic liquids
show similar, high CO2 solubility, regardless of the cation. Baltus et al. published a study increasing the length of the alkyl chain on the imidazolium
cation from [BMIM][NT f2 ], to [HMIM][NT f2 ] and [OMIM][NT f2 ] where the

40

Basics & Background

Henry law constants only decreased from 37 bar to 30 bar at 25 C, which is


in good agreement with the results of Shariati et al., who also obtained slightly
higher solubilities for longer alkyl chains [144,145] . Camper et al. investigated
additional ionic liquids and also obtained an anion dependency of the carbon
dioxide solubility [146] . Lowest carbon dioxide solubilities were obtained for
dicyanamide [dca] and triflate [OT f ] as anions. The carbon dioxide solubilities reported in open literature are relatively high compared to the solubility
of other gases. This could be a limiting factor concerning the application of
ionic liquids in the WGSR, whereas the decrease in viscosity of the ionic liquid
through carbon dioxide enhances mass transfer and should have a positive
effect on the WGSR. From the anions investigated in literature the use of [dca]
or [OT f ] as anion in the ionic liquid would be most favorable for the use as
solvent in the WGS reaction.

From the solubility information available in the literature, the 1-butyl-2,3dimethylimidazolium cation ([BMMIM]+ ) in combination with [OT f ] was
chosen for the use as solvent in our WGSR experiments. [BMMIM][OT f ] combines reasonable carbon monoxide and water solubility with relatively low
carbon dioxide solubility, whilst the hydrogen solubility is low as for all ionic
liquids.

2.3 Immobilization of homogeneous catalysts

One of the most challenging issues in homogeneous catalysis is successful separation of product and catalyst, coupled with successful catalyst recycling [15] .
In order to tackle this issue, different immobilization/recycling strategies have
been developed. These are classified as depicted in Figure 2.7.

2.3 Immobilization of homogeneous catalysts

41

catalyst
immobilization

multiple liquid -phase

biphasic aqua /
solvent

heterogenization

anchoring

physisorption

biphasic ionic
liquid / ...

supported
aqueous phase

micelles

supported
liquid phase

phase-change

recovery

scCO 2
Dp

precipitation

fluorous phase
DT

extraction

membranes

supported ionic
liquid phase

Figure 2.7: Immobilization concepts for homogeneous catalysts.

One concept of immobilization involves multiple fluid phases. This concept


is covered in the following chapter. Additionally, multiple reaction phases
can be realized by micro-biphasic systems, namely micelles [147] . In order to
employ continuous gas-phase reaction with homogeneous catalysts, the concept of heterogenization is used. The catalyst can be also dispersed on a solid
support, or anchored by linking ligands [148] . If a liquid support is dispersed on
a support material, this is called supported liquid phase catalysis [149] . A first
version employed high-boiling organics [150] , whereas later supported aqueous
phase [151] and supported ionic liquid phase systems were developed [16] . The
separation of catalyst and products can also involve a phase transition, where
the system changes from a mono- to a multiphase system when variables such
as temperature or pressure are changed [15] . A typical strategy is the use of
supercritical CO2 , where a pressure change induces this phase change [152] . A
thermo-regulated change is possible by the use of fluorous phases [153] . Independently of these concepts where the catalyst basically stays in the reactor
all the time, recovery and recycling concepts can be applied, which involve a
post-treatment of the reactor effluent [120] . Precipitation of the active homogeneous catalyst from the reaction phase is possible, which is typically induces
by a change in pH value. Also back-extraction of the catalyst by helper solvents can be applied to recover the catalyst. A last concept is the application of

42

Basics & Background

membranes, which can be used both for separation and for immobilization [154] .
A detailed insight into this topic is available in reviews of Cole-Hamilton [120] or
the extensive book of Cornils and Herrmann [15] . The following sub-sections focus on the recent developments from multi-phase systems towards Supported
Ionic Liquid Phase (SILP) catalysis.
2.3.1 Multi-phase catalysis
Multi-phase catalytic systems consist of an immobilizing phase containing the
catalyst and the ligand inventory and a second phase, preferably the product phase. So substrates need to be dissolved in the catalyst phase to some
extent and a miscibility gap between catalyst and product phase must exist.
Inherent problems of this concept arise from possible mass-transfer limitations
at the liquid-liquid phase boundary and from the fact, that even small crosssolubilities of the catalyst into the product phase leads to leaching. A suitable
catalyst phase should have the following properties [120] :
Good solubility of substrates.
Low solubility of products.
Excellent immobilization of catalyst (leaching < 0.1 ppm).
Catalyst is not negatively influenced by solvent.
Technical processes that utilize this concept focus primarily on good immobilization, because homogeneous catalysts mostly contain expensive precious
metal centers such as Rh or Ru where even small leaching would severely influence process economics. In this case, ligands are tuned to satisfy selectivity
needs but also to provide very efficient immobilization of the complex inside
the catalyst phase.
Fluid-fluid-multiphase catalysis got commercialized in the Shell Higher Olefine Process (SHOP) and the Ruhrchemie/Rhne-Poulenc Process [155] . In the
SHOP a Nickel-phosphine-complex is utilized to convert ethylene into linear
-olefines, which are intermediates for the production of surfactants (linear

2.3 Immobilization of homogeneous catalysts

43

-olefinesulfonates) or are used as co-monomers in polymerizations [156] . The


Ruhrchemie/Rhne-Poulenc process involves the hydroformylation of olefines
into aldehydes in a biphasic process using water and the olefine product phase.
In this case a rhodium catalyst is modified with a water-soluble triphenylphosphintrisulfonate (TPPTS) to immobilize the catalyst in water [157] . Especially
the Ruhrchemie/Rhne-Poulenc process suffers of low substrate solubility inside the catalyst phase. But both processes remain economic because of good
immobilization although space-time yields are low.
Multi-phase transition metal catalysis with ionic liquids has been successfully
demonstrated for example by Chauvin et al. [112] . Ionic liquids show good immobilization of the catalyst together with stabilization and sometimes even
increased activity. Recent applications of ionic liquids in catalysis are summarized in reviews by Plechkova and Seddon [158] , Wasserscheid [159] , Welton [100] ,
Dupont [119] and Gordon [160] .
2.3.2 Supported catalysts
In order to circumvent drawbacks of homogeneous catalysis, immobilization
on solid materials, sometimes called heterogenization is one focus of catalysis research [15] . Transformation of homogeneous reactions into heterogeneous
processes tries to combine benefits of both worlds - namely high catalytic activity and selectivity from homogeneous and easy catalyst recycling, handling
and stability from heterogeneous catalysis [149] . Additionally, a highly porous
support creates a large interfacial area leading to effective mass transfer. Porous
heterogeneous catalysts are well studied and their characterization and application are basics in teaching reaction engineering. Treatment of pore diffusion
limitations, film diffusion and internal & external heat transfer is analogous in
supported catalysts as for typical heterogeneous catalysts.
First approaches to immobilize homogeneous catalysts on support materials
utilized ion exchange resins, but those systems suffered from deactivation,
leaching and low selectivity [161,162] . Additionally, strategies to link catalysts on
supports via covalent bonding was described, but were also limited to special
types of reactions [150] . Homogeneous catalysis typically utilize a liquid phase
for the reaction, so a logical alternative approach was s creating this liquid

44

Basics & Background

phase inside a highly porous support. The idea of using a liquid film inside
a porous support for heterogenized catalysis evolved in the 1970s [150,163] . In
this case high-boiling organics were utilized. Later on, the use of water was
discussed [151] . But all those Supported Liquid Phase Catalysts suffered primarily
from the fact that on longer operation in continuous gas-phase contact, the
liquid phase got stripped out from the porous support leaving a deactivated
catalyst behind. Reason for this behavior was the high vapor pressure of the
liquid phase at reaction temperature leading to fast evaporation [18] .
2.3.3 Supported Ionic Liquid Phase (SILP) catalysis
In 2002 Mehnert et al. published the concept of using ionic liquids as immobilizing phase in supported catalysts for hydrogenations [16] - so most people claim
that he invented the SILP concept. Deeper view into literature reveals, that
actually Valkenberg in the group of Hlderich in Aachen reported on FriedelCrafs Alkylation employing supported chloroaluminate ionic liquids back in
2001 [164] . However, their systems involved surface reacted chloroaluminate
films on silica of which the liquid nature is doubtful.
Despite that, the concept raised a lot of attention, basically because it circumvents the main concern about Supported Liquid Phase catalysis, namely
stripping out the liquid phase: Ionic liquids with their very low vapor pressure
(mostly in the 108 Pa range) are not subject to be stripped out from the support
material.
Application of SILP materials in slurry systems are generally limited by cross
solubility issues. Even marginal solubility of the ionic liquid in the liquid reaction mixture would lead to leaching of a significant part of the very small
amount of ionic liquid on support. Therefore gas-phase catalysis is the preferential application field of SILP-catalysts, with the extremely low ionic liquid
volatility being the key factor. The concept of Supported Ionic Liquid Phase
(SILP) catalysts is schematically depicted in Figure 2.8.
The SILP catalyst appears as a solid, but the active species are dissolved in
the ionic liquid on the support and thus act as a homogeneous site with high
specificity and uniform nature. This results in the combination of homogeneous catalysis with high specificity and selectivity together with attractive

2.3 Immobilization of homogeneous catalysts

45

Figure 2.8: Supported Ionic Liquid Phase (SILP) - A homogeneous catalyst dissolved
in an ionic liquid dispersed on a highly porous support. Drawing courtesy
of Martin J. Schneider.

features of heterogeneous catalysts, such as large interfacial reaction area, easy


separation of products and catalyst, high system stability and the potential to
established process engineering technology such as fixed-bed reactors.
SILP catalysts are especially interesting for continuous gas-phase reactions,
where the advantage of using a liquid with very low vapor pressure can be
fully exploited. Gaseous or vapor-phase substrates can diffuse through the
pore space of the support, dissolve in the thin ionic liquid catalyst film and react herein. Products then diffuse out of the catalyst phase into the pore system
and further out of the catalyst particle. The amount of ionic liquid used in the
preparation of the SILP catalyst is crucial for the performance. Liquid loading
is defined as dimensionless ratio between the liquid volume VIL and support
pore volume Vpore [25] .
In order to form a continuous thin layer of ionic liquid on the inside walls of
the pores, a sufficient amount of ionic liquid must be present. Distribution
and dispersion of the ionic liquid inside the pores is important and dependent
on the pore radii distribution of the support, the capillary forces, the wetting characteristics of the liquid and possible ionic liquid-support interactions.

46

Basics & Background

Accordingly, the catalyst layer is generally 20 or less, corresponding to a


diffusion layer of only a few ion pairs thickness. Thereby diffusion problems
that can be found in bulk applications especially for the relatively viscous ionic
liquids are rather unlikely. Typically the ionic liquid catalyst phase in the SILP
catalyst is confined to the surface of the support only by physisorption. Electrostatic interactions (e.g. between anion/cation of the ionic liquid and surface
Si OH groups) and capillary / adhesive forces interacting in the pores of the
support provide the immobilization of the film.
SILP catalysts are prepared by impregnation techniques using a volatile solvent miscible with the ionic liquid to initially reduce viscosity of the IL for
the impregnation process. Subsequently, a transition metal catalyst can be dissolved in the IL/solvent mixture before the solvent is removed by evaporation
leaving the ionic liquid catalyst layer dispersed on the support. An additional
preparation strategy was recently developed by Sd-Chemie AG. In this case,
a catalyst / ionic liquid solution is sprayed onto the support material, which
is fluidized by an inert gas flow, so that efficient mixing is ensured. This fluidized bed method, which is also highly suitable for a technical scale-up of the
fabrication of SILP catalysts, is depicted in Figure 2.9.
Both straight-forward synthesis strategies enable quick preparation of samples for catalytic test, so that even screening studies can be easily carried out.
During the last years several research groups have been active in further developing the SILP concept for catalysis and separation technologies. The group
of Riisager and Fehrmann at DTU Lyngby, Denmark together with the group
of Wasserscheid published as early as 2003 the first successful application of
SILP materials in continuous gas-phase hydroformylation [17,21] .
Other groups established nucleophilic substitutions [165] , hydroamination [166]
and prochiral reaction systems [167] . Additionally, SILP materials were applied
in a supercritical CO2 environment [168] . Reviews by Zhao [149] , Riisager [23] and
Gu [18] summarize recent work to a further extent.
Continuous work in the Wasserscheid group in Erlangen was carried out for
Hydroformylation [25,169]

2.3 Immobilization of homogeneous catalysts

47

Figure 2.9: Preparation of Supported Ionic Liquid Phase (SILP) by fluidized bed spray
impregnation with resulting technical substrates. Drawing/photo courtesy
of Dr. N. Szesni.

Friedel-Crafs Alkylation [26,170,171]


Desulfurization [172,173]
(Asymetric) Hydrogenation [174]
In this work, results on water-gas shift catalysis using supported ionic liquid
phase materials will be presented. Parts of this work have been previously
published in peer reviewed journals [175177] .

3 Experimental
3.1 Chemicals
3.1.1 Substrates
The WGS reaction was performed in this thesis in different operation modes,
namely low pressure with model gas mixture, high pressure with model gas
and high pressure with realistic synthesis gas mixture. In all cases, nitrogen
(Linde Gas AG, 5.0, > 99.999 %) was used as inert atmosphere and balance. For
model gas experiments, carbon monoxide (Linde Gas AG, 3.7, 99.97 %) and
bi-distilled water (de-ionized, reverse osmosis treated helium degassed) were
used as substrates. Additionally, carbon dioxide (Linde Gas AG, 4.5, 99.995 %)
was used as co-substrate.
In realistic synthesis gas experiments a specialized gas mixture from Linde AG
was used. This contained 8 Vol% carbon monoxide, 13 Vol% carbon dioxide,
4 Vol% nitrogen and hydrogen as balance. Again bi-distilled water was used.
Substrates are summarized in Table 3.1.
Table 3.1: Substrates used in this work.

Material

Manufacturer

Purity

Nitrogen

Linde

> 99.999 % (5.0)

Carbon monoxide

Linde

> 99.97 % (3.7)

Carbon dioxide

Linde

> 99.995 % (4.5)

Water

CRT

reverse osmosis

3.1.2 Homogeneous catalysts


A large variety of transition metal complexes were evaluated as potential homogeneous WGS catalysts in this work. All used complexes are summarized
in Table 3.2.

48

3.1 Chemicals

49

Table 3.2: Homogeneous catalysts used in this work.


ID

Formula

CAS #

Soluble in

CRT-01

Ru Nano

CRT-02

Ru3 (CO)12

639.3

15243-33-1

Toluene

CRT-03

[Ru(acac)3 ]

398.4

14284-93-6

DCM

CRT-04

OsCl3

296.6

14996-60-2

Aqua

CRT-05

Os3 (CO)12

906.8

15696-40-9

DCM

CRT-06

IrCl3

298.6

14996-61-3

Aqua

CRT-07

Ir4 (CO)12

1105.0

11065-24-0

Toluene

CRT-08

[PPh3 Ir(CO)Cl]

780.3

14871-41-1

THF

CRT-09

RhCl3

209.3

20765-98-4

Aqua

CRT-10

PdCl2

177.3

7647-10-1

Aqua

CRT-11

MoCl5

273.2

10241-05-1

Aqua

CRT-12

CuCl2

170.5

10125-13-0

Aqua

CRT-13

ReCl3

292.6

13569-63-6

Aqua

CRT-14

FeCl3

162.2

7705-08-0

Aqua

CRT-15

[(bipy)Ru(Cl)2 ]

484.3

15746-57-3

Toluene

SC-01

[(CO)4 Mo(bipy)]

364.2

15668-64-1

THF

SC-02

[(tmeda)Cu(Cl)(OH)]

232.2

160492-47-7

DCM

SC-03

[(C5 H4 N 4 COOH)2 PdCl2 ]

423.5

52613-99-7

DCM

SC-04

[(C5 H5 )Fe(CO)2 I]

303.9

12078-28-3

DCM

SC-05

[(bipy)Cu(Cl)2 ]

290.6

22393-36-8

DCM

SC-06

RuCl3

225.4

14898-67-0

Aqua

SC-07

[Ru(CO)(H2 O)Cl2 ]

219.0

44252-76-8

Aqua

SC-08

(bipy)Ru(CO)(H2 O)(Cl)2

368.8

new by SC

THF

SC-09

[(CO)4 Mo(bdmpzm)]

414.3

119268-12-1

DCM

SC-10

[(bipy)Ru(CO)2 Cl2 ]

386.2

75598-28-6

Methanol

SC-11

[Ru(bdmpzm)(CO)2 (Cl)2 ]

432.3

new by SC

DCM

SC-12

[Ru(CO)3 Cl2 ]2

256.0

22594-69-0

Aqua

SC-13

[Ru(dppe)(CO)2 (Cl)2 ]

626.4

57638-64-9

THF

SC-14

[Ru(CO)2 Cl2 ]

230.0

16369-40-7

Aqua

SC-15

Cs[Ru(CO)3 Cl3 ]

432.0

new by SC

Aqua

SC-16

K[Ru(EDTA)]

428.4

76095-13-1

Aqua

M/gmol1

continued on next page

50

Experimental

ID

Formula

TUM-01

[Rh(CO)2 Cl(1, 3 Ph2 Im 2

CAS #

Soluble in

new by TUM

DCM

new by TUM

DCM

442.5

221023-54-7

DCM

M/gmol1

yliden)]
TUM-02

[Rh(CO)Cl2 (4, 5 Cl2 1, 3


Bz2 Im 2 yliden)]

TUM-03

[Rh(CO)2 Cl(4, 5 Cl2 1, 3


Ph2 Im 2 yliden)

TUM-04

[RuH2 (CO)PPh3 ]

919.8

25360-32-1

DCM

TUM-05

[RuH(CO)(Cl)PPh3 ]

954,2

16971-33-8

DCM

TUM-06

[Rh(CO)2 Cl(4, 5(CN)2 1, 3

new by TUM

Toluene

Ph2 Im 2 yliden)]
TUM-07

[(bipy)PdBr2 ]

422.2

15227-54-0

DCM

TUM-08

[(bipy)PdBr2 (OCCH3 O)]

504.5

new by TUM

DCM

TUM-09

[(bipy)Pd(CF3 OOC)2 ]

488.6

157378-12-6

DCM

TUM-10

[Ru(CO)3 Cl3 ] [PhN(Me)3 ]+


[Ru(CO)3 Cl3 ] [Ru
(phen)(CO)3 ]+
[Ru(CO)3 Cl2 I] [1, 2 (CN)2
3, 5 (Me)2 IM]+
[Ru(CO)3 Cl2 I] [MMIM]+
[Ru(CO)3 Cl2 I] [1, 2 Cl2
3, 5 (Me)2 IM]+

427.7

new by TUM

ACN

689.7

new by TUM

DCM

530.1

new by TUM

Aceton

480,0

new by TUM

DCM

548.9

new by TUM

DCM

306.1

new by TUM

DCM

1798.0

new by TUM

Toluene

1918.3

new by TUM

Toluene

[Ru(CO)3 Cl2 Br]2 [2, 3 diMe

622.1

new by TUM

Methanol

530.0

new by TUM

Methanol

494.1

new by TUM

Methanol

TUM-11
TUM-12
TUM-13
TUM-14

TUM-15

[(Gly)Ru(CO)3 Cl]

TUM-17

[NEt4 ]Na2 [Ru8 ( CO3 )4 (


Cl)4 (CO)16 ]

TUM-18

[PPN]2 [Ru4 (

O)(

Cl)4 (CO)10 ]
TUM-19

1 (2 (3 Me 1 H Im
1 yl)Et) 1 H IM]2+
TUM-20

[Ru(CO)3 Cl2 Br] [Br

EMIM]+
TUM-21

[Ru(CO)3 Cl2 I] [MMMIM]+

In total: 51 transition metal complexes tested.

3.1 Chemicals

51

Synthesis of novel catalysts


All syntheses were carried out using standard Schlenk techniques. All complexes were synthesized during the course of the Ph.D. thesis of Dr. Agnes
Bittermann [178] . Parts of the synthetic procedures have been published [179] .
Synthesis of RuBr3

2.25 g (10 mmol) of RuCl3 H2 O were washed three

times with 40 ml concentrated aqueous HBr. The excess solvent was removed
in vacuum and the remaining solid was dried.
Synthesis of RuI3

2.25 g (10 mmol) of RuCl3 H2O were washed three times

with 40 ml concentrated aqueous HI. The excess solvent was removed in vacuum and the remaining solid was further dried.
Synthesis of [Ru(CO)3 Cl2 ]2

RuCl3 was mixed with 40 ml concentrated aque-

ous HCl and 40 ml formic acid. The mixture was heated for 17 h under reflux.
The solvent was removed in vacuum and the remaining yellow solid was further dried. Yield = 95 %. IR (KBr): max /cm1 = 2145, 2072, 2027. IR (EtOH):
max /cm1 = 2136, 2065, 1995.
Synthesis of [Ru(CO)3 Br2 ]2

RuBr3 was mixed with 40 ml concentrated aque-

ous HBr and 40 ml formic acid. The mixture was heated for 17 h under reflux.
The solvent was removed in vacuum and the remaining red solid was further
dried. Yield = 73 %. IR (KBr): max /cm1 = 2134, 2072, 2054.
Synthesis of [Ru(CO)3 I2 ]2

RuI3 was mixed with 40 ml concentrated aqueous

HI and 40 ml formic acid. The mixture was heated for 17 h under reflux.
The solvent was removed in vacuum, formed iodine was sublimed and the
remaining red-brown solid was further dried. Yield = 88 %. IR (KBr): max /cm1
= 2118, 2056, 2014. IR (EtOH): max /cm1 = 2118, 2054, 1990.
Synthesis of [Ru(CO)3 Cl2 I][1, 3 Dimethylimidazolium] Two equivalents 1,3Dimethylimidazoliumiodide and one equivalent of [Ru(CO)3 Cl2 ]2 were dissolved in 10 ml dried EtOH and the yellow-orange suspension was stirred
overnight at 25 C, yielding a pale orange solution. The solvent was removed

52

Experimental

in vacuum and the remaining orange solid was dried in high vacuum. Yield =
100 %. 1 H NMR (MeOD d4): = 9.03 (s, 1H, CH), 7.58 (s, 1H, HCCH), 7.58 (s,
1H, HCCH), 3.98 (s, 6H, CH3 ).

13

C NMR (MeOD d4): = 198.90, 197.32, 194.68,

188.50, 186.99, 186.82, 184.98 (CO), 138.40, 138.30 (CH), 124.70, 124.62 (HCCH),
36.94, 36.91 (CH3 ). 1H NMR (CDCl3 ): = 9.77 (s, 1H, CH), 7.11 (s, 1H, HCCH),
7.11 (s, 1H, HCCH), 4.08 (s, 6H, CH3 ).

13

C NMR (CDCl3 ): = 185.22 (CO),

138.40, 138.95 (CH), 122.66 (HCCH), 37.50 (CH3 ). IR (KBr): max /cm1 = 2112,
2034, 1951, 1939. IR (EtOH): max /cm1 (CO) = 2110, 2043, 1989. IR (CH2 Cl2 ):
max /cm1 (CO) = 2127, 2121, 2051.
Synthesis of [Ru(CO)3 I3 ][1, 3Dimethylimidazolium] Two equivalents 1,3-Dimethylimidazoliumiodide and one equivalent of [Ru(CO)3 I2 ]2 were dissolved
in 10 ml dried EtOH and the orange-brown suspension was stirred overnight
at 25 C, yielding a dark orange solution. The solvent was removed in vacuum
and the remaining red solid was dried in high vacuum. Yield = 100 %. IR
(EtOH): max /cm1 (CO) = 2102 (strong), 2034 (strong), 1989 (weak).
Synthesis of [Ru(CO)3 Cl2 I][4, 5 Dichloro 1, 3 dimethylimidazolium] Two
equivalents 4,5-Dichloro-1,3-dimethylimidazoliumiodide and one equivalent
of [Ru(CO)3 Cl2 ]2 were dissolved in 10 ml dried EtOH and the yellow suspension
was stirred overnight at 25 C, yielding a yellow solution. The solvent was
removed in vacuum and the remaining yellow solid was dried in high vacuum.
Yield = 100 %. 1H NMR (MeOD d4): = 9.30 (s, 1H, CH), 3.95 (s, 6H, CH3).
13

C NMR ( = 196.12, 189.67, 188.57, 187.10, 186.87, 185.06 (CO), 137.81(CH),

121.07 (CCl), 35.94, 35.91 (CH3). 1 H NMR (CDCl3 ): = 10.00 (s, 1H, CH), 4.08
(s, 3H, CH3 ), 4.07 (s, 3H, CH3).

13

C NMR (CDCl3 ): = 185.05 (CO), 137.87(CH),

119.74 (CCl), 36.26 (CH3 ). IR (EtOH): max /cm1 (CO) = 2119, 2112, 2059, 2036,
1995, 1958. IR (CH2 Cl2 ): max /cm1 (CO) = 2121, 2116, 2049.
Synthesis of [Ru(CO)3 Cl2 I][4, 5 Dicyano 1, 3 dimethylimidazolium] Two
equivalents 4,5-Dicyano-1,3-dimethylimidazoliummiodide and one equivalent
of [Ru(CO)3 Cl2 ]2 were dissolved in 10 ml dried EtOH and the orange-brown
suspension was stirred overnight at 25 C. After 24 h the reaction mixture
consisted still of a brown suspension. The solvent was removed in vacuum

3.1 Chemicals

53

and the remaining orange-brown solid was dried in high vacuum. Yield =
100 %. 1 H NMR (MeOD d4): = 9.76 (s, 1H, CH), 9.44 (s, 0.26H, CH) 4.17
(s, 6H, CH3), 4.09 (s, 1.5 H, CH3).

