| Preface |
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xix | |
| Acknowledgments |
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xxi | |
| About the Author |
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xxiii | |
| 1 Introduction |
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1 | (6) |
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6 | (1) |
| 2 Composition of Crude Oils and Petroleum Products |
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7 | (24) |
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8 | (6) |
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12 | (2) |
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2.2 Aromatic Hydrocarbons |
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14 | (1) |
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2.3 Heteroatomic Organic Compounds |
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15 | (3) |
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15 | (3) |
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18 | (1) |
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18 | (2) |
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20 | (2) |
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22 | (1) |
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2.7 Resins and Asphaltenes |
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23 | (1) |
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24 | (1) |
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24 | (1) |
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24 | (1) |
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2.11 Products Composition |
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25 | (5) |
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2.11.1 Liquefied Petroleum Gas (LPG) (C3 and C4) |
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26 | (1) |
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2.11.2 Gasoline (C3 to Gil) |
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26 | (1) |
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2.11.3 Condensate (C4, C5 and C6 >) |
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27 | (1) |
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2.11.4 Gas Fuel Oils (C12 to C19) |
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27 | (1) |
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27 | (1) |
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28 | (1) |
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2.11.7 Fuel Oils # 4, 5, and 6 |
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28 | (1) |
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28 | (1) |
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29 | (1) |
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30 | (1) |
| 3 Characterization of Petroleum and Petroleum Fractions |
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31 | (32) |
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31 | (6) |
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3.1.1 Crude Oil Properties |
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32 | (1) |
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32 | (1) |
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3.1.3 Boiling Point Range |
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33 | (1) |
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3.1.4 Characterization Factor |
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33 | (1) |
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3.1.5 The Universal Oil Product Characterization factor, Kuop |
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34 | (1) |
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3.1.6 Carbon Residue, wt% |
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34 | (2) |
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3.1.7 Nitrogen Content, wt% |
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36 | (1) |
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3.1.8 Sulfur Content, wt% |
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36 | (1) |
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3.1.9 Total Acid Number (TAN) |
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36 | (1) |
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3.1.10 Salt Content, pounds/1000 barrels |
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36 | (1) |
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3.1.11 Metals, parts/million (ppm) by weight |
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36 | (1) |
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3.1.12 Pour Point (°F or °C) |
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36 | (1) |
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37 | (1) |
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3.2.1 Whole crude oil average properties |
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37 | (1) |
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3.2.2 Fractional properties |
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37 | (1) |
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3.3 Crude Cutting Analysis |
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37 | (1) |
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37 | (9) |
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3.5 Laboratory Testing of Crude Oils |
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46 | (12) |
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3.5.1 True Boiling Point (TBP) Curve |
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46 | (1) |
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3.5.2 ASTM D86 Distillation |
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46 | (1) |
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47 | (2) |
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3.5.4 Conversion Between ASTM and TBP Distillation |
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49 | (5) |
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3.5.5 Petroleum Pseudo-Components |
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54 | (1) |
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3.5.6 Pseudo-Component Normal Boiling Points |
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55 | (1) |
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3.5.7 ASTM D1160 Distillation |
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55 | (1) |
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3.5.8 Determination of ASTM IBP, 10%, 20-90% Points of Blend |
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55 | (1) |
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56 | (1) |
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3.5.10 Initial Boiling Point Determination |
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56 | (1) |
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3.5.11 ASTM End Point of Blend |
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56 | (1) |
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56 | (1) |
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3.5.13 Flash Point, °F, as a Function of Average Boiling Point |
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57 | (1) |
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3.5.14 Smoke Point of Kerosenes |
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57 | (1) |
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3.5.15 Luminometer Number |
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57 | (1) |
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3.5.16 Reid Vapor Pressure (RVP) |
