REFINERY PROCESS MODELING

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APraCfiatl'Guide

to Sfead, State MOdeling
01 Petroleum Processes .
FIRST EDITION

REFINERY

PROCESS MOuELING

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A Practical Guide to Steady State Modeling of Petroleu m Processes
(Using Commercial Simulators)

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First Edition

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Gerald L. Kaes

Consulting Chemical Engineer Chemical Process Simulation Colbert, Georgia

The Athens Printing Company
Athens, Georgia

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Refinery Process Modeling First Edition

.ISBN: 0-9679274-0-4

Copyright (£)2000 by Kaes Enterprises, Inc. All rights reserved. Printed in the United States of America. This book or parts thereof may not be reproduced in any form without permission.

Published by: Kaes Enterprises, Inc. 522 Kingston Road Colbert, Georgia 30628 Phone: (706) 788-3366 FAX: (706) 788-3366 email: KAESENTER@aol.com

First printing: March 2000

The mformation contained in this book is believed to be accurate and reasonable. However, the author and K aes Enterprises, Inc. do not guarantee the accuracy or completeness of any information published herein and shall nor be responsible for any errors, omissions.ior damages arising ora of {he lise of this In/ormal;')n. Thrs book is published with the intent to supply in/ormation and is no! an attempt to render cng;':ecnng or other professional services. The user oj in/ormation published here ill is solely responsible for the acc;iTc0' and applicability of calculations based on this information.

They say that behind every good mall is a good woman. Anything good I have accomplished lowe to my wife Barbara who has encouraged and SUpported me these many years. This book is lovingly dedicated fa her.

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At the urging of several colleagues, I decided to record many of the tips and tricks for computer simulation of petroleum processes I have amassed over the past thirty-eight years. In this way, perhaps I can partially repay the technical debt lowe to the many engineers who helped me develop my skills as a young engineer. I was fortunate to begin my career in an era when corporations sought to develop young engineers through intensive training and apprenticeship programs. Unfortunately, the bottom line thinking of today no longer allows such an approach. The young engineer isoften thrust into a plant environment with little or no training. Hopefully, this book will serve in some small capacity to provide some practical training for the younger engineers. If you are locking for technical elegance this may not be the book for you. Frankly, in my experience with modeling petroleum refinery processes (with commercial simulators) I have encountered little that is elegant. I chose to focus onthe more practical aspects of engineering. Engineering theory is good and necessary; however, it is based on perfect processes and simplifying assumptions. Any practicing engineer knows it is necessary to apply experience factors to reconcile theoretical expressions with real world processes. This is the focus of this book. It is noteworthy to remind the reader that this book was written for steady state models for petroleum processes. By definition, for a steady state process, there is always <[ perfect material balance and heat balance. Any engineer who has conducted a plant test knows that real plants seldom operate at steady state. This must always be taken into consideration when developing steady state models. I must also stress that this book was written for engineers who use commercial software for their simulation efforts. Because of the enormous overhead associated with developing and maintaining simulation software, most corporations today have abandoned their own efforts in favor of a vendor-supplied simulation program. While this is the most cost-effective approach, it is not always the best technical approach. Commercial simulators must be based on open literature methods. This does not allow the use of proprietary data that might be useful in improving the accuracy of simulation results. .~evertheless. it is possible to develop accurate and useful models for petroleum processes ·..... commercial simulators. The author has had extensive experience with the ·ith Hyprotecr .. Ltd HYSIM, and HYSYS programs, and the SimSci PROVISION>< program. Howe ... the principles in this book are not simulator specific and may be applied with 'er. any simulator having the features required for simulation of petroleum processes. Gerald L Kae s

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TABLE OF CONTENTS Chapter 1 - Introduction to. Steady State Simulation
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1.1 The Steady State Process 1.2 O ynaml".~ S'Imu I' anon 1.3 Steady State Simulation Program Features I .3.1 Pure Component Data Library 1.3.2 Non-Library Components 1.3.3 Thermodynamic Methods. 1.3.4 Physical and Transport Properties 1.3.5 Simulated Laboratory Tests 1.3.6 Unit Operation Calculations : 1.3.7 Special Flow Sheet Modules : 1.3.8 Graphical Interface 1.4 Steady State Simulation Chapter Programs

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2 - Composition

of Petroleum Refinery Feed Stocks

2.1 Crude Oil Properties

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2.2 Crude Oil Composition 2.3 Crude Oil Assay 2.4 Crude Oil Blending

Chapter

3 - Laboratory

Testing of Petroleum Streams
(TBP)

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3.1 True Bolling Point Distillation 3.2 ASTM D86 Distillation 3.3 ASTM D1160 Distillation 3.4 API Gravity ~

3.5 Reid Yapor Pressure (R.Y.P.) 3.6 Chromatographic Simulated Distillations..
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3.7 Flash Point 3.8 PourPoint

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3.9 Viscosity
3. 10 Octanes 3. 1 1 Cetane Chapter 4 - Developing Petroleum

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Pseudo-components : 25 '25 26 28

4.1 Pseudo-component Normal Boiling Points 4.1.1 Conversion 6f086 Distillations 4.1.1.1 086 Cracking Corrections 5

TABLE OF CONTENTS (continued)
4.1.2 4.1.3 4.1.4 Conversion ofD1160 Distillations Conversion of Simulated Distillations Selection ofTBP Cut-point Ranges of Pseudo-component of Pseudo-component Enthalpies Gravities Molecular Weights 29 29 31 33 35 36

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4.2 Development 4.3 Development

4.4 Pseudo-component

and Critical Propenies

Chapter

5 - Limitations

of Petroleum Pseudo-components
Distillations

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.5.1 Prediction
5.2 Prediction

of Laboratory

of True Stream Composition of Refinery of Laboratory Reactors Tests : :

5.3 Simulation 5.4 Simulation

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Chapter

6 - Thermodynamics K Values

for Petroleum Calculations
on K values :

6.1 Equilibrium

6.2 Effect of Non-Hydrocarbons

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6.3 Hydrocarbon-Water
6.4 Enthalpies 6.5 Recommended

Systems

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Methods

for Petroleum

Systems

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6.6 Thermodynamic Chapter 7 - Practical

"Rules ofThumb"

Distillation

Principles
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7.1 Theoretical Considerations........................ 7.1.1 Inside-out Distillation Algorithm 7.1.2 Column Conventions 7.1.3 Initial Solution Estimates 7.1.4 Non-converged Column Solutions ~ 2 S' .. ~ J. imu I'anon 0f Exisnng Co Iumns 7.2.1 Gathering the Information , 7.2.2 Defining the Separation Zones 7.2.3 Translation of Actual trays to Theoretical 7.2.4 Defining Performance Specifications.. 7.2.5 Tray Rating

" Trays ,. " . ,

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7,3 Troubleshooting Actual Columns , ,., .., 7.3.1 Difficulties Matching Real Column Operations 7.3.2 Diagnosis of Column Operational Problems

Chapter

8 - Crude Distillation

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8.1 Crude Distillation Units' Generallnformation 8.1.1 Process Description 8.1.2 Typical Ope.ations and Controt.
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8.1.3 Schemes to Increase Crude Processing Capacity 8.1.3.1 Main Column Considerations . . 8.1.3.2 F umace C· apaclty C onslid eratrons S.2 Crude Distillation Units: Simulation of Existing Columns 8.2.1 Definition of the Crude Oil.. 8.2.1.1 Crude Assay Oata 8.2.1.2 Crude Oil Data from Product Blending 8.2.2. Collection of Operating and Laboratory Data 8.2.3 Translation of Actual Trays to Theoretical Trays 8.2.3.1 Main Column Stripping Zone 8.2.3.2 Main Column Flash Zone 8.2.3.3 Main Column Wash Zone 8.2.3.4 Pumparound Zones 8.2.3.5 Side Product Draw Zones.. 8.2.3.6 Top Section of Main Column 8.2.3.7 Side Stripping Columns 8.2.4 Crude Column Overhead System ~.2.S Solution Techniques: Inside! Out Column Algorithm 8.2.5.1 Initial Estimates 8.2.5.2 Initial Model Phase 8.2.5.3 Tuning the Model _ 90 90 . 93 95 95 95 98
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112 112· 113 113 114 115 115 116 119 119 119 123 . ~ 129 129 130 130 131 131 134 135 136 136 137 138 138 140 141 141 145 148

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Chapter 9.l

9 - Vacuum

Distillation

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Vacuum Oistillation: General Information 9. I . 1 Process Description 9.1.2 Typical Operations and Control..