13

C NMR (MeOD d4): = 196.07, 189.47,

188.39, 188.22, 187.01, 186.74, 185.01 (CO), 143.89 (CH), 117.30 (CCN), 106.35
(CN), 38.08 (CH3 ). 1H NMR (CDCl3 ): = 10.53 (s, 1H, CH), 4.37 (s, 6H, CH3 ). IR
(EtOH): max /cm1 (CO) = 2112, 2063, 2045, 1994. IR (CH2 Cl2 ): max /cm1 (CO)
= 2123, 2117, 2052.
Synthesis of [Ru(CO)3 Cl2 I][1, 2, 3 Trimethylimidazolium] Two equivalents
1,2,3-Trimethylimidazoliumiodide and one equivalent of [Ru(CO)3 Cl2 ]2 were
dissolved in 10 ml dried EtOH and the orange suspension was stirred overnight
at 25 C, yielding a red solution after 24 h. The solvent was removed in vacuum
and the remaining red-brown solid was dried in high vacuum. Yield = 100 %.
1H NMR (CDCl3 ): = 7.33 (s, 2H, HCCH), 3.90 (s, 6H, NCH3), 2.75 (s, 3H,
CCH3 ).

13

C NMR (CDCl3 ): = 186.96, 185.52, 183.79 (CO), 144.58 (NCCH3 ),

122.67 (HCCH), 36.44 (NCH3), 11.34 (CCH3 ). IR (EtOH): max /cm1 (CO) = 2116,
2047, 1992. IR (CH2 Cl2 ): max /cm1 (CO) = 2124, 2048, 1980 (weak).
Synthesis of [Ru(CO)3 Cl2 I][3 (2 Bromoethyl) 1 methylimidazolium] Two
equivalents 3-(2-Bromoethyl)-1-methylimidazoliumiodide and one equivalent
of [Ru(CO)3 Cl2 ]2 were dissolved in 10 ml dried EtOH and the yellow suspension
was stirred overnight at 25 C, yielding a yellow solution after 24 h. The solvent
was removed in vacuum and the remaining yellow-green solid was dried in
high vacuum. Yield = 100 %. 1 H NMR (CDCl3 ): = 9.72 (s, 1H, NCH), 7.42 (s,
1H, HCCH), 7.19 (s, 1H, HCCH), 4.89 (t, 2H, J = 5.2 Hz, NCH2), 4.08 (s, 3H, CH3 ),
3.85 (t, 2H, J = 5.2 Hz, BrCH2 ).

13

C NMR (CDCl3 ): = 185.45, 185.26, 185.11,

184.84 (CO), 138.20 (NCH), 122.84, 122.46 (HCCH), 51.60 (NCH2), 37.50 (CH3 ),
30.96 (BrCH2 ). IR (EtOH): max /cm1 (CO) = 2125, 2052, 1994. IR (CH2 Cl2 ):
max /cm1 (CO) = 2126, 2053, 1997 (weak).
Synthesis of [Ru(CO)3 Cl2 I][1, 1 Dimethyl3, 3ethylenediimidazolium] Two
equivalents 1,1-Dimethyl-3,3-ethylenediimidazoliumiodide and one equivalent of [Ru(CO)3 Cl2 ]2 were dissolved in 10 ml dried EtOH and the yellow
suspension was stirred overnight at 25 C, yielding a yellow solution after 24

54

Experimental

h. The solvent was removed in vacuum and the remaining yellow-green solid
was dried in high vacuum. Yield = 100 %. 1 H NMR (CDCl3 ): = 9.72 (s, 1H,
NCH), 7.35, 7.12 (2x s, 2x 2H, HCCH), 4.90 (m, 4H, CH2), 4.10, 3.86 (2x s, 2x 3H,
CH3 ), 2.81 (s, 3H, CCH3 ).

13

C NMR (CDCl3 ): = 185.10 (CO), 145.25 (CCH3 ),

137.52 (NCH), 122.79, 122.22, 98.56, 97.58 (HCCH), 51.85 (CH2 ), 30.89 (NCH3 ),
1.17 (CCH3 ). IR (EtOH): max /cm1 (CO) = 2124, 2062, 2051, 1995. IR (CH2 Cl2 ):
max /cm1 (CO) = 2125, 2053.
3.1.3 Ionic liquids
Table 3.3 shows the list of applied ionic liquids in this work. The selection was
made according to the methodology in Chapter 2.2.
Table 3.3: List of ionic liquids.
Name

Short

CAS #

Origin

1-butyl-2,3-

[BMMIM][OT f ]

302.32

765910-73-4

Merck KGaA

dimethylimidazolium triflate
1-butyl-2,3-

[BMMIM][NT f2 ]

419.39

174899-83-3

Merck KGaA

188.7

98892-75-2

Merck KGaA

[EMIM][Me(OH)PO2] 206.18

-a

CRTb

143314-17-4

Merck KGaA

M/gmol1

dimethylimidazolium
trifluoromethanesulfonate
3

1-butyl-2,3dimethylimidazolium

[BMMIM]Cl

chloride
4

1-ethyl-3methylimidazolium

methylphosphonate
1-ethyl-3-

[EMIM][OAc]

methylimidazolium acetate
AmmoEng Methylphospho-

nate
Tetratbutylphosphonium

[Bu4 P][Me(OH)PO2]

170.21

-c -a
186.13

-a

Merck KGaA
CRTb

methylphosphonate
a No

b Synthesis described below.


CAS number has been assigned yet.
substance from fatty acids. Assay component.

c Bio-derived

The ionic liquids entry 4 (1-ethyl-3-methylimidazolium methylphosphonate)


and 7 (tetratbutylphosphonium methylphosphonate) in Table 3.3 were synthesized in-house by the following procedure. A cooled solution of either

3.1 Chemicals

55

1-ethyl-3-methylimidazolium hydroxide or tetrabuylphosphonium hydroxide


in water was mixed with a stoichiometric amount of methylphosphonic acid
(CAS# 993-13-5) and stirred for 30 minutes at room temperature. After removal
of water in vacuo the pure ionic liquid was obtained with a yield of 100%.
3.1.4 Additives
The additives used in this work were weak organic bases, namely aminofunctionalized quarternary ammonium salts, as listed in Table 3.4. Structural
motives similar to ionic liquids were used.
Table 3.4: List of weak organic bases used as additives.

Name

Structure

M / g mol1
F
F

F
N

1 Trimethyl-4pyridinylammonium

286.27

C
O
S

triflate
F

2 Trimethyl-4-

pyridinylammonium

224.01

B
F

tetrafluoroborate
F
F

3 3-dimethylamino-

294.33

N,N,N-trimethyl-N-

S
O

propylammonium
triflate
F

4 3-dimethylaminoN,N,N-trimethyl-N-

N
B
F

232.07

propylammonium
tetrafluoroborate
These ionic bases were synthesized for the first time, so a new work-up protocol
was developed . In case of entry 1, trimethyl-4-pyridinylammonium triflate,
the preparation was carried out as follow: To a cooled (-78 C) solution of

Synthesis carried out at Sd-Chemie AG by M. Kaiser and Dr. N. Szesni.

56

Experimental

5.0 g (40.9 mmol) 4-dimethylaminopyridine in dry dichloromethane 4.86 ml


(43 mmol; 1.05 eq) methyltriflate were added. The resulting clear solution
was stirred for 30 min and then allowed to warm to ambient temperature by
removing the dry ice / acetone bath. After further 30 min stirring the solvent
was removed in vacuo to give 11.6 g (40.5 mmol; 99 %) of the product as a white
solid. For the other weak organic bases, analogous procedures were used.
3.1.5 Support materials
The partial dehydroxylation of the support (Silica gel 100, Merck KGaA) was
performed by heating the commercial material at 450 C in synthetic air for 16 h
followed by storage in vacuum prior to use. Other support materials boehmite
(Pural TH100, Sasol) and -alumina (Sd-Chemie AG) were not calcined prior
to use.
Properties of the applied support materials are summarized in Table 3.5.
Table 3.5: Support material properties used in this work. Determined by Quantrachrome QuadraSorb SI.

Material

Manufacturer

SBET a
2 1

Vpore b
3 1

dpore c

Pretreatment

m g

cm g

nm

160

1.10

23.7

none

-Alumina Sd-Chemie AG

101

0.51

17.2

none

Xerogel

334

0.97

12.1

calcination

Boehmite

Pural TH100, Sasol


Silica 100, Merck KGaA

16 h @ 450 C
a Determined
c DFT

by BET adsorption isotherm.


fitted pore width.

BJH comulative pore volume.

3.2 SILP catalyst preparation


The applied SILP materials were prepared by impregnation of the highly
porous support material with a solution containing the dissolved catalyst precursor and the ionic liquid in a volatile solvent. An appropriate solvent for
preparation was chosen according to preliminary studies on solubility of the
desired catalyst complex. Typically precursors were soluble in either water,

3.2 SILP catalyst preparation

57

tetrahydrofurane (THF), acetone, toluene, ethanol or dichloromethane(DCM)


(cf. Table 3.2 on page 49).
The catalyst precursor / ionic liquid / support slurry was transferred to a rotary
evaporator, where the volatile solvent was subsequently removed in vacuum
producing a free-flowing SILP catalyst (for < 0.4 mlIL ml1
pore ). In order to
prevent degradation of catalyst precursors, all synthesis was performed under
argon atmosphere using standard Schlenk techniques.
Figure 3.1 illustrates the synthesis procedure in a schematic manner.

Catalyst
Ionic
Support

Ligand
Liquid

Solvent
removal

Solvent

Figure 3.1: Preparation scheme for Supported Ionic Liquid Phase (SILP) catalysts.

The detailed preparation of the applied SILP catalyst materials is described for
the catalyst SW-S-120.
The ionic liquid 1-butyl-2,3-dimethylimidazolium chloride (mIL = 0.298 g, nIL =
1.58 103 mol) was dissolved in 30 ml of bi-distilled water to finally yield an
-value of 0.1. After complete dissolution of the IL, [Ru(CO)3 Cl2 ]2 (mcatalyst =
0.203 g, ncatalyst = 3.95 104 mol, nRu = 7.9 104 mol) was added to give a clear
yellow solution. Presence of the IL facilitates the dissolution of the ruthenium
complex as anionic complex [Ru(CO)3 Cl3 ] . Finally the support material Alumina (msupport = 4 g) was added. The resulting suspension was stirred for
tstir = 20 min. Subsequently the water was removed on a rotary evaporator
to obtain a dry, free-flowing SILP catalyst powder, which was stored in vacuo
(pvacuum < 4 103 mbar) until the start of the catalytic testing.
Table 3.6 summarizes the resulting catalyst properties.

58

Experimental

Table 3.6: Properties of a typical SILP WGS catalyst. Data from SILP catalysts SW-S-120
as used in WGS experiment SW-WGS-123.

Description

Property

Value Unit

Catalyst mass

m[Ru(CO)3 Cl2 ]2

0.203

Catalyst molar mass

M[Ru(CO)3 Cl2 ]2

512.01

Moles of catalyst

n[Ru(CO)3 Cl2 ]2

0.395 mmol

Ionic liquid mass

m[BMIM]Cl

0.298

Ionic liquid molar mass

M[BMIM]Cl

188.70

Moles of Ionic liquid

n[BMIM]Cl

1.58 mmol

Ionic liquid density

[BMIM]Cl

1.08a g cm3

Ionic liquid volume

V[BMIM]Cl

Support mass

mAlumina

4.0

Support apparent density

SILP

0.5

g cm3

Ruthenium loading

wRu

0.02

Pore filling grade

Content of catalyst in IL

xRu

Average IL layer thicknessb hIL

g
g mol1
g
g mol1

0.276 cm3

gRu g1
Support

0.1 cm3IL cm3


Pore
0.07 molRu mol1
IL
6.9

a Density

at 298 K. [180] .
with the hypothetical assumption that the volume of the
ionic liquid forms a continuous uniform layer on any inner surface.

b Calculated

3.3 Continuous test-rig


All experiments were carried out in a continuous test-rig (Figure 3.2) with
online analysis via a Varian 4900 Micro-gas-chromatograph (Micro-GC). The
rig was originally built by Dr.-Ing. Tobias Weiss and was completely revamped
at the beginning of this thesis. After revamping, a condensation and coldspot free operation suitable for the desired experiments was achieved and
maintained. A flowsheet of the rig is depicted in Figure 3.3.
Parts that are in contact with the reaction gases are entirely made of stainless
steel 1.4571. The reactor is also made of stainless steel 1.4571 (pmax = 65 bar,
Tmax = 350 C, V = 35 ml, di = 10 mm).
Thermo couples TIC 1-9 ensure temperature control in the six heating areas
H1-H6. All stainless-steel parts were heated by Horst thermal heating tape

3.3 Continuous test-rig

59

Figure 3.2: Photo of the experimental rig. 1) mass flow controllers, 2) controlled evaporator and mixer (CEM), 3) reactor , 4) micro GC.

and heated up to 190 C. Because water is easily condensing in so called coldspots, a multi-layer insulation of the entire reactor rig was established. First,
the heating tape itself that was put in parallel to the stainless-steel pipes and
fixed with heat-durable Horst nylon tape. As a second layer, a thin and flexible
glass-wool tape was put tightly around the heating tape to ensure good contact
of heating and pipes. A thicker glass-wool fabric was applied in two layers to
insulate the inner layers and provide a homogeneous temperature profile. On
the very outside red silicon rubber insulation was installed to further prevent
hotspots. At an inner temperature of 190 C, the outer silicon insulation had a

60

Experimental

Vacuum Ventilation

PIC

TIC

P5

T3

V-4

V-10

V-9

H5

V-6

V-5

PI
P1

TI

PI

T2

P4

MFC

TI

PI

T5

V-1

P2

MFC
PI

H6

V-2
TIC

P3

H1

T6

MFC
V-3

TIC

V-17

TIC

H4

T1

H2

T7

TIC

H3

De-Gas

T8

TIR
T9

MFC

Aqua
Bidest.

V-26

V-7

TIC

Samson

T10

CEM
V-18

V-8

TIC

TIC

T4

T11

H7

Off-Gas

TIC
V-15
T14

CO

CO2

N2

Micro-GC

Dry-Filter
(CaCl2)

V-14

Condensate

Figure 3.3: Flowsheet of the experimental rig

surface temperature of around 55 C as measured by a laser pyrometer. Inside


the pipes, thermocouples measured the temperature of the flowing gas. When
heating the pipes to 190 C, the gas reached a temperature of 175 C at stable
operation conditions as measured at the mixing intersection T2 and before the
reactor T5.
A three-zone heating jacket (Horst) around the reactor (H1-H3) offers a maximum reaction temperature of 300 C. Inside the catalyst bed, a thermocouple
records the current temperature. In order to reach 120 C in the catalyst bed,
the Horst heating jacket had to be set at 142 C.
An additional Samson valve can be used for high pressure experiments up to
ptotal = 35 bar. Water is condensed behind the reactor at Tcondensor = 2 C and

3.3 Continuous test-rig

61

an additional hydrophobic membrane filter (Geniefilters.com) ensures that a


dry gas stream enters the Micro-GC. In a first set of experiments, a desiccant
cartridge containing CaCl2 was installed instead of the hydrophobic membrane.
This cartridge was replaced by a dry filter, because condensing water can lead
to transport of the salt into the gas-chromatograph. As we found, this incident
destroys the microscopic piezo injector valves.

3.3.1 Dosing of substrates


Volumetric flows of nitrogen (V N2 = 0250 mlN min1 ), carbon monoxide (V CO =
0 150 mlN min1 ) and carbon dioxide (V CO2 = 0 150 mlN min1 ) were adjusted
by a digital mass flow controller (MFC 5860 S) from Brooks Instrument. In
the experiments where synthesis gas was applied the nitrogen flow controller
was utilized to dose that substrate. Consistent mass flow of water (m H2 O = 0
0.03 g min1 / V H2 O = 0 37 mlN min1 ) was ensured by a Controlled Evaporator
and Mixer unit (Bronkhorst CEM / LiquiFlow HighFlow Series). The nitrogen
flow through the evaporator carries the water and is then mixed with the
residual gas streams before entering the reactor. Generally, the mass flow
controllers suffered from bad reproducibility, so that frequent recalibration
was performed to ensure stable operation.

3.3.2 Analytics / Gas chromatography


In order to obtain composition data for the gas flows leaving the reactor, a
quantitative micro gas chromatography system was used.
The Micro GC Varian 4900 is equipped with a MS5A (Molar sieves 5 , 10 m)
and a PPQ (PolarPlot Q, 10 m). The MS5A column was applied for carbon
monoxide detection and the PPQ column for carbon dioxide detection. Helium (Linde, 5.0, > 99.999 %) was used as carrier and reference gas for the
thermal conductivity detectors. Further description of gas chromatography
with thermal conductivity detectors can be found in standard literature. Detailed information about the column-parameters are given in Table 3.7.

62

Experimental

Table 3.7: Representative parameters for the GC-columns in the Varian CP 4900 MicroGC WGS effluent gas analysis.

MS 5

PPQ

TCD

TCD

Helium

Helium

40 C

100 C

Detection time

120 s

120 s

Column head pressure

250 kPa

300 kPa

Injection time

50 ms

50 ms

Detector
Carrier / reference gas
Temperature

0.309 min 0.244 min

Retention time CO

0.618 min 0.244 min

Retention time CO2

0.309 min 0.349 min

Retention time N2

a Isothermal

operation.

b Internal

standard.

After a GC injection, the obtained peaks were automatically detected and


integrated by use of the Varian Star 6.1 software. With an additional, selfdeveloped Visual Basic macro a direct transfer of the obtained data into Excel
was possible.
The time interval between two measurements was typically 8 minutes, so that
one data point was obtained every ten minutes. Molar ratios xi for carbon
monoxide and carbon dioxide were calculated from the obtained peaks by
means of calibration curves. A typical chromatogram is depicted in Figure 3.4.
To verify calibration, certain test gas mixtures were injected regularly, resulting
in good agreement between calibration and test gases.
A detection of possible side-products was possible in two ways. On one hand
low boiling side products such as methane, methanol or ethane could be detected via GC. On the other hand high-boiling compounds could be identified
in off-line GC measurements from the condensate. Fortunately in almost any
experiments, the online-GC showed no other peaks than nitrogen, hydrogen,
carbon monoxide, carbon dioxide and traces of water. The condensate was
frequently analyzed by offline GC resulting in the fact, that pure water was
found. In the high-pressure experiments, traces (< 100 ppm) of linear aliphatic
alcohols, such as ethanol and propanol were found.

3.4 Calculation procedures


MS5
N itrogen (0. 309)

mV olts

600
500
400
300
200
100
0

C arbonmonoxide (0. 618)

PPQ
S ample (0. 244)

V olts

63

2
1

C arbondioxide (0. 349)

0
0.1

0.2

0.3

0.4

0.5
Minutes

0.6

0.7

0.8

0.9

Figure 3.4: Chromatograms of a typical injection during a WGS run in the applied
two-column Micro-GC (Varian CP 4900).

Selectivity calculations are not listed and and selectivity results are not plotted,
as the selectivity was always > 99% towards the desired products.

3.4 Calculation procedures


To clarify the way of obtaining catalytic performance data, the methodology of
calculation procedures are listed in the following sections.
3.4.1 Degree of conversion
From the definition of conversion, the following formula was derived for a
continuous system:
XCO =

n CO,0 n CO
n CO,0

(3.1)

Assuming, that the reaction is constant in volume and gases are behaving
ideally one could substitute with
xi =

n i
V total

(3.2)

resulting in
XCO =

xCO,0 xCO
xCO,0

(3.3)

64

Experimental

The molar fractions xi are obtained from the micro GC with a calibration function i that transfers the peak area Ai into a corresponding value using the
following relation.
xi =

Ai
i

(3.4)

In order to check the obtained conversion a second method of calculation was


also applied. Herein the assumption was used, that the carbon mass balanced
can be closed by
n CO,0 = n CO + n CO2

(3.5)

This was used to substitute xCO,0 in (3.3) using (3.2) .


X CO =

xCO2
xCO + xCO2

(3.6)

Equation (3.6) just involves values obtained by GC.


The agreement between X CO and XCO was better than 98 % in all experiments,
directly leading to the conclusion that side-products were just formed in traces
so that selectivity was close to SCOCO2 100 %.
3.4.2 Turn over frequency, rate of reaction and turn over number
To compare the activity of the immobilized catalysts with homogeneous systems, the turn over frequencies were calculated as follows:
TOF =

xCO2
n CO2
= V total
ncatalyst
ncatalyst

(3.7)

As the analytics are located after the cold trap, the molar fraction obtained in
the GC is changed by the fact, that water is removed from the gas-stream before
entering the GC.
V total = V GC + V H2 O,condensed

(3.8)

This is corrected via a conversion dependent term.


V H2 O,condensed = (1 XCO ) V H2 O,0

(3.9)

3.4 Calculation procedures

65

So that
h
i xCO
2
TOF = V GC + (1 XCO ) V H2 O,0
ncatalyst

(3.10)

The turn over frequency is reported in molCO2 mol1


h1 = h1 .
catalyst
Technically, the TOF is a rate of reaction, but as a rate of reaction is usually
normalized to a volume, the following expression was used.
0cCO2 ,out

1
re f f,WGSR =
CO2
|{z}

z}|{
dcCO2
n CO2
=
dt
V total h

(3.11)

= 1

This results in a rate of reaction with the unit mol m3 s1 .


To evaluate catalyst stability the dimensionless turn over number TON was
calculated as the integral number of converted moles.
TON =

(3.12)

TOF dt

This integration was numerically performed by usage of the trapezoidal rule


for all measured values in the given time frame.
TON =

t
X
t + tt

int

=0

TOF TOFtint

(3.13)

3.4.3 Space-time yield


In order to evaluate the economic feasibility of the new catalyst systems, a
space-time yield was calculated using the molar flows and the apparent density
of the catalyst.
STYCO2 =

n CO2 MCO2
mSILP
SILP

(3.14)

This value is just an estimate, because the apparent SILP density was either
determined by calculations from packing models [181183] or by metering.

66

Experimental

3.4.4 Gas hourly space velocity


The gas hourly space velocity (GHSV) is a dimensionless substitute for the residence time. It defines a ratio between volume flow at standard conditions and
catalyst volume. Values for this typical parameter in industrial heterogeneous
catalysis were calculated as follows.
GHSV =

298 K,1013.25 mbar


V total,0
mSILP
SILP

(3.15)

3.5 Catalyst testing procedure


3.5.1 Work protocol
In a typical experiment mSILP = 4 g of a SILP-catalyst were placed in the reactor
on the stainless steel frit (7 m) and covered with glass wool. The reactor was
then closed, tested for leaks and heated up under nitrogen gas flow (V N2 =
40 mlN min1 ) until the reaction temperature of TR = 120 C was reached. Now
the reactor was set in by-pass mode and left under inert nitrogen atmosphere
while the substrate flows were adjusted. First the water mass flow controller
(Bronkhorst LiquiFlow) was set onto the required mass flow. In the controlled
evaporator and mixer (CEM) unit, the water is constantly evaporated in a
capillary entrainment evaporator. The nitrogen flow was used as entrainment
gas for the CEM unit.
After stable conditions in the evaporator, the flows of carbon monoxide and
nitrogen were adjusted to reach the desired partial pressure ratios. As internal
check gas-samples of the flow were taken by means of GC to falsify calibration
errors in either micro GC or mass flow controllers. As soon as stable operations
were reached, the flow was directed through the reactor and the gas-mixture
analyzed by means of a micro GC. The experiments were carried out under
ambient pressure, H2 O : CO ratios between 0.2 : 1 to 4 : 1, and temperatures
between 100 and 160 C.
The heterogeneous reference catalyst ShiftMax 240 (Cu / ZnO / Al2 O3 ) SdChemie AG and the Au-nanoparticle catalysts had to be activated/reduced
prior to use. For these experiments 2 g of the catalyst was placed in the reactor

3.5 Catalyst testing procedure

67

and heated up to 220 C with a heating rate of approximately 2 C min1 under


a constant flow of 125 mlN min1 reduction gas (2 % H2 in He). After reaching
the reaction temperature, the system was left 16 h to reduce completely.
3.5.2 Determination of effective kinetic parameters
In case a catalyst showed sufficient stability (stable operation in a XCO = 1 %
interval for t > 18 h), a standard procedure was followed to determine kinetic
parameters such as apparent Arrhenius-type activation energy EA and partial
reaction orders with respect to substrates nCO and nH2 O . In all cases the residence time / GHSV was maintained by adjusting the mass flows. To obtain
kinetic data even in a integral reactor (PFTR) a differential operation mode
(CSTR) was realized by leaving the conversion at XCO < 5 %.
The standard procedure was implemented as follows.
1. Record stable reference point at standard reaction conditions (TR = 120 C,
p = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, balance N2 , GHSV = 1000 h1 ) for
t > 3 h.
2. Begin temperature variation. (Takes typically 1 working day)
Make sure, that reactor is in differential operation mode of XCO < 5 %.
Otherwise adjust GHSV respectively.
a) Set reactor temperature to TR = 100 C and adjust mass flows according to ideal gas behavior (increase by approx 4 %). Wait until
stable operation conditions. Hold for at least 4 GC injections.
b) Increase reactor temperature to TR = 110 C, 130 C and 140 C with
same adjustments and procedures as before.
c) Return to reference point and check activity for deactivation. Determine re f f as average of at least 4 GC data points only if reference
point is met by XCO = 1 %. Otherwise stop experiment.
d) Calculate EA via slope of Arrhenius-plot (ln re f f -T1 -plot) in kinetic
regime.
3. Leave system running overnight at reference conditions.