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57 | (1) |
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3.5.17 Vapor Pressure of Narrow Hydrocarbon Cuts |
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58 | (1) |
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58 | (1) |
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58 | (1) |
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59 | (1) |
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59 | (1) |
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3.9 Determination of the Lower Heating Value of Petroleum Fractions |
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59 | (1) |
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3.10 Aniline Point Blending |
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60 | (1) |
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3.11 Correlation Index (CI) |
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60 | (1) |
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3.12 Chromatographically Simulated Distillations |
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61 | (1) |
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62 | (1) |
| 4 Thermodynamic Properties of Petroleum and Petroleum Fractions |
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63 | (48) |
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4.1 K-Factor Hydrocarbon Equilibrium Charts |
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64 | (8) |
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72 | (2) |
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74 | (6) |
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4.3.1 Vapor Pressure Determination using the Clausius-Clapeyron and the Antoine Equations |
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75 | (5) |
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80 | (7) |
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4.4.1 Conversion to Saybolt Universal Viscosity |
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80 | (2) |
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4.4.2 Conversion to Saybolt Furol Viscosity |
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82 | (1) |
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4.4.3 Equivalents of Kinematic (cSt), Saybolt Universal (SUS), and Dynamic viscosity |
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82 | (1) |
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4.4.4 Viscosity of Liquid Hydrocarbons |
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83 | (1) |
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84 | (3) |
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87 | (2) |
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89 | (1) |
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89 | (1) |
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90 | (1) |
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4.8 Molecular Type Composition |
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90 | (6) |
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4.9 Critical Temperature, Tc |
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96 | (1) |
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4.10 Critical Pressure, Pc |
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97 | (1) |
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4.11 Pseudo-Critical Constants and Acentric Factors |
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98 | (1) |
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4.12 Enthalpy of Petroleum Fractions |
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99 | (1) |
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4.13 Compressibility Z Factor of Natural Gases |
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100 | (5) |
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4.14 Simulation Thermodynamic Software Programs |
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105 | (5) |
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110 | (1) |
| 5 Process Descriptions of Refinery Processes |
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111 | (38) |
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111 | (4) |
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5.2 Refinery and Distillation Processes |
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115 | (5) |
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5.3 Process Description of the Crude Distillation Unit |
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120 | (12) |
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5.3.1 Crude Oil Desalting |
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121 | (1) |
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5.3.2 Types of Salts in Crude Oil |
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122 | (1) |
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122 | (5) |
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5.3.4 Pumparound Heat Removal |
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127 | (3) |
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5.3.5 Tower Pressure Drop and Flooding |
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130 | (1) |
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130 | (1) |
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5.3.7 Rectifying Section of the Main Column |
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130 | (1) |
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5.3.8 Side Stripping Columns |
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130 | (1) |
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5.3.9 Crude Column Overhead |
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130 | (1) |
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5.3.10 General Properties of Petroleum Fractions |
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130 | (2) |
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5.4 Process Variables in the Design of Crude Distillation Column |
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132 | (2) |
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5.4.1 Process Design of a Crude Distillation Column |
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133 | (1) |
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134 | (4) |
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5.5.1 Overall Check of Simulation |
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135 | (1) |
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5.5.2 Other Aspects of Design |
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136 | (1) |
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5.5.3 Relationship between Actual Trays and Theoretical Trays |
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137 | (1) |
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5.6 Process Description of Light Arabian Crude Using UniSini Simulation Software [ 12] |
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138 | (6) |
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141 | (1) |
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5.6.2 Performance Specifications Definition |
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142 | (1) |
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142 | (1) |
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5.6.4 Degree of Separation |
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142 | (1) |
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142 | (1) |
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143 | (1) |
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5.6.7 Overhead Temperature |