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9 ._ V acuum O'1St! anon U'S' I '11' ruts: irnu I'auon 0 f'Exi xisting Columns 9.2.1 Definition of the Topped Crude Oil 9.2.1.1 Crude Assay Data 9.2.1.2 Topped Crude Oil Data from Product Blending 92.1.3 Molecular Weight Estimation 9.2.2 Adjustments to the Topped Crude Oil. 9.2.3 Collection of Operating and Laboratory Data ~ 9.2.4 Translation of Actual Configuration to Theoretical trays 9.2.4.1 Steam Stripping Zone for Wet Vacuum Units 9 2.4.2 Boot Cooler Circuits ' 9.2.4.3 Light Gas Oil Zone .. 9.2.4.4 Heavy Gas Oil Zone 9.2.4.5 Wash Grid and Flash Zone 9.2.5 Solution Techniques: inside! Out Algorithm 92.5.1 Initial Estimates 9.2.5.2 Initial Model Building Phase ~ 92.5.3 Tuning the Model Chapter 10 - Refinery Reaction Systems
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.1.2. 1 Quench (Desuperheating) Zone ·.1....2 4 2 Heavy Cycle Oil Zone .3 Slurry Strippers 11.2...2.6 Stoichiometric Conversion Reactor Chapter 11 .·.2..2.-.· ·· · .1 Process Description 11: 1.·· ~ · ·· ..1 Black Box Reactor ModeL. ·.1..····.2.···.7 Ether Processes 10.· ·. ..::.'.3 Light Cycle Oil Zone 11.1.1.2 Coking 10.....· · · ·..2 Collection of Operating and Laboratory Data 11. 11.1._ .·..2. ··.. •• ..4 AI ky lation and Polymerization 10. · · ·.. •••••·•• ..· · .··· .·················· . 204 ··..· ···. .. 1... : ···· . --.1 Catalytic Cracking 10.. ---___.General Information 10. .. .· 204 205 207 208 208 ··.1.·· 1 12...2.2 T ANtE Processes ~ · ······················· ·····._-.. ___.. 11..2 Catalytic Polymerization 10.=.-.2 Hydrocracking and Hydrotreating 10.····· .1..2. ·· 11.4 Main Fractionator 11._..2.··· ··.1.6 HydrogenPlants 10.3.... • • .3 Reforming and Isomerization 10.2..···· .:::..1.· ···· ·.4.2.2.:!:.4. 5 Overhead System s .···· ..1. .2.4.······· 148 150 153 153 157 160 160 0 •• : • ..1 MTBE Processes 10.2 Main Fractionators 11..2 Isomerization 10.··.1.1 Alkylation 10.-"==" _ .2...:. • ·· ··· · ·...1..1.1 Hydrocracking 10.1 Definition of the Reactor Effluent...··.2.3 Empirical Predictive Reactor 10..FCC (Fluid Catalytic Cracking) Processes 11.5 Thermal andCoking 10.1.1.1 Reactor Processes.5..__ .· ·.1 FCC Reactors 11.7.4 FCC Gasoline Splitters : 11. ~ \ 10..·...3..2.5..7._..4.··· ·:· ·· · · · 164 7 16 167 172 174 174 178 181 183 183 186 188 188 i90 10. ...-..·· 211 2 t2 212 217 217 220 222 223 224 225 226 227 228 11.3 Reactor Modeling ·······....2..2 Modified Black Box Reactor 10.··.2....1 Catalytic Reforming 10.::_.2.1 Visbreaking 10.1.2 FCC Processes: Simulation of Existing Units 11.1.1.4 Free Energy Minimization Reactor (Gibbs) 10.2 Reactor Processes: Simulation Techniques 10.2 Typical Operations and Control.5 Equilibrium Reactor 10.· ·· 11.2 Hydrotreating 10..5 FCCGasPlants 193 196 198 200 " · ··· ·····...'~~...1.4.1.1...· ··.....1 FCC Processes: Genemllnformation 11.. .··· ·..44 Heavy Naphtha Zone 11..~-.TABLE OF CONTENTS (continued) 10.

.2. S' I' f Exi .2..)~ 2~'" 232 233 233 233 234 234 12 .7....2.5..Hydrogen Processes .2 2 Collection of Operating and Laboratory Data 13....1 Initial Estimates: Main Fractionator 1 i .. I Process Description 12....... I.1.1 Recycle Estimate 12..1 Blocked Operations Chapter 13 .2 Typical Operations and Control.5..2.. 12.Catalytic Reforming Processes 236 236 237 239 241 242 242 243 243 245 246 248 248 249 249 249 250 12. 1 Definition of the Reactor Emuent.2.... P .- 251 251 252 253 255 255 256 2 56 256 258 260 262 262 13.2 Initial Estimates: FCC Gas Plant Columns 11..TABLE OF CONTENTS (continued) 11.7. I Hydrotreating Processes: General Information 13....5 Recycle Loops ~ 12.5...2.1..2....1 Primary Absorber 11..6 CCR Catalyst Systems · 12....4 Stabilizer 11.2..7 Solution Techniques 12..2. irnu anon 0 xrsting Ul1Its.. 11. 13.3 Secondary Absorber..5 C3! C4 Splitter 1 ] ..2.5.2..... 1...l A Separators! Gas Treating 13 1 5 Product Stabilizers (Strippers) 13 '") H\'d ~.. 11..2..4 Stabilizer Modeling 12.2. .12 Typical Operations and Control 13 I 3 Hydrotreating Reactors l3.2.2 Catalytic Reforming Processes: Simulation of Existing Units 12...2..5 Gas Plant Columns : 11....2.5 Modeling Stabilizer (Stripper) Columns 9 ...7.6...5...2.3 Reactor Modeling 12..2 Stripper I 1. Chapter 229 229 230 230 23 J 23: .24 Modeliog Separators! Gas Treating 13.7.......6 Recycle Loops.2....1 ...3 Reactor Modeling 13...2.1 Definition of the Reactor Effiuent..2.....2... 1 Hydrotreating: Process Description 13......1... I Recycle Estimates 11. I Catalytic Reforming Processes: General Information 12.3 Initial Model Phase I 1.....4 Tuning the Model.5 Stabilizer Tower Operations 12.. rotr eanng rocesses...4 Reformer Separator Operations 12..5.2.2.. 12. 13...2........7....7 Solution Techniques: Inside! Out Column Algorirhm 11.3 Catalytic Reformer Reactors 12..2 Collection of Operating and Laboratory Data 12.2.

2 Modeling Reactors in Hydrogen Plants 13.1 Blocked Operations '" 13.3.: 1.4.: 290 290 292 292 14 .1.7.3 Modeling Amine Treaters 13 ......1 Hydrocracking: Process Description 13.6.7 Solution Techniques 13.5 Steam! Water Systems Chapter l4.4.4.7 Solution Techniques 13.1 Initial Estimate for Recycle Hydrogen 13.4.4 Hydrocracking Processes: Simulation of Existing units »: 13.6.3..2 Typical Operations and Control...4.2.:.1 j':' 280 280 281 282 282 283 283 284 286 287 288 288 ~ 289 290 . 13.Thermal Visbreaking: Processes General Information 1 1 visbreaking: Process Description 293 294 296 296 1..4 Modeling Separators! Gas Treating 13..3 Reactor Modeling 13...6 Recycle I Purge Gas Calculations 13 .6.4 Energy Recovery __ 13.6.6 Quench Hydrogen Produ_ct Separation '" .4..2.2 Collection of Operating and Laboratory Data 13.4.3..2 Reactor Calculations for the Design Case...1 Collection of Operating and Laboratory Data 13. ..6..7: 1 B locked Operations 13..5...1 Heat of Reaction 13.4.i.6..4...5.. 266 266 '267 269 269 270 270 270 271 272 274 276 277 279 279 13..4...2.4. 1.3 Hydrocracking Reactors 13.6.. 13.. 13.2 Recycle! Quench Hydrogen Techniques 13..... 13.3 Hydrocracking Processes: Generallnformation 263 264 : 265 265 13.1 Definition of the Reactor Effiuent..4...5.6.1 Hydrogen Plants: Process Description 13.3.4 Modeling PSA Units 13.5 13.3 Hydrogen Plant Reactors 13..5.3.6 Recycle / Purge Gas Calculations 13..5 \ ~odeling Fractionation Columns.Separators! Gas Treating 13....5 Hydrogen Plants: General Information 13.4...1..TABLE OF CONTENTS (continued) 13..3...3.3 Visbreaking Reactions 142 Product Separation Processes: Simulation of Existing Processes 10 14::: Visbreaking 296 .6 Hydrogen Plants: Simulation of Existing Units 13.2 Typical Operations and Control...2 Typical Operation and Control 13. Initial Estimate for Recycle Hydrogen 13...3.

.l HF Reactcirs..... ..1 Reactors: HF Processes 15.Alkylation Alkylation Processes Processes: General Information .........LO ection 0 i 5 6 3 Reactor Modeling.2 H2S04 Reactors : : 5..2.....2. .--... p...-.2........ . •.. Chapter 15.....3. 1 Typical Operations and Control: HF Processes.4..2 Alkylation Processes: Process Description 15. 336 337 337 338 341 .....2 Typical Operations and Control: H2S04 Processes 15'-i Alkylation Reactors ] 5........2 Oepropanizers.1 Definition of the Coke Drum Outlet (Reactor Effluent) 14. r 56.3 Coking Reactions " Separation · ...2 311 313 315 Process Description: H2S04 Alkylation Units .4.....) 14. 15:..... fO peratmg an d L a boratory Data .... Collection of Operating and Laboratory Data: 14.1 Process Description: HF Alkylation Units 15....5.6.2. 15. 15.......2.1 .3......1 Definition of the Reactor Effiuent 1 ~ 6 ') ~ II .4 Product ... 335 335 . 156.3..)_-' 323 "')6 .... 15....2 Typical Operation and Control 14.2 Reactors: H2S04 Processes 15.2 14..6...3 Reaction Modeling 14.....1 Delayed Coking: ProcessDescription 14.1 304 304 307 308 309 311 311 15 .. ..3.3.6.....6...5 Product Separation I ) 6 Al k I' • f Exrsting U' " 'y atron Processes: S· I' irnu atron 0 nits 15.)_ 328 329 329 ..56 Alkylate Splitters j 5 66 Modeling ofRecycles Chap[er 16 .....6.3...5...--'''.3 Reaction Modeling ~ 14..3 Delayed Coking: General Information 14...2 Collection of Operating and Laboratory Data: 14......4..4 Modeling Main Columns . 331 333 33::..4.4 Coking: Simulation of Existing Processes 14.... I 5 6 5 I Propane HF Strippers..... 14..4.....2........ Debutanizers 15. 322 " ')~ .. 14.3...4.4 Isostrippers in HF Processes 5 15...~ .5. (see aneous rocesses IJ 318 3I8 319 32 I 321 322 .5...4 Modeling Fractionator Columns J 4..\1' II . Processes IS 6.TABLE OF CONTENTS (continued) Definition of the Soaker Outlet......4 Modeling the Acid Systems ]56 5 Modeling of Distillation Columns....6. 297 298 299 300 301 30l 302 303 ~O~ ) . Alkylation Processes: Typical Operations and Control I 5 3. 15.3 Deisobutanizers in f'hSO...