68

Experimental
4. Begin partial pressure variation for CO. (Takes typically half working
day).
Make sure, that TR = 120 C is within the kinetic operation region of the
catalyst. Otherwise set reference point to a lower temperature.
a) Set CO mass flow to its double value resulting in pCO = 0.2 bar while
leaving water mass flow untouched (pH2 O = 0.2 bar) and decreasing
the nitrogen mass flow in order to compensate the increase in CO
mass flow. Wait until stable operation and hold for at least 4 GC
injections.
b) Set CO partial pressures to pCO = 0.15, 0.133, 0.12 and 0.07 bar and
follow same procedure as before.
c) Return to reference point and falsify activity from deactivation. Determine re f f as average of the 4 GC data points only if reference point
is met by XCO = 1 %. Otherwise stop experiment.
d) Calculate nCO by differential analysis via a ln re f f -ln pCO -plot of the
complete 5 data points.
5. Begin partial pressure variation for H2 O. (Takes typically half working
day).
The procedure is identical to the one described for CO with the partial
pressure levels adjusted to pH2 O = 0.4, 0.3, 0.15, 0.1 bar.
6. Leave system running overnight at reference conditions.
7. In some cases also a residence time / GHSV variation was performed.
a) Set flows of all mass flow controllers to 4 the usual value. Wait
until equilibrated and take at least 4 GC samples.
b) Adjust flows to 2, 3 and 0.5 with the same procedure.
c) Return to reference point and falsify activity from deactivation.
d) Plot XCO -t-diagram. Ensure that TOFCO is constant.
8. Perform additional tests.

3.5 Catalyst testing procedure

69

In case, the carbon mass-balance was found to be not closed within 5%, a
sample for offline GC analysis was taken in order to check for possible sideproducts.
3.5.3 Reproducibility and error estimation
In order to ensure stable operation of the rig regular reproducibility tests were
conducted with a standard catalyst at standard screening conditions. To check
the complete strain of errors the following procedure was applied:
1. Batch reproducibility.
Two batches of a catalyst were produced and subsequently tested.
2. Run reproducibility.
Out of one batch of catalysts two subsequent runs were performed. This
test was performed at least monthly.
In all cases the results were reproducible within a TOFCO = 2 % interval.
A rough error propagation estimation procedure was performed as follows.
The reproducibility of the micro GC including the drift compensation was
found to be in an interval of xCO 1 %. The mass flow controllers of nitrogen
and water showed excellent reproducibility in the range of m i 2 %, whereas
the carbon monoxide mass flow controller was subject to substantial drift leading to an error of m CO 5 %. According to the data sheet of the used Ni Cr Ni
thermocouples, these provided an accuracy of T = 0.1 C.
A scattering analysis was performed based on the GC data taken. From this
data a standard gaussian distribution was found leading to a 2 (95.5 % confidence) interval of XCO = 1 %.

4 Results and Discussion


The work presented in this thesis has been carried out in close collaboration
with the industrial partner Sd-Chemie AG and the project partners within
the BMBF project (Entwicklung und Einsatz neuartiger "Supported Ionic Liquid
Phase (SILP)"- Katalysatoren fr die Wassergas-Shift-Reaktion bei sehr niedrigen
Temperaturen, FKZ 03X2012H) as mentioned before. Catalysts investigated
followed several "generations", meaning that depending on the results of one
experimental phase, decisions for the further development were taken and new
parameters were investigated [184] . The overall strategy of this work is depicted
in Figure 4.1.
kinetic
investigations

screening
of catalysts

synthesis of
novel catalyst

influence
parameters?

catalyst
optimization

(TU Munich, Sd-Chemie AG)

scale-up /
cross-tests
(Dr. Szesni @ Sd-Chemie AG)

Figure 4.1: Work strategy for this dissertation.

This straightforward multi-step strategy was inspired by reviews of BuzziFerraris [185] , Dautzenberg [186] and Farruseng [187] on catalyst development and
optimization.
After optimization the existing experimental rig, a detailed screening of literature known precursors, transition metal chlorides and carbonyls took place in
this first phase of the project. It was followed by testing and characterization
of newly developed precursors. The outcome of this first phase is just a few
tables (cf. Section 4.3 on page 78), but it took almost two years to evaluate
this library and to tackle specific issues. This phase involved around 6500
hours time-on-stream testing with an average time-on-stream of 48 hours per
catalyst. For systems that did show stable operation mode, kinetic parameters
were determined as described in section 3.5.
In a second phase, influence parameters of the catalyst were systematically in-

70

4.1 Benchmarking of the experimental setup

71

vestigated, varied and optimized leading to a substantially optimized catalyst.


Here another 4500 hours time-on-stream were invested, with an average time
of experiment of 86 hours.
With these further developed catalysts, in a third phase, application specific
optimization and benchmark experiments were conducted. This included
long-term stability tests of up to 700 hours and experiments under typical
reformate synthesis gas conditions for the desired technical application. These
results were used to promote a further scale-up of the technology together with
the industrial partners that is currently ongoing.

4.1 Benchmarking of the experimental setup


At the beginning of the studies described here, the experimental rig was completely revamped and optimized for the ultra low temperature water-gas shift
reaction. Because of that, a kind of benchmark procedure was carried out in
order to ensure reproducibility and to exclude uncontrollable side activities by
blank tests.
4.1.1 Reproducibility
The following reproducibility experiments were conducted after every modification of the rig or after 4 months of operation in order to verify, that every
part of the rig was still operating in the correct manner.
Two different types of reproducibility experiments were performed. On one
hand, so called run reproducibility was tested by preparing a large batch of SILP
catalyst, splitting the batch in two parts and tested in consecutive runs. On
the other hand batch reproducibility was verified by preparing two batches of
catalyst with identical parameters and compare results of those to batches. The
results of one set of tests are depicted in Figure 4.2.
These tests show excellent reproducibility for both run and batch tests, with an
agreement in degree of conversion by 1 %. This standard run was performed
bi-monthly in order to check the rig and perform a common benchmark on both
analytics and rig. In all cases the margin of error was typically in a range of
5 %, which could be further reduced by recalibration of the -GC and column
bake-out.

72

Results and Discussion

30
SW-WGS-116
SW-WGS-118

25

SW-WGS-119

15

CO

/ %

20

10
5
0

10

15

20

25

30

t / h

Figure 4.2: Reproducibility tests with SILP catalysts.  compared to  shows run
reproducibility.
120 C, pabs

 compared to shows batch reproducibility.

= 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV =

4 g, wcat = 2 %, ionic liquid [BMMIM][OT f ], =

1000 h1 , m

0.1mlIL ml1
pore ,

T =
cat

support ma-

terial -alumina, precursor [Ru(CO)3 Cl2 ]2

4.1.2 Blank tests


Before running any catalytic experiments, the rig was subject to a number of
consecutive blank runs. First, a blank run without catalyst was performed,
which involved heating of reactor and peripheral lines to typical conditions
in inert atmosphere before introducing carbon monoxide and water. Both at
ambient pressure and also at 10 bar only traces of carbon dioxide (xCO < 5 ppm)
were found in the first 2 hours of reaction, that disappeared completely on
a longer term. Consequently the rig was considered inert and suitable for
catalytic runs.
These tests were repeated frequently, especially after runs, that showed substantial catalyst leaching via volatile carbonyl components. In this case a larger

4.1 Benchmarking of the experimental setup

73

carbon dioxide concentration was found, so that a standard cleaning procedure


had to be developed. This involved flushing the rig with acetone to remove
transition metal traces and subsequent baking out at 200 C under high nitrogen flow. After this procedure, the carbon dioxide concentration in the outlet
leveled back to xCO < 5 ppm.
To validate inertness of the support materials, these were tested in analogous
way to the rig blank test. 4 g of the support material were introduced in
the reactor and exposed to reaction atmosphere. -alumina, boehmite and
silica showed no significant conversion of carbon monoxide towards carbon
dioxide. Again it was concluded that these materials are inert at the reaction
conditions of T = 120..180 C, pabs = 1 bar, pCO = 0.1 bar, pH2O = 0.2 bar, GHSV =
1000 h1. Additionally, the support materials were coated with the ionic liquid
[BMMIM][OT f ] at a pore filling grade of = 0.1mlIL ml1
pore without any transition metal dissolved in the ionic liquid. Also in this case, no conversion was
found. So both support material and ionic liquid can be considered as inert
components with regard to their water-gas shift activity.
In order to evaluate the role of the ionic liquid a comparison between a standard
SILP catalyst and a catalyst without the ionic liquid, i.e. with physisorbed
metal complex, was carried out. A catalyst without ionic liquid basically
means: dispersed precursor on support material. Interestingly, the transition
metal salt showed indeed a low activity in WGS. The activity-time profiles are
depicted in Figure 4.3.
Whereas the system with the ionic liquid showed an increasing activity over the
first 60 hours on stream, the catalyst without the ionic liquid almost remained
at a constant level of activity over that timeframe. After the experiment, the
condensate of the catalyst without ionic liquid showed a green/yellow coloring
attributed to dissolved ruthenium compounds. ICP-AES measurements of
the condensate yielded ruthenium content in the range of 500 ppm, which is
obviously related due to stripping of volatile ruthenium carbonyl compounds
from the catalyst. In conclusion, the ionic liquid increases activity of the catalyst
and additionally stabilizes the catalyst by lowering the rate of stripping of
volatile catalyst components.

74

Results and Discussion

0.5
no IL
= 0.1

0.3

TOF / mol

CO2

mol

Ru

-1

0.4

0.2

0.1

0.0
0

10

20

30

40

50

60

70

t / h

Figure 4.3: Activity vs. time profile for a SILP catalyst with and without Ionic lqiuid. 
contains an ionic liquid, whereas  was prepared without. T = 120 C, pabs =
1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, wcat = 2 %,
ionic liquid [BMMIM][OT f ], = 0.1mlIL ml1
pore , support material -alumina,
precursor RuCl3

4.2 Reference measurements


To evaluate our measurements relative to data recently published, experiments
using well-established heterogeneous catalysts were carried out in our rig. In
this context, a commercial catalyst from Sd-Chemie AG and a supported gold
nanoparticle catalyst as published by Mendes et al. were tested [9] .
4.2.1 Commercial ShiftMax 240
The commercial catalyst was supplied by the industrial partner Sd-Chemie
AG and treated by a standard activation protocol. In these experiments 2 g
of the catalyst fraction (500..1000 m diameter) was introduced into the rig
and first flushed with nitrogen for 20 minutes at 20 C. After this, the catalyst

4.2 Reference measurements

75

was heated up slowly (3 C min1 ) to 230 C in an reductive environment (5 %


hydrogen in nitrogen) and kept at 230 C for three hours. Maximum conversion
of hydrogen was found in the range of 120 to 180 C, which was detected
qualitatively via the GC. At 230 C the conversion again was zero, indicating
that the catalyst was completely reduced and activated.
Under nitrogen flow the reactor temperature was lowered to reaction temperature and flows of carbon monoxide and water were started. It is worth
mentioning, that the catalyst was introduced into an idealized model synthesis
gas mixture, which means, just carbon monoxide and water - no hydrogen,
carbon dioxide and methane were present in the feed flow. This is a substantial
difference to a real synthesis gas, which is also the reason for the high degrees
of conversion. Additionally, due to limitations of the mass flow controllers the
gas hourly space velocity (GHSV) was only 2500 h1. As depicted in Figure 4.4,
the conversion is 96.8 % at 160 C, 88.8 % at 140 C and still 70.6 % at 120 C.
Unfortunately, due to these high conversions a direct calculation of the Arrhenius-type activation energy was not possible because of the concentration
gradient in the integral reactor. Higher GHSV values could not be realized at
the time due to limitations of mass flow controllers and minimum amount of
catalyst.
Calculation of a specific activity per catalyst mass or volume is possible in
several ways: One could normalize the converted / formed amount of carbon
dioxide per moles of active component (namely copper) or one could use the
amount of active sites as determined per temperature programed reduction
(TPR) experiments. TPR data were provided by Sd-Chemie AG as the certificate of non-analysis denied in-house analytics of the ShiftMax catalyst. An
active surface of Aactive = 22.1 m2 g1 was given from these experiments. So
the amount of active moles can be estimated by the following approximation.
In the following it is assumed, that the active surface consists of Cu-atoms in
oxidation state 0. The active copper surface is first modeled by projection area
of copper atoms (area of a circle), with atomic radius of 127.8 pm.
ACu =

r2Cu
2


2
= 127.8 1012 m = 5.13 1020 m2

(4.1)

More common is a normalized value per mole or gram, so a multiplication by

76

Results and Discussion

100
160
80
150

140
40

T / C

CO

/ %

60

130
20
120
0

20

40

60

80

100

120

140

160

t / h

Figure 4.4: Activity of a ShiftMax240 over time at varying temperatures.


120..160 C, pabs
2500 h1 , mcat =

1 bar, pCO

0.1 bar, pH2 O

T =

0.2 bar, GHSV

2 g.

the Avogadro number NA gives the value per mole and further division with
the molar mass the amount per gram.
2 1
ACu = 5.13 1020 m2 NA = 30900.29 m2mol1
Cu = 486.27 m g

(4.2)

Dividing the theoretical area per moles copper by the measured value leads to
the moles of active material per gram of industrial catalyst.
nCu,active

22.1 m2 g1
Aactive,measured
cat
= 7.152 104 molactive g1
=
=
cat (4.3)
1
2
ACu
30900.29 m molCu

This number is just an estimate, but probably better, than a normalization per
total copper content.
The numbers where activity is normalized on total copper content are of course
way lower than the values, where just active surface is covered. From the

4.2 Reference measurements

77

Table 4.1: Specific activity values for a ShiftMax 240 catalyst. T = 120..160 C, pabs =
1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 2500 h1 , mcat = 2 g.

T / XCO /

TOFa/

% molCO2 molCu h

TOFb/

STY /

kgCO2 m3cat h1

molCO2 molact h

160

96.8

34.8

364.3

171.2

140

88.8

33.6

347.6

165.2

120

70.6

29.9

309.1

140.1

a Normalized

b Normalized

per total moles of copper.


on active surface.

comparison of the two activity values, one can estimate that about 10% of the
total copper present forms an active center.
Additionally, one could calculate a space-time yield, namely the amount of
carbon dioxide formed per catalyst volume and hour, which is the final benchmark for most technical benchmark. Results are compiled in Table 4.1. In
general, the ShiftMax 240 catalyst shows excellent long-term stability in this
environment, but due to condensation issues, a restart after a shutdown phase
is not possible.
4.2.2 Supported gold nano particle LTS catalysts
Supported gold nano particles are a promising alternative to conventional catalyst systems. Recently the group of Mendes et al. [9] published a comprehensive
study on those catalyst systems as mentioned in subsubsection 2.1.2.2 . As the
authors point out, the support material ceria is superior in terms of activity
compared to alumina and titania. This is in agreement to the reference measurements taken in this work, which are listed in Table 4.2. The pre-reduction
of the catalyst was carried out in the same manner as described as described in
the original reference [9] . Even at this low space velocity, both catalyst did not
show superior activity and high conversions. The activity data obtained can
not be directly compared to the values given in Mendes [9] . This is related to the
fact, that the experiments carried out by Mendes used a very high ratio of water
to carbon monoxide of 7.46 (35.39 % H2 O, 4.74 % CO in Helium), which clearly
enhances the catalyst activity and favors conversion as depicted in Figure 2.2.
Although, the acquired turn over frequency of the ceria supported catalyst

78

Results and Discussion

Table 4.2: Specific activity values of supported gold nanoparticles.

120..160 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 780 h1 , mcat =
4 g, wAu = 0.02 gAu g1
.
Cat

XCO / %

TOFa/

kgCO2 m3cat h1

160

7.5

5.9

13.2

Alumina 140

3.7

5.1

6.8

120

1.7

1.4

3.2

160

32.6

23.5

47.2

140

15.9

12.4

24.9

120

6.0

5.2

10.3

Material

T/

Ceria
a Normalized

C molCO2 molAu h

STY /

per total moles of gold.

reaches a good value of 32.6 at 160 C. However the obtained space-time yields
are still a factor of 4 lower than the ones obtained for the commercial ShiftMax
catalyst. After about 24 h time-on-stream, both catalysts lost about 10% of their
activity. The authors also mention, that the catalysts were not stable, but they
only performed test of 10 h time-on-stream maximum.
For both catalysts, an Arrhenius type activation energy was determined from
the reaction rates obtained at different temperatures. In case of the alumina
supported catalyst an EA of 51.6 kJ mol1 (R2 = 0.997) was obtained. For the
ceria supported catalyst the value was found to be 59.4 kJ mol1 (R2 = 0.993).
It is worth mentioning, that for those catalyst a peak assigned to methane
appeared in the chromatogram. Also the condensate was "smelly" and showed
presence of methanol and traces of higher alcohols, as qualitatively analyzed
by GC-MS.

4.3 Screening of Precursors


In a first set of experiments, transition metal complexes that have been investigated previously in the literature as potential homogeneous WGS catalysts were used to prepare novel SILP catalysts. Systems based on transition
metal chlorides and metal carbonyl clusters were examined afterwards. Finally, newly synthesized systems were investigated. All systems were pre-

4.3 Screening of Precursors

79

pared using calcined silica as support material and a pore filling grade of
= 0.1 mlIL ml1
pore of the ionic liquid [BMMIM][OT f ] as immobilizing film (catalyst loading wcat = 0.02 gmetal g1
support = 2%).
4.3.1 Literature-known precursors
In the 1940s Yoneda et.al. published first approaches on homogeneously basecatalyzed WGS [43] . Between 1977 and 1984 the groups of Pettit (2.1.5.1), Ford
(2.1.5.2) and Laine (2.1.5.3) published several homogeneous systems active in
the WGS reaction. Several of these systems are listed in Table 4.3 and have been
applied for the first time in a continuous catalytic reaction within this work .
Preparation of these SILP catalyst always involved choosing the right solvent,
that had to dissolve the precursor and the ionic liquid, but also should be easily removable. In general, first tetrahydrofurane (THF) was tested, followed
by dichloromethane (DCM), acetone, toluene, water and methanol - the exact
choice for each precursor was already listed in Table 3.2 on page 49. The acquired supported ionic liquid phase catalysts exhibited always a free-flowing
powder behavior, but depending on the transition metal center also a large
variety of colors were obtained as depicted in Figure 4.5.

Figure 4.5: Different Supported Ionic Liquid Phase (SILP) WGS Catalysts.
left to right: a) [Ru(CO)3 Cl2

I] [1, 2

From

(Cl)2 3, 5 (Me)2 Imidazol]+ , b)

(bipy)Ru(CO)2 Cl2 , c) [Ru(CO)3 Cl2 ]2 , d) Ru(CO)(H2 O)Cl2 , e) Ru(CO)2 Cl2 , f)


(tmeda)Cu(Cl)(OH), g) (bipy)Cu(Cl)2 , h) Rh(TPPTS).

Except for the completely inactive complex [(tmeda)CuClOH] all systems exhibited minor activity in the beginning of the experiment. The best system, copper

Results presented in this section of the thesis were already published in Appl.Cat.A. [176]

80

Results and Discussion

Table 4.3: Comparative study on the WGS activity of literature known precursors in
form of their SILP catalysts. T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O =
0.2 bar, GHSV = 1000 h1 , mcat = 4 g, wcat = 0.02 gmetal g1
support , ionic liquid
[BMMIM][OT f ], = 0.1mlIL ml1
pore , support material silica.

Precursor

TOF / h1

TOF / h1

TOF / h1

Reference

(t=0)a

(t = 2h)b

(stat)c

for
complex

[(CO)4 Mo(bipy)]

0.08

0.02

Hor [188]

[(tmeda)Cu(Cl)(OH)]

Bhushan [189]

[(C5 H4 N 4

0.06

0.01

Qin [190]

COOH)2PdCl2 ]
4

[(C5 H5 )Fe(CO)2 I]

0.08

0.04

Cariati [191]

[(bipy)Cu(Cl)2 ]

0.40

0.04

Mediavilla [73]

[Ru(CO)(H2 O)Cl2 ]

0.06

0.11

0.27

Haukka [91]

[(CO)4 Mo(bdmpzm)]

0.10

0.03

Hor [188]

[(bipy)Ru(CO)2 Cl2 ]

0.07

0.06

Haukka [91]

[Ru(bdmpzm)(CO)2 (Cl)2 ] 0.16

0.04

Moreno [192]

10

[Ru(CO)3 Cl2 ]2

0.14

0.15

0.32

Haukka [91]

11

[Ru(dppe)(CO)2 (Cl)2 ]

0.26

0.01

Moreno [192]

12

[Ru(CO)2 Cl2 ]

0.13

0.17

0.56

Haukka [91]

13

K[Ru(EDTA)]

0.35

0.07

Khan [83]

a Initial

activity instantly after starting the reaction. b Level of activity after 2 hours
time-on-stream. c Level of activity in a stationary operation state. "-" indicates that
no stationary point was reached.

complex [(bipy)CuCl2 ] reached an initial TOF of 0.4 h1. Only the rutheniumbased complexes [Ru(CO)(H2 O)Cl2 ], [Ru(CO)3 Cl2 ]2 and [Ru(CO)2 Cl2 ] showed
an activating behavior and reached a stable level of activity after about 24 h
time-on-stream. All other systems showed a fast deactivation as indicated
by declining TOF numbers after 2 hours time-on-stream and a non-detectable
activity after 24 hours. This deactivation cannot be attributed to stripping of
volatile compounds, since no traces of catalytically active material were found
in the installed PFA tube installed behind the reactor. Obviously most of these

4.3 Screening of Precursors

81

complexes form inactive species under the employed conditions. Because of


their low activity no selectivity analysis was performed.
Since the promising complexes all contained chloride and/or CO as ligands,
further experiments focused on catalysts containing those structural motives.
4.3.2 Transition metal chlorides
Ford and co-workers [193] initially investigated ligand-modified rhodium complexes (e.g. [(bpnp)Rh2 (O2 CCH3 )3 ][PF6 ]) upon their WGS-activity, but later
observed significantly higher activities for much simpler RhCl3 -systems (see
also 2.1.5.2 on page 19) [14] . A mononuclear rhodium-carbonyl-complex forming under reaction conditions was suggested to be the active species.

0.30

0.20

RuCl

mol

Ru

-1

-1

0.25

TOF / mol

CO2

CuCl
OsCl

0.15

PdCl
FeCl

0.10

RhCl
IrCl

ReCl

0.05

MoCl

0.00
0

10

12

14

16

18

20

Time / h

Figure 4.6: Activity vs. time-on-stream curves for various metal chlorides immobilized as SILP materials in [BMMIM][OTf] on silica. Degree of conversion < 5 %. T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV =
1000 h1 , mcat = 4 g, wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ],
= 0.1 mlIL ml1
pore , support material silica.

Comparative screening experiments of the chlorides of various transition metals were carried out again in the form of continuous SILP catalysis . Mainly

Results presented in this section of the thesis were already published in Appl.Cat.A. [176]

82

Results and Discussion

group VIIIb metals and transition metals were chosen . Table 4.4 summarizes
the turnover numbers obtained from the investigated metal chlorides whereas
Figure 4.6 shows the respective activity over time plot. All chlorides except
Table 4.4: Comparative study on the WGS activity of various metal chlorides in form
of their SILP catalysts.

T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O =

0.2 bar, GHSV = 1000 h1 , mcat = 4 g, wcat = 0.02 gmetal g1


support , ionic liquid
[BMMIM][OT f ], = 0.1mlIL ml1
pore , support material silica.

Precursor

TOF / h1

TOF / h1

(t= 2 h)a

(t = 20 h)b

RhCl3

0.07

0.013

PdCl2

0.68

0.055

MoCl5

0.004

0.003

CuCl2

0.27

0.12

ReCl3

0.009

0.007

FeCl3

0.238

0.061

OsCl3

0.70

0.11

IrCl3

0.29

0.05

RuCl3

0.12

0.26

a Initial

activity instantly after starting the


reaction. b Level of activity after 2 hours
time-on-stream.

RuCl3 - showed strong deactivation in the first 2 hours time on-stream. Activities after 10 hours time-on-stream were far below 0.1 molCO2 mol1
h1 and the
metal
respective conversions were all below 0.1 %. RhCl3 , ReCl3 and MoCl5 exhibited
levels of conversion that were in the range of uncertainty of measurement. In
contrast to that, RuCl3 showed significantly higher WGS-activity and a completely different activity-time profile as depicted in Figure 4.6. One could also
rank the activity of transition metal chloride in WGS from that data after 20
hours time-on-stream to: RuCl3 OsCl3 CuCl3 > FeCl3 > PdCl2 IrCl3 >
RhCl3 > ReCl3 > MoCl5 .
The RuCl3 system activated from 0.12 molCO2 mol1
h1 after 2 hours on-stream
metal

This set of experiments was carried out in the master thesis of Martin J. Schneider

4.3 Screening of Precursors

83

up to 0.40 molCO2 mol1


h1 after 50 hours on-stream. The activation behavior
metal
was attributed to the slow formation of the active species or active cluster. As
ruthenium carbonyl complexes are known to be active in the WGS reaction a
similar intermediate seems likely (see also IR measurements in 4.4.6) [10,11] .
Because conversion was very low and even carbon dioxide was almost at
the lower detection limit, the identification of possible side products was not
possible.

