Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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4. Selective Side‐Chain Oxidation of Alkyl Aromatic Compounds Catalyzed by Cerium Modified Silver Catalysts ....................................................................................................................................................101 4.1 Introduction .....................................................................................................................................102 4.2 Experimental ...................................................................................................................................103 4.2.1 Catalyst synthesis .....................................................................................................................103 4.2.2 Catalyst testing .........................................................................................................................104 4.2.3 Catalyst characterization ..........................................................................................................105 4.3 Results .............................................................................................................................................106 4.3.1 Catalytic side chain oxidation of p‐xylene by impregnated Ag/SiO2 ........................................106 4.3.2 Comparison of impregnated catalysts with flame spray pyrolysis (FSP) derived catalysts ......111 4.3.3 Extension to further alkyl aromatic compounds ......................................................................115 4.4 Discussion and mechanistic considerations ....................................................................................118 4.5 Conclusions ......................................................................................................................................121 4.6 References .......................................................................................................................................122 5. Experimental Determination, Modeling and Utilization of the Phase Behavior in the Selective Oxidation of Alcohols in Pressurized CO2 ..................................................................................................125 5.1 Introduction .....................................................................................................................................126 5.2 Experimental ...................................................................................................................................127 5.2.1 Experimental setups .................................................................................................................127 5.2.1.1 View cell for phase behavior measurements ....................................................................................... 127 5.2.1.2 Continuous reactor for catalytic reactions in pressurized CO2 ............................................................. 128 5.2.2 Experimental procedures .........................................................................................................129 5.2.2.1 Experimental determination of the phase behavior ............................................................................ 129 5.2.2.2 Catalytic studies.................................................................................................................................... 130 5.2.3 Phase behavior modeling .........................................................................................................132 5.3 Results .............................................................................................................................................134 5.3.1 CPA parameters of pure compounds .......................................................................................134 5.3.2 CPA of binary mixtures .............................................................................................................136 5.3.3 Application of the CPA equation of state for phase behavior modeling ..................................137 5.3.4 Benzyl alcohol oxidation as a function of pressure ..................................................................139 XII
5.3.5 Macroscopic mass transport in the two phase region .............................................................142 5.3.5 Influence of oxygen in the single phase and two phase region ...............................................143 5.3.6 Higher reaction temperature ...................................................................................................144 5.4 Discussion ........................................................................................................................................145 5.5 Conclusions ......................................................................................................................................149 5.6 References .......................................................................................................................................150 6. Aerobic Epoxidation of Olefins Catalyzed by the Cobalt‐Based Metal‐Organic Framework STA‐ 12(Co) ........................................................................................................................................................152 6.1 Introduction .....................................................................................................................................153 6.2 Experimental ...................................................................................................................................154 6.2.1 Materials ...................................................................................................................................154 6.2.2 MOF synthesis ..........................................................................................................................154 6.2.3 Catalytic test reactions .............................................................................................................155 6.2.4 Catalyst characterization after reaction ...................................................................................156 6.2.5 Flame atomic absorption spectroscopy (F‐AAS) ......................................................................156 6.2.6 X‐ray absorption spectroscopy (XAS) .......................................................................................156 6.2.7 Electron paramagnetic resonance (EPR) ..................................................................................156 6.3 Results .............................................................................................................................................157 6.3.1 Synthesis of the MOF and characterization .............................................................................157 6.3.2 STA‐12(Co) as heterogeneous epoxidation catalyst in DMF ....................................................159 6.3.3 Heterogeneous vs. homogeneous catalysis .............................................................................162 6.3.4 Influence of reaction parameters .............................................................................................164 6.3.5 Amines as inhibitors .................................................................................................................166 6.3.6 Involvement of radical species .................................................................................................167 6.3.7 Co‐epoxidation of styrene and (E)‐stilbene ..............................................................................168 6.3.8 Formation of oxidizing species .................................................................................................169 6.3.9 EXAFS investigations under reaction conditions ......................................................................170 6.4 Discussion ........................................................................................................................................172 XIII
Page 1 and 2: TECHNICAL UNIVERSITY OF DENMARK (DT
Page 3 and 4: Preface The present dissertation su
Page 5 and 6: the carboxylic acid, ceria inhibite
Page 7 and 8: Resume Denne afhandling giver indle
Page 9 and 10: hvorimod mængden af katalysator ku
Page 11: 2.3.8 Oxidation of sulfides .......