2.1. 379 · Glossary B -Referenc-e:s Appendix C .2.4.<.1 Processes That May Be Modeled with Commercial Simulators 16. I.1.2 Amine Treaters: Simulation Techniques ~ 16..1 Asphalt Processes : 16.3 TAt'vtE Processes 16.2.4 Chemical Treatment Processes 16.2 Lubricating Oil Processes 16.Subject Iadex Biography of Author .2.1.' _387 39'7 /2 .1 Amine treaters: General Information 16.1.1 Catalytic Polymerization: General Information 16.1.2 MTBE Processes 16. · 358 359 359 360 360 361 363 .2.1. - 341 341 342 · 343 344 345 347 349 350 351 352 352 356 ·..2 TAME Processes: Simulation Techniques .3 Aromatic Extraction 16..TABLE OF CONTENTS (continued) 16.5 Diffusion! Adsorption Processes Appendix Appendix A.1.2 Catalytic Polymerization: Simulation Techniques 16.3.2.1 TAME Processes: General Information 16.1.1.1..2 Processes for Which Commercial Simulators Are Inadequate 16.4 Amine Treaters 16.3.4.] . 1 Catalytic Polymerization 16.1 MTBE Processes: General Information 16.2. .2 MTBE Processes: Simulation Techniques 16.1.

The techniques presented in this book are generally not simulator specific and may be applied to any commercial simulator program which has the features necessary to model the petroleum processes. The commercial software is cost effective. To overcome these limitations. steady state simulation continues to be the major tool for ana'ysis and design of chemical processes." ". 341 341 342 343 344 Chapter 1 Introduction to Steady State Simulation . . There are many commercial programs available that may be used to model the petroleum processes. and every unit of mass entering the precess in the feed stocks leaves the process in the products. some mass is converted to coke which is deposited on the catalyst.. the use of the same program at all sites provides a measure of standardization and also minimizes training costs Commercial steady state simulation software is well established in the marketplace. 5t2. ~ - -.--. For companies with multiple sites.j. ~-~ . . While ~ecenl advances in computer technology have made possible the use of dynamic simulation for large process flow sheets. 345 347 349 350 351 The modeling. Therefore.. for this case the total units of mess entering and leaving the process are still the same. This mass leaves the reaction separately from {he other reaction products and it must be considered when calculating the mass balance jar the process.~ . however. a licensee may have a vendor incorporate proprietary methods and data into a private version of the software. The steady state concept has been applied widely in chemical engineering to the design and evaluation of individual unit operations and processes consisting of multiple unit operations. For many of the petroleum reactors.. . it may represent a compromise in technology since only open-literature and vendor-developedmethods are provided.1 Th e Steady State Process By definition. .. Common software is available to both engineering contractors and operating companies. .. techniques in this book are for steady state simulation. the law of conservation of mass is perfectly upheld. A major advantage of commercial software is stanJardization of methods and data. however. plant design models may be constructed using the simulation program of choice for an operating company.1t a:1)' chemical process has a perfect material and heat balance in the steady This principle also applies to the individual unit operations within the process.-'~' . .. The development and maintenance of general purpose simulation programs is costly. and most engineering 'contractors and operating companies have abandoned their efforts in favor of licensing or purchasing commercially developed software.'. Only in the C2. 352 352 356 358 359 359 160 )60 161 163 ~79 i87 i97 1. That IS.5eof a chemical reaction is mass transformed.

oi Introduction to Steady State Simulation '.·hich a process variable or variables are changed with time. and these time periods should never be used for steady state representation of the process. feed stock composition and rate changes. shut-downs. For design it is also necessary to consider maximum and minimum limits which may occur during start-ups.!: . Processes may deviate greatly from steady state during start-ups and shut-downs. changes in specifications and rates for products. The steady state operation is defined as the 24-hour test period. This type of dynamic model is useful for analysis of control schemes such as those used for :istillation operations.4 [ 'f ~ 1. The heat or energy-balance is also perfect for a steady state process. the units of energy entering the process in the feed stocks and other heat sources such as process heaters must leave the process in the products and heat sinks such as coolers. In the petroleum industry. it is likely that the process deviated from the steady state during that time period."j •• '"".' . The principle also applies to chemical reaction within the process. .. For example. For each snapshot in time. Time dependent simulation is called dynamic simulation and is discussed briefly in the section following. Deviations are caused l::.. the steady state concept is used to represent the average operation ofa process for a period of elapsed time. Since each steady state condition represents only one point in time. 4 f :!! . and start-ups and shut-downs for the process or individual unit operations within the process. and upset conditions for the process. this type of model cannot properly analyze the dynamic ?eriormance of some unit operations such as compressors where surges of material are ?focessed curing start-up or upset conditions.2 . ~ :.2 Dynamic Simulation The most basic form of dynamic simulation is a series of steady state simulations in ·.I I· i. a steady state operation may be defined for the average operation of the plant for a longer period of time such as a month. the energy must balance. Rather. a plant test is conducted for a period of 24 hours and the process inputs and outputs of material and energy are recorded for that period of time.. For both cases. In similar fashion. perfectly across the reactor and the overall process.-. Time is not a variable in steady state analysis. the evaluation of operating dynamics requires a modified approach in which time is introduced as a variable.. where the reaction heat is supplied for endothermic reactions and removed for exothermic reactions. That is. Steady state simulation is widely used for the design and analysis of chemical processes. However. Endothermic reaction heat is normally supplied by a heat source while exothermic reaction heat is usually removed in the products and heat sinks.. ::-:e steady state condition of perfect material and energy balance is maintained.. the steady state time is commonly expressed in terms of one twenty-four hour day. set point changes in the process because of minor upsets. Regardless of the length of time chosen to define a steady state operation.

-\11 commercia! simulators have large pure component libraries containing data for the various classes of chemical compounds encountered in chemica! processing plants. . A product stream from one unit operation may become a feed stream to another and so forth. limited-scope dynamic modules were developed for use In plant start-ups and shut-downs. All of the unit operation calculations are based on feed streams comprised of distinc: chemical components. but most of the data . 1. thermodynamic methods. Hlst?nc. Portability is an 'important feature for engineering programs. It is probable that. Nevertheless. therefore. The calculation platform of most interest is the personal computer (PC). dynamic simulation models will find widespread use in operator training and determination of optimum set points for large chemical processes. Vendors may develop these data for less common components. particularly for modeling ?f large processes. and operator training. and all commercial simulation programs provide a graphical interface. in the future. t.1 Pure Component Data Library . Ease of use is important for PC products. In this fashion. the greater share of process modeling today is steady state simulation and this is the focus of this book. it is convenient [0 store calculated results from the unit operations as streams. Laptop PC's have become very popular because of their portability. sheet building modules.es that required for ste~dy. state models. for which various thermophysical properties are available Calculated results always include product streams comprised of the same chemical components (or corresponding reaction-produced components).3 True dynamic simulation requires sophisticated.3. the process flow sheet is constructed using the streams as the connectors. In past years. and a user interface for program input and output. time dependent models for the unit operations. 1. unit operation calculations. especially for engineers who commonly visit operating plants in many locations.". process control. transport properties.3 Steady State Simulation Program Features Commercial data library. The number of calculation~ req_uired for dynamic models is many ti~.n which process information may be entered and retrieved via a process flow diagram (PFD). and all vendors offer PC versions of their products. simulated laboratory tests. physical and special flow simulation programs provide a common list of features: a pure component estimation procedures for non-library components.ally.he spee~ and storage ca?acltJes for computers have limited the use of dynamic simulation. Current advances in computer technology have made possible the consideration of dynamic simulation models for large process flow sheets.