4.3.3 Transition metal carbonyls


In the literature WGS-activity of various transition metal carbonyls has been
intensively studied [11,194] . In particular, WGS activity of the carbonyls of iridium, osmium and ruthenium was investigated (see also 2.1.5.2 on page 19). So
immobilization of these carbonyl complexes in form of their SILP systems was
carried out and the performance of these materials was investigated under the
continuous conditions of a low temperature WGS experiment . The obtained
catalytic results are depicted Figure 4.7.
The iridium carbonyl showed the highest activity, whilst the osmium carbonyl
exhibited almost no activity. With a degree of conversion of 0.02 % for osmium,
0.05 % for ruthenium and 0.16 % for iridium after 10 hours on-stream, the WGS
activities of all carbonyl complexes were negligible. Interestingly, the activities reported in the literature for these transition metal carbonyl complexes are
considerably higher, in case of Ru3 (CO)12 even by 4 orders of magnitude [50] .
However, most of these studies were carried out at high pressures. Ford
and coworkers [51] investigated Ru3 (CO)12 and Ir4 (CO)12 under ambient pressure (pCO = 0.9 bar) at 100 C and found activities of 0.12 molCO2 mol1
h1 and
metal
0.23 molCO2 mol1
h1 respectively, which corresponds very well to the results
metal
of our SILP catalysts.
Furthermore, Graziani and coworkers [195] investigated Os3(CO)12 heterogenized on type-X zeolites and found WGS-activity of 0.024 molCO2 mol1
h1 at
metal
T = 265 C, pH2 O = 0.11 bar and pCO = 0.45 bar. All these activities at ambient
pressures are comparable to those obtained with the SILP-systems. Hence,
high pressure could be a prerequisite for high activity of the transition metal

The corresponding results of this section were already published in Appl.Cat.A. [176]

84

Results and Discussion

0.15
Ir (CO)
4

12

Ru (CO)
3

-1

Os (CO)

12

0.10

TOF / mol

CO2

mol

Ru

-1

12

0.05

0.00
0

10

12

14

16

18

20

Time / h

Figure 4.7: Activity vs. time-on-stream curves for various metal carbonyls immobilized as SILP systems in [BMMIM][OTf] on Silica100. Degree of conversion < 5 %. T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV =
1000 h1 , mcat = 4 g, wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ],
= 0.1 mlIL ml1
pore , support material silica.

carbonyls, especially in the case of Ru3 (CO)12 . Slegeir et al. suggested the activation of the metal carbonyl (e.g. Ru3 (CO)12 cluster to Ru(CO)5 ) to be favored
by increase in carbon monoxide pressure [50] .
4.3.4 Catalysts with bipyridine ligands
In the literature, the investigation of bipyridine ligand systems in WGS catalysis
was in the focus of several research groups (see also chapter 2.1.5.4 and 2.1.6.1
) [68,80,91] . Some of the most interesting systems were also tried in form of SILP
catalysts. Haukka in the group of Pakkanen introduced (bipy)Ru(CO)2 Cl2 in
1995 [91] . This test was performed in the beginning of this thesis, as silica
supported catalyst. Additionally, (bipy)Ru(CO)(H2 O)Cl2 and (bipy)Ru(CO)2 Cl2
were later investigated on -alumina. All three time-on-stream profiles are
depicted in Figure 4.8. Summarizing, all three catalyst did not show activity,
that would justify further focus on these systems.

4.3 Screening of Precursors

85

0.3
[(bipy)Ru(CO) Cl ] on
2

-alumina

[(bipy)Ru(CO) Cl ] on silica
2

-1

[(bipy)Ru(CO)(H O)Cl ] on
2

-alumina

0.2

TOF / mol

CO2

mol

Ru

-1

0.1

0.0
0

10

12

14

16

18

20

Time / h

Figure 4.8: Activity vs.

time-on-stream plot for pyridine modified ruthe-

nium carbonyls as SILP systems in [BMMIM][OTf] on silica.

shows (bipy)Ru(CO)2 Cl2 on silica,  on -alumina and shows


(bipy)Ru(CO)(H2 O)Cl2 on -alumina. Degree of conversion < 1 %. T =
120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat =
1
4 g, wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.1 mlIL mlpore ,

support material as indicated.

On silica, the (bipy)Ru(CO)2 Cl2 deactivated within 24 hours on stream from


a starting value of 0.06 molCO2 mol1
h1 down to 0.04 molCO2 mol1
h1 at a
metal
metal
conversion of less than 0.2 %. On -alumina, a similar activity of less than
0.1 molCO2 mol1
h1 was recorded during 65 hours time-on-stream.
metal
(bipy)Ru(CO)(H2 O)Cl2 showed a slightly better activity starting at 0.22
molCO2 mol1
h1 , but also significantly lost activity down to 0.07 molCO2 mol1
h1
metal
metal
after 18 hours.
Haukka reported activities of TOF > 600 h1 (cf. also subsubsection 2.1.6.1) for
(bipy)Ru(CO)2 Cl2 systems on silica [92] . This could level could not be reached
by our SILP systems by far. However, it has to be taken into account, that
Haukkas experiments were carried out at elevated pressure in the range of 10
bar. Interestingly, their paper does not list specific reaction conditions, such as
residence time, partial pressures or total pressure - and no claim about stability

86

Results and Discussion

is made.

4.3.5 Novel catalyst systems


Based upon the aforementioned results, novel ruthenium-based catalyst systems were synthesized and tested as catalyst precursors in SILP WGS activity . Preparation of these complexes was performed by Dr. Agnes Bittermann and Prof. Dr. Peter Hrter from the Chair of Inorganic Chemistry
at the Technical University of Munich as part of their involvement in the
BMBF WING project. Additional cationic complexes were synthesized by
Sd-Chemie AG. Remaining catalysts were purchased from Alfa Aesar. Details about the preparation and characterization is listed in the Experimental
Section (cf. Section 3.1.2 on page 51)
Activities of the different complexes were found to vary substantially. One
group of SILP systems exhibited an activating behavior, other systems showed
almost stable activity profiles and a third group of SILP catalysts exhibited
rapid deactivation. In full agreement with the previous results, ruthenium
based complexes showed the best activities in the WGS reaction under the
employed conditions.
All palladium complexes (entries 1-3 in Table 4.5) deactivated within the first 2
hours on stream, or even showed an activity below the detection limit in case
of entry 4. Also the N-heterocyclic carbene rhodium complexes (entries 5-7
in Table 4.5) were not active in WGS. The catalytic results are summarized in
Table 4.5.
Results for the ruthenium based systems can be categorized into two classes:
Deactivating or inactive catalysts (Table 4.6, entries 1-8) and activating systems
(Table 4.6, entries 9-15). These classes are separated in Table 4.6 by a line.
Whilst ruthenium based complexes in entries 1-5 of Table 4.6 showed a deactivating behavior, the ionic complexes (Table 4.6, entry 9-15). showed the highest
activity reported for homogeneous WGS catalysts under ambient pressure and
ultra-low temperature conditions so far.
Interestingly, the ionic complexes in the lines 7 and 8 do not show these activating behavior, whereas literature always attribute a high activity to cluster

Parts of these results were already published in Appl.Cat.A. [176]

4.3 Screening of Precursors

87

Table 4.5: Comparative study on the WGS activity of novel palladium and rhodium
precursors in form of their SILP catalysts. T = 120 C, pabs = 1 bar, pCO =
0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, wcat = 0.02 gmetal g1
support ,
ionic liquid [BMMIM][OT f ], = 0.1mlIL ml1
pore , support material silica.

TOF /

TOF /

TOF /

h1

h1

h1

(t=0)a

(t = 2 h)b (stat)c

0.36

0.16

0.18

0.04

0.21

0.03

6 [Rh(CO)2 Cl(4, 5Cl2 1, 3Ph2Im2yliden)d 0

Precursor

1 [(bipy)PdBr2 ]d
d

2 [(bipy)PdBr2 (OCCH3 O)]


3 [(bipy)Pd(CF3 OOC)2 ]d
4 [PdBr2 (1, 1

Me2

3, 3

methylenediimidazoline 2, 2 diylidene)]d
5 [Rh(CO)2 Cl(1, 3 Ph2 Im 2 yliden)]d
7 [Rh(CO)2 Cl(4, 5 (CN)2 1, 3 Ph2 Im 2
yliden)]d
a Initial

activity instantly after starting the reaction.


of activity after 2 hours time-on-stream.
c Level of activity in a stationary operation state. "-" indicates that no stationary point was
reached. d Prepared by TU Munich.
b Level

complexes [6,196] . Possibly, the low partials pressures of carbon monoxide favors
a reaction pathway with lower nuclearity ruthenium centers. Additionally, the
ionic complex in line 6 of Table 4.6 also exhibited no activity. Complexes listed
in lines 1-4 of Table 4.6 employ ligands that are strongly coordinating forming very stable complexes, which is possibly the reason, why these do not
transform into an active form.
In contrast to that, the mixed-metal complex which is listed in line 9 of Table 4.6
also exhibited a very interesting activity, which gave a new starting point for the
development of cationic ruthenium complexes that use metallic co-catalysts.
This strategy is still subject of an ongoing optimization study at Sd-Chemie
AG. As depicted in Figure 4.9, the activation behavior of the complexes listed
in lines 10,11 and 13 of Table 4.6 is different, although the cation is identical.
The anion seems to play a key role in the development of the active catalytic

88

Results and Discussion

Table 4.6: Comparative study on the WGS activity of novel ruthenium precursors
immobilized as SILP catalysts. T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O =
0.2 bar, GHSV = 1000 h1 , mcat = 4 g, wcat = 0.02 gmetal g1
support , Ionic liquid
[BMMIM][OT f ], = 0.1mlIL ml1
pore , Support material Silica 100.

Precursor

TOF /

TOF /

TOF /

h1

h1

h1

(t=0)a

(t = 2 h)b (stat)c

[RuH2 (CO)PPh3 ]

0.08

[RuH(CO)(Cl)PPh3 ]

0.06

[Ru(acac)3 ]

0.15

0.02

0.48

0.46

0.12

0.06

0.53

0.22

[(Gly)Ru(CO)3 Cl]

[PPh3 Ir(CO)Cl]

[Ru(CO)3 Cl2 Br] [Br EMIM]

[NEt4 ]Na2 [Ru8 ( CO3 )4( Cl)4 (CO)16 ]d

+d

[PPN]2 [Ru4 ( O)( Cl)4 (CO)10 ]

Cs[Ru(CO)3 Cl3 ]e

0.88

0.91

2.04

0.60

0.70

2.10

0.14

0.17

0.40

12 [Ru(CO)3 Cl2 I] [1, 2(CN)2 3, 5(Me)2IM]

0.40

0.45

0.60

13 [Ru(CO)3 Cl2 I] [MMIM]

0.60

0.80

2.20

2.58

2.50

2.18

0.10

0.20

1.03

15 [Ru(CO)3 Cl2 Br]2 [2, 3 diMe 1 (2 (3 0.92

1.48

1.56

10 [Ru(CO)3 Cl3 ] [PhN(Me)3 ]

+d

11 [Ru(CO)3 Cl3 ] [Ru (phen)(CO)3 ]

+d

+d

+d

13 [Ru(CO)3 Cl2 I] [MMMIM]

+d

14 [Ru(CO)3 Cl2 I] [1, 2 Cl2 3, 5 (Me)2 IM]

+d

2+d
f

Me 1 H IM 1 yl)Et) 1 H IM]
a Initial

activity after starting the reaction.


of activity after 2 hours time-on-stream.
c Level of activity in a stationary operation state; "-" indicates that no stationary point was
d Prepared by TU Munich.
e Prepared by Sd-Chemie AG.
reached.
f IM = Imidazolium heterocycle.
b Level

species and its final activity. Interestingly, very attractive catalyst activities
were obtained with the anionic ruthenium-complexes in which the charge is
counterbalanced by an imidazolium cation, such as [MMIM]+ (cf. entries 12-15
in Table 4.6). This higher activity might be attributed to a better and faster
solubility of the complex in the ionic liquid, because of the similar structural

4.3 Screening of Precursors

89

1.8

1.6

1.2

TOF / mol

CO2

mol

Ru

-1

1.4

1.0

0.8
[Ru(CO) Cl ][PhNMe ]
3

0.6

[Ru(CO) Cl I][MMIM]
3

[Ru(CO) Cl ][PhRu(CO) ]

0.4

0.2

0.0
0

10

15

20

Time / h

Figure 4.9: Activity vs.

time-on-stream curves for newly developed cationic

ruthenium complexes immobilized as SILP catalysts in [BMMIM][OTf]


on silica.

 [Ru(CO)3 Cl2 I][MMMIM],  [Ru(CO)3 Cl3 ][PhNMe3 ],

[Ru(CO)3 Cl3 ][PhRu(CO)3 ]. Degree of conversion < 1 %. T = 120 C, pabs =


1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, wcat =
1
0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.1 mlIL mlpore , support

material silica.

imidazolium motives.
In any case, no side products could be determined in any of the experiments
listed in Table 4.6 indicating a selectivity of close to 100%.

4.3.6 Gas-phase stripping of volatile catalyst compounds


It is known from the literature that some ruthenium carbonyl complexes are
volatile - they tend to sublime even at slightly elevated temperatures [90] . In
particular ruthenium complexes that contain chlorine, water and carbonyls
show this tendency.
Indeed, in the first set of our SILP water gas shift experiments employing

90

Results and Discussion

RuCl3 as precursor, a distinct catalyst behavior was observed . As mentioned


previously, the catalyst showed an increasing activity within the first hours
on stream and then deactivated with a linear loss of activity as depicted in
Figure 4.10. This deactivation could be clearly attributed to the loss of volatile

1.0

TOF / mol

CO2

mol

Ru

-1

1.5

0.5

0.0
0

20

40

60

80

100

Time / h

Figure 4.10: Activation and deactivation of a RuCl3 SILP catalyst on silica at elevated
temperature and pressure.
compounds gives a

dTOF
dt

Deactivation due to stripping of volatile


= 0.0144.

Degree of conversion 10 %.

T = 160 C, pabs = 10 bar, pCO = 1 bar, pH2 O = 2 bar, GHSV = 500 h1 , mcat =
1
4 g, wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.1 mlIL mlpore ,

support material silica.

ruthenium compounds from the SILP material, as the condensate (non reacted
excess water, that is condensed after the reactor in a cold trap) showed clearly
visible a yellowish color. Additionally, the SILP catalyst itself turned its color
from a dark brownish/grey color to a light grey color after the reaction. Subsequent ICP-AES measurements showed significant ruthenium contents in the
condensate (range of several hundred ppm ). The condensate was reduced by
evaporation of water so that some g of a yellow substance was isolated. The

Parts of the results presented in this section were already published in PCCP [175]
A detailed calibration for the spectrometer for ruthenium was not available

4.3 Screening of Precursors


substance was used for NMR

91
13

C and 1 H experiments in order to determine

possible catalyst intermediates. In these investigations, peaks for carbonyl


groups were identified, but a defined structure could not be determined. Additionally, Fourier-transformed Infrared spectroscopical measurements of the
solution were performed. Again, several peaks in the region of 2150 to 1950
cm1 wavenumbers indicate the presence of ruthenium carbonyl species, as
depicted in Figure 4.11. According to Roberto et al., who reported stripping of
ruthenium carbonyls from silica supports in a CO-atmosphere at T > 150 C, a
compound showing peaks of (CO) at 2115w, 2088s, 2077s, 2031vs and 1995w
cm1 could be [Ru3 (CO)10 Cl2 ] [86] . Indeed this peaks were observed, so it is likely
that this compound is the one subliming from the active catalyst resulting in
loss of activity. As more experiments at ambient pressure were performed to
0.22

2030

0.20
0.18

2088 2077

0.16
0.14
Adsorbance

0.12
0.10

2115

0.08

2030

0.06
0.04

2116

2087 2077
2060

0.02
-0.00
-0.02
-0.04
2150

2100

2050

2000
1950
Wavenumbers (cm-1)

1900

1850

Figure 4.11: Fourier-transformed infrared spectrum of volatile ruthenium compounds


that have been stripped out via gas-phase from the SILP WGS catalyst.

optimize leaching behavior, a transparent poly-fluoroacetate (PFA) tube was


installed in the reactor effluent line to visibly detect even traces of volatile
ruthenium compounds by color-change of the tube. Depending on the type
of experiments, the tubes showed first a green color fading to red after exposure with air, when they were replaced after a experiment and subject to aerial

92

Results and Discussion

oxidation. After longer oxidation a black substance was left behind, possibly
ruthenium oxide. In Figure 4.12 this behavior is depicted.

Figure 4.12: Poly-fluoroacetate (PFA) tubes that show colored precipitate of volatile
ruthenium compounds that have been stripped out of the SILP reactor. a)
shows a tube right after the reaction with green precipitate, b) after 12h of
exposure to air, c) after longer exposure to air.

Experiments show, that several parameters influence the tendency of loosing


ruthenium from a SILP catalyst via the gas-phase. First, the precursor has
substantial influence - catalysts containing RuCl3 have a higher tendency for
sublimation than those prepared with cationic ruthenium complexes. Especially for RuCl3 , elevated partial pressures of carbon monoxide (> 1 bar) highly
increased the rate of stripping, as subsequent experiments showed.
It was observed, that more active catalysts show a lower loss of active material,
which indicates, that the active component itself is not leaching, whereas another ruthenium compound that is formed from the precursor under CO and
H2 O atmosphere is rapidly stripped out. The immobilization of the ruthenium
is also influenced by the ionic liquid and the support material, but these factors
are discussed within the following sections. Ruthenium complex chemistry
under WGS conditions is rather challenging and involves a large variety of
mono- and multinuclear compounds [90,196,197] .
Also the optical appearance of the applied SILP catalysts substantially change
over time. Figure 4.13 shows a photography of the RuCl3 SILP as described in
this section before and after reaction. Whereas the catalyst has a dark brown,
almost black appearance right after preparation, this color changes to yellow

4.3 Screening of Precursors

93

Figure 4.13: Photography of a RuCl3 -SILP before (left) and after (right) the WGS reaction. Additionally, a catalyst is depicted, that was taken out of the reactor
right at the maximum activity (middle)

at the maximum activity. When components are stripped out, first a grayish
and finally a almost colorless material is left behind.
The question of which components are formed and which are stripped out is
part of an ongoing study in collaboration with the group of Prof. J. Libuda of
the Chair of Physical Chemistry II in Erlangen.
4.3.7 General trends
In accordance with the literature data, ruthenium based complexes exhibited
by far the highest activity. Furthermore, only ruthenium complexes showed
reasonable stability over 24 h time-on-stream in the continuous WGS reaction.
Amongst the tested ruthenium complexes, the simple RuCl3 precursor was one
the most active ones. However, it showed a rather long induction period of
more than 24 h. It was assumed that this long induction period stems from
the slow formation of a ruthenium carbonyl species, being the active catalyst
complex.
In order to facilitate this formation step, ruthenium carbonyls were used as
precursors directly. However, their activity was surprisingly low. The best
results in terms of induction period and activity were obtained with novel
ruthenium complexes in which anionic Ru-complexes were paired with imidazolium cations.

94

Results and Discussion

These first results indicated that the Supported Ionic Liquid Phase concept
offers a very efficient way to screen transition metal complexes for catalytic
activity under very controlled steady-state condition. Different from classical
batch experiments, this method provides information on catalyst formation
and deactivation phenomena making the selection of the most promising candidates and structural motives for the further development of even more active
WGS catalysts much more reliable and effective.
In summary, 51 different precursors were screened as SILP catalysts upon their
water-gas shift activity in a total of 5700 hours time-on-stream including reproducibility tests. 28 ruthenium based precursors were screened and showed
in general highest activity. 6 palladium, 4 rhodium and 3 precursors for iridium, copper, molybdenum were also tested. In addition, two osmium and iron
precursors were also checked.

4.4 Optimizations of catalyst systems


Supported Ionic Liquid Phase catalyst provide a full toolbox to perform systematic optimization strategies. Objectives for catalyst optimization are stability,
activity, selectivity, low cost and robustness . Parameters for the optimization
process are illustrated in Figure 4.14.
Materials
Catalyst

Parameters

SILP Catalyst

precursor

Catalyst
Loading

IL

Ionic liquid

Loading
Optimization focus

Support
material

Additives

Stability
High activity
High selectivity
Low cost
Robustness

Basicity

Solvents

Figure 4.14: Building blocks in supported ionic liquid phase catalysts.

The relevant components of the catalyst involve precursor, ionic liquid, support

Parts of these results were already published in Chem.Cat.Chem. [177]

4.4 Optimizations of catalyst systems

95

material and possibly additives such as co-catalysts or stabilizers. Inherent


parameters of the SILP catalyst, such as ionic liquid and catalyst loadings can
be altered independently. Of course, there are possible cross-influences, e.g. by
modifying the inner surface area of a material, usually also the pore structure
is altered.
In the following sections the systematic optimization of a model SILP catalyst
will be reviewed in detail. As standard / reference case the following catalyst
system was selected (arguments given in brackets):
Precursor: RuCl3 , wcat = 0.02 gRu g1
support
(activating behavior, cheap, easily available)
Ionic liquid: [BMMIM][OT f ], = 0.1 mlIL ml1
pore
(stable and compromise in solubilities (cf. Section 2.2.3))
Support material: silica
(previous results and experiences from other SILP work in Erlangen)
Starting from this standard case, several parameters of this reference catalyst
were changed. Additionally, a screening at the industrial partner was carried
out, that validated the trends obtained in our work with model synthesis gas
also for a typical reformate synthesis gas. For reference, these results are also
integrated here.
It is worth mentioning, that even at high conversions of > 50 %, no side products such as methane, ethane, acetone, methanol, ethanol and so alike could
be detected either by on-line GC of the gas-phase nor through offline measurements of the condensate. Because of that, no comments on selectivity are given,
as it was found to be close to 100% and the mass balance on carbon could be
closed to 100 % 3%.
4.4.1 Variation of the support material
In previous studies in our research group, extensive studies in hydroformylation were carried out using Silica 100 from Merck as support material [21] . So
our first choice for the support material was also calcined silica. This support
was also used in the screening studies (cf. 4.3 on page 78) mentioned before. By

96

Results and Discussion

more detailed reviews of literature, the idea evolved to try support materials
with different more basic properties .
Of course not only the materials itself was changed, but also inherent parameters such as pore size distribution, inner pore volume and inner surface area.
To still allow proper comparison of the catalytic performance, intensive parameters such as pore filling grade and loadings were kept. The results from
the time-on stream study are displayed in Figure 4.15.

TOF / mol

CO2

mol

Ru

-1

-1

silica

-alumina
boehmite

20

40

60

80

100

Time / h

Figure 4.15: Activation profiles for SILP WGS catalysts with various support materials.
 uses silica,  -alumina and boehmite as support. Degree of conversion 10 %. T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV =
1000 h1 , mcat = 4 g, precursor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid
[BMMIM][OT f ], = 0.1 mlIL ml1
pore .

The catalyst that was supported on silica (identical to the one in subsection 4.3.2)
1
started off with an initial activity of 0.1 molCO2 mol1
and reached a final level
Ru h

of 0.9 molCO2 mol1


h1 after 64 hours time-on-stream. A commulated turn over
Ru
number of 44 was obtained after 100 hours time-on-stream. Effective kinetic

The results of this section were already published in Chem.Cat.Chem. [177]

4.4 Optimizations of catalyst systems

97

parameters were determined to an apparent activation energy of 57.1 kJ mol1


and partial reaction order of 0.02 with respect to carbon monoxide and 1.05 with
respect to water. These parameters were obtained in a single run, as depicted
in Figure 4.16 demonstrating impressively the potential of SILP catalysts for
kinetic studies of homogeneous catalysts.
Activation energy

-12

-1

E =60.7 kJ mol

ln(r

eff

3
-14

0.0023

0.0024

0.0025

0.0026

0.0027

-1

T / K

-12

Ru

-13

=1.05

H2O

eff

ln(r

CO2

TOF / mol

mol

-1

-1

Partial reaction orders

-14
n

=0.02

CO

-15
-2.5

-2.0

-1.5

-1.0

-0.5

ln(p )
i

0
0

20

40

60

80

100

120

140

t / h

Figure 4.16: Single-run determination of kinetic parameters for a SILP WGS catalyst. 1:
water partial pressure variation pH2 O = 0.1 . . . 0.4 bar, 2: carbon monoxide
variation pCO = 0.1 . . . 0.4 bar, 3: temperature variation T = 100 . . . 160 C.
T = 120 C, pabs
1000 h1 , m

cat

= 1 bar, pCO

= 0.1 bar, pH2 O

= 0.2 bar, GHSV =

= 4 g, precursor RuCl3 , wcat = 0.02 gmetal g1


support , ionic liquid

[BMMIM][OT f ], = 0.1 mlIL ml1


pore , support: silica.

After a stable operation point was reached, first a variation of partial pressure
of water was carried out, followed by a variation of carbon monoxide partial
pressure. Finally, a temperature variation in the range of 100 to 160 C was
performed. After any variation, the initial operation point was set again, in
order to check for deactivation.

98

Results and Discussion

When -alumina was used, a significant increase of activity was immediately obtained. The initial activity of 1.7 molCO2 mol1
h1 increased to a level
Ru
1
of 4.6 molCO2 mol1
after 95 hours time-on-stream resulting in a turn over
Ru h

number of 376 after 100h. This is already a five-fold increase compared to the
silica supported catalyst. The apparent activation energy was determined to
60.7 kJ mol1 , which is in the same range as measured previously for the silica based system. In contrast to the almost unchanged activation energy, the
partial reaction orders with respect to water and carbon monoxide showed a
significant change.
A value of 0.34 was obtained for carbon monoxide, which shows, that in case
of alumina as support material an influence of carbon monoxide partial pressure onto overall rate of reaction exists. Possibly, the association of carbon
monoxide to the active center is now controlling the overall catalytic cycle,
being rate determining. The lowered partial reaction order of water that was
determined to 0.84 indicates, that water is no longer the only rate determining
species. Alumina is a more basic support material, so another equilibrium of
water and hydroxide ions exists in the ionic liquid layer than in case of a silica
support. Consequently, in case of alumina a higher concentration hydroxide
should be present, because of the dynamic equilibrium between water and
hydroxide, surface and catalytic cycle. As pointed out in the theoretical part,
most postulated mechanisms on ruthenium catalyzed water gas shift involve
the addition of a hydroxide anion in the catalytic cycle rather than association
of water. One generalized catalytic cycle for metal carbonyls in the water gas
shift as proposed by Ford et al. is depicted in Scheme 4.1. So a higher local
concentration of hydroxide should indeed speed up this step in the catalytic cycle. One could speculate, that the increased support basicity finally determines
the higher overall activity. It is worth mentioning, that the change in support
material also lowered the stripping of volatile ruthenium compounds significantly. So, increased basicity not only enhances activity, but also improves the
immobilization of the ruthenium catalyst on the SILP catalyst system tested.
As another basic support, an alumina material in the boehmite state was used.
Here, a very high initial activity of 6.3 molCO2 mol1
h1 was observed that slowly
Ru
1
increased up to 8.5 molCO2 mol1
in the following 230 hours on stream. The
Ru h

4.4 Optimizations of catalyst systems

99
OH-

H2

Ru

CO

CO

H
Ru

Ru
H

OH

OHH 2O

Ru

CO2

Scheme 4.1: Generalized WGS catalyzed reaction scheme for metal carbonyls in alkaline environment(cf. section 2.1.5.2) [5] .

apparent Arrhenius-type activation energy in the range of 100..120 C was


determined to 60.5 kJ mol1 , which is in good agreement with the measurements
for the -alumina. Additionally, the partial reaction order with 0.39 for carbon
monoxide and 0.79 match those of the previously mentioned very well. This
leads to the conclusion that the actual mechanistic background is similar for
both cases. All kinetic data together with the activity data is summarized
in Table 4.7 on page 101.
It is still unclear, why the boehmite supported catalyst shows such a high initial
activity and no pronounced activation phase.
4.4.2 Addition of organic bases
To validate the influence of basicity, novel catalysts were prepared, into which
additional basicity was introduced by weak organic bases. For this purpose
novel basic compounds were synthesized that incorporate structural motives
similar to ionic liquids to ensure a good mixing / solubility. The addition of
an organic base to the immobilized ionic liquid challenges the stability of the
resulting SILP material in two different respects. On the one hand, the organic
base may be lost during operation due to its vapor pressure. On the other
hand, ionic liquids have been reported to display stability problems under
basic conditions, mainly due to the formation of carbenes by abstraction of the
most acidic C2 H proton of the imidazolium heterocycle [119] . Therefore, ionic
liquids with C2 -methylated imidazolium ions have been exclusively applied.

