●Chapter 1 An overview of catalytic selective hydrogenation of benzene into cyclohexene 1
1.1 Selective hydrogenation of benzene into cyclohexene and its downstream products 1
1.2 Foreign developmental history and status in catalytic selective hydrogenation of benzene 6
1.3 Domestic research and progress on selective hydrogenation of benzene 14
1.4 Main technological indexes of typical selective benzene hydrogenation catalysts 22
References 25
Chapter 2 Benzene selective hydrogenation thermodynamics， heterogeneous catalytic kinetics catalysis mechanisms and scientific significance 33
2.1 Thermodynamics of benzene selective hydrogenation 34
2.1.1 Thermodynamic data 34
2.1.2 Effect of temperature 34
2.1.3 Effect of pressure 35
2.1.4 Effect of inert gas 35
2.2 Heterogeneous catalysis kinetics of benzene selective hydrogenation 35
2.2.1 Macroscopic kinetics 35
2.2.2 Heterogeneous catalysis kinetics equations 40
2.2.3 Apparent activation energy 43
2.2.4 Selectivity and yield of cyclohexene 44
2.2.5 Microscopic kinetics 46
2.3 Heterogeneous catalysis mechanisms and scientific significance of selective hydrogenation of benzene into cyclohexene 50
2.3.1 Heterogeneous catalysis mechanisms 50
2.3.2 Scientific significance of high selectivity and yield of cyclohexene 53
References 56
Chapter 3 The first-generation catalysts for selective hydrogenation of benzene to cyclohexene—Ru-M-B/ZrO2(M=Fe， La) amorphous alloys 58
3.1 Preparation and characterization of Ru-M-B/ZrO2 amorphous alloy catalysts 59
3.2 The roles of components in amorphous alloy catalyst Ru-B/ZrO2 64
3.2.1 The role of B in amorphous alloy catalyst Ru-B/ZrO2 64
3.2.2 The role of M in amorphous alloy catalyst Ru-B/ZrO2 65
3.2.3 The role of ZrO2 in amorphous alloy catalyst Ru-B/ZrO2 66
3.3 The operating conditions of Ru-M-B/ZrO2 amorphous alloy catalysts 66
3.3.1 Effect of temperature 66
3.3.2 Effect of hydrogen pressure 67
3.3.3 Effect of mixing rate 67
3.3.4 Effect of additives 67
3.4 Pilot-scale study of amorphous alloy catalyst Ru-M-B/ZrO2 70
3.4.1 Intermittent pilot 70
3.4.2 Continuous pilot 71
References 74
Chapter 4 The second-generation catalysts for selective hydrogenation of benzene to cyclohexene—Ru-Zn-Na2SiO3-PEG-10000 77
4.1 Influence of Na2SiO3 on the catalyst performance of Ru-Zn 78
4.1.1 Catalyst activity and selectivity of pre-modified Ru-Zn 78
4.1.2 Washing catalyst with pure water 79
4.1.3 Adding NaOH and Na2SiO3 in reaction slurry 84
4.2 Effect of PEG-10000 on the performance of Ru-Zn catalyst 85
4.2.1 Alcohol additives 85
4.2.2 Amine additives 93
4.3 Main performance indexes of the second-generation catalytic system of Ru-Zn-Na2SiO3-PEG-10000 for benzene selective hydrogenation 99
4.3.1 The working mechanisms of Na2SiO3-PEG-10000 on Ru-Zn catalyst 99
4.3.2 Main performance indexes of Ru-Zn-Na2SiO3-PEG-10000 catalytic system 101
References 104
Chapter 5 The third-generation catalysts of benzene selective hydrogenation to cyclohexene—Ru-M (Zn， Mn， Fe， La， Ce) Nano-bimetallic system 106
5.1 Effect of transition metal and rare earth elements on the catalysis performance of Ru-based catalysts 107
5.1.1 Preparation and characterization of Ru-M (transition elements) catalysts 107
5.1.2 Activity and selectivity of Ru-M (transition elements) catalysts 115
5.1.3 Preparation and characterization of Ru-M (rare earth elements) catalysts 119
5.1.4 Activity and selectivity of Ru-M (rare earth elements) catalysts 122
5.2 The third-generation catalysts for selective hydrogenation of benzene—Ru-M (Zn， Mn， Fe， La， Ce) nano-bimetallic system 126
5.2.1 Nano Ru-Zn catalyst 126
5.2.2 Nano Ru-Mn catalyst 137
5.2.3 Nano Ru-Fe catalyst 145
5.2.4 Nano Ru-La catalyst 150
5.2.5 Nano Ru-Ce catalyst 158
5.3 The main technical indicators of the third-generation catalysts 164
References 171
Chapter 6 The fourth-generation catalysts of benzene selective hydrogenation to cyclohexene —Ru-Zn BZSS core-shell catalysts 174
6.1 Effect of Zn precursor on the properties of Ru-Zn catalysts 174
6.1.1 Effect of Zn precursor 175
6.1.2 Characterization of the Ru-Zn catalysts prepared with different Zn precursors 186
6.2 Effect of Zn content on the performance of Ru-Zn catalysts 193
6.2.1 Effect of Zn content 193
6.2.2 Characterization of Ru-Zn catalysts 195
6.3 Development of the fourth-generation Ru-Zn BZSS catalysts 202
6.3.1 Preparation of Ru-Zn BZSS catalysts 202
6.3.2 Reduction of Ru-Zn catalysts 203
6.3.3 Evaluation of catalyst activity and selectivity 205
6.3.4 Catalyst characterization 211
6.3.5 Surface modification and reaction mechanism 214
6.4 Industrial applications of the fourth-generation catalysts 215
6.4.1 Effect of impurity ions on wall 215
6.4.2 The precursors of Zn promoters 217
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