. Entropies are used for isentropic calculations such as compression and expansion..ftware. ... =:a:C"'"'TO::"A . These data and other relevant parameters are kept in thermodynamic data banks in commercial simulators. The user may also supply thermodynamic parameters as program input..-~-----~_. -. 1. 1.2 Non-Library Components No simulator is complete without procedures to estimate thermophysical properties for non-library components.3 Thermodynamic Methods I ).._ .3.'.must be estimated from such correlating parameters as normal boiling point. particularly the first two.. I..3.. Many of the thermodynamic parameters are vendor-developed. Enthalpies and entropies are commonly calculated using expressions derived from equations of state that relate the enthalpy of the mixture to the enthalpy of the mixture in the ideal gas state.:. Ideal gas enthalpies are computed for each component and pseudocomponent using polynomial equations in temperature.:: f~ :. emhalpies.. .-. Some vendors also allow the licenser to incorporate private technical libraries within their sc..-. '-" . These properties are necessary for the unit operation calculations. .._. and entropies..1 !i? h1 Thermodynamic data include vapor-liquid equilibrium ratios (K values).. there are also recognized sources for data such as the DECHEhLA-\ Chemistry Data Series. Petroleum pseudo-components are discussed in more detail in Chapters 4 and 5_ Simulation programs Jacking petroleum pseudo-component capabilities are not suited to the modeling of the petroleum processes.4 usually-come from recognized reputable sources. Calculation methods for K values include equations of state. For petroleum streams.. liquid activity coefficients. ' . The concept of pseudo-components is used. Liquid activity coefficients are calculated with standard equation forms using pre-determined coefficients. specific gravity.:. The accuracy of the K values predicted by the various thermodynamic methods is largely determined by the quality of the thermodynamic data bank information and user-supplied parameters. Open literature estimation procedures are commonly employed in which component properties are related to chemical structure.:_-. Common sources for pure component 2 data include the PPDS' and DIPPR libraries. where a pseudo-component represents a certain 'boiling point range of the feed stock. and molecular weight. .. and empirical formulae. however.' The accuracy of an equation of state is improved by incorporation of tuning factors based on pure component binary vapor-liquid equilibrium data. structural data are not available for non-library components and properties.

1.3.n the same scientific principles Commercial simulators provide individual unit operations as building blocks that may be linked together via the process streams to form the process flow sheet. heat transfer. octane numbers. Some tests such as octane. these operations are not needed for the petroleum processes and are omitted from discussion. thermal conductivities. tluid flow.4 Physical and Transport Properties It is useful to calculate physical and transport properties for the feed and product streams in a simulation model. and stream density. densities. and adsorption. absorption. K values are used in a calculation procedure to determine the vapor and liquid portions of a mixture at a given temperature and pressure. pour point. An additional subset of unit operations is available for handling solids and inorganic processes. pour points. and mass transfer operations such as distillation. Lnit operations include the following: vapor-liquid equilibrium separation.3. Transport properties such as viscosities. weight. vapor pressures. and volume units. and how well the composition effect can be represented with the components and pseudo-components used in the model. Laboratory tests include distillations. and viscosity nearly defy correlation because they are so composition dependent. however.6 Unit Operation Calculations in chemical engineering to divide processes into a series of calculation steps called unit operations. cetane numbers. reaction. One or two liquid It is convenient . and liquid surface tension are commonly computed usmg the principle of corresponding states . Ii --~ . stripping.''. freeze points. Most commercial simulators include methods to simulate these tests. flash points. The individual unit operations have common techniques and are based o. and viscosities.3. diffusion. More discussion on laboratory tests is given in Chapter 3. Accuracy of the simulated test depends on two factors: how well actual test data can be correlated into a predictive equation. which commonly appear in process after process.5 Simulated Laboratory Tests The sped fications for petroleum' products are based on standardized laboratory tests.1. or determined based on the average properties for the stream Properties computed from individual component data include stream total flow in mole. The fundamental unit operation is vapor-liquid equilibrium separation (also known as "flash" separation). These properties may be calculated using the individual component contributions.5 1. .

and the column operating conditions. washing the heavier components down the column. It is sometimes desirable to impose additional performance specifications on the solution.. Reflux flows down the column. every tray is at vapor-liquid equilibrium and has both liquid and vapor products. in which the vapor product from one separation ascends to the next higher as a feed and the liquid descends to the next lower as a feed...... Distillation calculations are based on steady state operation.. 1. Finally.. compressors. and Gibbs free energy minimization. .. ··t . every column has a perfect mass balance for every component for every tray as well as for the entire column.. . in which a unit operation product stream is returned to an upstream operation for re-processing. a simple drum is used for flash separations. with the vapor leaving in an overhead line and the liquid or liquids drawn out of the bottom of the drum. there is a perfect energy balance for every tray and the entire column. In plant operations..- . The flash separation principle is used as a subset of nearly every other unit operation. Heat transfer calculations include heat exchangers. Liquid from the bottom of the column is warmed by a heat source (reboiler) and the re-sultant vapors are returned to the bottom tray of the column as stripping vapor. and some of the liquid is returned to the top tray as reflux.... Stream mixers and splitters (or tees) are used tel combine and split flow sheet streams corresponding to stream junction points in the process flow sheet... and coolers.... Fluid flow operations include pumps. -. related to the product qualities. carrying the lighter components in the feed up the column.. pipes. phases are considered to be in equilibrium with one homogenous vapor phase.... including stoichiometric. Distillation and its subsets of absorption and stripping are the most important unit operations in petroleum processes. kinetic.. _. The distillation process consists of a vertical series of inter-linked flash separations... Some processes have recycles..7 Special Flow Sheet !\lodules Severa: auxiliary modules are used in process modeling._.-..w-. The stripping vapor flows upward through the column.3. starting from an assumed set of product flows and tray temperatures Several methods have been devised to solve the matrix describing the various mathematical relationships for the column. and valves.. The recycle stream will reach a constant '. The separation steps are designated as theoretical trays and the composite group of trays is called a column. Diffusion and adsorption seldom have application and are omitted in the discussion below. The vapor from the top tray is condensed..._r __ . A variety of reactor types may be provided... At solution. equilibrium.t! _. quantities. _ ••.6 ". furnaces. Distillation calculations are iterative. Likewise.

3. III the as the lux have an empirical stream separation module. Alberta.8 G ra phicaJ In terrace The graphical capabilities of PC's are useful for simulation programs. The following listed programs are general process simulation programs with petroleum pseudo-component capabilities: Program Name . This reduces errors in definition of the flow sheet is also a convenient means to provide the operating data for the individual operations. rate. IvfA.PD\· PLUS I:·H£MCAD 10 /ot Program Vendor n: :JESIG:V II HYSllvf HYSYS Apsen Technology Chemstations. . The user build a PFD visually on the screen... Inc. Hyprotech. in which a new recycle stream composition is predicted. feedback controllers are used to adjust an upstream process variable such as temperature to produce a desired downstream result such as a product quality. Other useful flow sheet modules include feed back and feed forward controllers.I..--S. These calculations may represent proprietary technology or a unit operation not provided by the program vendor. . Windows Simulation Company Hyprotech.4 Steady State Simulation Programs Over one hundred and thirty programs are listed in the A. TX. Canada Calgary. temperature. may and unit unit 1. Ltd. Most simulators have accelerator techniques for recycle calculations. Ltd. Another useful concept provided in many simulators is a user-defined calculation block in which special calculations may be defined. USA Calgary. TX. based on two or more previously calculated compositions.the downstream product stream is directly substituted as a feed to the upstream operation. Vendor Location Cambridge. All simulators om 1. . The PFD may also be used to retrieve calculated results for specific operations. USA Houston.7 Ipes " !rgy Composition. and pressure in the steady state. This module finds utility in shortcut representation of auxiliary process flow sheets within the main process flow sheet. USA Houston. Alberta.: .nder the category "Process Design/Simulation". Canada !. r.E. This procedure is repeated until the recycle stream reaches the steady state. Feed forward controllers are used to set downstream operating conditions based on calculated upstream results. Software Directory' -. in which a feed stream is separated into two streams using a defined set of individual component separation factors.Ch. To model the recycle calculation.-.

The reader is encouraged to contact souware vendors directly fer 'i more information on specific products. CA. This is not meant to imply that other products cannot be used to produce satisfactory results. Bryan Research & Engineering Brea.. and PROVISION programs for which the author has extensive experience. USA PROSIM Notes: l) HYSYS is the future replacement for HYSIM. examples and simulator specific information are limited to the HYSIA1. Inc. HYSYS. It has both steady state and dynamic simulation capabilities.! '"3 I Ii ) Hort b MY' _".:!".o :j PD-PLUS PROVISION Deerhaven Technical Software Burlington. . When presented in this book. MA. USA Bryan. This list is not intended to be a complete list of every simulation program applicable to petroleum processing nor is this book intended to be a treatise on the relative merits of the above products. USA . .wr: .j' . TX. Simulation Sciences.

47 St.. 2 DIPPR Data Compilation of Pure Compound Properties. Laboratory . Institute of Chemical Engineers. American 345 E... . l\ty 10017 (January 1998). American St. New York. Institute: . 4 '7 . and 4 1998 CEP Software Directory. NY 10017. the German Society for Chemical Apparatus.9 1 PPDS (Physical Property Data Service) and the National Engineering association with the Institute of Chemical Engineers. 345 E. England.f Biotechnology.n Chemical Engineers. New York. 3 DECHEMA . Chemical Engineering.