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143 | (1) |
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144 | (1) |
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5.6.9 Side Stream Stripper |
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144 | (1) |
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144 | (1) |
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5.7 Troubleshooting Actual Columns |
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144 | (1) |
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5.8 Health, Safety and Environment Considerations |
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145 | (3) |
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148 | (1) |
| 6 Thermal Cracking Processes |
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149 | (38) |
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152 | (1) |
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152 | (2) |
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6.3 Pressure Survey in a Vacuum Column |
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154 | (2) |
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6.4 Simulation of Vacuum Distillation Unit |
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156 | (1) |
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157 | (7) |
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157 | (4) |
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6.5.2 Delayed Coker Yield Prediction |
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161 | (1) |
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162 | (1) |
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6.5.4 Thermodynamics of Coking of Light Hydrocarbons |
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162 | (1) |
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163 | (1) |
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164 | (6) |
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165 | (2) |
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167 | (1) |
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168 | (2) |
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6.6.4 Heavy Coker Gas Oil (HCGO) Production |
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170 | (1) |
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6.6.5 Light Coker Gas Oil (LCGO) Production |
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170 | (1) |
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6.7 Fractionator Overhead System |
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170 | (2) |
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172 | (1) |
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6.9 Hydraulic Jet Decoking |
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173 | (1) |
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6.10 Uses of Petroleum Coke |
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174 | (1) |
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174 | (1) |
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175 | (1) |
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6.13 Safety and Environmental Considerations |
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175 | (1) |
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6.14 Simulation/Calculations |
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176 | (1) |
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177 | (7) |
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6.15.1 Visbreaking Reactions |
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180 | (1) |
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6.15.2 Visbreaking Severity |
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180 | (1) |
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6.15.3 Operation and Control |
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180 | (1) |
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6.15.4 Typical Visbreaker Unit |
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181 | (1) |
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6.15.5 Typical Visbreaker Unit with Vacuum Flasher |
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182 | (1) |
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6.15.6 Typical Combination Visbreaker and Thermal Cracker |
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183 | (1) |
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183 | (1) |
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184 | (1) |
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6.17 Health, Safety and Environment Considerations |
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185 | (1) |
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186 | (1) |
| 7 Hydroprocessing |
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187 | (72) |
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7.1 Catalytic Conversion Processes |
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187 | (7) |
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7.1.1 Hydrocracking Chemistry |
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188 | (2) |
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7.1.2 Hydrocracking Reactions |
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190 | (1) |
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7.1.3 Typical Hydrocracking Reactions |
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191 | (3) |
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194 | (2) |
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195 | (1) |
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7.2.2 Reactor Temperature |
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195 | (1) |
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195 | (1) |
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7.2.4 Hydrogen Recycle Rate |
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195 | (1) |
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195 | (1) |
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7.2.6 Heavy Polynuclear Aromatics |
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196 | (1) |
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196 | (1) |
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196 | (4) |
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7.4.1 Catalyst Performance |
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197 | (1) |
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7.4.2 Loss of Catalyst Performance |
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197 | (1) |
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7.4.3 Poisoning by Impurities in Feeds or Catalysts |
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198 | (2) |
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7.4.4 The Apparent Catalyst Activity |
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200 | (1) |
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7.5 Poor Gas Distribution |
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200 | (1) |
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7.6 Poor Mixing of Reactants |
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200 | (1) |
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7.7 The Mechanism of Hydrocracking |
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200 | (1) |
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7.8 Thermodynamics and Kinetics of Hydrocracking |
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201 | (3) |
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7.9 Process Design, Rating and Performance |
