Cross-Metathesis of Propene Using Supported Ionic Liquid Phase (SILP) Catalysts [Elektronische Ressource] / Soebiakto Loekman. Betreuer: Peter Wasserscheid

De
Cross-Metathesis of Propene Using Supported Ionic Liquid Phase (SILP) Catalysts Kreuzmetathese von Propen mittels Supported Ionic Liquid Phase (SILP) Katalysatoren Der Technischen Fakultät der Universität Erlangen-Nürnberg Zur Erlangung des Grades DOKTOR-INGENIEUR Vorgelegt von Soebiakto Loekman Aus Surabaya, Indonesien Erlangen, 2011 Als Dissertation genehmigt von der Technischen Fakultät der Universität Erlangen-Nürnberg Tag der Einreichung: 27. Oktober 2010 Tag der Promotion: 29. Juli 2011 Dekan: Prof. Dr.-Ing. habil. Reinhard German 1. Berichterstatter: Prof. Dr. rer. nat. Peter Wasserscheid 2. Berichterstatter: Prof. Dr.-Ing. habil. Karl-Ernst Wirth For my family Contents Acknowledgment................................................................................................................... V Kurzfassung ........................................................................................................................ VII Abstract................................................................................................................................ IX 1 Introduction................................................................................................................ 1 2 Theory .......................................................................................................................
Publié le : samedi 1 janvier 2011
Lecture(s) : 32
Source : D-NB.INFO/1016569165/34
Nombre de pages : 170
Voir plus Voir moins


Cross-Metathesis of Propene Using
Supported Ionic Liquid Phase (SILP)
Catalysts

Kreuzmetathese von Propen mittels Supported
Ionic Liquid Phase (SILP) Katalysatoren

Der Technischen Fakultät der
Universität Erlangen-Nürnberg
Zur Erlangung des Grades

DOKTOR-INGENIEUR


Vorgelegt von
Soebiakto Loekman
Aus Surabaya, Indonesien


Erlangen, 2011


















Als Dissertation genehmigt von
der Technischen Fakultät der
Universität Erlangen-Nürnberg


Tag der Einreichung: 27. Oktober 2010
Tag der Promotion: 29. Juli 2011
Dekan: Prof. Dr.-Ing. habil. Reinhard German
1. Berichterstatter: Prof. Dr. rer. nat. Peter Wasserscheid
2. Berichterstatter: Prof. Dr.-Ing. habil. Karl-Ernst Wirth

















For my family

Contents
Acknowledgment................................................................................................................... V
Kurzfassung ........................................................................................................................ VII
Abstract................................................................................................................................ IX
1 Introduction................................................................................................................ 1
2 Theory ....................................................................................................................... 3
2.1 Propene..................................................................................................................... 3
2.2 Metathesis ................................................................................................................. 7
2.2.1 Overview.................................................................................................................... 7
2.2.2 Heterogeneous metathesis catalysts ......................................................................... 8
2.2.3 Homogeneous metathesis catalysts........................................................................... 9
2.2.4 Metathesis mechanism .............................................................................................12
2.2.5 Catalyst deactivation mechanisms............................................................................14
2.2.6 Thermodynamic aspects of metathesis.....................................................................18
2.2.7 Immobilization of homogeneous metathesis catalysts...............................................22
2.2.7.1 Aqueous multiphase systems ...................................................................................22
2.2.7.2 Ionic liquid multiphase systems ................................................................................24
2.2.7.3 Solid supports...........................................................................................................28
2.3 Supported Ionic Liquid Phase (SILP) technology ......................................................35
2.3.1 Concept and applications..........................................................................................35
2.3.2 SILP metathesis........................................................................................................37
3. Experimental.............................................................................................................39
3.1. SILP catalyst preparation..........................................................................................39
3.2 Batch autoclave experiments....................................................................................40
3.3 Continuous gas-phase experiments..........................................................................41
3.4 Thermogravimetry.....................................................................................................49
4. Results and discussion .............................................................................................50
4.1 Batch autoclave experiments....................................................................................50
I 4.2 Continuous fixed-bed gas-phase experiments with SILP catalyst..............................55
4.2.1 Reproducibility ..........................................................................................................55
4.2.2 Influence of air and moisture.....................................................................................56
4.2.3 Influence of feedstock purity .....................................................................................57
4.2.4 Activity of non-supported catalyst..............................................................................58
4.2.5 Temperature variation...............................................................................................59
4.2.6 Support material variation .........................................................................................63
4.2.7 Variation of catalyst precursor...................................................................................66
4.2.8 Variation of ionic liquid..............................................................................................70
4.2.8.1 Anion influence .........................................................................................................70
4.2.8.2 Cation influence........................................................................................................73
4.2.8.3 Variation of ionic liquid loading..................................................................................80
4.2.8.4 Isomerization behaviour of Grubbs catalysts.............................................................84
4.3 Continuous physisorbed Ru-Grubbs catalyst experiments ........................................89
4.3.1 Screening of catalyst precursors...............................................................................89
4.3.2 Variation of support material .....................................................................................92
4.3.3 Variation of propene partial pressure ........................................................................93
4.3.4 Variation of residence time........................................................................................96
4.4 Catalyst conditioning studies.....................................................................................98
4.4.1 Catalyst without ionic liquid film.................................................................................98
4.4.1.1 Nitrogen treatment prior to reaction...........................................................................98
4.4.1.2 Vacuum treatment during reaction ............................................................................99
4.4.2 Catalyst with ionic liquid content .............................................................................100
4.4.2.1 Nitrogen treatment prior to reaction.........................................................................100
4.4.2.2 Nitrogen treatment during reaction..........................................................................101
4.4.2.3 Vacuum treatment during reaction ..........................................................................102
4.4.2.4 Ethene treatment prior to reaction...........................................................................103
4.4.2.5 Ethene treatment during reaction............................................................................107
II 4.4.3 Thermal stability of the SILP system ........................................................................108
4.4.4 Catalyst with organic liquid .......................................................................................111
5. Conclusion and outlook ............................................................................................113
6. References ...............................................................................................................117
7. Appendix...................................................................................................................120
7.1 Thermodynamic aspects of metathesis ....................................................................120
7.2 Continuous gas-phase reactor setup........................................................................125
7.3 Overview of MFC correction factors .........................................................................129
7.4 Pressure drop calculation .........................................................................................138
7.5 Synthesis of vinyl-functionalized ionic liquids ...........................................................139
7.5.1 Synthesis of [BVIM][BF ] ..........................................................................................140 4
7.5.2 Synthesis of [BVIM][NTf ]143 2
7.5.3 Viscosity measurements of [BVIM][BF ] and [BVIM][NTf ] .......................................146 4 2
7.5.4 Differential scanning calorimetry of [BVIM][NTf ]......................................................148 2
List of abbreviations .............................................................................................................149

III
IV

Soyez le premier à déposer un commentaire !

17/1000 caractères maximum.