Page 15 and 16: Chapter 1 Introduction With its gre
Page 17 and 18: 1. Introduction Scheme 1‐1: High
Page 19 and 20: 1. Introduction Figure 1‐2: Phase
Page 21 and 22: 1. Introduction [28] S. Bawaked, N.
Page 23 and 24: 2.1 Introduction 2.1 Introduction E
Page 25 and 26: 2.2.1 Synthesis of gold catalysts 2
Page 27 and 28: 2.2 Catalyst synthesis for oxidatio
Page 29 and 30: 2.2 Catalyst synthesis for oxidatio
Page 31 and 32: 2.3 Selective liquid‐phase oxidat
Page 33 and 34: Table 2-1: Overview over alcohol ox
Page 45 and 46: Ph O O Ph (4) (5) 2.3 Selective liq
Page 51 and 52: Table 2-4: Side-chain oxidation of
Page 53 and 54: 2.3.4 Oxidation of cyclohexane 2.3
Page 55 and 56: Table 2-5: Oxidatin of cyclohexane.
Page 59 and 60: Table 2-6: Ring hydroxylation of ar
Page 63 and 64:
Table 2-7: Aerobic oxidation of ami
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Table 2-8: Oxidation of hydroquinon
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2.3 Selective liquid‐phase oxidat
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Table 2-9: Oxidation of silanes wit
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Table 2-10: Oxidation reactions cat
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2.4 Strengths and opportunities of
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Page 79 and 80:
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2.6 References 2.6 References [1] M
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2.6 References [56] H. Tumma, N. Na
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2.6 References [113] C. Keresszegi,
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2.6 References [169] Q. Zhu, Y. Lia
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2.6 References [223] M. Fetizon, M.
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Chapter 3 Selective Liquid-Phase Ox
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3.2 Experimental 3.2.1 Catalyst pre
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3.3 Results Scattering amplitudes a
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Absorption (a.u.) 1.2 1.0 0.8 0.6 0
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Conversion (%) 100 90 80 70 60 50 4
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3.3 Results Figure 3‐5: In situ X
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3.3 Results Table 3‐2: Conversion
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3.3 Results In order to gain insigh
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3.3 Results the cost of selectivity
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3.4 Discussion synergetic interacti
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3.5 Conclusions to corroborate the
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3.6 References [29] T. Mitsudome, Y
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Chapter 4 Selective Side-Chain Oxid
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4.2 Experimental single‐step flam
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4.2 Experimental alcohol (Aldrich,
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4.3 Results Scheme 4‐1: Oxidation
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4.3 Results Figure 4‐2: Formation
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4.3 Results oxidation by either 2,6
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Absorption (a.u.) Absorption (a.u.)
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4.3 Results atomic mixing of Ag and
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4.3 Results Figure 4‐7: Influence
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4.4 Discussion and mechanistic cons
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4.5 Conclusions heterogeneous radic
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4.6 References [29] S.I. Zabinsky,
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Chapter 5 Experimental Determinatio
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5.2 Experimental The most important
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5.2 Experimental Eurotherm 2216e te
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Figure 5-1: Schematic view of the e
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(Eq. 5‐5) AB i j ε AB i j β 5.2
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(a) (b) (c) (d) (e) (f) (g) (h) (i)
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5.3 Results two association sites o
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Pressure (bar) 150 145 140 135 5.3
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5.3 Results Figure 5‐7: Oxidation
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Weight (g) 5.3 Results Figure 5‐8
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5.4 Discussion catalytic reactions
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5.4 Discussion corresponding CO2‐
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5.5 Conclusions 5.5 Conclusions The
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5.6 References [29] I. Tsivintzelis
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6.1 Introduction 6.1 Introduction A
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6.2 Experimental [38]. In a typical
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6.3 Results out in 1 mm quartz tube
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6.3 Results Figure 6‐2: Structure
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6.3 Results Figure 6‐4: Epoxidati
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6.3 Results Figure 6‐6: Compariso
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6.3 Results Figure 6‐8: Influence
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6.3 Results investigated the epoxid
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6.3 Results Figure 6‐10: Co‐epo
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6.3 Results Figure 6‐11: EXAFS an
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6.4 Discussion would need to be for
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6.5 Conclusions Formation of the ep
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6.6 References [28] J. Perles, N. S
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Chapter 7 Concluding Remarks 7.1 Co
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7.2 Final remarks and outlook speci
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Acknowledgements Acknowledgements T
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Curriculum Vitae Matthias Josef Bei
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