100

Results and Discussion

Usage of strong bases such as sodium or potassium hydroxide was not a


possibility, because stability of even C2 -methylated ionic liquids against these
very strong bases is poor and would lead to rapid decomposition.
As non-volatile basic additive ethyl-dimethyl-4-pyridinylammonium triflate
was used and added in a 1:1 molar ratio to the ionic liquid. This value was just
a "quick guess", but a detailed optimization was not focus of this study.
In case of support materials silica and -alumina the addition of the organic
base had a clearly positive impact on activity as depicted in Figure 4.17. The
-alumina with the added base showed also a linear deactivation, but in this
case no ruthenium was found neither in thetransparent PFA tube nor in the
condensate. So this form of deactivation is obviously of different nature then
in previous experiments.
14

TOF / mol

CO2

mol

Ru

-1

-1

12
10
8

3x increase for
-alumina

6
4
2

5x increase for
silica

20

40

60

80

100

120

Time / h

Figure 4.17: Activity increase of a SILP WGS catalyst by addition of the organic base
ethyl-dimethyl-4-pyridinylammonium triflate (closed symbols with base)
for silica () and -alumina (). Degree of conversion 10 %. T =
120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat =
4 g, precursor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ],
= 0.1 mlIL ml1
pore , support material as indicated.
1
In case of silica, the maximum turn over frequency reached 4.5 molCO2 mol1
Ru h

4.4 Optimizations of catalyst systems

101

when the base was added. This is almost exactly the value that was reached for
the -alumina without addition of the base. Thus, addition of the base leads
to a five-fold increase in activity. Additionally, the effective kinetic parameters
changed significantly (see Table 4.7).
Table 4.7: Final level of activity, activation energy and partial reaction orders
for SILP WGS catalysts with different support materials and added
bases.

Degree of conversion 10 %.

T = 120 C, pabs = 1 bar, pCO =

0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precursor RuCl3 , wcat =
1
0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.1 mlIL mlpore , support

material as listed.

Support

Basea TOFb tind c TOFmax d TON(100h)


h

EA e
kJ mol

nCO

nH2 O

silica

0.1

64

0.9

44

57.1

0.02 1.05

silica

0.2

140

4.5

220

40.7

0.4

-alumina

1.7

95

4.6

376

60.7

0.34 0.84

-alumina

1.2

26

12.0

1091

50.6

0.37 0.82

boehmite

6.3

230

8.5

662

60.5

0.39 0.79

boehmite

2.8

105

14.6

890

25.2

0.78

a base

= ethyl-dimethyl-4-pyridinylammonium triflate.
c time until maximum activity was reached.
TOF after 1h time-on-stream.
d maximum activity reached after induction period.
e in the range of 100..120 C, 10 C steps.
b initial

Activation energy in the temperature range of 100 . . . 120 C was lowered to


40.7 kJ mol1 possibly due to first influence of mass transfer limitations. Most
interestingly, the partial reaction orders were 0.4 for carbon monoxide and 0.78
which is almost the same as for the alumina case leading to the conclusion that
the change in basicity leads in both cases to a similar rate determining step that
possibly involves carbon monoxide addition. Most interestingly, the addition
of the base also decreases the tendency of stripping volatile ruthenium compounds from the support. After 100 hours time-on-stream the coloring of the
tube was negligible. ICP-AES measurements of the condensate showed only a
minor presence of ruthenium.
When adding the organic base to the -alumina SILP system, the activity is

102

Results and Discussion

also significantly increased by a factor of 2.5. In this case the final level of
activity 12 molCO2 mol1
h1 is also reached much faster (26 instead of 95 hours).
Ru
The activation energy dropped from 60.7 kJ mol1 to 50.6 kJ mol1 , but the partial
reaction orders stayed in the same range, namely 0.37 for carbon monoxide and
0.82 for water. This leads to the conclusion that the rate determining step in the
catalytic cycle is not further changed by additional basicity, but the formation
of the active species is promoted.
The addition of the base to the boehmite support also results in a higher final
1
level of activity of 14.6 molCO2 mol1
Ru h . The latter was reached after 105 hours

on stream. Assuming classical heterogeneous catalyst behavior, one could conclude, that significantly lowered activation energy of 25.2 kJ mol1 is caused by
mass transfer limitation from pore diffusion, as the new value is about half of
D
the previous value ( EA +E
), as depicted in Figure 4.18. Even though, the cata2

lyst without the added base also showed a possible mass transfer limitation at
temperatures above 120 C, which was not clearly confirmed by a particle size
variation (cf. subsection 4.5.4). Here the activation energy was determined to
26.2 kJ mol1 , whereas at lower temperatures in the possible kinetic regime an
activation energy of 60.5 kJ mol1 was found. Interestingly, the slope in the possibly mass transfer influenced regime of the catalyst with and without added
organic base almost exhibited the same value. Unfortunately the partial reaction orders could not be determined for the base modified case, because of a
power outage resulting in a multi-week shutdown.
The addition of an organic base raises additional issues regarding systems
stability. To clarify the influence of base addition on thermal stability, especially
in the temperature range of 100 to 160 C, a thermogravimetric (TGA) analysis
has been carried out comparing these two types of catalysts as depicted in
Figure 4.19.
In the temperature region between 100 and 160 C the catalyst without organic
base showed a mass loss of about 0.5%, whereas the catalyst with the organic
base resulted in a mass loss of about 0.75%. Within this temperature range
the heating rate was maintained at 0.5 C min1 so that this measurement took
about 80 minutes. As the samples were dried at 100 C for 3h without significant

4.4 Optimizations of catalyst systems

103
T / C

140

130

120

110

100

-10.2
-10.4

-1

= 25.2 kJ mol

R = 0.995

-10.6
-10.8

ln(r

eff

-11.0
-11.2

-11.4

-1

= 26.2 kJ mol

R = 0.991

-11.6
-11.8
E

-12.0
-12.2
0.0024

-1

= 60.5 kJ mol

R = 0.983

0.0025

0.0026
-1

/ K

0.0027

-1

Figure 4.18: Activation energy determination by Arrhenius plot for a boehmite supported SILP WGS catalyst with () the organic base ethyl-dimethyl4-pyridinylammonium triflate and without (). Degree of conversion
10 %. T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV =
1000 h1 , mcat = 4 g, precursor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid
[BMMIM][OT f ], = 0.1 mlIL ml1
pore

loss (less than 0.5% loss in 3h) of material and can be considered dry, the loss of
material might be attributed to stripping of volatile compounds. The material
with the organic base probably showed a somewhat higher mass loss, because
more organic material is present.
Comparing the final loss of mass at 500 C, the SILP catalyst with organic base
lost about 29.5%, whereas the material with just the ionic liquid and catalyst
lost 19%. If one calculates the mass percentage of ionic liquid and organic
base present in the SILP catalyst, this fraction adds up to 29.9% mass percent,
which matches the TGA value, as one can assume that all organics "burned off"

104

Results and Discussion

Mass / %

Mass / %

80

-19%

100.0

90

-29.5%

100

99.5

99.0
100

120

140

160

T / C
70

-1

0.5 K min

10 K min

-1

RuCl

on

RuCl

with organic base on

-alumina
-alumina

60
100

150

200

250

300

350

400

450

500

T / C

Figure 4.19: Thermogravimetric analysis of SILP catalysts with and without organic base. Insert enlarges the interesting temperature region of 100
to 160 C. Both graphs have the signal of the plain support material alumina subtracted. Precursor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.34 mlIL ml1
pore , organic base ethyl-dimethyl-4pyridinylammonium triflate, support material -alumina.

at 500 C. On the other hand, this value leads to the conclusion, that the fresh
RuCl3 is not stripped from the catalyst, as its weight percentage is about 3%. In
case the ruthenium trichloride was stripped off, a value of >32% should have
been observed.
The same observation can be made for catalyst without the organic base. Here,
the mass fraction of ionic liquid present in the SILP catalyst is 18.5%, whereas
a loss of 19% was observed. Again no stripping of RuCl3 can be assumed, as
the weight loss of the additional 3.5% content was not found.
In summary the catalyst with the organic base adds a measurable thermal instability to the SILP system, especially in the temperature range of 100 to 160 C.

4.4 Optimizations of catalyst systems

105

The practical relevance of this finding for long-term catalyst performance remains to be clarified.
This set of experiments was not conducted for further improvement of the
activity, but for clarification of the influence of basicity.
4.4.3 Variation of ionic liquid loading
In order to determine the right pore ionic liquid filling grade for the final
optimized catalyst a set of experiments was carried out. Figure 4.20 shows the
acquired final activity for different pore filling grades of SILP systems under
investigation.

Ru

TOF

max

/ mol

CO2

mol

-1

-1

0
0.10

0.15

0.20

0.25

pore filling grade

0.30

/ ml

IL

ml

0.35

0.40

-1
pore

Figure 4.20: Final level of activity for SILP catalysts with different pore filling grades
. Dotted line shows a possible fit. Degree of conversion 10 %. T =
120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat =
4 g, precursor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ],
= 0.1..0.4 mlIL ml1
pore , support material -alumina.

The highest final activity was reached for a pore filling grade of 34 %.
Activation energy is the range of 100 to 120 C follows a similar trend. At lower

106

Results and Discussion

loadings, the activation energy was measured as 44.6 kJ mol1 at 10%, whereas
34% IL loading gave (as mentioned previously) 60.7 kJ mol1 . At 40% loading,
the value again decreased to 52.3 kJ mol1 . These three cases are depicted in the
Arrhenius type plot in Figure 4.21.
T / C

140

130

120

110

100

-11.4

ln(r

eff

-12.0

-12.6

= 0.4
= 0.34
= 0.1

-13.2
0.0024

0.0025

0.0026
-1

/ K

0.0027

-1

Figure 4.21: Arrhenius type activation energy determination for SILP-WGS catalysts with different ionic liquid loadings. Degree of conversion 10 %.
T = 100..140 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV =
1000 h1 , mcat = 4 g, precursor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid
[BMMIM][OT f ], = 0.1..0.4 mlIL ml1
pore , support material -alumina.

The interpretation of these values is rather complex. At a loading of 10%, the


layer thickness in case of a homogeneous film structure would result in about
5. This fully theoretical value makes of course no sense, as it is in the same
order of magnitude as the size of one ionic liquid ion pair. From this finding,
two possible interpretations arise, which are depicted in Figure 4.22.
As depicted in Figure 4.22 a), it is obvious that at lower pore filling grades mi-

4.4 Optimizations of catalyst systems

107

Figure 4.22: Schematic interpretation of ionic liquid distribution in the pore network of
a support material with meso- and micropores. a) flooding of micropores,
b) clogging of micropores.

cropores are flooded due to capillary forces, whereas the leftover ionic liquid
forms droplets in the mesopores. At higher pore fillings a more or less continuous film in the mesopores is formed. If one estimates the amount of ionic
liquid, that is possibly trapped in micropores, this volume would be about
0.037 ml g1 for this specific alumina support, which means about 8% of the
total pore volume. In case, that the pore filling grade is 10%, possibly most of
the ionic liquid is trapped in micropores. So one could debate, if a catalyst at
10% pore filling grade where most ionic liquid is trapped in micropores has still
a homogeneous nature or if a corner-case between heterogeneously dispersed
material and homogenous catalyst is existing, which makes interpretation of
these values even more difficult.
Another possible interpretation could be a clogging of the micropores, which
is illustrated in Figure 4.22 b). In this case a continuous film in the mesopores
forms, whereas the micropores are blocked and left empty. The surface area
that micropores add to the total inner surface area is about 92%, but just about
8% of the volume. Consequently, when calculating the average ionic liquid
layer thickness for the surface area contributed by mesopores ( 8.1 m2 g1 ), a
value of about 4 nm is obtained. This value indeed suggests that a continuous film is formed. However, when increasing the loading from 10% to 34%
this would result in a layer thickness of 14 nm, which is not realistic, because
the average pore diameter in the mesopores is just 17.2 nm. The question, how
the ionic liquid is distributed in porous support materials remains open and

108

Results and Discussion

is focus of ongoing studies in the work group. Possibly a combination of both


corner cases explained here is actually present.
In the low temperature regime a macrokinetic pore-diffusion influence is negligible but at elevated temperatures a clearly lowered slope in the Arrhenius-plot
is observable, especially for the catalysts with very low ionic liquid loading. If
the loading of the ionic liquid is further increased beyond a certain level, a second effect occurs which can be attributed to mass transport in the ionic liquid
film. This ascending-descending behavior of the activity depending on ionic
liquid loading was also described previously by other groups for supported
liquid phase catalysts [25,198] .
It is worth mentioning, that Arrhenius-type activation energies are just a very
rough model estimation for SILP catalysts, because in these highly complex
systems, not only rates of reaction are influenced by temperature, but also
parameters such as film viscosity, diffusion coefficients and solubility (Henry
coefficients). This also means, that the rates of absorption of substrates in
the ionic liquid films is altered. Thus, temperature influence several parameters that have direct impact on the final activity, so that a straightforward
interpretation as in heterogeneous is hardly possible.
Integrated modeling of SILP catalysts including those aspects is currently in
the focus of the doctoral thesis of Alexander Buchele at the Chair of Separation
Processes (Prof. Arlt) in Erlangen.
For all tested ionic liquid loadings the partial reaction order values with respect to carbon monoxide are in the range of 0.4 0.04, which matches the
experimental error. In case of water, the order is about 0.97 at 10% loading and
decreases subsequently (0.91 at 20%, 0.87 at 30%) to a value of 0.84 at 34%. At
40% loading, the value is 0.85 again. This trend might be related to the fact,
that a certain amount of ionic liquid is needed before a right environment for
the hydroxide equilibrium in this layer can be ensured. As indicated earlier,
this equilibrium is influenced by the supports basicity.
In order to further clarify the IL influence on microkinetic aspects of WGS

4.4 Optimizations of catalyst systems

109

catalysis, a model catalyst study is a very attractive option. This is currently


conducted at the Chair of Physical Chemistry II in the group of Prof. J. Libuda
in the context of on-going collaborations within the EAM research cluster.
In a second set of experiments in the laboraties of our industrial partner SdChemie AG, the same variation of pore filling grade variation was performed.
In this case, a real synthesis gas atmosphere was used. Because of a more
different setup and support material, the values of ionic liquid loading variation
are not directly comparable. Figure 4.23 gives an overview of two sets of
variation for the ionic liquids [BMMIM][OT f ] and [BMMIM][NT f2 ].
In both cases, a maximum of activity was obtained at 10 mass% of ionic liquid
loading, which corresponds to the findings as discussed above. Note that in
this case a loading of 10 mass% equals a pore filling grade of 30%. The level
of activity for the triflate was higher than for the more hydrophobic bistrifluoromethylsulfonylimide, which is attributed to a lower water solubility resulting
in a lower effective water concentration. Interestingly also a "leveling-off" effect
at higher loadings was found: While at lower loadings a steeply increased activity was found, activity decreased only gradually by using loadings beyond
the maximum.
In summary, in all observed cases, a maximum in activity was found around
0.10 gIL g1
support , which corresponds to a pore filling grade of 34% for -alumina
and 10% for silica.
4.4.4 Variation of metal loading
Optimization of the amount of active component in a catalyst is the most costsensitive variable. Ruthenium is a precious metal with a price of about 3.61
e per gram (155 $ per troy ounce as of 1.11.2010), so it accounts for a significant
amount of the catalyst cost. However, the catalytic activity is directly correlated
to the amount of ruthenium. This case deserves a distinction between spacetime-yield which is the final technical objective and a specific intrinsic catalytic
activity expressed by a turn over frequency. In two independent experimental
series that are listed in Table 4.8, the loading of the activity component was
varied therefore.

110

Results and Discussion

[BMMIM][OTf]
[BMMIM][NTf ]
2

Conversion X

CO

/ %

10

0
0,0

0,1

0,2

0,3

pore filling / g

IL

0,4

-1

support

Figure 4.23: Degree of conversion for SILP WGS catalyst with different ionic liquid loadings in reformate synthesis gas.

 uses [BMMIM][OT f ], 

employs [BMMIM][NT f2 ]. Dotted lines show a possible fit. T =


140 C, pabs = 3 bar, V dry = 40 mlN min1 , Gas-to-steam: 3:1, Syngas composition: 75 %H2 , 8 %CO, 13 %CO2 , 4 %N2 , mcat = 0.2 g, precursor
[Ru(CO)3 Cl2 ]2 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ] and
[BMMIM][NT f2 ], wIL = 0.1..0.4 gIL g1
support , support material -alumina.

Both -alumina and silica exhibit a maximum space-time-yield is obtained for


a catalyst loading of 2 gmetal g1
support . In case of -alumina a space-time yield of
65.1 kgCO2 m3
h1 is reached at this loading, which is about 15 times the value
SILP
of the silica supported system.
For both support materials, the turn-over-frequency is decreasing for increasing amounts of active component. This may to be related to a beginning
mass-transfer limitation possibly due to pore-diffusion. Another hint, that

4.4 Optimizations of catalyst systems

111

Table 4.8: Final level of activity, activation energy and partial reaction orders for
SILP catalysts with different loadings of RuCl3 on silica and on alumina. Degree of conversion 10 %. T = 120 C, pabs = 1 bar, pCO =
0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precursor RuCl3 , wcat =
1
0.005..0.03 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.1 mlIL mlpore , sup-

port material silica.

Support

Loading

Max TOFa

Max STY

gmetal g1
support

kgCO2 m3
h1
SILP

EA b
kJ mol

nCO

nH2 O

1 silica

0.005

1.02

1.1

86.4

-c

-c

2 silica

0.01

0.43

1.3

84.3

-c

-c

3 silica

0.02

0.34

2.8

83.7

4 silica

0.03

0.23

1.4

80.3

5 -alumina

0.01

17.1

39.9

88.6d

0.12 0.47

0.34 0.84

0.02 1.05
-c

6 -alumina

0.02

14.1

65.1

60.7

7 -alumina

0.03

12.4

31.1

43.2d

-c

a At

120 C. b In the range of 100..150 C, 10 C steps. c Value not determined due


to deactivation. d In the range of 100..120 C, 10 C steps.

macrokinetic phenomena play a role in this case is expressed by the fact, that
the acquired effective activation energy is decreasing. In case of -alumina,
comparing entries 5 and 7 in Table 4.8, the activation energy is less than half,
which could be related to the textbook-known behavior that in the transition
regime between pore-diffusion and kinetic regime a activation energy in the
form (EA +ED )/2 is found. But once again one should mention, that temperature
also influences several parameters of the catalyst system, such as solubilities
and viscosities.

4.4.5 Variation of the ionic liquid


Having selected alumina as support material, four different types of ionic
liquids were tested for their activity . Additional focus of the following experiments was on long-term stability and immobilization of the volatile ruthenium
compounds. The initial selection of [BMMIM][OT f ] was based on the solu

Parts of these results of this section were already published in Chem.Cat.Chem. [177]

112

Results and Discussion

bilities as pointed out in the theoretical part. Besides that, low coordination
tendency was an argument for that specific ionic liquid.
In order to study influence of the ionic liquid, other candidates were selected, namely [BMMIM][NT f2 ] as hydrophobic candidate and [BMMIM]Cl
which contains the highly coordinating chloride anion. In parallel to that
a slightly more basic phosphonium ionic liquid [Bu4 P][Me(OH)PO2] and the
ionic liquid [EMIM][Me(OH)PO2 ] were tested. In addition to those, another basic imidazolium ionic liquid [EMIM][OAc] and AmmoEng methylphosphate
[R4 N][Me(OH)PO2] were selected. Figure 4.24 shows the results of a timeon-stream study for SILP catalysts with the ionic liquids [Bu4 P][Me(OH)PO2],
[BMMIM]Cl and [EMIM][Me(OH)PO2 ] in comparison to [BMMIM][OT f ].

TOF / mol

CO2

mol

Ru

-1

-1

10

5
[Bu P][Me(OH)PO ]
4

[BMMIM][Cl]
[BMMIM][Otf]
[EMIM][Me(OH)PO ]
2

50

100

Time / h

Figure 4.24: Time on stream activity profiles for SILP WGS catalysts with different ionic liquids.

Degree of conversion 10 %.

T = 120 C, pabs =

1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precur1
sor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid varied, = 0.34 mlIL mlpore ,

support -alumina.

[EMIM][Me(OH)PO2 ] showed a very low activity. This might be related to

Trademark of Merck KGaA.

4.4 Optimizations of catalyst systems

113

the fact, that the imidazolium cation with its acidic C2 H in the heterocycle
gets deprotonated leading to decomposition and resulting in an inactive catalyst [119] . The tetraalkyl ammonium ionic liquid AmmoEng methylphosphate
[R4 N][Me(OH)PO2] (not shown) also exhibited low activity, which is also possibly related to decomposition. The results for [EMIM][OAc], which is not
depicted, is also not resulting in an active catalyst. In all three cases, the turn
over number after 100h on stream is less than 100.
1
[Bu4 P][Me(OH)PO2] shows a very high initial activity of around 10 molCO2 mol1
Ru h ,

but deactivated slightly which is summarized by a turn over number of 890


after 100 hours on stream. Effective kinetic parameters were determined to an
activation energy of 58.7 kJ mol1 and partial reaction orders of 0.18 for carbon
monoxide and 0.56 for water. These values are interestingly a lot lower than
for any other SILP catalysts that have been investigated. The catalyst rapidly
deactivated when the temperature was increased up to 140 C during the temperature variation. When returning back to 120 C, about 40% of the activity
was lost. This temperature sensitivity is problematic for a real-life application,
because even small hotspots can severely damage the catalyst.
The catalysts with the [BMMIM]+ cation almost show an identical activation
behavior, but the stability of the catalyst that uses the chloride anion is slightly
better. Effective kinetic parameters of both catalysts are almost identical. In
case of the chloride ionic liquid activation energy in the range of 100..120 C was
calculated to 57.9 kJ mol1 (60.7 kJ mol1 for the triflate) whereas partial reaction
order analysis gave 0.41 (0.34 for triflate) for carbon monoxide and 0.87 (0.84
for triflate) for water. The better stability of the chloride containing catalyst
is attributed to a "chloride reservoir" that provides a better immobilization of
the active complex . As the chloride is also coordinating, the local chloride
concentration at the catalyst is increased, which results in stronger interaction
between ionic liquid and complex.
After 200 hours time-on-stream the amount of stripped catalyst components
was lowered significantly with [BMMIM]Cl being the ionic liquid film, as
no coloring of the out-flow PFA tubings was visibly detected. Whereas the

Private communication from Dr. N. Szesni (Sd-Chemie AG).

114

Results and Discussion

turnover number of the triflate catalyst was calculated to 376 after 100 hours
and 730 after 200 hours, the chloride catalyst resulted in 351 and 810, respectively.
At the laboratories of Sd-Chemie AG in Heufeld cross-test on the triflate and
the chloride systems were carried out. Results from this study in a model
reformate syngas are depicted in Figure 4.25.

150
[BMMIM]Cl

Ru

100

TOF / mol

CO2

mol

-1

-1

[BMMIM][OTf]

50

T=140C

10

20

T=160C

30

40

50

T=140C

60

70

t / h

Figure 4.25: Time on stream activity profiles for SILP WGS catalysts with different
ionic liquids in reformate synthesis gas (Data from Dr. N. Szesni, SdChemie AG).  uses [BMMIM][OT f ],  employs [BMMIM]Cl.
140 . . . 160 C, pabs

T =

= 3 bar, H2 75%, CO 8%, CO2 13%, N2 4%, steam to

gas = 1:3, pCO = 0.02 bar, pH2 O = 0.083 bar, GHSV = 16000 h1 , mcat = 0.2 g,
precursor [Ru(CO)3 Cl2 ]2 Bz(Et)3 NCl, wcat = 0.02 gmetal g1
support , ionic liquid
varied, = 0.34 mlIL ml1
pore , support -alumina.

It is clearly visible that the catalyst using the triflate ionic liquid shows a linear
deactivation starting from a TOF of 75 molCO2 mol1
h1 (XCO 35 %) down to
Ru
1
17 molCO2 mol1
(XCO 8 %), which equals a loss of activity
Ru h

d TOF
dt

= 0.967. At

4.4 Optimizations of catalyst systems

115

140 C the chloride system reaches a stable space-time yield of 385 kgCO2 m3
h1
SILP
that increases up to 680 kgCO2 m3
h1 at 160 C.
SILP
This underlines that the chloride ionic liquid is a better choice for the SILP
WGS catalyst preparation compared to the triflate.