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204 | (6) |
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7.9.1 Operating Temperature and Pressure |
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205 | (1) |
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7.9.2 Optimum Catalyst Size and Shape |
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205 | (1) |
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7.9.3 Pressure Drop (AP) in Tubular/Fixed-Bed Reactors |
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205 | (2) |
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7.9.4 Catalyst Particle Size |
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207 | (1) |
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208 | (2) |
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210 | (4) |
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7.11 Factors Affecting Reaction Rate |
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214 | (1) |
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7.12 Measurement of Performance |
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215 | (1) |
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7.13 Catalyst-Bed Temperature Profiles |
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216 | (1) |
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7.14 Factors Affecting Hydrocracking Process Operation |
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217 | (1) |
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7.15 Hydrocracking Correlations |
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217 | (11) |
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7.15.1 Maximum Aviation Turbine Kerosene (ATK) Correlations |
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219 | (1) |
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7.15.2 Process Description |
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220 | (4) |
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7.15.3 Fresh Feed and Recycle Liquid System |
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224 | (1) |
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7.15.4 Liquid and Vapor Separators |
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225 | (1) |
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7.15.5 Recycle Gas Compression and Distribution |
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226 | (1) |
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7.15.6 Hydrogen Distribution |
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226 | (1) |
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7.15.7 Control of the Hydrogen System |
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226 | (1) |
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227 | (1) |
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7.16 Hydrocracker Fractionating Unit |
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228 | (3) |
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7.16.1 Mild Vacuum Column |
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230 | (1) |
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230 | (1) |
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231 | (3) |
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7.18 Hydrotreating Process |
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234 | (6) |
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7.18.1 Process Description |
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237 | (1) |
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237 | (3) |
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7.18.3 Hydrotreating Catalysts |
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240 | (1) |
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7.19 Thermodynamics of Hydrotreating |
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240 | (3) |
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243 | (2) |
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7.21 Naphtha Hydrotreating |
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245 | (5) |
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7.21.1 Hydrotreating Correlations |
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245 | (3) |
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7.21.2 Middle Distillates Hydrotreating |
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248 | (1) |
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7.21.3 Middle Distillate Hydrotreating Correlations |
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248 | (2) |
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7.22 Atmospheric Residue Desulfurization |
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250 | (8) |
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7.22.1 High-Pressure Separator |
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252 | (1) |
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7.22.2 Low-Pressure Separator |
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252 | (1) |
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7.22.3 Hydrogen Sulfide Removal |
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252 | (1) |
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7.22.4 Recycled Gas Compressor |
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252 | (1) |
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252 | (1) |
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7.22.6 Fractionation Column |
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253 | (1) |
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7.22.7 Operating Conditions of Hydrotreating Processes |
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253 | (5) |
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7.23 Health, Safety and Environment Considerations |
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258 | (1) |
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258 | (1) |
| 8 Catalytic Cracking |
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259 | (46) |
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259 | (3) |
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8.2 Fluidized Bed Catalytic Cracking |
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262 | (7) |
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8.2.1 Process Description |
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262 | (7) |
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8.3 Modes of Fluidization |
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269 | (1) |
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270 | (3) |
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8.4.1 Secondary Reactions |
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272 | (1) |
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8.5 Thermodynamics of FCC |
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273 | (5) |
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8.5.1 Transport Phenomena, Reaction Patterns and Kinetic models |
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273 | (3) |
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8.5.2 Three- and Four-Lump kinetic models |
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276 | (2) |
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8.6 Process Design Variables |
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278 | (3) |
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279 | (1) |
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8.6.2 Process Operational Variables |
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280 | (1) |