it is primarily a mixture of compounds containing hydrogen and carbon (hydrocarbons). Crude oil is a naturally occurring liquid resource produced from wells drilled into the earth. the elementary composition of crude oil usually falls within the following ranges.000 distinct hydrocarbon compounds from a single sample of Oklahoma crude oil.~ . such complete analyses are not conducted on crude oils. It is possible to make some generalizations about the nature of crude oil. and no attempt is made to analyze for pure components in crude oil except for the low boiling point distilled components (or light ends)._. According to Gary and Handwerk'....---- . . nitrogen. 10 !'I i: . greater than fifty percent of the world's known reserves are located in the geographical region known as the "Middle East". naphthene base. -'-. ~'- . or asphalt base.14 0-3 0-0. . Project 6 has succeeded in isolating over 16. sulfur. h 1: Chapter 2 Composition of Petroleum Refinery Feed Stocks The primary raw material for all of the petroleum processes is crude . depending on the geographical region from which it is produced.. First. . Element Carbon Hydrogen Sulfur Nitrogen % by weight 84 . The depth of crude oil wells and methods used to produce the oil vary widely around the world.. In fact. However.6 Crude oil is classified roughly according to the predominant family of hydrocarbons it contains as paraffin base..l.-~.P.. 2. The relative values for crude oils depend on the processing costs and the market values for the-associated products. __ '.. For this reason. Crude oil bases vary greatly with geography.._..-.87 11 .... In general.. :L Crude oil is produced in all comers of the globe. this region will continue to be a strategic focal point for the nations of the world.------ ii il .. The nature and chemical composition of crude oil also vary widely. Additionally. and some inorganic salts are also found in most crude oil mixtures. A. . crude oil may vary widely in composition within the same producing field. ' I i . The refining scheme is dependent on the crude oil base.1 Crude Oil Properties Crude oil is a very complex mixture of thousands of hydrocarbons. A number of simple tests are used to evaluate crude oils as potential refinery feeds.oi1.. aromatic base...

the pressure of the TBP still is gradually reduced during a TBP distillation test to a low of approximately 40 mm of mercury (Hg) for the heaviest portion of the crude oil. The expression for API is non-linear. the following: J) Gravity. and specific gravities must be used when calculating the gravity for blends. Therefore. Nelson. where T" is the mean a verage boiling point of the sample in degrees Rankine and sp. and a higher value indicates a Jess dense material. Crude oil API gravities vary widely with the crude base.O. it is not possible to determine the complete boiling point range for most crude oils because the oils thermally degrade above temperatures of approximately 650 degrees F (344 degrees C) and a pressure of one atmosphere.0 API to light paraffinic. A temperature of 650 degrees F and pressure of 40 mm Hg correspond to a temperature measurement at atmospheric pressure of 900 to 950 degrees F (483 to 5 10 degrees C) for most crude oils. gr. The API gravity is an inverse relationship when compared to the specific gravity.934 specific gravity).1 11 These tests include. a large percentage of the crude oils that are produced and refined have API gravities in the range 20 to 40 degrees API. (0.·:.825 to 0. This test is performed in an apparatus with sufficient fractionation to recover samples of the various products that can be distilled from the crude oil. According to Nelson 6 and others. API The density of petroleum oil is expressed in the United States as APr gravity.) ~ 131_5 The specific gravity or API gravity is relative to the density of water at 60 degrees F (15. from heavy Venezuelan crude oils of 10.gr. and The mo~t commonly used characterization :'. condensates of 70 API.5 / sp. where API gravity is related to specific gravity as follows: Degrees API = (14 J. 3) Characterization Factor factor is that proposed by Watson. [he maximum boiling point for crude oil mixtures is greater than 1400 degrees F (760 degrees C). However. It is defined as: K = [T " ] 03)3 / sp.1urphy·. Results for the test are reported at one atmosphere of pressure. It is also useful to note as a reference point that the API gravity of water is W. gf. 2) Boiling Point Range The boiling point range for a crude oil is determined with a true boiling point distillation test (TBP). Unfortunately.9 degrees C). .

the lower its value as a refinery feed stock. the factor is in the range 10. A factor of 10. The additional processing for sour crude oils involve hydrogen treating processes to convert the sulfur to H2S that can be removed. ~ • i 1 . In general. the higher the carbon residue for a crude oil. the lower the API gravity for a crude oil the higher the sulfur content.. pounds/1000 barrels All crude oil contains some inorganic salts. . . i iT 'I I. If the salt content exceeds 10 pounds 11000 barrels of crude oil it is necessary to remove the salts prior to distillation of the crude oil to reduce corrosion in the crude distillation column and its overhead condensers . \\"1 .1 t2 Composition of Refinery Feed Stocks is the specific gravity at 60 degrees F relative to water.. Note that this factor is a rough indicator of the hydrocarbon class (or composition) for the crude oil. Most of the nitrogen in crude oil is contained in the highest boiling fractions.i i e @ Q i . % ~.0 or less indicates an aromatic material and a factor of 15. I' . i i . \\1 8 i f i i :1 (. and zinc..5 to 12. In general.( I' j\ .. It is a measure of the asphalt content in the crude oil and the quantity of the lubricating oil portion that may be recovered as product. 8) Nitrogen Content. It is also used to determine the yields from coking processes and as a measure of the coke deposited on the catalyst for catalytic cracking processes. with low API sweet crude oils and high API sour crude oils. 7) Metals. copper. Other metals include arsenic. High nitrogen content crude oil may require special processing to remove the nitrogen. Metals tend to concentrate in the heavier fractions of the crude oil where they act as poisons for the catalytic and hydrogen cracking processes. However.. !. t. wt % Sulfur content and API gravity have the greatest influence on the value of crude oil • The sulfur content of crude oil varies from a trace to greater than five weight percent.5. I !! Ii . .J 4) Sulfur Content. High sulfur content crude oils are known as "sour" crude oils and require more extensive processing than low sulfur or "sweet" crude oils. with the most common being nickel and vanadium. Nitrogen compounds in crude oil reduce the activity of cracking catalysts. there are exceptions to this rule.j % This property is determined by destructively distilling a sample to elemental carbon (coke) in the absence of air. generally in the form of chlorides. etc. This characterization factor has been related to viscosity.0 indicates a paraffinic material. '~I 6) Salt Content. so that almost any laboratory data may be used to estimate it. 1 I i i ii . . molecular weight. iron. parts! million (ppm) by weight Numerous metals occur in crude oil..i _. 5) Carbon Residue. For most crude oil. critical temperature.

coking. paraffins. however. and aromatics. that is. All of the above mentioned properties are indicators of the composition for a crude oil. or a modified FCC operation. In oil refineries olefins are created in the cracking processes. Naphthenes have at least one saturated ring and range from cyclopentane through complicated multiple condensed-ring compounds. it is necess3.-\ large quantity of crude oil assay data are available for the crude oils of the world. naphthenes.2 Crude Oil Composition Three general classes of hydrocarbons are present in crude oil. Aromatics have a! least one unsc. For some iight crude oils and condensates. This makes it dlflicult to c1assi fy most crude oils as one particular class of hydrocarbons. Paraffins in crude oil range in boiling point from methane to compounds with boiling points exceeding 1000 degrees F 8 (53 degrees C).3 CrUde Oil Assay Data . 2. a complete chemical breakdown can be determined through the light naphtha portion (normal boiling point 200 degrees F) with chromatography. it is necessary to verify the quality and quantity of asphalt that can be produced from a given crude oil in the icboratory For crude oils that do not yield specification grade asphalt products. related' to the concentration of aromatic compounds and asphaltenes in the heaviest portion.13 Pour point is a measure of the paraffinicity or waxiness of a crude oil. A typical assay contains the fOllowing information for the crude oil: . This portion includes pentanes and other light components with normal boiling points below 100 degrees_F (38 degrees C). many of the data are available in Open literature.turated ring and range from benzene through multiple condensed-ring Slnlcrures with 56 carbon atoms or more. Conversely. Some of the data are company proprietary. Asphalt Content of crude oil is directly. a low pour point indicates an absence of paraffins and! Or a presence of aromatic compounds which tend to lower the pour point. While there are generalizations useful for predicting asphalt production from crude oil. a true component breakdown is not usually detennined for most CI ude oil samples except for the low boiling portion. As Iong side chains are added to ring compounds they become more paraffinic in their properties and behavior. 2. but such data are not typically available for most crude oil samples. As previously stated.ry to process the heaviest portion in allother heavy oil process such as a hydrocracking. Signitlcant quantities of olefins do not naturally Occur in petroleum. A waxy crude oil has a high pour point. it congeals at a temperature higher than room temperature.

Many refineries process more than one crude oil. First. such as two to four weeks. light hydrocarbon yields (C1(\). Therefore. weight percent sulfur. percent asphaltene. However. viscosities. It is important to note that crude oil assay data change over time for any crude oil.tirne periods. pour point. research octanes for gasoline fractions. process design. Choosing data for a longer time period. caused by two factors. weight percent carbon residue.. for refineries that process multiple crude oils. weight percent nitrogen. and cetane number for diesel fuels.. Secondly. metal contents. 2) Fractional properties: Boiling point or cut-point range and yield on crude. . flash point. it is highly unlikely that the monthly average crude oil mixture from accounting data is an accurate representation of the crude oil ruixture that was processed during the test run. as new wells and fields are brought on line. naphthene and aromatic contents for reforming stock. For this reason it is good practice. " 2. Reid vapor pressure. smoke and freeze points for kerosenes. is helpful in damping variations in crude oil distillation yields caused by day to day fluctuations in the crude oil mixture. This presents some problems for test runs conducted over short. a crude oil sample represents a mixture of the crude oil produced in many wells and possibly many crude oil fields. and ships. The individual crude oils may be transported to the refinery via trucks. Since most refineries do not have sufficient crude oil storage to isolate the various crude oils as they are received. ii' .14 1) Whole crude oil average properties: Composition of Refinery Feed Stocks Gravity. This is. to request a confirming sample for a crude oil mixture being used in 11. the crude oil in the storage tanks is a mixture of the crude oils received by the refinery. The net result is that the crude oil mixture processed in the crude oil distillation unit varies as the crude charge tank mixture changes. pipelines. salt content. A genera' rule is to be wary of crude oil assays that are more than two years old when accurate simulation work is required. properties as shown above for whole crude oils. bottom sediment and water (8 S & W). the composition of the mixture changes. and boiling point curve. The volumes of the individual crude oils received by the refinery are available from the refinery accounting system.4 Crude Oil Blending . the crude oil itself cbanges in composition over time as it is produced from a given well.

