Heterogeneously Catalyzed Oxidation Reactions Using ... - CHEC

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5.2.3 Phase behavior modeling CHAPTER 5 Modeling of the phase behavior of relevant systems was done using the Cubic plus Association (CPA) Equation of State (EoS, Eq. 5‐2) [21‐23]: (Eq. 5‐2) P system pressure R ideal gas constant T temperature b co‐volume parameter RT α ( T ) 1 RT ⎛ ∂ lng⎞ P = − − ⎜1 + ρ ⎟∑xi∑ (1 − X A ) i Vm − b Vm( Vm + b) 2 Vm ⎝ ∂ρ⎠ i Ai α(T) temperature dependent energy parameter Vm molar volume g(ρ) radial distribution function ρ molar density xi XAi fraction”) molar fraction of compound i association term (fraction of A‐sites on compound i which are unassociated, “monomer The first two terms are identical to the Soave‐Redlich‐Kwong EoS; three substance specific parameters are needed, i.e. b and for calculation of α(T) according to Eq. 5‐3 both a0 and c1. (Eq. 5‐3) Tr α( T) = α ⎡ o 1 + c1(1 − Tr) ⎤ ⎣ ⎦ reduced temperature α0, c1 energy parameters 2 The third term describes the association of molecules, the critical part being the association term XAi (Eq. 5‐4). (Eq. 5‐4) X Ai = 1+ ρ The association term can be simplified depending on the type of association scheme, i.e. the number j of association sites on the molecules and the cross association [27]. The association strength Δ is calculated according to Eq. 5‐5. 1 ∑xj∑XBΔ j j Bj Ai B j 132 AiB
(Eq. 5‐5) AB i j ε AB i j β 5.2 Experimental association energy (measure for the hydrogen bond strength) association volume bij co‐volume of the mixture; b = 0.5( b + b ) ij i j � � �� and � � �� are additional substance specific parameters necessary when association between molecules occurs. The radial distribution function g(ρ) is obtained from Eq. 5‐6. (Eq. 5‐6) 1 g( ρ) = 1−1.9 ⋅(0.25 ⋅bρ) Within this study, the conventional mixing rules for determining the co‐volume and energy parameter were employed, i.e. (Eq. 5‐7) b= ∑ xb i i (Eq. 5‐8) α = ∑∑ xi x jα ij with α ij = αiα j ( 1− kij ) i j where kij is a binary interaction parameter. The binary interaction parameter kij was fitted to experimental data of binary systems for use in ternary systems and is the only required parameter for non‐associating compounds. The CR‐1 combining rule was used for determining the cross‐association energy (Eq. 5‐9) and cross association volume (Eq. 5‐10) for mixtures where both compounds are self‐associating. (Eq. 5‐9) (Eq. 5‐10) AB i i AB ε + ε i j ε = εcross = 2 A B i j β = β = cross β i AB j j A B i β A B j j The cross‐association, i.e. associative interaction between different kinds of molecules, can alternatively be calculated from the modified CR‐1 combining rule (Eq. 5‐11) for systems with only one self‐associating compound (i.e. the other is inert); βcross was fitted from binary systems data [28]. (Eq. 5‐11) AB ⎡ i j AB ⎛ε⎞ ⎤ i j Δ = g( ρ) ⎢exp ⎜ ⎟−1⎥bijβ RT ⎟ ⎢⎣ ⎝ ⎠ ⎥⎦ AB associating = cross = i j ε ε i ε 2 First, the respective binary parameters were obtained from fitting to experimental data for binary mixtures. Having obtained the binary interaction parameters and parameters for pure compounds, the phase behavior of two ternary systems, i.e. benzyl alcohol – O2 – CO2 and benzaldehyde – water – CO2 was modeled. Modeling was done by Ioannis Tsivintzelis [29]. AB i j 133
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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
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Table 2-10: Oxidation reactions cat
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2.4 Strengths and opportunities of
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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
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 and 122: 4.3 Results Scheme 4‐1: Oxidation
Page 123 and 124: 4.3 Results Figure 4‐2: Formation
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: Figure 5-1: Schematic view of the e
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
Page 173 and 174: 6.3 Results Figure 6‐2: Structure
Page 175 and 176: 6.3 Results Figure 6‐4: Epoxidati
Page 177 and 178: 6.3 Results Figure 6‐6: Compariso
Page 179 and 180: 6.3 Results Figure 6‐8: Influence
Page 181 and 182: 6.3 Results investigated the epoxid
Page 183 and 184: 6.3 Results Figure 6‐10: Co‐epo
Page 185 and 186: 6.3 Results Figure 6‐11: EXAFS an
Page 187 and 188: 6.4 Discussion would need to be for
Page 189 and 190: 6.5 Conclusions Formation of the ep
Page 191 and 192: 6.6 References [28] J. Perles, N. S
Page 193 and 194: Chapter 7 Concluding Remarks 7.1 Co
Page 195 and 196: 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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