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8.7 Material and Energy Balances |
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281 | (2) |
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281 | (1) |
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282 | (1) |
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283 | (1) |
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8.9 FCC Yield Correlations |
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284 | (2) |
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8.10 Estimating Potential Yields of FCC Feed |
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286 | (4) |
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290 | (2) |
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292 | (4) |
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8.12.1 Deep Catalytic Cracking |
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293 | (1) |
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8.12.2 Shell's Fluid Catalytic Cracking |
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294 | (1) |
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8.12.3 Fluid Catalytic Cracking High Severity |
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295 | (1) |
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8.12.4 Fluid Catalytic Cracking for Maximum Olefins |
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295 | (1) |
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8.13 Refining/Petrochemical Integration |
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296 | (1) |
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296 | (1) |
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8.15 Troubleshooting for Fluidized Catalyst Cracking Units |
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297 | (1) |
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8.16 Health, Safety and Environment Considerations |
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298 | (1) |
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8.17 Licensors' Correlations |
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299 | (1) |
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8.18 Simulation and Modeling Strategy |
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300 | (4) |
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304 | (1) |
| 9 Catalytic Reforming and Isomerization |
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305 | (34) |
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305 | (1) |
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306 | (1) |
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9.3 Feed Characterization |
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306 | (2) |
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9.4 Catalytic Reforming Processes |
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308 | (4) |
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9.4.1 Role of Reformer in the Refinery |
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309 | (1) |
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9.4.2 UOP Continuous Catalytic Regeneration (CCR) Reforming Process |
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310 | (2) |
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9.5 Operations of the Reformer Process |
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312 | (4) |
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9.5.1 Effect of Major Variables in Catalytic Reforming |
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314 | (2) |
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9.6 Catalytic Reformer Reactors |
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316 | (1) |
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9.7 Material Balance in Reforming |
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317 | (3) |
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320 | (2) |
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9.8.1 Naphthene Dehydrogenation to Cyclohexanes |
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320 | (1) |
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9.8.2 Dehydrocyclization of Paraffins to Aromatics |
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321 | (1) |
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9.8.3 Dehydroisomerization of Alkylcyclopentanes to Aromatics |
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321 | (1) |
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9.8.4 Isomerization of n-Paraffins |
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321 | (1) |
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9.9 Hydrocracking Reactions |
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322 | (1) |
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322 | (2) |
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324 | (2) |
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326 | (1) |
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326 | (1) |
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326 | (3) |
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9.15 Modeling of Naphtha Catalytic Reforming Process |
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329 | (1) |
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329 | (2) |
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330 | (1) |
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9.16.2 Isomerization Reactions |
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331 | (1) |
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9.17 Sulfolane Extraction Process |
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331 | (2) |
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9.17.1 Sulfolane Extraction Unit (SEU) Corrosion Problems |
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332 | (1) |
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9.17.2 Other Solvents for the Extraction Unit |
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333 | (1) |
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333 | (3) |
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9.18.1 Aromatic Separation |
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335 | (1) |
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9.19 Hydrodealkylation Process |
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336 | (1) |
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9.19.1 Separation of the Reactor Effluents |
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337 | (1) |
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337 | (2) |
| 10 Alkylation and Polymerization Processes |
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339 | (26) |
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339 | (1) |
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10.2 Chemistry of Alkylation |
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340 | (2) |
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342 | (1) |
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343 | (2) |
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10.5 Alkylation Feedstocks |
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345 | (1) |
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346 | (1) |
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10.7 Sulfuric Acid Alkylation Process |
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346 | (1) |
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347 | (4) |
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10.9 Kinetics and Thermodynamics of Alkylation |
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351 | (3) |