27. (1994). 6. W.23.125. 25. 3rd edition. .I' 15 . p. p. Inc. Gary and Glenn E. (March 25.1968). Marcel Dekker. Ind. Oil & Gas J.. Marcel Dekker.126. 7. Handwerk.. p. James H. Gary and Glenn E. Petroleum Refilling Technology Economics. Nelson. 3rd edition. 1460 (1935). Petroleum Refining Technology and Economics. New York. Characterization of Petroleum Fractions. (1994).. Eng. Handwerk. New York. Inc. L. Chem. James H. Gild 8.

dy sharply in order of boiling point. there is a range of end point test results that satisfy this specification . In representing the steady state operation. most petroleum streams consist of a continuum of components from various hydrocarbon classes.: . :".. Bureau of Mines Hempel method and the ASTM D-285 test procedure are most commonly used. it is important to remember that the laboratory test results for process streams can vary somewhat It may not be possible or desirable to precisely match one particular set of test results for a given pr:ocess stream because of real time variations in the process and the accuracy and repeatability inherent in the laboratory tests. There are no standard test procedures for TBP distillations. Moreover. In general. Thus. specifications for petroleum products allow a range of acceptable test results. such analyses are net usually necessary since the qualities (compositions) of the intermediate and final products are controlled to meet simple laboratory tests. it is often more realistic to look at average test resuits for a given time period instead of single samples. Gal)' and Handwerk'o state that there is a trend toward using a 15:5 distillation (ASTM D-2892) instead of the TBP. According to Nelson'. These tests are designed to be quick. and assuming that the other test specifications can be satisfactorily met. . the ASTM D86 end point for a gasoline blend must be less than or equal to 432 degrees F (223 degrees C)... . and repeatable within a reasonable accuracy. The U. it is a good approximation of the separation that may be expected in an actual distillation column. This method is conducted using 15 theoretical stages and a still reflux ratio of 5: 1. it is not unusual to see variances in ASTM D86 temperature points of 10 to 20 degrees F (5.. set points. Inspection of laboratory test results for streams in a petroleum process show that the test results vary with time within some acceptable range. When developing steady state simulation models.1 ~. etc. A component by component analysis is neither practical nor oost-effec_tive and is rarely performed in the laboratory. inexpensive.r. Simpler. S. any equipment that accomplishes a good degree of fractionation is termed "true-boiling-point" equipment.! 3. In fact. mixture components relati·.1 True Boiling Point Distillation (TBP) l~ 11 L! I I ! The TBP distillation is the best representation of the true composition for a petroleum stream. I iJ Ii i:1 II I! !. .Chapter 3 Laboratory Testing of Petroleum Streams Because they are derived from crude oil. These variances are caused by changes in the process feed stock.6 to 11 degrees C). within reason. the time and expense required for this test restricts its use to crude oil samples. For example. less costly tests are used for control-of the refining processes. Unforrunately. Because the TBP distillation tends to separate the individual.L . Products are collected and 16 .

The condenser tube is cooled in an ice water bath and the test procedure" specifies the condensing temperature shall be maintained bet ween 32 and 40 degrees F (0 to 4. Table 3. j ts I II I i c·· I ~1 . Application of this test is limited to the temperature at which the oil begins to decompose or crack.' } r ~. and no liquid reflux is returned to the flask.5 degrees C). When the cracking temperature is reached.:\ . expected qualities for the products.2 ASTI\1 D86 Distillation ('. The ASTM D86 distillation is a non-fractionating distillation that is run at laboratory room temperature and pressure. . It has been widely used for process unit control and finished product specifications.cmpcratures are significant and must not be ignored. the pressure of the TBP still is gradually reduced as this temperature is approached to avoid cracking the sample and distorting measurement of the true components in the oil. causing variances in the cracking temperature threshold. The DSG distillation was originally called the Engler distillation since a simple Engler distillation flask is used.1 ::\ '. For many TBP apparatuses. ~ 11\ :\ .is . The exact cracking temperature for an oil sample depends on its chemical composition..17 from the TBP still that correspond to the boiling point ranges for the desired Additional tests are performed on these fractional products to determine the . All distilled vapors are removed from the still and condensed. Petroleum oils begin to thermally decompose or crack at a temperature of approximately 6~O degrees F (344 degrees C) at one atmosphere. As previously mentioned. Temperatures are reported at a pressure base of 760 mm Hg For high altitude laboratories the barometric pressure corrections to the observed . til :. Therefore. III presents temperature corrections for various laboratory barometric pressures. True boiling point temperatures are always reported al a pressure of760 rnm Hg (one atmosphere). the minimum pressure obtainable is 40 mm of Hg. Paraffin base oils crack at lower temperatures than aromatic base oils. 3. The highest temperature Ih3t can be measured at this pressure for most crude oils is in the range of 925 to 975 degrees r t496 to 526 degrees C) when corrected to a pressure base of one atmosphere. this test is often approximated using correlations that relate the TBP temperatures to temperatures measured by other types of laboratory distillation stills. The light components that boil at temperatures lower than the condensing temperature are lost from the distilled product. the temperature of the vapors from the still no longer increase since light cracked products begin exiting the still. Because of the laboratory time required and the subsequent high cost for TBP distillations. 1 . The ASTM 086 distillation is the most common laboratory distillation used by petroleum refiners.the approximate temperature at which petroleum oils begin to crack is 650 degrees F (344 degrees C) at one atmosphere..\ \ .

Thefilla! boiling point or "end point" is the highest temperature recorded during the test. The total volume of the distillate is recorded as the recovery. The test is similar 10 the ASTM D86 method with the notable exception tha: the sample is distilled at a reduced pressure to inhibit cracking...distillation points are reproducible within 2 ml. Any liquid left in the still after the end point temperature is recorded is cooled and measured as the residue.._ . Typical samples for which 0 I 160 distillations are useful are heavy heating oils. Intermediate . 19 21 22 ..~VJ 1 tal Vtt. The difference between 100 milliliters and the sum of the recovery and the residue is recorded as the loss.. 18 Laoorasory 1 e:)".uIU . One hundred milliliters of sample are distilled and the vapor temperature versus volume reco .3 ASTi\1 D1160 Distillation The ASTM 01160 laboratory distillation is designed for high boiling samples in which there is significant cracking at atmospheric laboratory pressures. cracker gas oil feeds....3 degrees C) for the initial boiling point and end point... F 572 12 13 14 15 16 597 10 11 622 8 648 7 8 8 673 5 6 698 4 4 4 5 66 724 2 50 100 9 10 11 ISO 200 250 300 350 400 450 500 550 600 650 17 18 12 13 14 15 16 6_ 7 7 8 8 9 2 3 3 J _) 9 10 12 5 13 13 14 15 16 17 18 18 19 10 11 12 12 13 14 14 15 16 .1"-' ---.. and residual oils. Repeatability of the test is purported to be plus or minus 6 degrees F (3.. -ered is recorded... u Table 3.. mm Hg H Observed Temp.If ...1 Temperature Corrections for Barometric Pressure Laboratory Pressure...9 degrees C)- 3. 23 24 17 18 9 10 19 20 21 11 11 12 6 7 7 7 8 8 9 25 26 700 22 :3 12 4 4 4 4 4 5 5 5 For use with ASTM D86 Distillations Temperature corrections are in degrees Fahrenheit.. of distillate which corresponds to six to seven degrees F (3_3 to 3. The distillation 13 ji ''. The initial boiling point is defined as the temperature at which the first drop of liquid leaves the condenser tube..

.6 degrees C) is combined with four parts laboratory air at 70 degrees F (21.. It is determined with a hydrometer corrected and reported at a basis 0[60 degrees F (15. etc. and 3.(2. According to Ne~for·gaso1inelifiheR:V.8 degrees C) and when the pressure gauge reaches a constant value this reading is recorded as the Reid vapor pressure. It.4 API Gravity This property has been previously discussed.P.9 degrees C).j)ut4ne.Lclin. The Reid vapor pressure is always reported in absolute pressure units of psi. The Reid vapor pressure is nearly the same as the true iactual] vapor pressure for gasoline streams as shown in data gathered by Nelson" and reported in Table 3. The accuracy of this test is highly dependent on proper sample handling since the major contributors to the Reid vapor pressure boil below room temperature. most commonly selected for ASTM D1160 tests is 10 rnm Hg. The largest deviations occur for the samples at the highest vapor pressures. petroleum stocks can be distilled to a maximum boiling point temperature of 950 to 1000 degrees F (510 to 538 degrees C) as reported on a 760 mm Hg basis.g". the percentage of butanes in the stream is approximately the same as the. VP.11.Y. . 3. The repeatability of the test is somewhat less than 0.4 degrees-C) in a bomb that has a pressure gauge attached to the lid. The reduced pressure used for 01160 di stillations produces a separation of components that is more ideal than that for D86 distillations. A modified Reid vapor pressure lest is also used to measure the vapor pressure of crude oils. In the test procedure for gasolines and naphthas. kpa.60 "method is sometimes used to ex-tend the TBP distillation curve for mixtures contaimng high boiling materials.rrangeof8ioT4psi. The 0.e{S.I!l.tempe'ratures are pressure corrected to a basis of 760 mm Hg for reporting At 10 mm Hg.p-L~.J!Q.5 Reid Vapor Pressure (R.correlateswell with tt~ nOfll}al butane content _~ the_§!'!. Lower pressures are sometimes used to extend this boiling point range for residual stocks. the D 1160 method closely approximates the TBP method.19 .5 psi.1ypicall¥-adjust Reid vapor the pressure of gasoline blends by adding or removin~. The bomb is placed in a constant temperature bath at 100 degrees F (37. one part of chilled Iiquid sample at 3G degrees F.ru.2 below. such as crude oils.) The Reid vapor pressure test" is used to measure the front-end volatility of products in the gasoline through heavy reforming naphtha boiling point range. In fact. bar. R. All observed . and the temperatures recorded for 50 percent distilled and higher are assumed to be identical to the corresponding TBP temperatures.