4.4.6 Optimization of the induction period


The induction period of the catalyst, that was discussed previously was also
a focus of the optimization . As known from the literature, determination of
an active species in homogeneously catalyzed processes is always tidy and
requires sophisticated spectroscopic techniques, as most active species are not
very long lived and only present in small amounts [199] . In situ spectroscopy
of supported ionic liquid catalysts itself is a current focus of separate research
activities within the cluster EAM between our group and the groups of Prof.
Libuda and Prof. Steinrck.
So in this work it was decided to take a quick preliminary approach before
starting with more detailed investigations. In order to get an insight into the
nature of the catalyst, an ex situ infrared spectroscopy approach was carried
out. A reference SILP WGS catalyst was prepared and put into the reactor,
until a significant activity was reached. Now the catalyst was taken out of
the reactor and washed with ethanol which was subsequently removed in
vacuo leaving behind the ionic liquid and the homogeneous catalyst. This
precipitate was mixed with potassium bromide and examined in a transmission
Fourier-transformed-infrared spectrometer. Acquired spectra are depicted in
Figure 4.26. These were compared to spectra recorded for various rutheniumcarbonyl-chloro complexes.
While a freshly prepared SILP RuCl3 catalyst shows no absorption in the region
between 2100 and 1700 cm1 (as there is no CO coordinated to the ruthenium),
the spectra obtained from the same SILP WGS catalyst after 48 h operation in
the WGS reactor display two bands at 2047 and 1970 cm1 (Figure 4.26, insert
a). The obtained spectrum fits remarkably well to the bands for [Ru(CO)3 Cl2 ]2
in THF where peaks are at 1986 and 2059 cm1. Roberto et al., who report 1985

Parts of the results presented in this section were already published in Chem.Cat.Chem. [177]

116

Results and Discussion

0.4

b)

a)
6

-1

4
0.2
1970
2047

TOF / h

Absorption

0.3

2
0.1

0.0
2100

2000

1900

50

100

-1

Wavenumber / cm

t / h

Figure 4.26: a) Infrared spectra recorded for a RuCl3 SILP WGS catalysts (extracted
by ethanol, crystallized, measured in KBr) before (dashed line) and after
(solid line) reaction. b) Comparison of the induction periods of SILP catalysts with RuCl3 precursor (  ) and a [Ru(CO)3Cl2 ]2 (N) at T = 120 C, pabs =
1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precursor
1
RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid varied, = 0.1 mlIL mlpore , sup-

port -alumina.

and 2060 cm1 for this complex [86] .


Interestingly, these bands differ from data available in literature, where the
dimeric [Ru(CO)3 Cl2 ]2 is reported with strong bands at 2129 to 2144 cm1 and
2066 to 2092 cm1 [200203] .
This is attributed to the fact, that in donor solvents such as tetrahydrofuran a
[Ru(CO)3 Cl2 ](THF) or [Ru(CO)3 Cl2 (THF)] is formed [86,192] . So it might be possible, that in case of the SILP catalyst a similar adduct such as [Ru(CO)3 Cl2 ](IL)
or [Ru(CO)3 Cl2 (H2 O)] will be formed.
The formation of [Ru(CO)3 Cl2 ]2 from RuCl3 under carbon monoxide containing

4.4 Optimizations of catalyst systems

117

atmosphere is further supported by earlier work of Roberto et al. [86] . Majumdar


et al. reported that [RuII (CO)3 Cl2 2 ]2 might be a WGS intermediate that further
reacts to [RuI2 (CO)4 ]2+ by decarboxylation and subsequent dinuclear reductive
elimination [196] .

Indeed, using separately synthesized [Ru(CO)3 Cl2 ]2 for the preparation of the
SILP material, a catalyst was obtained that showed high WGS activity right
from the first minutes time-on-stream while the respective catalyst prepared
with RuCl3 required 95h time-on-stream to obtain the same level of activity
as depicted in Figure 4.26, insert b). As the absolute amount of moles of
ruthenium was the same in both cases (half moles of the dimeric precursor
1
was used), the almost identical activity of 4.6 molCO2 mol1
indicates, that the
Ru h

dimeric species is directly involved into the catalytic cycle. The exact involvement into the catalytic cycle is not easily to be determined, but an involvement
as resting state species seems to be the most probable hypothesis.
An additional hint, that the dimeric ruthenium carbonyl is somehow involved
in the catalytic cycle is given by a visible comparison of the catalysts as depicted
in Figure 4.27.

Figure 4.27: Photography of a fresh RuCl3 SILP on -alumina before (left) and after
(middle) the WGS reaction. Additionally, a catalyst is depicted, where
instead [Ru(CO)3 Cl2 ]2 is used as precursor (right).

When comparing the catalyst samples depicted in the middle and the right

118

Results and Discussion

of Figure 4.27, the apparent color of the catalysts almost perfectly match - the
catalyst prepared from RuCl3 that was on stream in WGS for about 100 hours
shows a slightly yellow color with a touch of orange, whereas a fresh SILP
catalyst which was prepared with [Ru(CO)3 Cl2 ]2 as precursor also shows the
same type of color.
As the induction period could be removed completely, the precursor [Ru(CO)3 Cl2 ]2
seems to be a very suitable catalyst precursor for ultra-low temperature WGS
catalysis with SILP materials.

4.4.7 Combination of beneficial trends


In the next step, a combination of the optimized individual building blocks
of the SILP-WGS system was tested. For this purpose a catalyst was prepared including all optimized parameters as described previously . Figure 4.28
shows the obtained activity vs. time profiles for two SILP catalysts containing
[Ru(CO)3 Cl2 ]2 as catalyst precursor, [BMMIM]Cl as ionic liquid and -alumina
as well as boehmite as support.
The catalysts are both initially active with a very high initial TOF of 19.2
1
1
molCO2 mol1
for -alumina and 21.8 molCO2 mol1
for boehmite. ConcernRu h
Ru h

ing long-term stability, the boehmite supported catalyst showed a better TON
of 2099 after 100 h on stream compared to the -alumina supported system,
which reached 1747. This means that the boehmite supported catalyst reached
96.8% of the possible TON for the TOF as reported.
During both runs a temperature variation between TR = 100 C and 160 C
and a partial pressure variation (pCO = 0.1 bar = const) with pH2 0 varying between 0.05 bar and 0.4 bar and vice versa) was carried out in order to determine
relevant kinetic parameters. Kinetic data is summarized in Table 4.9.
The rather low activation energies indicate that possibly mass transfer limitation due to pore diffusion limitation is falsifying the experiments. Due to
limitations of the setup, notably mass flow controllers and reactor design,
a conversion of less than 10% could not be always maintained in this particular experiments. Interestingly, the boehmite supported catalyst showed

Parts of the results presented in this section were already published in Chem.Cat.Chem. [177]

4.4 Optimizations of catalyst systems

119

40

CO

= 55.7 2 kJ mol

-1

= 0.01 0.1

H2O

= 0.73 0.1

TOF / h

-1

30

20

10
-alumina
boehmite

20

E = 41.0 2 kJ mol

-1

CO

40

60

80

= 0.17 0.1

H2O

= 0.93 0.1

100

120

t / h

Figure 4.28: Activity vs.

time profile for two optimized SILP WGS catalysts

with support materials boehmite () and -alumina () including


a temperature and partial pressure variation for the determination
of effective kinetic parameters.

T = 120 C, pabs = 1 bar, pCO =

0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 . . . 5000 h1 , mcat = 4 g, precursor
[Ru(CO)3 Cl2 ]2 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM]Cl, =
0.1 mlIL ml1
pore , support material as indicated.

almost no dependency of the rate of reaction on carbon monoxide partial pressure, whereas the -alumina supported catalysts had a low dependency (see
Table 4.9 for details). In both cases a higher dependency on water partial pressure was found.
So one can give a possible kinetic rate equation similar to ones for heterogenous
catalysts [27,29] .
re f f

!

pH 2 O pH 2
EA
nCO nH2 O nH2 nCO2
= k0 exp
p p
1
p p
pCO pCO2
T CO H2 O H2 CO2


(4.4)

120

Results and Discussion

Table 4.9: Summary of kinetic data for the optimized SILP WGS catalysts. Due to
limitations of the mass flow controllers, degrees of conversion during catalytic measurements were in the range of XCO 15% T = 120 C, pabs =
1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 . . . 5000 h1 , mcat = 4 g,
precursor [Ru(CO)3 Cl2 ]2 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM]Cl,
= 0.1 mlIL ml1
pore , support material -alumina and boehmite.

Max TOFa TON(100h)

Support

Max STYa
kgCO2 m3
h1
SILP

EA b nCO
kJ mol

nH2 O

1 -alumina

19.2

1747

94.1

41.1 0.17

0.93

2 boehmite

21.8

2099

127.2

55.7 0.01

0.73

a At

120 C.

b In

the range of 100..120 C, 10 C steps.

Notably, this experiment also showed that the SILP WGS catalysts are capable
to approach equilibrium conversion as a value of 99.87 % was reached at 140 C
and water to carbon monoxide ratio of 4:1 - at this point a space-time yield of
STY 261 kgCO2 m3
h1 was realized. This level of activity was stable over
SILP
night (14 hours) with a minimal loss of activity of about 3.4%. In this case the
TOF was 35.1 h1 at stable operation under 140 C / 4:1 and after 14 hours this
value reduced to 33.9 h1 . When the catalyst was set at 140 C and a H2 O : CO
ratio of 2 : 1 this loss of activity was not observed - the catalyst achieved at
stable TOF. In all cases, no formation of by-products was observed.
In order to characterize these new and attractive catalysts further, a study in
a micro-reactor system, that can realize higher GHSV values is crucial. In the
beginning of this work, such high catalytic activities were not expected, so that
our rig was not commissioned for an optimal testing of such highly active WGS
catalysts.
The systematic development of a SILP catalyst by individual optimization
of ionic liquid, support, additive and metal complex variation resulted in
cooperative interplay of these influencing factors. The catalysts showed an
enhanced activity, which is by more than two orders of magnitude higher
compared to the initial steps with the RuCl3 on silica system. Additionally, the

Because of limitation with the mass flow controllers, the TOF values reported here at these
very high conversions (X > 90%) are falsified by the concentration gradient.

4.4 Optimizations of catalyst systems

121

induction period could be eliminated and the stability significantly enhanced,


which is quantitatively expressed by the difference between TOFmax 100 h vs.
TON(100h). Catalyst performance data for the different optimization levels
already presented in this thesis is summarized in the following Figure 4.29.

2500

TON / -

2000
1500
1000
[Ru(CO)2Cl3]2
500

RuCl3 + base
RuCl3

0
silica

-alumina

boehmite

Figure 4.29: Comparison of TOFmax 100 h (blue + red) and TON(100h) (blue) values showing activation/deactivation effects (red) for different SILP WGS
catalysts in this work. T = 120 C, pabs = 1 bar, pCO = 0.1 bar, pH2 O =
0.2 bar, GHSV = 1000, h1 , mcat = 4 g, precursor [Ru(CO)3 Cl2 ]2 , wcat =
1
0.02 gmetal g1
support , ionic liquid [BMMIM]Cl, = 0.1 mlIL mlpore , support as

indicated.

It is clearly visible, that the optimized catalyst clearly outperforms the previous
catalyst "generations" presented in previous chapters in both total activity
and stability. The silica based systems show very low TON values and even
deactivate significantly (-51% on plain RuCl3 and 50% with added base). In
the first case, this is mainly attributed to leaching. With added base, mainly
formation of inactive species, is assumed to be the main reason for catalyst
deactivation.

122

Results and Discussion

When the SILP catalyst is supported on -alumina, the deactivation is 18% and
reduces to about 9% when the organic base is added. The optimized alumina
supported system also looses about 9% of activity over the first 100h time-onstream. In all cases almost no stripping of volatile ruthenium compounds was
detected.
For the boehmite supported catalyst, the plain system with RuCl3 shows 22%
deactivation. When the base is added, the difference of TOFmax 100 h and
TON(100 h) is 39%. To be precise, this system does not suffer from deactivation,
but as the maximum TOF is reached after 100 hours only, the TOFmax 100 h
differs from the TON(100 h). In case of the optimized catalyst, the deactivation
of about 3.7% is really a very slow loss of activity, but not related to stripping
of ruthenium compounds.

4.5 Application specific characterization


After the SILP catalyst was optimized, questions of possible technical applications arised. On one hand, the restart capability was a key issue of this study.
In another set of experiments, long-term stability was analyzed. Finally, tests
at elevated pressure and with a typical synthesis gas were performed.
4.5.1 Restart behavior & condensation tolerance
For a potential use in distributed hydrogen generation scenarios, the possibility
of sudden shut-down and rapid restart is crucial. One has to distinguish between different modes of shut-down, where different parameters are changed,
namely: substrate flow (CO, H2 O), heating and if a inert flushing occurs or
even the catalyst is prone to oxidation by air. This substantially influences the
impact of a shut-down cycle on the catalyst lifetime.
If the flow of substrates just stops and heating is left on, no condensation occurs
and, in theory, the catalyst should catalyze the reaction of the remaining feed
towards the equilibrium. Basically this case equals an extrapolation to ultralong residence times, so possibly the formation of side-products is fostered.
But in case, the heating is shut-off, condensation of water could occur. For
heterogeneous catalysts, this behavior is critical, because it leads to deactiva-

4.5 Application specific characterization

123

tion [8,204] . Guo et al. reported a deactivation of about 15% in three cycles for a
copper / zinc catalyst system in daily start-up / shut-down catalyst [8] .
In order to avoid this deactivation, one could shut-down heating after flushing
with inerts, such as nitrogen in order to "dry" the catalyst.
Additionally, the presence of air leads to oxidation of the catalyst. Again, for
classical heterogeneous catalysts (copper based), this severely influences activity.
To evaluate our optimized SILP catalysts under these practically relevant conditions, a shut-down scenario was created, where just the flow of substrates
was replaced by a nitrogen flow for 1, 2 or 24 hours. In a second case, substrate
flows were stopped and the reactor was cooled down (heating off) and later
restarted. The third case involved taking the catalyst out of the reactor after
cooling down and storing it in an open glass flask in laboratory air for a week.
In all tested cases, the SILP catalysts were active after the shutdown phase without showing deactivation, loss of activity or increased side-product formation.
Interestingly, in case of the off-rig storage, the color of the catalyst slightly
changed from a lighter to a darker yellow, but activity was not influenced by
that.
Selected shutdown / activity profiles for the three different shutdown scenarios
are depicted in Figure 4.30.
After the restart, especially for scenarios involving condensation, a kind of
overshooting was observed. This is related to the fact, that the kinetic dependence on water condensation is positive, so that a higher water condensation
results in an increased overall rate of reaction. The amount of water, that is
in the SILP after such a shut-down includes the water that is bound in the
ionic liquid, condensed water in pores and inter-particle water. Due to these
different three parts of embedded water, an exact determination of the total
water amount is difficult. Within 5 hours on stream, the catalytic activity was
entirely back to the value, that was determined before the shutdown.
These experiments show impressively, that the optimized SILP WGS catalyst
is not prone to deactivation by oxidation or condensation. The oxidation
tolerance might be related to the fact, that oxygen solubility in ionic liquids

Results and Discussion

-1

124

0,4

no flow

CO2

mol

TOF / mol

CO2

TOF / mol

heating off

flush

Ru

flush

b)

Ru

-1

mol

a)
0,8

0,4

0,2

0,0

0,0
116

118

40

120

60

80

100

t / h

t / h

20

restart

c)

15

flush

in air

TOF / mol

CO2

mol

Ru

-1

after 12d

10

0
270

280

290

570

580

590

600

610

620

t / h

Figure 4.30: Shut-down and re-start behavior of a SILP WGS catalysts. a)  2h shutdown of a RuCl3 on silica catalyst (N2 flow, heating on), b)  20h shutdown after cooling down of RuCl3 on silica (stop flow, heating off), c)
re-start after 12d storage in air of a RuCl3 on -alumina. T = 120 C, pabs =
1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precursor as indicated, wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM]Cl,
= 0.1 mlIL ml1
pore , support as indicated.

is rather low [129] . So the local concentration of oxygen is low and potentially
does not lead to oxidation of the ruthenium complex forming Ru(0) black. In
general, oxidation sensitivity of dissolved Ru-complexes can be expected to be
much lower compared to activated Cu(0) surfaces.
4.5.2 Self-healing behavior
As already mentioned, all investigated SILP catalysts with RuCl3 on silica
showed significant stripping of volatile ruthenium compounds over runtime.
Temperatures above 140 C cause significant deactivation and increased strip-

4.5 Application specific characterization

125

ping. Addition of an organic base almost eliminated stripping below 150 C


as mentioned previously. The same was found for the change of the support
material from silica to aluminum oxide. Here the more polar surrounding
could obviously inhibit the formation of volatile ruthenium carbonyls very
effectively. All SILP systems for which a temperature variation was carried out
showed stable activity at 140 C except the SILP catalyst with 2 wt% ruthenium
loading on aluminum oxide with base addition. When performing temperature
variation, it was observed that at temperatures of > 140 C a deactivation took
place for a catalyst, that was prepared with the added base ethyl-dimethyl4-pyridinylammonium triflate. This was not related to stripping of volatile
ruthenium compounds, as the catalyst returned to the initial activity after the
temperature was lowered to < 140 C again. In Figure 4.31 this behavior is
depicted.
As clearly visible from Figure 4.31, the catalyst loses activity as soon as the
temperature reaches 140 C. After lowering the temperature again, the catalyst
showed an re-activating effect. Initially after the temperature was lowered, the
activity was 8.4 h1 , which is about 23% lower than the value of 10.9 h1 before
the variation. 24 hours later, the activity had re-established to 10.2 h1, which
represents just an irreversible deactivation of 7%.
This leads to the conclusion, that elevated temperature favors the formation
of an inactive resting state species, so that the amount of material, that is
catalytically active is reduced resulting in lower overall activity. At lower
temperatures, the equilibrium concentration of this inactive species is lower, so
that the active species is subsequently formed. As the regain in activity takes
about 24h, it is likely that this process requires substrates and is kinetically
hindered, which is in contrast to the deactivation at high temperatures, which
occurs fast.
The existence of this "self-healing" is indeed useful for technical operation - as
hot-spots lead to just temporarily inactive resting-state domains, that reactivate
as the hot-spot is no longer there. In literature, a self healing effect of water gas
shift catalysts has not been described previously. Exact details on what actually
happens with the SILP catalyst on a molecular basis in these self-healing cycles,
is focus of an ongoing study.

126

Results and Discussion

15

140

100

10

TOF / mol

CO2

80
60
5

T / C

mol

Ru

-1

120

40
20

0
100

110

120

130

140

150

0
160

Time / h

Figure 4.31: Self-healing behavior of a SILP WGS catalysts.

T = 120 C, pabs =

1 bar, pCO = 0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precursor RuCl3 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], =
0.1 mlIL ml1
pore , support material -alumina, added base ethyl-dimethyl4-pyridinylammonium triflate.

4.5.3 Long-term investigations


In order to study the long-term behavior of one SILP WGS catalysts, stability
tests were carried out for selected systems. Note, that the systems described
here were not the optimized systems, but representatives of an earlier generation. The reason was, that the rig had to available for a continuous 650h (4
weeks) run, which was just possible during a summer vacation. Such long
stability tests are typically carried out in industry, but rarely in academia.
The following Figure 4.32 depicts the long term behavior of catalysts on two
support materials.
The data for these supported systems was discussed previously (cf. Table 4.7),
whereas the longer term behavior is shown here. If one just examines the first

4.5 Application specific characterization

127

10

Ru

TOF / mol

CO2

mol

-1

-1

2
boehmite
-alumina

200

400

600

t / h

Figure 4.32: Long term investigation of SILP WGS catalysts with different support materials.  uses a boehmite,  uses -alumina. T = 120 C, pabs = 1 bar, pCO =
0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precursor RuCl3 ,
1
wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.1 mlIL mlpore ,

support material as indicated.

100h on stream, the boehmite supported catalyst seems perfectly stable - but
after about 110h time-on-stream an increase of activity from about TOF 6.5 h

to TOF 8.5 h1 after 250h is observed. After reaching this value, an almost
linear decrease of activity was observed. As no ruthenium was found in the PFA
tube and in the condensate, this deactivation was attributed to decomposition
of the catalyst complex itself. This is underlined by the fact, that the color of the
catalyst after reaction was dark grey to almost black which could be attributed
to formation of ruthenium black.
The 645h run of the boehmite supported catalyst reached a turn over number

of 4480, which gives an average TOF of 6.9 h 1 . Average space-time yield was
41.7 kgCO2 m3
h1 , with a maximum of 52.6 kgCO2 m3
h1 after 260h time-onSILP
SILP

128

Results and Discussion

stream.
4.5.4 Use of technical support materials
In previous runs, powder-like support materials were used. For application in
industrial environments, catalysts are typically formed in extrudates, agglomerates or monoliths [155] . This is related to the fact, that pressure drop in the
catalyst bed is significantly reduced.
In case of spherical particles pressure drop can be calculated through the
Carman-Kozeny or Ergun relation depending on the Reynolds number [183] .
Both relations involve a quadratic influence of the volume-specific surface of
the particle on the resulting pressure drop. The volume specific surface itself
is lower for larger particles as the volume of a spherical particle scale by the
power of 3, whereas the surface by the power of 2. Additionally, larger particles form more inter-particle porosity, which also reduces pressure drop.
In order to test the optimized SILP WGS catalyst system also on technical
support materials, a spherical, agglomerated -alumina with a diameter of
about 5 mm was used. The primary preparation method was analogous to
the powdered support materials. After a homogenous solution of catalyst
precursor and ionic liquid in the solvent was prepared, the agglomerated
support was added to the solution and carefully stirred. The subsequent
removal of the solvent in the rotary evaporator resulted in dry, impregnated
catalyst spheres.
These particles are fairly large compared to the powders previously used,
so the possibility to analyze distribution of ionic liquid and catalyst in the
particle arised. Catalyst spheres were cut in half and polished, before they
were introduced into a scanning electron microscope (SEM) with an energydispersive X-ray spectroscopy (EDX) unit, that enables elemental analysis [205] .
Results of a SEM-EDX analysis of the newly prepared and a used SILP WGS
catalysts are depicted in Figure 4.33.
As the measurement show, a good distribution of both catalyst and ionic liquid
was obtained, whereas the outer shell of the catalyst contains more catalytic
material than the inner part of the catalyst. Interestingly, the dispersion of both
ruthenium and ionic liquid got significantly better after a catalyst was used in

4.5 Application specific characterization

129

Figure 4.33: SEM-EDX topical analysis of a spherical SILP WGS catalyst, cut in half and
polished. Top row: fresh catalyst, Bottom row: used catalyst. Left: SEM
image of the catalyst sphere cut in half. Right: EDX map of the catalyst
sphere showing ruthenium (purple representing precursor) and sulfur
(blue representing ionic liquid) distribution. wcat = 0.02 gmetal g1
support , ionic
liquid [BMMIM][OT f ], = 0.1 mlIL ml1
pore , support material agglomerated,
spherical -alumina.

the WGS reaction, as depicted in Figure 4.33.


This underlines, that the catalyst is subject to restructuring under reaction conditions. It is worth mentioning, that a quantitative analysis of the distribution
is not adequate, because the preparation of the sample, especially the polishing
of the surface influences the absolute content of materials at the surface. Qualitative interpretation leads to the conclusion, that on one hand the distribution
of both catalyst and ionic liquid is more homogeneous over the support material after reaction, but on the other hand, that a kind of aggregation of those

130

Results and Discussion

also occurs. This means, that after reaction the catalyst shows spots with high
local concentration of ionic liquid and ruthenium, and parts where the concentration is lower. The concentration at the outer shell is obviously lower - and as
no significant amount (< 10 ppm) of ruthenium were found in the condensate,
this yield the conclusion, that the the overall amount of ruthenium is the same
in the catalyst before and after reaction, but the distribution changed.
When visibly comparing the catalyst, before and after a reaction it is also
remarkable, that depending on the position in the reactor the color slightly
differs as depicted in Figure 4.34.

Figure 4.34: Photography of a RuCl3 SILP on spherical -alumina before (left) and after
(middle) a reaction. Additionally, a catalyst is depicted, where some of
the spheres where crushed (right).

As seen from the right catalyst in Figure 4.34, even if the different spheres have
different color when compared to each other, each sphere itself has the same
color inside and outside.
In a first set of experiments, the catalyst spheres were impregnated by the incipient wetness method as described previously and introduced in the continuous
rig. A direct comparison of the powdered and agglomerated spherical alumina
reveals an increased activity as depicted in Figure 4.35. This fact directly contradicts the previous speculations (cf. subsection 4.4.2, 4.4.3 and 4.4.4), as the
use of the agglomerated material equals the increase in dparticle typically used in
reaction engineering to check for pore diffusion influences.

4.5 Application specific characterization

131

20
-3

STY = 52.6 kg

CO2

cat

-1

TOF / mol

CO2

mol

Ru

-1

15

10

STY = 99.8 kg

-3

CO2

cat

-1

5
powder
spheres

20

40

60

80

Time / h

Figure 4.35: Activity comparison of catalysts supported on powdered -alumina ()


and spherical agglomerated alumina (). T = 120 C, pabs = 1 bar, pCO =
0.1 bar, pH2 O = 0.2 bar, GHSV = 1000 h1 , mcat = 4 g, precursor RuCl3 , wcat =
1
0.02 gmetal g1
support , ionic liquid [BMMIM][OT f ], = 0.1 mlIL mlpore , support

material as indicated. Both with ethyl-dimethyl-4-pyridinylammonium


triflate.