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354 | (1) |
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10.11 HF and H2SO4 Mitigating Releases |
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354 | (2) |
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356 | (1) |
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10.13 A New Technology of Alkylation Process Using Ionic Liquid |
|
|
356 | (1) |
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10.14 Chevron - Honeywell UOP Ionic liquid Alkylation |
|
|
357 | (1) |
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10.15 Chemical Release and Flash Fire: A Case Study of the Alkylation Unit at the Delaware City Refining Company (DCRC) Involving Equipment Maintenance Incident |
|
|
358 | (4) |
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|
362 | (3) |
| 11 Hydrogen Production and Purification |
|
365 | (16) |
|
11.1 Hydrogen Requirements in a Refinery |
|
|
365 | (1) |
|
|
|
366 | (2) |
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11.3 High-Temperature Shift Conversion |
|
|
368 | (1) |
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11.4 Low-Temperature Shift Conversion |
|
|
368 | (1) |
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|
|
368 | (1) |
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11.6 Purification of Hydrogen Product |
|
|
369 | (1) |
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11.7 Hydrogen Distribution System |
|
|
370 | (1) |
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11.8 Off-Gas Hydrogen Recovery |
|
|
371 | (1) |
|
11.9 Pressure Swing Adsorption (PSA) Unit |
|
|
371 | (4) |
|
11.10 Refinery Hydrogen Management |
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|
375 | (2) |
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11.11 Hydrogen Pinch Studies |
|
|
377 | (2) |
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|
379 | (2) |
| 12 Gas Processing and Acid Gas Removal |
|
381 | (57) |
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|
381 | (2) |
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12.2 Diesel Hydrodesulfurization (DHDS) |
|
|
383 | (1) |
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12.3 Hydrotreating Reactions |
|
|
383 | (5) |
|
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|
388 | (3) |
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|
|
388 | (1) |
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12.4.2 Gas Processing Methods |
|
|
389 | (1) |
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12.4.3 Reaction Gas Processes |
|
|
390 | (1) |
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12.4.4 Sweetening Process |
|
|
390 | (1) |
|
|
|
390 | (1) |
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|
|
391 | (10) |
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12.5.1 Sulfur Recovery Processes |
|
|
393 | (8) |
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|
|
401 | (1) |
|
12.6 Physical Solvent Gas Processes |
|
|
401 | (1) |
|
12.6.1 Physical and Chemical Processes |
|
|
402 | (1) |
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12.6.2 Advantages and Disadvantages of the Sulfinol® Process |
|
|
402 | (1) |
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|
402 | (1) |
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12.8 Solution Batch Process |
|
|
403 | (2) |
|
12.9 Process Description of Gas Processing using UniSim® Simulation |
|
|
405 | (5) |
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12.10 Gas Dryer (Dehydration) Design |
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|
410 | (5) |
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|
412 | (1) |
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12.10.2 Pressure Drop (AP) |
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|
413 | (1) |
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|
413 | (2) |
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12.11 Kremser-Brown-Sherwood Method-No Heat of Absorption |
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|
415 | (6) |
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12.11.1 Absorption: Determine Component Absorption in Fixed Tray Tower (Adapted in part from Ref. 12) |
|
|
415 | (2) |
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12.11.2 Absorption: Determine the Number of Trays for Specified Product Absorption |
|
|
417 | (1) |
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12.11.3 Stripping: Determine the Number of Theoretical Trays and Stripping Steam or Gas Rate for a Component Recovery |
|
|
418 | (2) |
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12.11.4 Stripping: Determine Stripping-Medium Rate for a Fixed Recovery |
|
|
420 | (1) |
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12.12 Absorption: Edmister Method |
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|
421 | (11) |
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12.12.1 Absorption and Stripping Efficiency |
|
|
427 | (5) |
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12.13 Gas Treating Troubleshooting |
|
|
432 | (2) |
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12.13.1 High Exit Gas Dew Point |
|
|
432 | (1) |
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12.13.2 High Glycol Losses |
|
|
432 | (1) |
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12.13.3 Glycol Contamination |
|
|
432 | (1) |
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12.13.4 Poor Glycol Reconcentration |
|
|
433 | (1) |
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12.13.5 Low Glycol Circulation - Glycol Pump |
|
|
433 | (1) |
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12.13.6 High Pressure Drop Across Contactor |
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|
433 | (1) |
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12.13.7 High Stripping Still Temperature |
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|
433 | (1) |
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12.13.8 High Reboiler Pressure |
|
|
433 | (1) |
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12.13.9 Firetube Fouling/Hot Spots/Burn Out |
|
|
433 | (1) |
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12.13.10 High Gas Dew Points |
|
|
433 | (1) |
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12.13.11 Cause - Inadequate Glycol Circulation Rate |
|
|
433 | (1) |
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12.13.12 Low Reboiler Temperature |
|
|
433 | (1) |
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12.13.13 Flash Separator Failure |
|
|
434 | (1) |
|
12.13.14 Cause - Insufficient Reconcentration of Glycol |
|
|
434 | (1) |
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12.13.15 Cause - Operating Conditions Different from Design |
|
|
434 | (1) |
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12.13.16 Cause - Low Gas Flow Rates |
|
|
434 | (1) |
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12.13.17 High Glycol Loss |
|
|
434 | (1) |
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12.14 Cause - Loss of Glycol Out of Still Column |
|
|
434 | (1) |
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|
|
435 | (1) |
|
12.16 Sour Water Stripping Process |
|
|
435 | (3) |
| References |
|
438 | (3) |
| Glossary of Petroleum and Technical Terminology |
|
441 | (92) |
| Appendix A Equilibrium K values |
|
533 | (14) |
| Appendix B Analytical Techniques |
|
547 | (10) |
| Appendix C Physical and Chemical Characteristics of Major Hydrocarbons |
|
557 | (16) |
| Appendix D A List of Engineering Process Flow Diagrams and Process Data Sheets |
|
573 | (50) |
| Index |
|
623 | |