09 17.1 1..r 20 lADOrWUfY J ~')H"~ uJ .3 9. They are summarized in Table 3.3 1. The most commonly used method" is as set forth in ASTM Standard D "2887-73.14 16.3 1.. --- - Table 3.~ I " ('I i i Product: Natural gasoline Natural gasoline Natural gasoline Natural gasoline Natural gasoline Light gasoline Light gasoline Natural gasoline Gasoline Straight-run gasoline Gasoline Gasoline Ref nery gaso line Gasoline Gasoline Gasoline r 3.0 5.09 21.03 2.16 5.6 Chromatographic Simulated Distillations Gas chromatography procedures have been developed to predict the boiling point distribution for a petroleum stock that corresponds to the distribution determined with the more lengthy TBP distillation method.1 1.!:ill< TruefReid 26_2 2~. This method is limited to petroleum fractions with a final boiling point 1000 degrees F (538 degrees C) or lower.04 5.4 1..0 12. and HTSD...092 17.07 1.8 18.4 8.: ! .05 !..10 1. psi Ratio Reid I. ( iii .0 15.1 1.0 6.8 20.0 2. g! 1 .z 1.0 1.0 1.9 v.3 1.0 8.17 8.~ . ( ! i .09 20. Equipment used for D2887 simulated distillations (sim-dists) has been highly automated .. There are four standard tests currently in use by refinery test laboratories: D3710.2 1. ) 11' I' .. Carbon disulfide is used for the carrier gas in this procedure..5 14.04 6. ~ . of " ..t i H .0 10.4 20.04 3. Vapor pressure.0 3.O 1.7 1.2 Relationship between the True and Reid Vapor Pressure for Miscellaneous Volatile Products". :1 I i F 'j'.3 below.. The sample must also have a boiling point range of no less than 100 degrees F (55 degrees C)..0 12.9 1.. I I l .04 10. 02887.9 12.07 12. D2887 extended. __ .

.~ ". Therefore.". . Crude oils and heavy residues have such high boiling points that the column temperature cannot be increased enough to recover the highest boiling fractions..". With good laboratory technique. the boiling point curve predicted using the paraffin stan. The sample in question is next introduced into the column and the retention times and the areas of the sample components are recorded.3 21 Table 3. crude heavy gas oil.-~' r-.ard calibration curve is lower than . . A careful choice of chromatographic conditions is used to cause the high boiling components to be eluted from the column some 500 to 600 degrees F (260 to 316 degrees C) below their normal boiling points.d. crude Standard Cs-C1S C5-C44 C5-C60 C~-CI2O Ran~ < 500 F <1015 F <1140 F <1382 F Report volume weight weight weight Basis % % % % Note: The standard is a mixture of normal paraffins with carbon number ranges as shown. As the technique is further developed and improved it most likely will replace the laboratory distillations. All of the methods work in similar fashion.3 Simulated Distillation Procedures Method 03710 D2887 D2S87-ext HTSD Application gasolines. This makes the test desirable for process control. '. . is a modification" to the D2887 procedure which extends the boiling range distribution of hydrocarbons to a final boiling point of approximately 1382 degrees F (750 degrees C). A calibration curve of retention time in the column versus normal boiling point is developed for the normal paraffin standard by progressively increasing the column temperature and recording the areas of the individual components at timed intervals. High temperature simulated distillation. the total area of the sample is not known and the boiling point curve for the sample cannot be determined accurately for these streams. The chromatographic column is first calibrated with a standard mixture of normal' paraffin hydrocarbons. HTSD.-~. naphthas cycle oils... in particular. The method has been found to have some limitations for mixtures containing aromatic compounds boiling higher than the gasoline range. gas oils heavy gas oil. the TBP distill arion. Thus. This modification shows great potential for analysis of heavy petroleum residues. These aromatic compounds have lower retention times than the normal paraffins of similar boiling points. reproducibility of boiling point curves using chromatography is much better than that for conventional laboratory distillations. The components in the sample are then assigned boiling points by using the calibration curve of retention time versus boiling point developed for the normal paraffin standard.

The open cup method is often used because of its simplicity. If no movement is detected for 5 seconds the solid point has been reached. The closed cup tester heats the oil at a rate of 1. and the Penskey Martens (ASTM D93) and the Tag (ASTM 053) closed cup methods..16.4 degrees C) to ensure that all wax is in solution. ----. The sample is now placed in a cooling bath that is maintained from IS to 30 degrees F (8. :f 3. This may be overcome by developing aromatic correction factors for the simulated distillation temperatures. The open cup method heats the oil at a rate of 10 degrees F (5. To determine the flash point.8 degrees F per minute and is the more precise of the two methods. multiple sets of correction factors are required to accurately represent the various refinery samples containing high boiling aromatic compounds. The . The same procedure is used to detenninc the cloud point of a petroleum oil.3 .6 degrees C)..temperature at which the vapors ignite is recorded as the flash point.- _ _r'_ • .7 Flash Point The flash point test determines the temperature at which the vapors from a petroleum oil will ignite or "flash". . The pour point is defined as the temperature 5 degrees F (2.> the actual boiling point curve for the sample.8 degrees C) higher than the pour point.6 degrees C) per minute with the test flame applied at 30 second intervals. 3.8 Pour Point The pour point test (ASTM D97) is useful in determining the waxiness of a petroleum oil. Cleveland open Clip method (ASTM 092). The cloud point is defined as the temperature at which a distinct cloudiness or formation of crystals appears in the bottom of the test jar. a sample is heated at a specified rate and an open flame introduced into the emitted vapors at specified time intervals.6 degrees C) higher than the closed cup flash point for the same sample.7 degrees C) below the pour point of the oil. ~-~.. Below flash points of 51 0 degrees F (266 degrees C).8 degree C) intervals and tilted to determine if the oil will flow. It is then cooled to 90 degrees F (32..8 degrees C) above the solid point. The test jar containing the oil is removed from the bath at 5 degree F (2.8 degrees C). A sample of oil is first heated to 115 degrees F (46. Therefore. Because the correction factors depend on the relative quantities of the aromatic compounds in the sample.)cn:uw.. Two basic procedures are used to determine the flash point: the '. the best accuracy that could be expected from this method is plus or minus 5 degrees F (2.. The cloud point is typically about 5 degrees F (2.22 Laboratory Testing of Petroleum .. the open cup flash point is approximately 10 degrees F (5.

Historically it was determined in a laboratory engine (ASTM engine test D613).23 The' viscosity of an oil is its internal resistance to flow and a measure of its usefulness as a lubricating substance. Sayboh viscosities are 088) is a similar test viscosities are reported used to convert Saybolt reported as seconds. The usual test temperatures are 100 and 210 degrees F (37. degrees C). Values for intermediate temperatures are read from this line. The time in seconds is measured for a sample of 60 cc of oil to flow from a container through a calibrated orifice at a prescribed temperature. The knocking value of the test sample is next determined and compared to the knocking value for the 224TMP standard to determine its octane. The current trend is to advertise the average octane from the two tests. F-l value... on which a straight line is used to connect two known viscosity! temperature points. i.e. F -1 octanes are higher than F-2 octanes because of test engine differences.2 degrees C).0 is assigned to 224TMP. 3. Tables are 2 viscosities to kinematic viscosities. API gravity. and . The F-2 octane is a better measure of the performance of the gasoline in a commercial automobile engine because the conditions of the F-2 test more closely approximate actual motoring conditions.11 Cetane The cetane number is used to measure the performance of a fuel in a diesel engine. Saybolt Furol at 122 and 210 degrees F (50. 3"10 Octanes The octane test is used to measure the knocking characteristics of a fuel in a laboratory gasoline engine. . ASTM D86 50 percent distilled. The engine is calibrated by measuring the knocking value for a standard material. Two octane tests are run for gasoline: the Research method (F-I) and the Motor method (F-2). An extensive evaluation of methods to compute cetane has been published by Collins and Unzelrnan" of the Ethyl Corporation.3 and 99 . but today it is usually calculated with a formula that relates cetane number. gasoline was sold by the higher.8 and 99. Historically. (R + M) !2. an octane number of 100. The Saybolt Furol viscosity test (ASTM for heavy fuel oils and uses a larger orifice. By definition. The Saybolt Universal viscosity test (ASTM 088) is the most common method used by refiners. Viscosities at other temperatures may be determined with ASTM viscosity paper. 2-2-4 trimethyl pentane (2241MP)..

