Contents
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
6.4.3 Zn content in the catalyst and absorption of BZSS on surface 220
6.4.4 Optimization of industrial preparation parameters 222
6.4.5 Industrial catalysts preparation 228
6.4.6 Industrial catalyst characterization 229
References 232
Chapter 7 Modulation of activity and selectivity of the benzene selective hydrogenation catalysts 234
7.1 Modulation of activity and selectivity of the benzene selective hydrogenation catalysts 235
7.1.1 Modulation methods 235
7.1.2 Modulation of Zn(OH)2 239
7.1.3 Modification of NaOH 243
7.1.4 Modification of alkaline salts 244
7.1.5 Effects of catalyst pretreatment and basic salt modulation 247
7.1.6 Examples of industrial catalyst modification 249
7.1.7 Effect modification of by H2SO4 252
7.2 Modulation mechanism of activity and selectivity of the catalysts for benzene selective hydrogenation 258
7.2.1 Catalyst structures and texture properties 258
7.2.2 SEM-EDX, XPS and ICP-AES analyses of the catalysts 262
References 267
Chapter 8 Catalyst deactivation and regeneration in benzene selective hydrogenation 268
8.1 Studies on deactivation of benzene selective hydrogenation catalysts 269
8.1.1 Deactivation of Ru catalysts caused by carbon deposition 269
8.1.2 The excessive adsorption of zinc sulfate and other salts 270
8.1.3 Corrosion of Fe, Cr, Ni on the reaction wall 271
8.1.4 Deactivation of catalysts due to other factors 272
8.1.5 Catalyst deactivation caused by sulfide 273
8.1.6 Catalyst deactivation caused by nitride 274
8.2 Pilot investigations on catalyst deactivation and regeneration 274
8.3 Investigations of deactivation and regeneration of industrial catalysts 282
8.3.1 Unusual deactivation of industrial catalysts 282
8.3.2 Regeneration of deactivated catalysts caused by sulfide poisoning 284
8.3.3 Regeneration of deactivated catalysts caused by DMAC 285
References 288
Chapter 9 The catalyst technologies and key facilities for benzene selective hydrogenation 289
9.1 Technologies and key facilities of benzene selective hydrogenation 290
9.1.1 Key facilities and technological processes for liquid phase selective hydrogenation of benzene 290
9.1.2 Operational scheme and performance 293
9.2 Key facilities and processes for catalyst preparation 295
9.2.1 Key facilities and processes 295
9.2.2 Catalyst preparation and main technical specifications 298
9.2.3 Key facilities and processes after improvement 303
9.2.4 Main technical specifications of improved catalysts 305
9.3 Catalyst preparation technologies for selective hydrogenation of benzene to cyclohexene 307
9.3.1 Monolayer-type catalysts for selective hydrogenation of benzene to cyclohexene and its preparation methods 307
9.3.2 Catalyst systems containing nanosized Ru catalyst and basic Zinc sulfate and its application for selective hydrogenation of benzene to cyclohexene 313
9.3.3 Preparation, modulation and regeneration methods for the catalysts for selective hydrogenation of benzene to cyclohexene 315
9.3.4 Catalyst for selective hydrogenation of benzene to cyclohexene and its preparation method 315
9.3.5 Ru-Y Ni catalyst for selective hydrogenation of benzene to cyclohexene and its application 316
9.3.6 Supported catalyst for selective hydrogenation of benzene to cyclohexene and its preparation method 317
9.3.7 Adsorbent for finely removing sulphides in benzene as well as its preparation method and application 320
9.3.8 A catalyst for selective hydrogenation of benzene to cyclohexene and its preparation method and application 323
9.3.9 Modulation methods for the activity and selectivity of Ru-Zn catalyst for selective hydrogenation of benzene to cyclohexene 324
9.3.10 Production system and preparation method of the catalyst for selective hydrogenation of benzene to cyclohexene 325
9.3.11 An in-situ regeneration method of the catalyst for selective hydrogenation of benzene to cyclohexene 325
References 326
Chapter 10 Selective hydrogenation of benzene to cyclohexene and incorporate device of its downstream products 327
10.1 The production technology of cyclohexanone through benzene selective hydrogenation to cyclohexene 328
10.2 Selective hydrogenation of benzene to cyclohexene and its downstream products sets 332
10.2.1 A unit for selective hydrogenation of benzene 332
10.2.2 The reaction devices and technology of selective hydrogenation of benzene to cyclohexene 334
10.2.3 Technology for partial hydrogenation of benzene which could recover the catalyst[5] 338
10.2.4 A gas-liquid-liquid-solid reaction device 340
10.2.5 A method to produce cyclohexene using high-purity benzene 343
10.2.6 A method for continuous production of cyclohexene 347
10.2.7 A method of producing caprolactam using high purity benzene 349
10.2.8 A high efficient cyclohexanone production method 355
References 359