Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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CHAPTER 4 other examples found in the literature [31, 32]. Figure 4‐2 depicts the typical development of the products during the reaction. After a short induction period p‐methylbenzyl alcohol and p‐ methylbenzaldeyhde were formed at approximately the same rate. Hence, both compounds are presumably formed simultaneously (though not necessarily in the same step) and hardly by successive oxidation. The formation of p‐toluic acid was first detected after an induction period. Thus, p‐toluic acid was formed via one (or more) of the intermediates, e.g. by reaction between aldehyde and peroxide. Figure 4‐1: Influence of carboxylic acid (p‐toluic acid) and CeO2 as additives on the oxidation of p‐xylene. Reaction conditions: 122 mmol p‐xylene, optionally 3 mol‐% p‐toluic acid and/or 50 mg CeO2, 100 mg biphenyl, 100 mg imp 10%Ag/SiO2‐900, oxygen atmosphere, 140 °C, 3 h reaction time. Silver has a complex interaction with oxygen influencing the catalytic properties [33, 34]. Different silver oxygen species can be formed in an oxygen containing atmosphere depending on the calcination temperature [35, 36]. Therefore, the effect of the calcination temperature on the catalytic performance was studied (Figure 4‐3). Within the temperature range investigated, the highest calcination temperature, i.e. 900 °C resulted in the most active silver catalyst with a significant increase in catalytic activity between 600 and 700 °C. After the high temperature treatment rather large silver particles with an average crystal size of 43 nm were observed 108
4.3 Results Figure 4‐2: Formation of p‐methylbenzyl alcohol (●), p‐methylbenzaldehyde (■) and p‐toluic acid (▲) during the oxidation of p‐xylene with FSP 1%Ag/10%CeO2‐SiO2. Reaction conditions: 122 mmol p‐xylene, 3 mol‐% benzoic acid, 100 mg biphenyl, 100 mg FSP 1%Ag/10%CeO2‐SiO2, oxygen atmosphere, 140 °C. Figure 4‐3: Yields of p‐methylbenzyl alcohol, p‐methylbenzaldehyde and p‐toluic acid obtained during the oxidation of p‐xylene with imp 10%Ag/SiO2 calcined for 1 h in air at temperatures between 300 °C and 900 °C in the presence of ceria and carboxylic acid. Reaction conditions: 122 mmol p‐xylene, 3 mol‐% p‐toluenic acid, 100 mg biphenyl, 100 mg imp 10%Ag/SiO2 calcined in air as indicated, 50 mg CeO2, oxygen atmosphere, 140 °C, 3 h reaction time. 109
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TECHNICAL UNIVERSITY OF DENMARK (DT
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Preface The present dissertation su
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the carboxylic acid, ceria inhibite
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Resume Denne afhandling giver indle
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hvorimod mængden af katalysator ku
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2.3.8 Oxidation of sulfides .......
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5.3.5 Macroscopic mass transport in
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Chapter 1 Introduction With its gre
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1. Introduction Scheme 1‐1: High
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1. Introduction Figure 1‐2: Phase
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1. Introduction [28] S. Bawaked, N.
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2.1 Introduction 2.1 Introduction E
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2.2.1 Synthesis of gold catalysts 2
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2.2 Catalyst synthesis for oxidatio
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2.2 Catalyst synthesis for oxidatio
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2.3 Selective liquid‐phase oxidat
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Table 2-1: Overview over alcohol ox
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Ph O O Ph (4) (5) 2.3 Selective liq
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Table 2-4: Side-chain oxidation of
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2.3.4 Oxidation of cyclohexane 2.3
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Table 2-5: Oxidatin of cyclohexane.
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Table 2-6: Ring hydroxylation of ar
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Table 2-7: Aerobic oxidation of ami
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Table 2-8: Oxidation of hydroquinon
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Table 2-9: Oxidation of silanes wit
Page 71 and 72: Table 2-10: Oxidation reactions cat
Page 73 and 74: 2.4 Strengths and opportunities of
Page 81 and 82: 2.6 References 2.6 References [1] M
Page 83 and 84: 2.6 References [56] H. Tumma, N. Na
Page 85 and 86: 2.6 References [113] C. Keresszegi,
Page 87 and 88: 2.6 References [169] Q. Zhu, Y. Lia
Page 89 and 90: 2.6 References [223] M. Fetizon, M.
Page 91 and 92: Chapter 3 Selective Liquid-Phase Ox
Page 93 and 94: 3.2 Experimental 3.2.1 Catalyst pre
Page 95 and 96: 3.3 Results Scattering amplitudes a
Page 97 and 98: Absorption (a.u.) 1.2 1.0 0.8 0.6 0
Page 99 and 100: Conversion (%) 100 90 80 70 60 50 4
Page 101 and 102: 3.3 Results Figure 3‐5: In situ X
Page 103 and 104: 3.3 Results Table 3‐2: Conversion
Page 105 and 106: 3.3 Results In order to gain insigh
Page 107 and 108: 3.3 Results the cost of selectivity
Page 109 and 110: 3.4 Discussion synergetic interacti
Page 111 and 112: 3.5 Conclusions to corroborate the
Page 113 and 114: 3.6 References [29] T. Mitsudome, Y
Page 115 and 116: Chapter 4 Selective Side-Chain Oxid
Page 117 and 118: 4.2 Experimental single‐step flam
Page 119 and 120: 4.2 Experimental alcohol (Aldrich,
Page 121: 4.3 Results Scheme 4‐1: Oxidation
Page 125 and 126: 4.3 Results oxidation by either 2,6
Page 127 and 128: Absorption (a.u.) Absorption (a.u.)
Page 129 and 130: 4.3 Results atomic mixing of Ag and
Page 131 and 132: 4.3 Results Figure 4‐7: Influence
Page 133 and 134: 4.4 Discussion and mechanistic cons
Page 135 and 136: 4.5 Conclusions heterogeneous radic
Page 137 and 138: 4.6 References [29] S.I. Zabinsky,
Page 139 and 140: Chapter 5 Experimental Determinatio
Page 141 and 142: 5.2 Experimental The most important
Page 143 and 144: 5.2 Experimental Eurotherm 2216e te
Page 145 and 146: Figure 5-1: Schematic view of the e
Page 147 and 148: (Eq. 5‐5) AB i j ε AB i j β 5.2
Page 149 and 150: (a) (b) (c) (d) (e) (f) (g) (h) (i)
Page 151 and 152: 5.3 Results two association sites o
Page 153 and 154: Pressure (bar) 150 145 140 135 5.3
Page 155 and 156: 5.3 Results Figure 5‐7: Oxidation
Page 157 and 158: Weight (g) 5.3 Results Figure 5‐8
Page 159 and 160: 5.4 Discussion catalytic reactions
Page 161 and 162: 5.4 Discussion corresponding CO2‐
Page 163 and 164: 5.5 Conclusions 5.5 Conclusions The
Page 165 and 166: 5.6 References [29] I. Tsivintzelis
Page 167 and 168: 6.1 Introduction 6.1 Introduction A
Page 169 and 170: 6.2 Experimental [38]. In a typical
Page 171 and 172: 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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