The obtained activity-time profiles of both catalyst show a similar shape with
an induction period of about 30 hours. In case of the spherical, agglomerated
support material, the apparent turn over frequency was 18.2 molCO2 mol1
h1 ,
Ru
1
whereas the powder gave 11.9 molCO2 mol1
Ru h . So, the efficiency of the cata-

lyst supported on the spherical alumina is higher, as the measured turn-over


number outperforms the one of the powder supported catalyst. This can be
attributed to better dispersion of the active material in the catalyst as discussed
before, but it is worth mentioning, that the values determined for the catalyst
spheres are just rough estimates: As the catalyst spheres have diameter of about
5 mm, while the inner diameter of the reactor is 10 mm, the packing includes

132

Results and Discussion

lots of porosity and strong wall effects are present. Additionally, a

LR
xp

> 50

should be maintained, which would mean about 0.25m of bed length would
be required to achieve a homogenous flow pattern [186] . But these amounts
of catalysts would require such high volume flows in order to maintain low
conversions (<10%), which could not realized in our current setup [206] . So the
catalytic values presented here are possibly influenced by macroscopic effects,
flow field inhomogeneities and occurrence of temperature and concentration
gradients. For an in-depth analysis of the catalytic performance of these catalyst spheres, a specialized set-up if needed.
Because of the ratio of reactor diameter to particle diameter dxRp , which is about 2

for the spheres and 30 for the powder, a different overall porosity and apparent

density is occurring [207] . To obtain a reasonable value for the apparent density,
the latter was both approximated by correlations and measured.
First of all, the inner porosity pore and the pure solid density s of the -alumina
is needed. For -alumina, a solid density of 3.95 g cm3 was used [208] . From the
BET measurements of the spheres and the powder, that showed cumulative
pore volume of Vp = 0.51 cm3 g1 , the inner porosity p can be calculated:
pore =

Vp
Vp
= 0.668
=
Vp + Vcat Vp + mcats

(4.5)

Porosity of the random packing inside the tubular reactor can be estimated by
the model of Jeschar, that uses the mean particle diameter xp and the reactor
diameter dR [181,207] .

bed = 0, 375 + 0, 34

xp
dR

(4.6)

By combinining internal and external porosity a total porosity can be determined [183] :
total = bed + (1 bed ) pore

(4.7)

From this value, the apparent density SILP can be estimated by using the solid
density solid :
calc = (1 total ) solid

(4.8)

4.5 Application specific characterization

133

For both support materials, this estimation was performed and compared to
the metered values. Results are listed in Table 4.10.
Table 4.10: Estimated and measured values for apparent densities of SILP catalysts.

Material

xp

xp
drohr

Jascher

total

g cm

m
spheres
powder

5500

calc
3

SILP
g cm3

1.8

0.562

0.855

0.574

0.58

350 28.6

0.387

0.796

0.803

0.80

With these values, a comparison of the space-time yields of both catalysts is


possible. Although, the observed turn over frequency was higher for the spherical support, the obtained space-time yield was significantly lower. Values of
h1 and 52.6 kgCO2 m3
h1 were calculated for the powdered sup99.8 kgCO2 m3
SILP
SILP
port material and the spherical alumina respectively.
After this proof of concept for the application of technical support materials
in the SILP preparation process, the classical powders were used in all further
experiments in order to minimize mass transfer influences (wall effects) and
lower overall catalyst volume and void space in the reactor.
4.5.5 Elevated pressure influence
In a set of experiments, the influence of elevated pressure onto the catalyst
activity was investigated. For these experiments, the optimized catalyst system
as described in Chapter 4.4.7 on page 118 was selected. As a significantly
higher activity was expected under elevated pressure and our experimental
rig is limited in total flows, some preliminary estimations had to be made.
As mentioned previously, WGS itself is almost independent on total pressure but as the ionic liquid layer is involved, a solution equilibrium (Henry) has to
be taken into account, that is influencing the local concentration at the active
catalyst.
Due to limitations of the experimental rig, it was not possible to maintain
the same partial pressures as previously used at atmospheric operation mode.
Because of this, the ratio of carbon monoxide to water was maintained at the
same ratio (=2), whereas the levels itself had to be increased from pCO,ptot =1bar =
0.1 bar

pCO,ptot =10bar = 1.0 bar with a resulting increase of water partial

134

Results and Discussion

pressure from pH2 O,ptot =1bar = 0.2 bar

pH2 O,ptot =10bar = 2.0 bar. Additionally, in

a first test-experiment it was seen, that a GHSV of 1000 h1 resulted in complete


equilibrium conversion of carbon monoxide. In order to see at least some
conversion less than equilibrium it was required to increase the gas hourly
space velocity. Limitations in doing so occurred from the following aspects:

LR
xp

> 25 (better > 50) [186]

N
Vtotal
< 200 mlN min1 (back pressure valve limitation)

Variation bandwidth for changes of parameters


Minimum flow of carbon monoxide (even at pCO 1 bar, the MFC operates at about 5%)
So one could calculate the minimum required catalyst volume / mass with the
requirement of Dautzenberg [186] .
hbed,min = LR,min = xp 25 = 350m 25 = 0.875 cm

(4.9)

This gives a minimum bed height of 0.875 cm for the average particle diameter
of 0.35mm. As the catalyst bed volume can be approximated with a cylinder
volume, a minimum bed volume can be estimated according to the following
equation.
Vbed,min = hbed,min di,R = 0.875 cm 1 cm = 2.75 ml

(4.10)

With this minimum volume and the SILP density given in Table 4.10, a minimum catalyst mass can be estimated.
mSILP,min = SILP Vbed,min = 0.8 2.75 ml 2.2 g
As Dautzenberg advises that

LR
xp

(4.11)

> 50 are even better, the regular 4 g SILP are

perfectly satisfying. In order to get higher TOFs with the limitation as mentioned above, the catalyst mass was set to 2 g of SILP, as even with this low
volume almost full conversion was achieved even at highest possible volume
flows.
With these settings, a catalytic run was carried out. The resulting activity vs.
time profile is depicted in Figure 4.36.

4.5 Application specific characterization

135

40

p / bar

-1

GHSV = 2500 h

-1

-1

GHSV = 2500 h

-1

-1

GHSV = 4500 h

GHSV = 2500 h

TOF / mol

CO2

mol

Ru

-1

60

10
GHSV = 4500 h

GHSV = 2500 h

-1

80

p
p
p

20

CO

H2O

total

20

40

60

80

Time / h

Figure 4.36: Parameter variation for the optimized SILP catalyst at elevated pressure as activity-time profiles ().

T = 120 C, pabs = 10 bar, pCO =

0.5 . . . 2.0 bar, pH2 O = 1.0 . . . 2.0 bar, GHSV = 2500 . . . 4500 h1 , mcat = 2 g,
precursor [Ru(CO)2 Cl3 ]2 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM]Cl,
= 0.34 mlIL ml1
pore , support material -alumina.

In complete analogy to the low pressure experiment, the catalyst shows no


induction phase and a very high activity of 41.8 molCO2 mol1
h1 at a conversion
Ru
of XCO = 99.97 % with a resulting space-time yield of 228 kgCO2 m3
h1 (cf. enSILP
try 1 in Table 4.11). This result shows, that the newly developed SILP catalyst
can deliver equilibrium conversion at 10 bar and 120 C operating pressure. In
technical operation, a carbon monoxide content of about 10 vol% is rather high,
but this experiment shows the possibility that even these high concentrations
can be handled. Over the course of 86h on stream, the activity is constant
within 1.5%, which is in the range of the experimental error (cf. entry 1 and
6 of Table 4.11).

136

Results and Discussion

Table 4.11: Activity of an optimized SILP catalyst at p = 10 bar, T = 120 C.

GHSV

pCO

pH 2 O

TOFa

XCO

STY

h1

bar

bar

molCO2 mol1
h1
Ru

kgCO2 m3
h1
SILP

2500

1.0

2.0

41.8

99.97

228.3

4500

0.5

1.0

36.0

85.42

196.7

4500

1.0

1.0

43.0

55.82

234.7

2500

1.0

1.0

28.9

74.29

155.5

2500

2.0

2.0

59.2

76.24

323.2

2500

1.0

2.0

41.4

99.88

224.9

a Potentially

falsified due to concentration gradients.

When the gas hourly space velocity is increased up to 4500 h1 the overall
conversion of the catalyst decreases, but at equal partial pressures (cf. entry
3 and 4 of Table 4.11) the turn over frequencies and space-time yield also increases. This is possibly related to the fact, that the average concentration of
the substrates carbon monoxide and especially water is higher in case of the
lower conversion (55%) at 4500 h1 .
Interestingly, an increased partial pressure of carbon monoxide leads to a higher
activity. In comparison of entry 2 and 3 (at 4500 h1 ) the turn over frequency
1
increases from 36 to 43 molCO2 mol1
Ru h , which is not even as significant (+ 19%)

as the change at the lower GHSV. When comparing entry 1 and 5 the turn
over frequency increases from 41.8 to 59.2 which equals an increase of 41%. Of
course this is falsified by these high conversions, but an overall trend seems to
exist.
The influence of water partial pressure on activity can be also clearly seen.
Increasing the partial pressure from 1 to 2 bar (entry 1 vs. 4) lifts the turn over
frequency from 28.9 molCO2 mol1
h1 to 41.8 (+ 44%), which is in good accorRu
dance to the mechanistic model for WGS described in the theoretical part. In
case of 2 bars water partial pressure and a carbon monoxide partial pressure
of 2 bars, the space-time yield adds up to 323.2 kgCO2 m3
h1 , which is, to our
SILP
best knowledge, the highest obtained value so far for homogeneous WGS.

4.5 Application specific characterization

137

After the experiment it was observed, that the condensate had a kind of "organic" smell, so that the latter was analyzed. Unfortunately the GC-MS present
at the work group does not tolerate water, so an off-site analysis at the SdChemie AG labs in Heufeld was carried out. This rough analysis gave traces of
ethanol, propanol and butanol present, with no exact determination of components. In a subsequent experimental run, this data was successfully reproduced
with a difference of 3% with a second batch of catalyst.
4.5.6 Synthesis gas tests
After these successful test at elevated pressures, a pre-mixed reformate synthesis gas mixture was used instead of the model gas. In model synthesis gas,
the WGS catalysts showed good performance, but as no products (hydrogen
and carbon dioxide) were present in the feed, the reaction was "easier" because
the distance to equilibrium was significant. For these tests the best catalysts
were taken - optimized SILP systems as previously presented on spherical,
agglomerated alumina supports and a reformate synthesis gas from Linde Gas
was used (composition: 7% CO, 13% CO2 , 5% N2 and 75% H2 ).
As the rig was originally not designed for this mode of operation, the exact
activity and behavior of the catalyst was hard to predict at the desired conditions, some preliminary test-runs were carried out to determine a suitable
window of operation. To operate the back-pressure valve (Samson) with its
inherent valve constant kv properly, a proof-of concept simulation using Aspen
Plus was carried out to calculate resulting gas viscosities at different operation
points to double-check.
Typically a steam to gas ratio of 3 or 4 to 1 is used in industrial operations. In
case of a typical reformate synthesis gas this 4:1 ratio results in a mixed feed
stream with a partial pressure of about 2 bars for water and 1 bar of carbon
monoxide (H2 O : CO 2 : 1). Unfortunately the combination of mass-flow
controller, controller evaporator & mixer (CEM) and Samson back-pressure
valve did not result in any stable mode of operation as depicted in Figure 4.37
in the first hours on stream.
The controlled evaporator and mixer showed fluctuation in flows and unstable
evaporation resulting in the fact, that from time to time the saturation vapor

138

Results and Discussion

100
deactivation due to
CEM malfunction

T and
2

GHSV

flush

variation

60

TOF / mol

CO2

mol

Ru

-1

80

40

20

40

80

120

160

200

Time / h

Figure 4.37: Parameter variation and stability for the optimized SILP catalyst at
elevated pressure in reformate synthesis gas as activity-time profile
(). p = 10 bar, T = 120 C, steam:gas = 1:8 (1:4 in the beginning),
synthesis gas: 7% CO, 13% CO2 , 5% N2 , 75% H2 , mcat = 2 g, precursor [Ru(CO)3 Cl2 ]2 , wcat = 0.02 gmetal g1
support , ionic liquid [BMMIM]Cl,
= 0.1 mlIL ml1
pore , support spherical -alumina.

pressure of water was reached which resulted in deactivation of the catalyst.


Stable operation conditions were realized by maintaining a partial pressure ratio of 1 : 1 and a resulting steam to gas ratio of approximately 1 : 8. As shown in
Figure 4.37, a stable operation could be achieved afterwards. In the subsequent
parameter variation, reactor temperature and gas hourly space velocity were
varied to study influences. Because of the high degrees of conversion, this data
is highly influenced by concentration gradients and just represents the influence of the parameters. Data points acquired during this run are summarized
in Table 4.12.
Even so that the overall values are influenced by gradients, general trends can

4.5 Application specific characterization

139

Table 4.12: Activity data for a SILP WGS catalyst in reformate synthesis gas. p = 10 bar,
T = 120 C, steam:gas = 1:8, synthesis gas: 7% CO, 13% CO2 , 5% N2 , 75%
H2 , mcat = 2 g, precursor [Ru(CO)3 Cl2 ]2 , wcat = 0.02 gmetal g1
support , ionic liquid
[BMMIM]Cl, = 0.1 mlIL ml1
pore , support spherical -alumina.

GHSV

TOFa

XCO

STY

h1

1
molCO2 mol1
Ru h

kgCO2 m3
h1
SILP

120

950b

39.8

60.2

78.1

120

1450b

47.4

47.3

92.9

120

1900

49.4

37.0

96.9

120

2400b

50.1

30.0

98.4

120

2900

48.5

24.2

95.2

102

1900b

21.9

15.6

43.8

108

1900

25.7

18.7

50.6

130

1900b

66.7

51.2

131.9

120

1900

79.5

59.9

162.9

10 100

1900c

24.3

17.3

50.6

11 110

1900

56.3

41.4

115.2

1900

87.0

67.3

174.8

12 129
a Potentially

falsified due to concentration gradients.


after significant deactivation. See text for details.
c Determined with a fresh catalyst.
b Determined

be taken from this first run in synthesis gas. By increasing the gas hourly space
velocity from 950 up to 2900 h1 , the degree of conversion is lowered stepwise.
The turn-over frequency reaches a maximum at a GHSV of 2400 and decreases
at higher and lower values, which is the same trend as observed for the spacetime yield. If one fits the degree of conversion by a reciprocal function and
extrapolates these values to a gas hourly space velocity of 0, in theory equilibrium conversion should be observed, whereas for highest GHSV values a
conversion of zero will result. This is the result of the interplay between rate of
reaction and residence time that results in an typical chemical engineering optimization problem where a reasonable compromise has to be found, expressed
by a maximum space-time yield. These three values are plotted as a function
of GHSV in Figure 4.38. As the catalyst was obviously already prone to some

140

Results and Discussion

deactivation, the resulting optimum point of operation is falsified. From the activity values as tabulated in Table 4.12 lines 3,6-8 an apparent activation energy
of 60.9 kJ mol1 was obtained, which is slightly higher than the value previously
obtained for the optimized catalyst. But it is worth mentioning that both values
are significantly influenced by gradients, as the reactor was not operating in
true differential mode during those measurements. Trends can be obtained
here, but a complete kinetic characterization would require a complete revamp
of the rig and should be subject of future industrial optimization.

100

60

STY, X

CO

, TOF

80

40
STY / kg

20

CO

-3

CO2

CO2

1000

-1

/ %

TOF / mol

cat

-1

mol

1500

-1

Ru

2000

2500

3000

-1

GHSV / h

Figure 4.38: GHSV variation for the optimized SILP catalyst at elevated pressure in
reformate synthesis gas as activity-time profiles ( refers to space-time
yield,  refers to conversion and represents turn over frequency.). p =
10 bar, T = 120 C, steam:gas = 1:8, synthesis gas: 8% CO, 13% CO2 , 4%
N2 , 75% H2 , mcat = 2 g, precursor [Ru(CO)3 Cl2 ]2 , wcat = 0.02 gmetal g1
support ,
ionic liquid [BMMIM]Cl, = 0.1 mlIL ml1
pore , support spherical -alumina.

In a subsequent run, the stable operation window of the SILP catalyst under
investigation was directly addressed, which resulted in stable mode of oper-

4.5 Application specific characterization

141

ation. By comparing lines 1 and 6 of Table 4.12 one can see the difference in
activity between the catalyst that has been deactivated by the initial unstable
conditions and a fresh one. The complete run data series from the fresh catalyst
is depicted in Figure 4.39.

100

60

TOF / mol

CO2

mol

Ru

-1

80

40

20
T
variation

40

80
Time / h

Figure 4.39: Stability for a fresh SILP catalyst at elevated pressure in reformate synthesis gas as activity-time profiles (). p = 10 bar, T = 120 C, steam:gas
= 1:8, synthesis gas: 7% CO, 13% CO2 , 5% N2 , 75% H2 , mcat = 2 g, precursor [Ru(CO)3 Cl2 ]2 , wcat = 0.01 gmetal g1
support , ionic liquid [BMMIM]Cl,
= 0.1 mlIL ml1
pore , support spherical -alumina.

As clearly visible the catalyst shows some deactivation losing about 8% activity
in 80 hours on stream, which was not due to loss of active material by stripping
volatiles, as no ruthenium was found in the condensate. Reason for this seems
restructuring of the active material as previously discussed in Figure 4.33. In
a temperature variation between 100 and 130 C, again an apparent activation
energy was determined. Here the value yields 61.8 kJ mol1 , which is about the
same value as determined with the spent catalyst listed before in Table 4.12,

142

Results and Discussion

lines 9-12. Just during temperature variation a sudden shut-down of the rig,
caused by the power outage of the institute due to construction (Friday afternoon) resulted in a water flooded rig and even worse, loss of synthesis gas
through a normally open valve.

100
Equilibrium conversion
at 160C

80

CO

/ %

60

40
-1

SILP (GHSV = 12000 h )

20

-1

SILP (GHSV = 20000 h )


-1

Cu/ZnO (GHSV = 12000 h )


-1

Cu/ZnO (GHSV = 20000 h )

120

160

200

T / C

Figure 4.40: Conversion of a SILP catalyst ( and ) compared to a commercial


Cu/ZnO catalyst ( and ) in reformate synthesis gas as function of
temperature and GHSV. Open symbols GHSV = 12000 h1 , closed symbols GHSV = 20000 h1 . Data from Sd-Chemie AG. p = 3 bar, T =
120 . . . 200 C, steam:gas = 1:3, synthesis gas: 8% CO, 13% CO2 , 4% N2 ,
75% H2 , mcat = 0.2 g, precursor [Ru(CO)3 Cl2 ]2 , wcat = 0.02 gmetal g1
support ,
ionic liquid [BMMIM]Cl, = 0.1 mlIL ml1
pore , support -alumina.

In additional experiments at the Sd-Chemie AG facilities with a rig, that was


revamped based on the expected activity data from Erlangen, deeper insight
into the SILP WGS catalysts could be achieved. These experiments are part
of a current scale-up and feasibility study related to the commercialization of
the catalyst system developed in this thesis. Based on the results in Erlangen,

4.5 Application specific characterization

143

a joint patent was filed. As a final result, a comparison of a state-of-the-art


heterogeneous Cu/ZnO/Al2 O3 low temperature shift catalyst and the optimized
SILP WGS catalyst developed in this thesis was carried out. Results from
performance of these two catalysts at different gas hourly space velocities and
temperatures are depicted in Figure 4.40.
The newly developed SILP catalyst shows a very high activity resulting in equilibrium conversion of 99.9% at GHSV of 12000 h1 and 160 C, which equals a
1
turn over frequency of 597.4 molCO2 mol1
Ru h . Compared to that, the state-of-the

art heterogeneous catalyst showed a conversion of 37% at the same conditions.


Comparing space-time yields for the depicted case, the SILP catalyst gives
1866 kgCO2 m3
h1 , which is about three times as high as the copper based
SILP
1
1
catalyst which shows 560 kgCO2 m3
cat h . At a space velocity of 20000 h , this

SILP catalyst reaches a TOF of 616.1 molCO2 mol1


h1 (XCO = 95 %) with a STY
Ru
of 2985 kgCO2 m3
h1 , which again outperforms the industrial catalyst by a
SILP
1
factor of three (1005 kgCO2 m3
at 32% conversion). If one extrapolates the
cat h

activity of the heterogeneous catalyst down to lower temperatures, this ratio


even increases. Based on these results, a second phase of optimization was
started at the industrial labs being the direct follow-up work to the research
presented in this work.
This final result shows the competitiveness of the developed catalyst system
against the classical low temperature shift catalysts in the temperature range
of 120 to 160 C. It also justifies further development of the SILP WGS catalyst
systems into a new class commercial catalysts for low pressure and dynamic
hydrogen production scenarios.

5 Summary
5.1 Summary / Abstract
The aim of this thesis was the development and optimization of ultra low
temperature water-gas shift (WGS) catalysts (T < 180 C) by the use of the Supported Ionic Liquid Phase (SILP) approach. This concepts involves immobilization of a homogeneous WGS catalyst in an ionic liquid film that is dispersed
on a porous support material - so a kind of heterogenization is achieved enabling
continuos gas-phase reaction in fixed-bed reactors.
Literature review
& conceptual design
Screening of 51
precursors
Optimization of
ionic liquid

fixed-bed
reactor
T = 120..160C
p = 1..10 bar

Variation of
support material
Kinetic & stability
studies

H2 + CO2

Systematic SILP ULT WGS optimization

CO + H2O

Real reformate gas


& feasibility tests

Figure 5.1: Scheme summarizing research strategy presented in this thesis. Development and optimization of novel homogeneous water-gas shift catalysts
immobilized in an ionic liquid and dispersed on a porous support material
using the Supported Ionic Liquid Phase (SILP) concept.

As the water-gas shift reaction is exothermic, lower operating temperatures


favor higher carbon monoxide equilibrium conversion. For applications in distributed hydrogen generation or fuel cell scenarios where low carbon monoxide
contents are required, water-gas shift catalysts face additional new challenges,
such as tolerance for condensation, rapid start-up/shutdown and restart capability. As the objective of the presented work was development of a commercially feasible CO clean-up technology, the main focus of this work was taken
on the following aspects:
Selection of a suitable catalyst precursor
Starting with the homogeneous metal complexes already known from literature as potential WGS catalysts, the immobilization as SILP catalysts on silica1

144

5.1 Summary / Abstract

145

a systematic screening was carried out. Transition metal chlorides and carbonyls such as ruthenium, iridium and osmium carbonyls were tested. In a
collaboration with the TU Munich novel catalyst precursors were synthesized
and tested upon their WGS activity.
In summary, 51 different precursors were screened upon their water-gas shift
activity in a total of 5700 hours time-on-stream continuous catalytic testing
at 120 C / 1bar including reproducibility tests. 28 ruthenium based precursors were screened and showed in general highest activity. 6 palladium, 4
rhodium and 3 precursors for iridium, copper, molybdenum were also tested.
Additionally, two osmium and iron precursors were also investigated.
Amongst the tested ruthenium complexes, the simple RuCl3 precursor was one
the most active ones, showing a rather long induction period of more than
1
24 h after which a final activity of 0.9 molCO2 mol1
(120 C / 1 bar / 0.1 bar
Ru h

CO, 0.2 bar H2 O) was reached. The best results in terms of induction period
and activity were obtained with novel ruthenium complexes in which anionic
Ru-complexes were paired with imidazolium cations, whose activity exceeded
1
2 molCO2 mol1
Ru h . This first generation of SILP WGS catalysts showed loss of

volatile ruthenium complexes by means of gas-phase stripping / sublimation,


that was successfully tackled by tuning system parameters.
These first results indicated that the SILP concept offers a very efficient way
to screen transition metal complexes for catalytic activity under continuous
steady-state conditions. In contrast to batch experiments, this method provides information on catalyst formation and deactivation phenomena. So a
selection of the most promising candidates and structural motives for the further development of WGS catalysts is much more reliable and effective.
Systematic optimization of the catalyst building blocks
As SILP catalysts consist of several building-blocks, namely catalyst or precursor, ionic liquid and support material, an independent optimization of those
can be performed. Additionally, parameters of these building blocks such
as catalyst and ionic liquid loadings, support parameters such as pore volume, internal surface area or even basicity can be optimized in order to obtain
an optimized catalyst. As starting point for the optimization a SILP catalyst
system consisting of RuCl3 (0.02 gRu g1
support ) in the ionic liquid [BMMIM][OT f ]

146

Summary

(0.1 mlIL ml1


pore ) on silica was taken.
A variation of the support material showed, that more basic support materials
such as -alumina or boehmite show superior activity compared to silica. To
confirm beneficial effect of basicity, additional experiments with an added weak
organic base added to the ionic liquid film were performed. These attempts
confirmed the positive influence of base addition on activity.
In a variation of ionic liquids, the ionic liquid [BMMIM]Cl showed a better
long-term stability compared to the initially used triflate. A follow-up variation
of the pore-filling grade yielded an optimum loading of 0.1 for silica and
0.34 for alumina. The catalyst metal loading was also optimized yielding an
optimum of 0.02 gRu g1
support .
In order to get rid of the rather long induction period, spectroscopical measurements of fresh and used SILP catalysts were performed. The results led to
the conclusion that the dimeric [Ru(CO)3 Cl2 ] species is formed in the activation
phase and is possibly an active or resting state species in the catalytic cycle. A
SILP catalyst prepared with this precursor showed indeed no induction period.
Combination of the optimized building blocks yielded in a level of activity
h1 . This represents an increase of
with turn-over frequency of 20 molCO2 mol1
Ru
more than an order of magnitude compared to the results of the first catalyst screening. Within these experiments, effective kinetic parameters such
as apparent activation energy and partial reaction orders were determined by
means of temperature and partial pressure variation. It is worth mentioning,
that the optimized catalyst was also able to yield equilibrium conversion of
99.8% without formation of by-products.
Application specific characterization and benchmarking
In order to evaluate suitability of the newly developed SILP WGS catalysts for
technical operations, long-term experiments up 700 hours on stream were performed showing good long term stability. Additional experiments at elevated
pressure were conducted to evaluate this influence with the result of increased
activity expressed by STY and TOF. This was attributed to increase substrate
solubility in the ionic liquid film.
As the previous experiments were conducted with powder-like support materials, the application of the SILP concept towards technical support materials

5.1 Summary / Abstract

147

such as agglomerated spherical alumina (dp = 4 mm) was evaluated. By SEMEDX measurements, the distribution of ionic liquid and catalyst was measured,
showing good dispersion, in particular after the catalytic experiments. The obtained SILP catalyst were also successfully tested in WGS, giving better activity
and slightly lowered space-time yields.
In a set of experiments, re-start behavior and condensation tolerance of the
newly developed catalysts was tested.

