Petroleum Radiation Processing

v

Contents

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 Efciency 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

vi Contents

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-Parafn Oil ................................................. 198

Chapter 3 Methods for Petroleum Processing Based on Radiation-Thermal

Cracking ........................................................................................... 211

3.1 Radiation Methods for High-Viscous Oil

and Bitumen Processing ........................................................ 211

3.2 Radiation Methods for Lubricating Oil Processing .............. 221

3.3 Radiation Processing of High-Parafnic 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

viiContents

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 Specic 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

viii Contents

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 Classication 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