Authors ........................................................ ix
Introduction ................................................... xi
Chapter 1 Theory of Radiation-Induced Cracking Reactions in
Hydrocarbons .................................................... 1
1.1 Thermal Cracking: Number of Propagation Steps, Cracking
Start Temperature, Reaction Rate ........................... 1
1.2 Radiation-Thermal Cracking ................................ 12
1.3 Other Estimations of Chain Length and Cracking
Temperature ............................................... 17
1.4 Low-Temperature Radiation Cracking ........................ 21
1.5 Thermodynamic Aspects of Radiation Cracking ............... 31
1.6 Mechanisms of Radiation-Excited Molecular State
Formation ................................................. 34
1.6.1 Lifetimes of Excited Molecules ..................... 34
1.6.2 Cage Effect ........................................ 36
1.6.3 Role of Isomerization Reactions in Hydrocarbon
Cracking ........................................... 39
1.6.4 Description of the Model ........................... 42
1.6.5 Radiation-Excited Unstable States Responsible
for Propagation of the Chain Cracking Reaction ..... 44
1.6.6 Radiation-Excited Unstable States Responsible
for Isomerization .................................. 45
1.7 Radiation Cracking of Extra-Heavy Oil and Bitumen ......... 48
1.7.1 Electron Irradiation of Extra-Heavy Oil in Static
Conditions ......................................... 48
1.7.2 Polymerization as a Limiting Factor for Light
Product Yields in Radiation Cracking of Heavy
Oil and Bitumen .................................... 50
1.7.3 Kinetic Model of Radiation-Induced Cracking of
Heavy Oil Feedstock ................................ 52
1.7.4 Radiation-Thermal Cracking ......................... 54
1.7.5 Low-Temperature Radiation Cracking ................. 56
1.7.6 Effect of Flow Conditions on the Efficiency of
High-Viscous Oil Radiation Processing .............. 59
1.8 Effect of Electron Beam Pulse Characteristics on the
Rate of Radiation-Thermal Cracking of Petroleum
Feedstock ................................................. 66
1.8.1 Accumulation of Radicals in Continuous and
Pulse Modes of Electron Irradiation ................ 67
1.8.1.1 Radical Recombination in Second-
Order Reactions ........................... 67
1.8.1.2 Radical Recombination in Arbitrary-
Order Reactions ........................... 72
1.8.1.3 Radiation Generation of Excited
Molecular States .......................... 73
1.8.1.4 Comparison with Experimental Data ......... 74
Chapter 2 Experimental Studies of Radiation-Thermal Cracking
in Hydrocarbons ................................................ 77
2.1 Early Studies of Hydrocarbon Radiolysis ................... 77
2.2 Experimental Studies of Radiation-Thermal Cracking of
Hydrocarbons .............................................. 91
2.2.1 General Characteristics ............................ 91
2.2.2 RT Cracking of Light Oil at Low and Moderate
Dose Rates of Ionizing Irradiation ................. 95
2.3 Radiation-Thermal Cracking of Aromatic and Naphthene
Hydrocarbons ............................................. 115
2.4 Radiation-Thermal Cracking of High-Viscous Oil and
Bitumen .................................................. 137
2.4.1 Heavy Oil Radiation Processing .................... 137
2.4.2 Effect of Reactor Material and Process
Temperature on the Yields of Light Fractions
in RTC of Oil Feedstock ........................... 157
2.4.3 Bitumen Radiation Processing ...................... 163
2.4.4 Coal Radiation Processing ......................... 184
2.4.5 Radiation-Induced Isomerization in the Process
of Radiation-Thermal Cracking of High-Viscous
Oil ............................................... 190
2.4.6 Radiation-Induced Polymerization in Conditions
of Radiation-Thermal Cracking of High-Paraffin
Oil ............................................... 198
Chapter 3 Methods for Petroleum Processing Based on
Radiation-Thermal Cracking .................................... 211
3.1 Radiation Methods for High-Viscous Oi1 and Bitumen
Processing ............................................... 211
3.2 Radiation Methods for Lubricating Oil Processing ......... 221
3.3 Radiation Processing of High-Paraffinic Oil and Oil
Wastes at Heightened Temperatures ........................ 241
3.4 Radiation Methods for High-Sulfuric Oil Processing ....... 248
3.4.1 Early Studies of Petroleum Radiation
Desulfurization ................................... 249
3.4.2 Sulfur Transformation Due to Oil Bubbling by
Ionized Air ....................................... 262
3.4.3 Sulfur Transfer at the Stage of Radiation-
Thermal Cracking of Ozonized Oil .................. 263
3.4.4 Radiation Methods for Desulfurization of Coal
and Heavy Oil Residua ............................. 276
3.5 Radiation-Thermal Processing for Regeneration and
Utilization of Desulfurization Catalysts and Sorbents .... 278
3.5.1 Removal of Carbon Precipitations by Radiation
Processing of Coked Catalysts ..................... 279
3.5.2 Effect of Radiation Processing on Basic
Technological Characteristics of Catalysts ........ 281
3.5.2.1 Retention of the Specific Surface of
Catalytic Systems ........................ 281
3.5.2.2 Retention of the Reactive Component
in Regeneration Modes of Catalyst
Radiation Processing ..................... 282
3.5.2.3 Pore Structure in Radiation-Processed
Catalysts ................................ 283
3.5.2.4 Effect of Radiation-Thermal
Processing on Mechanical
Characteristics of Industrial Catalysts .. 283
3.5.3 Catalyst Utilization .............................. 285
3.5.3.1 Application of Radiation-Thermal
Processing for Molybdenum Extraction
from Catalysts of Hydrodesulfurization
Processes in the Process of Solid Waste
Utilization .............................. 286
3.5.3.2 Catalytic Activity of Oxide Contacts
after Radiation-Thermal Processing ....... 286
Chapter 4 Complex Radiation-Thermal Treatment and Radiation
Ozonolysis of Petroleum Feedstock ............................. 289
4.1 Application of the Ionized Air and Ozone-Containing
Air Mixtures for Enhanced Thermal and Radiation-Thermal
Cracking ................................................. 289
4.2 Application of the Ionized Air in Low-Temperature
Radiation Processing ..................................... 298
4.2.1 Gasoline .......................................... 298
4.2.2 Diesel Fuel ....................................... 298
4.2.3 Light Gas Oil Fraction (SB-250°C) ................. 300
4.2.4 Gas Oil (SB-300°C) ................................ 301
4.2.5 Furnace Oil ....................................... 304
4.2.6 Heavy Gas Oil of Atmospheric Distillation ......... 312
4.3 Mechanism of Combined Action of Low-Temperature
Ionizing Irradiation and Radiation Ozonolysis ............ 317
Chapter 5 High Dose-Rate Radiation Processing of Petroleum
Feedstock in a Wide Temperature Range ......................... 319
5.1 Classification of Radiation Chain Cracking Reactions
in Hydrocarbons .......................................... 322
5.2 High-Temperature Radiation-Thermal Cracking (350°C-
450°C) ................................................... 327
5.3 Low-Temperature Radiation Cracking (200°C-350°C) ......... 329
5.3.1 Cold Radiation Cracking (PetroBeam Process) ....... 333
References .................................................... 345
Index ......................................................... 357
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