In all cases the catalyst could be

restarted, even after a 10 day storage in air. This opens exciting new application perspectives and represents a unique selling point vs.

classical

CuO/ZnO/Al2 O3 systems
All homogeneous catalysts described so far, were tested with ideal feeds containing only the substrates needed for the WGS. Reformate synthesis gas feeds,
which are realistic for scenarios, such as hydrogen generation for fuel-cell applications or biogas clean-up, also contain other components like hydrogen,
carbon dioxide, nitrogen, methane or even sulfur-bearing impurities. The best
catalyst system were tested in such a reformate syngas feed containing 75%
H2 , 8% CO, 13% CO2 , 4% N2 and a steam to gas ratio of 3:1 both in the in-house
rig and in cross-tests at the industrial partner Sd-Chemie AG in Heufeld. The
activity of the newly developed SILP WGS catalyst reached about 90% conversion at 140 C and a GHSV of 12000 h1 , which is a higher values, than the
commercial catalyst can obtain at 180 C and the same GHSV.
At 160 C the optimized SILP catalyst reached a conversion of 99.8%, which
equals equilibrium conversion and a corresponding turn over frequency of
1
597 molCO2 mol1
Ru h . Comparing space-time yields, the SILP catalyst achieved

about 1866 kgCO2 m3


h1 in these experiments, whereas the industrial state of
SILP
1
the art catalyst obtained 560 kgCO2 m3
cat h . One should mention that the indus-

trial CuO/ZnO/Al2 O3 catalyst was of course not developed for this synthesis-gas
composition and temperature range. Nevertheless the very promising results
obtained with the new SILP catalysts under reformate syngas conditions show
the great potential of this concept for commercialization in the near future.

148

Summary

5.2 Zusammenfassung / Kurzfassung


Ziel dieser Arbeit war die Entwicklung und Optimierung von Niedertemperatur (T < 180 C) Wassergas-Shift (WGS) Katalysatoren durch die Anwendung
des Supported Ionic Liquid Phase (SILP) Konzepts. Dieser Ansatz beinhaltet
die Immobilisierung eines homogenen Katalysators in einer ionischen Flssigkeit, welche auf einen hochporsen Trgermaterial dispergiert ist. Dadurch
wird eine Art heterogenisierung des homogenen Katalysators erreicht, welche
die Anwendung in kontinuierlichen Gasphasenreaktionen in Festbettreaktoren

CO + H2O

Literaturrecherche &
Konzeptentwicklung
Screening von 51
Katalysatoren
Optimierung der
ionischen Flssigkeit

fixed-bed
reactor
T = 120..160C
p = 1..10 bar

Variation des
Trgermaterials
Kinetische Messung
& Stabilittstest

H2 + CO2

Reale Reformat-Gas
& Re-start Versuche

Systematische Entwicklung der SILP Systeme

ermglicht.

Abbildung 5.2: Zusammenfassung der Arbeitsstrategie in dieser Dissertation. Entwicklung und Optimierung neuartiger Supported Ionic Liquid Phase
(SILP) Katalysatoren, in welchen ein homogener WGS Katalysator in
einer ionischen Flssigkeit immobilisiert und auf einem porren Trger dispergiert wird.

Da die Wassergas-Shift Reaktion exothermer Natur ist, fhren niedrigere Betriebstemperaturen zu einem hheren Gleichgewichtsumsatz bezogen auf Kohlenstoffmonoxid. Fr Anwendungen in Bezug auf dezentrale Wasserstofferzeugung oder Brennstoffzellen, wo niedrige Kohlenstoffmonoxidrestkonzentrationen bentigt werden, sind an WGS Katalysatoren noch weitere neue Anforderungen gestellt: Toleranz gegenber Kondensation, gutes An- und Abfahrverhalten in instationrem Betrieb sowie Wiederanfahr-Mglichkeit. Zur Entwick-

5.2 Zusammenfassung / Kurzfassung

149

lung einer konomisch sinnvollen/interessanten, neuartigen Klasse von WGS


Katalysatoren, wurde in dieser Arbeit besonderen Wert auf den folgenden
Aspekten gelegt:
Auswahl geeigneter Katalysatoren
Beginnend mit einer Literaturrecherche nach potentiellen homogenen Katalysatoren fr die WGS wurde die Immobilisierung dieser als SILP Materialien
auf Silica durchgefhrt. Im anschlieenden systematischen Screening wurden
bergangsmetallchloride und -carbonyle auf ihre WGS Aktivitt berprft.
Mit den Ergebnissen aus diesem Screening wurden in Zusammenarbeit mit
der TU Mnchen neuartige Katalysatoren entwickelt.
Zusammenfassend wurden 51 verschiedene Katalysatoren in rund 5700 h
Versuchszeit im kontinuierlichen Festbettreaktor bei 120 C und 1 bar Betriebsdruck auf deren WGS Aktivitt in Form von SILP Katalysatoren berprft. Es
wurde 28 Ruthenium-, sechs Palladium-, vier Rhodium- und je drei Katalysatoren auf Iridium-, Kupfer- und Molybdn-, sowie je zwei auf Osmium und
Eisen-Komplexe getestet.
Von den untersuchten Systemen zeigten die Ruthenium-Systeme die besten
Ergebnisse, wobei das einfache RuCl3 hier besonders attraktiv erschien. Allerdings zeigte es eine Induktionsphase von mehr als 24 h nach der eine maximale
1
Aktivitt von 0.9 molCO2 mol1
(120 C / 1 bar / 0.1 bar CO, 0.2 bar H2O) erzielt
Ru h

wurde. Vielversprechende Ergebnisse in Bezug auf Aktivierungsphase und


Aktivitt zeigten neuartige Ruthenium-Komplexe, in welchen anionisches Ruthenium mit Imidazolium-Kationen gepaart war: Hier wurden Aktivitten von
1
ber 2 molCO2 mol1
erreicht.
Ru h

Diese ersten Resultate zeigen, dass sich das SILP Konzept als schneller und effizienter Weg zum Screening von homogenenen Katalysatoren unter stationren
Betriebsbedingungen eignet. Im Gegensatz zu instationren Experimenten in
Satzreaktoren geben die Experimente in kontinuierlichem Betrieb zustzlich
Aufschlu ber Anfahrverhalten und Stabilitt. Hierdurch ist eine Auswahl
und Bewertung von Katalysatoren belastbarer und effektiver.
Systematische Optimierung der SILP Katalysatorbausteine
Da ein SILP Katalysator aus einzelnen Bausteinen (Katalysator, ionischer Flssigkeit (IL) und Trgermaterial) besteht, liegt es nahe, diese unabhngig von-

150

Summary

einander zu optimieren. Zustzlich sind jedem dieser Bausteine entsprechende


Parameter wie z.B. Katalysator- oder IL-Beladung, Porenvolumen und innere Oberflche des Trgermaterial oder auch Basizitt zugeordnet, die ebenso
variiert und angepasst werden knnen. Als Startpunkt fr die Optimierung
wurde ein System bestehend aus dem Katalysator RuCl3 (0.02 gRu g1
Trger ) in der
ionischen Flssigkeit [BMMIM][OT f ] (0.1 mlIL ml1
Pore ) auf Silica festgelegt.
Eine Variation der Trgermaterialien zeigte, dass diese mit erhhter Basizitt
(z.B. -Alumina oder Bhmite) im Vergleich zu Silica deutlich erhhte katalytische Aktivitten aufweisen. Um den positiven Effekt der Basizitt auf
die endgltige Aktivitt zu besttigen, wurden Experimente mit Zusatz einer schwachen organischen Base im SILP Katalysator durchgefhrt. Auch in
diesen Experimenten wurde die Aktivittssteigerung durch erhhte Basizitt
beobachtet.
In der Variation der ionischen Flssigkeiten zeigte [BMMIM]Cl eine bessere
Langzeitstabilitt als das ursprnglich verwendete Triflat. Die optimale Beladung in Form des Porenfllgrades liegt hierbei abhngig vom Trgermaterial
bei 0.1 fr Silica und 0.34 fr Alumina. Bei der Anpassung der Katalysatorbeladung ergab sich ein Optimum bei 0.02 gRu g1
support .
Um die verhltnismig lange Induktionsperiode zu verkrzen, wurden FTIR Messungen durchgefhrt, bei denen neu hergestellte mit benutzten SILP
Katalysatoren verglichen wurden. Beim Vergleich mit Referenzspektren ergab
sich, dass offensichtlich das dimeren [Ru(CO)3 Cl2 ] in der Induktionsphase gebildet wird. Ein SILP Katalysator der mit [Ru(CO)3 Cl2 ] als aktive Komponente
hergestellt wurde, zeigte in der Tat keinerlei Aktivierungsphase.
Mit diesen unabhngig voneinander angepassten Bausteinen wurde ein opti1
mierter Katalysator hergestellt, welcher eine Aktivitt von 20 molCO2 mol1
Ru h

zeigte. Im Vergleich zu der ersten Generation ist das eine Steigerung um


mehr als eine Grenordnung. Auch konnte der Gleichgewichtsumsatz von
99,8% ohne die Bildung von Nebenprodukten nachgewiesen werden. Durch
Temperatur- und Partialdruckvariation der Substrate wurden zustzlich die
effektiven kinetischen Parameter wie Aktivierungsenergie und partielle Reaktionsordnungen ermittelt.

5.2 Zusammenfassung / Kurzfassung

151

Anwendungsspezifische Charakterisierung
Fr eine konomische Betrachtung der SILP Katalysatoren wurden LangzeitVersuche mit ber 700 Betriebsstunden durchgefhrt, bei denen eine sehr gute
Langzeitstabilitt ermittelt wurde. In nachfolgenden Experimenten wurde zudem das Verhalten bei erhhten Betriebsdrcken untersucht. Dabei ergab sich,
dass erhhter Betriebsdruck in ebenso erhhten Raum-Zeit Ausbeuten und
Aktivitten resultiert, was der erhhten Substratlslichkeit im IL-Film zugerechnet wird.
Alle bisherigen Experimente nutzten feinkrnige Trgermaterialien, die fr
einen technischen Einsatz nur beschrnkt geeignet sind. Daher wurde eine
bertragung der entwickelten Katalysatorsysteme auf technische Trger, wie
z.B. sphrisches Alumina, berprft. In einer REM-EDX Analayse wurde eine
gute Verteilung von Katalysator und IL ermittelt. Im nachfolgenden Katalytischen Test ergaben sich verbesserte Aktivitten aber etwas niedrigere RaumZeit Ausbeuten.
Weitergehend wurde das Wiederanfahrverhalten und die Toleranz gegenber
Wasserkondensation der neuentwickelten Katalysatoren berprft. In allen
Fllen konnten die Katalysatoren ohne Aktivittsverlust wieder genutzt werden. Auch ein Katalysator, welcher mehr als 10 Tage in der Luft gelagert wurde
zeigte keine Deaktivierung. Diese Aspekte sind im Vergleich zu klassischen
CuO/ZnO/Al2 O3 Katalysatoren ein deutlicher Vorteil.
In allen in der Literatur beschriebenen homogenen Katalysatoren wurden
diese lediglich mit idealisierten Substratstrmen getestet. Fr realistische Betrachtung der Katalysatoren wurden daher Versuche in einem realistischen
Reformat-Synthsegas, wie es z.B. fr Brennstoffzellen-Anwendungen oder in
der Biogas-Aufreinigung zu erwarten ist, durchgefhrt. Die besten Katalysatorsysteme wurden nun in einem Reformat-Synthesegas mit 75% H2, 8% CO,
13% CO2 , 4% N2 und einem Dampf zu Gas Verhltnis von 3:1 sowohl im Laborreaktor als auch bei Kreuzversuchen beim Industriepartner Sd-Chemie
AG getestet. Die SILP WGS Katalysatoren zeigten 90% Umsatz bei 140 C und
einer GHSV von 12000 h1 , was hher ist, als ein kommerzieller Katalysator
bei 180 C und identischer GHSV erzielen kann.
Bei 160 C erreichte der optimierte SILP Katalysator einen Umsatzgrad von

152

Summary

99,8% (Gleichgewichtsumsatz) bei einer korrespondierenden Aktivitt von


597 molCO2 mol1
h1 . Im Vergleich der Raum-Zeit-Ausbeuten bertrifft der SILP
Ru
Katalysator in diesen Experimenten mit ber 1866 kgCO2 m3
h1 die
SILP
1
560 kgCO2 m3
des industriellen CuO/ZnO/Al2 O3 Katalysators deutlich. Diese
cat h

letzten vielversprechenden Ergebnisse zeigen das Potential der in dieser Arbeit


neu entwickelten SILP WGS Katalysatoren auch unter Reformat-Synthesegas
Bedingungen und ebnen den Weg hin zu einer kommerziellen Nutzung in der
nahen Zukunft.

Appendix
A Calibration curves
A.1 Mass flow controller - carbon monoxide
15

-1

10
/ ml min

real

= V

mfc

* 1.1871

real

R = 0.9958

measured values
linear fit

10
V

mfc

/ ml min

15

-1

Figure 0.3: Mass flow controller calibration for carbon monoxide. p = 1 bar(atm).

A.2 Mass flow controller - carbon dioxide


15

real

/ ml min

-1

10

real

= V

mfc

* 1.1361

R = 0.9824

measured values
linear fit

5
V

mfc

10
-1

/ ml min

Figure 0.4: Mass flow controller calibration for carbon dioxide. p = 1 bar(atm).

II

Appendix

A.3 Mass flow controller - nitrogen

50

40

real

= V

mfc

* 1.0154

real

/ ml min

-1

R = 0.9976

30

20

10
measured values
linear fit

10

20

30
V

mfc

40

50

60

-1

/ ml min

Figure 0.5: Mass flow controller calibration for nitrogen. p = 1 bar(atm).

250

200

real

= V

mfc

* 1.007

real

/ ml min

-1

R = 0.9973

150

100

50
measured values
linear fit

50

100

150
V

mfc

200

250

-1

/ ml min

Figure 0.6: Mass flow controller calibration for nitrogen. p = 10 bar(atm).

A Calibration curves

III

A.4 Micro Gas chromatograph

2,5x10

CO2

= x

CO2

* 1.66975x10 + 588954

R = 0.9997
7

1,5x10

A / V s

2,0x10

1,0x10

CO

= x

CO

* 1.27644x10 + 1.76875x10

R = 0.9995
6

5,0x10

carbon monoxide
carbon dioxide

0,0
0,00

0,05

0,10

0,15

x / i

Figure 0.7: Gas chromatograph calibration for carbon monoxide and carbon monoxide.

IV

Appendix

B Acronyms
[BMIM]

1-Butyl-3-methylimidazolium

[BMMIM]

1-Butyl-2,3-dimethylimidazolium

[EMIM]

1-Ethyl-3-metylimidazolium

GC

Gas-chromatography

GHSV

Gas hourly space velocity

-GC

micro gas-chromatograph

IL

Ionic liquid

IM

Imidazolium heterocycle

[OT f ]

Trifluoromethanesulfonate (Triflate)

PFA

polyflouroacetate polymer

PFTR

Plug-Flow Tubular Reactor

SAPC

Supported Aqueous Phase Catalysis

SILP

Supported Ionic Liquid Phase

SLPC

Supported Liquid Phase Catalysis

[NT f2]

Bis(trifluoromethyl)sulfonylimid (BTA)

TOF

Turn-Over-Frequency

C Nomenclature
Latin Letters
n

Molar flow

Gas constant

Ai

Peak area

Concentration

D
dpore
EA

mol
s
J
molK

N/T

N/L3

Diffusion coefficient

mol
l
m2
s

L2 /T

Pore diameter

nm

Activation energy

kJ
mol

Rate coefficient

k0

Collision factor

s1

1/T

Molar mass

kg
mol

M/N

Nomenclature

Mass

kg

Molar amount

mol

Pressure

bar

M/TL2

L2 /M

re f f
S

Effective rate of reaction


Selectivity

SBET

BET surface area

m2 g1

STY

Space time yield

1
kgCO2 m3
cat h

T
TOF
V
Vpore

Temperature
Turn over frequency
Volume
specific pore volume

Weight fraction

Degree of conversion

Molar fraction

x, y, z

Coordinates

K
molCO2 mol1
h1
metal
m

m3
kg
gi g1
re f

M/L3 T

M/MT
L3
L3 /M
M/M

J
mol

ML/T2 N

Greek Letters

Pore filling grade

Layer thickness

Activity coefficient

Calibration factor

Chemical potential

Peak width

Density

Residence time

Dimensionless time

Porosity

Superscripts
, , Partial reaction order

s
kg
m3

T
M/L3

VI

Nomenclature

Subscripts
0
i, j, k

Initial
Species / Component

D List of Schemes
1.1

The water-gas shift reaction . . . . . . . . . . . . . . . . . . . . .

2.1

The water-gas shift reaction . . . . . . . . . . . . . . . . . . . . .

2.2

The redox and formate mechanism. . . . . . . . . . . . . . . . . .

2.3

Proposed base-catalysed WGS reaction scheme by Yoneda [43] . .

14

[44]

2.4

Proposed base-catalyzed WGS reaction scheme by Royen

. . .

14

2.5

Proposed base-catalysed WGS reaction scheme by Elliott [46] . . .

15

2.6

[48]

. 16

Proposed base-WGS catalyzed reaction scheme by Schuchard

[10]

2.7

Proposed WGS catalyzed reaction scheme for iron carbonyl

2.8

Proposed WGS catalyzed reaction scheme for triruthenium dodecacarbonyl [50] . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.9

18
18

Proposed WGS catalyzed reaction scheme for ruthenium carbonyl [51] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

20

2.10 Revised WGS reaction scheme for ruthenium carbonyls [11] . . .

21

2.11 Proposed scheme for the photo-catalyzed water-gas shift reaction using ruthenium bipyridines [64] . . . . . . . . . . . . . . . . .

22

2.12 Proposed scheme for the water-gas shift reaction using ruthenium bipyridines [68] . . . . . . . . . . . . . . . . . . . . . . . . . .

23

2.13 Acidic WGS reaction scheme by Fachinetti. . . . . . . . . . . . .

25

4.1

Generalized WGS catalyzed reaction scheme for metal carbonyls


in alkaline environment(cf. section 2.1.5.2) [5] . . . . . . . . . . . .

99

E List of Figures
2.1

Pathways from resources towards hydrogen processes. . . . . .

E List of Figures

VII

2.2

WGS Equilibrium conversion as function of pH2 O /pCO and T . . .

2.3

The two-step industrial WGS setup. . . . . . . . . . . . . . . . .

2.4

Bi-functional catalysis study by Thinon . . . . . . . . . . . . . .

12

2.5

Typical ionic liquid anions and cations. . . . . . . . . . . . . . .

30

2.6

Effect of alkyl chain length on CO solubility . . . . . . . . . . . .

36

2.7

Immobilization concepts for homogeneous catalysts.

. . . . . .

41

2.8

SILP Scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

45

2.9

SILP Preparation in a fluidized bed. . . . . . . . . . . . . . . . .

47

3.1

SILP preparation scheme. . . . . . . . . . . . . . . . . . . . . . .

57

3.2

Photo of the experimental rig . . . . . . . . . . . . . . . . . . . .

59

3.3

Flowsheet of the experimental rig . . . . . . . . . . . . . . . . . .

60

3.4

Chromatograms of a typical injection during a WGS run in the


applied two-column Micro-GC (Varian CP 4900). . . . . . . . . .

63

4.1

Work strategy for this dissertation. . . . . . . . . . . . . . . . . .

70

4.2

Reproducibility tests with SILP catalysts . . . . . . . . . . . . . .

72

4.3

Comparison of a SILP catalyst with / without Ionic Liquid . . .

74

4.4

Activity of a ShiftMax240 over time at varying temperatures . .

76

4.5

Colorful different SILP WGS catalysts. . . . . . . . . . . . . . . .

79

4.6

Activity vs. time-on-stream curves for various metal chlorides .

81

4.7

Activity vs. time-on-stream curves for various metal carbonyls

84

4.8

Activity vs. time-on-stream plots for pyridine modified ruthenium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.9

85

Activity vs. time-on-stream curves for cationic ruthenium complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

89

4.10 Activation and Deactivation of a ruthenium catalyst. . . . . . . .

90

4.11 FT-IR spectrum of volatile ruthenium compounds. . . . . . . . .

91

4.12 PFA tubes colored by volatile ruthenium compounds. . . . . . .

92

4.13 SILP catalyst before, during and after reaction. . . . . . . . . . .

93

4.14 SILP catalyst building blocks . . . . . . . . . . . . . . . . . . . .

94

4.15 Variation of the support material. . . . . . . . . . . . . . . . . . .

96

4.16 Single-run determination of kinetic parameters. . . . . . . . . .

97

4.17 Actity increase by addition of an organic base. . . . . . . . . . . 100


4.18 Arrhenius plot for a boehmite + organic base system. . . . . . . 103

VIII

List of Figures

4.19 Thermogravimetric analysis of SILP catalysts with and without


organic base. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4.20 Variation of the pore filling grade. . . . . . . . . . . . . . . . . . 105
4.21 Arrhenius plots for catalysts with different pore fillings. . . . . . 106
4.22 Scheme for ionic liquid distribution in SILP catalysts. . . . . . . 107
4.23 Conversion of SILP catalysts in reformate syngas with different
ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
4.24 Variation of the ionic liquid. . . . . . . . . . . . . . . . . . . . . . 112
4.25 Stability of catalysts with different ionic liquids in synthesis gas. 114
4.26 IR spectra from fresh and used SILp catalysts. . . . . . . . . . . . 116
4.27 Photography of SILP catalysts with different precursors. . . . . 117
4.28 Time-on-stream profiles for optimized SILP WGS catalysts. . . . 119
4.29 Comparison of TOF*100h and TON(100h) values for different
SILP catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.30 Shut-down and re-start behavior of a SILP WGS catalysts. . . . 124
4.31 Self-healing of a SILP WGS catalysts. . . . . . . . . . . . . . . . . 126
4.32 Long term experiments with different support materials. . . . . 127
4.33 SEM-EDX analysis of a spherical SILP WGS catalyst. . . . . . . . 129
4.34 Photography of spherical SILP catalysts. . . . . . . . . . . . . . . 130
4.35 Activity comparison of spherical and powder alumina. . . . . . 131
4.36 Parameter variation at 10bar. . . . . . . . . . . . . . . . . . . . . 135
4.37 Stability run for a SILP catalyst in synthesis gas. . . . . . . . . . 138
4.38 GHSV variation for a SILP catalyst in synthesis gas. . . . . . . . 140
4.39 Stability run for a fresh SILP catalyst in synthesis gas. . . . . . . 141
4.40 Conversion of a SILP catalyst vs. Cu/ZnO at different GHSV
values and temperatures. . . . . . . . . . . . . . . . . . . . . . . . 142
5.1

Summarizing Scheme. . . . . . . . . . . . . . . . . . . . . . . . . 144

5.2

Zusammenfassung der Arbeitsstrategie. . . . . . . . . . . . . . . 148

0.3

Mass flow controller calibration for carbon monoxide. . . . . . .

0.4

Mass flow controller calibration for carbon dioxide. . . . . . . .

0.5

Mass flow controller calibration for nitrogen. . . . . . . . . . . .

II

0.6

Mass flow controller calibration for nitrogen. . . . . . . . . . . .

II

0.7

GC calibration curves. . . . . . . . . . . . . . . . . . . . . . . . .

III

List of Tables

IX

F List of Tables
2.1

WGS activity of metal carbonyls reported by Pettit . . . . . . . .

17

2.2

WGS activity of metal carbonyls reported by Ford . . . . . . . .

19

2.3

WGS activity of supported ruthenium bipyridines by Pakkannen. 28

2.4

Typical property ranges of ionic liquids. Modified from own


publication [99] and references therein. . . . . . . . . . . . . . . .

32

3.1

Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

48

3.2

Homogeneous catalysts used in this work. . . . . . . . . . . . .

49

3.3

Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

54

3.4

Organic bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

55

3.5

Support material properties . . . . . . . . . . . . . . . . . . . . .

56

3.6

Typical properties of a SILP catalyst. . . . . . . . . . . . . . . . .

58

3.7

GC Method details. . . . . . . . . . . . . . . . . . . . . . . . . . .

62

4.1

Specific activity values of a ShiftMax 240 . . . . . . . . . . . . . .

77

4.2

Specific activity of supported gold nano particles . . . . . . . . .

78

4.3

Comparative study on the WGS activity of literature known


precursors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

80

4.4

Comparative study on the WGS activity of various metal chlorides 82

4.5

Comparative study on the WGS activity of novel Pd and Rh


precursors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

87

4.6

Comparative study on the WGS activity of novel Ru precursors.

88

4.7

Activity and kinetic parameters of catalysts with different supports and basicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

4.8

Variation of the RuCl3 loadings. . . . . . . . . . . . . . . . . . . . 111

4.9

Kinetic data for the optimized SILP catalysts. . . . . . . . . . . . 120

4.10 Estimated and measured values for apparent densities of SILP


catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
4.11 Activity of an optimized SILP catalyst at 10 bar. . . . . . . . . . 136
4.12 Activity data for a SILP catalyst in synthesis gas. . . . . . . . . . 139

List of Tables

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