Company. Inc. Nelson. H. Villalanti.. 23. Petroleum Refining Technology and Economics. p. 15. i~ I i f 11. p. Petroleum Refinery Engineering. 1995 Al. "Better Cetane Prediction Equations Developed". p. n 19.Meeting. McGraw-Hili Book 10. Inc. This concept is discussed further in Chapter 4. Marcel Dekker. M(:tfiod 01 ]60. Jansen and P. 4th edition. James H. (1958).CoHe. G. (1994). 18. Petroleum Refinery Engineering. 133. American Society Philadelphia. p. 14. Laboratory Testing of Petroleum Streams all of the above mentioned laboratory tests are used to evaluate the qualities processes. J. (1958)..e ". W. 1982). "Hydrocarbon Characterization Temperature Simulated Distillation".lbJd. Part 24. of feed stocks and products from the petroleum References: 9. 148. important in simulation since they can be used to define petroleum pseudo-components to represent the streams for the unit operation calculations.E. Spring National. PA (1982). Testing and Materials. 95. G. PA (1982). ~t and Unzclman. L. American Society for Testing Philadelphia.24 In summary. Part 23. 4th edition. Method D86-IP 123. Kaes from K M. New York. L. 12. Inc. 1995). Part L I I 13.. p. .27. Method D2887-73. Gary and Glenn E_ Handwerk. Personal Communication. Ibid. Method 0323-56.C. Collins.. Mcfiraw-Hill Company. L. and Materials. Oil & GasL.160. (Jur. Ibid. 138 for Book 17. W. 3rd edition.. (March 19-23. by High Houston. . I (1964). They are. Texas. New York. 16. . Nelson.Ch. New York. Buster. D.

it is necessary to represent all process streams with discreet components for which thermophysical properties may be defined. For a pseudo-component. Laboratory distillations and various other properties are predicted for these streams from their compositions. 4.apter 4 Developing Petroleum . Since most of the actual components are unknown for petroleum streams. As mentioned previously. petroleum pseudocomponents are developed to represent the unknown components in these streams. Pseudo-components represent pre-defined boiling point ranges or cut-point ranges on the TBP distillation curve for the stream being characterized.1 Pseudo-component Normal Boiling Points The first step in development of pseudo-components is definition of the pseudocomponent cut-point ranges on the stream TBP distillation curve. The conversion step introduces another degree of uncertainty into the characterization of petroleum streams since the distillation inter-conversion methods are based on a limited number of samples of limited accuracy. it is the necessary first step when an actual TBP distillation is unavailable Pseudo-component cut-point ranges are next defined and applied to the actual predicted TSP distillation curve. or is 25 . another type of laboratory distillation is used and a correlation is used to convert the test data to the corresponding 760 mm Hg TBP distillation. and molecular weight. Alternately. The compositions for all flow sheet streams are represented with actual components and pseudo-components. However. Pseudo-components For the unit operation calculations. Each pseudo-component corresponds to several unknown actual components. Three correlating parameters are commonly used to estimate thermophysical properties for petroleum pseudo-components: normal boiling point. these parameters are the weight averaged values for the TBP cut-point range of the pseudo-component. specific gravity. TBP distillations are seldom' run in the laboratory because of the time required and the associated high cost. Properties highly influenced by chemical class such as pour point are difficult to predict accurately with pseudo-components since a pseudo-component may represent several actual components of more than one chemical class. The normal boiling point for each pseudo-component defined as the weight average temperature for its cut-point range. Open literature correlations enable the prediction of any of these three parameters from the other two.

Dec F 107 57 40 97 43 10 10-30 30 139 68 182 58 240 77 165 242 Starting Point 30-50 50 " {f' ~:'j . Commercial simulators determine these points by quadratic interpolation of the predicted TBP curve. This correlation has found widespread acceptance by petroleum refiners. . The first graph relates the D86 50 % distilled temperature to the TBP 50 % distilled temperature. and 95. DegF Diff.. e. Dec F TBP. 30-50 %.1 Conversion of D86 to Data with the Edmiste. and 90100 % distilled. aI. et..ji !~.1. .1.. This method consists of two graphs.. 80.1 below.r and Okamoto Method (Figure 4. 90-100 100 458 No provision exists for conversion of other distilled percents. 20. 10-30 %. Note that the Edmister and Okamoto method always predicts a distillation curve with a positive slope. A revision of this 21 method was published by Edmister and Okamoto in 1959 and is illustrated in Figure 4. 70-90 %. ~ l! -: !' 50-70 70 70-90 90 60 300 65 365 60 425 76 318 75 393 65 .. itr. The second graph is a family of curves relating the D86 temperature slopes to the TBP temperature slopes for segments of the distillation curve as follows: 0-10 %.{..1. .1) Corresponding D86 Temp. American Petroleum Institute (API) Technical Data Books published prior to 1987 present the Edmister. method as Figure 3Al.1.1 Conversion of D86 Distillations The most widely accepted methods for conversion of D86 distillations to TBP distillations are derivatives of the Edmister and Pollockl() correlation. Deg F 32 % Distilled 0 0-10 D86. 50-70 %. 40.g. Table 4. The method is illustrated in Tabie 4. 5... 60.26 Developing Petroleum r seuao-componaos 4. 'I " k . TBP Temp. DitT.

! ··1 . The following equation form was used for all inter-conversions: \ \ where: T "" Absolute temperature. Degrees F of o 40 60 80 100 1.>0 140 160 160 ASTM 086 Temperature Difference.::: designate atmospheric TBP and ASTM 086 data. the Riazi and Daubert method was not widely accepted by petroleum refiners and a new study was commissioned for its replacement. II iii . ~ ~ " /. . correlations.':'l v. . et. ' IL' 10 40 20 j 10.~ L .I I . 'I' --~. ':II-K 'l. 70. Deg F 120 100 80 60 ~ r'" " ". Oeg F The 1987 API Technical Data Book introduced a new method for conversion of D86 to TBP. Conversion of D86 Distillation to TBP Distillation 21 ' Method of Edmister and Okamoto Figure ".:1 L r I 1~r 10( 1'l'1p% OJ. The point by point approach to interconversion sometimes predicted TBP distillation curves with regions of negative slope for petroleum streams with small boiling point ranges.: ::6 1. ASTM 086 50 %..160 140 10 ~ 'A''h ~ rI Art' 1#. Ct ~ ~~ l&: ~ "..! \ . 50. the Riazi and Daubert correlation resulted in prediction of TBP distillation curves that were inconsistent for some cases.b... ". respectively Unfcrtunately.1A: 50% conversion :lOCI 160 110 1/ V /. This method was based on work done by Riazi and Daubert=: and was based on a different approach from the earlier Edmister.1 .c = unique constants corresponding to 0. deg R Sg "" Stream average specific gravity.' 20 ///.18: Volumetric slope conversions Figure ". and 95 % distilled TBP.al. 90..' ~ T8P 50 % minus 086 50 %.27 Figure 4. 10.: I ! . Because of these anomalies. API a.30.086. Deg F 7'D 10 :10 TBP Temperature Difference. " c 10~ .

30-50 %. degrees F. this simple equation is a gross oversimplification for the cracking of petroleum stocks in which chemical class is the controlling factor.his method. The correction is applied to ASTM D86 temperatures greater than 475 degrees F (246.. however.00473 (T) . 50-70%. Although the more recent versions of the API Technical Data Book no longer include . All of the methods discussed above are in the open-literature and have been incorporated '+ into commercial simulators/ The 1987 Riazi. 4. correction to be added to observed D86 temperature. et. temperature increments for the following ranges are added and subtracted to develop the complete TBP curve: 0-10 %. distillation curve for which cracking is occurring. E.1. Developing Petroleum Pseudo-components n In 1994 the results of the new study were published by Professor T. The D86 and TBP data used by Riazi and Daubert were refit to different equation forms. However. At this writing. 70-90 %. The author recommends that this cracking correction not be used. The new correlation first converts the 086 50 % distilled temperature to the TBP SO % distilled temperature. it is likely that the new correlation is a significant improvement over the 1987 Riazi and Daubert correlation. Observe that this is the same approach taken by Edmister. et.' Furthermore.~ Calculation of the cracking correction is illustrated in Table 4.1. al. and 90-100 % distilled... .al.2.. most t commercial simulators still make it available. Daubert.~ l degrees F . However.28 . T = observed D86 distillation temperature..and Daubert method.1. there is insufficient industrial experience with the new correlation to confirm this claim. Professor Daubert reports that the new correlation is more accurate than the older Edmister.. correlation. I .1 D86 Cracking Corrections Figure 3ALl of API Technical Data Books published prior to 1987 presents an equation to correct observed ASTM DS6 temperatures for cracking. it can result in' distillation curves with negative slopes that are a physical impossibility. A better approach is to use distillation probability paper to adjust the portion of th::. 0.4 degrees C) and is calculated with the following equation: .~ 10gl0 0 :.. J < . Based on the SO % distilled point. !. should not _be used since it does not always produce satisfactory results. . 587 where: 0:. 10-30 %.

Correction curves are given to adjust the D 1160 temperature differences for the segments o.2 that no correction is applied to the D 1160 temperatures for 50 percent distilled and higher.6.29 Table 4. This limits the usefulness of the test for residual materials such as topped crude oil that may have final boiling points in excess of 1600 degrees F (87] degrees C). I0 %.2 Conversion of D1160 Distillations The Edmister and Okamoto" method is used to convert ASTM Dl160 distillation data to TBP distillation data.2 and has a pressure base of 10 mm Hg for the D 1160 distillation and the predicted TBP distillation. Note from Figure 4. The method is given in Figure 4. Therefore. F 506 560 618 6S1 753 -.Temperature. The first method for conversion of D2887 distillation data to TBP data was published by Riazi and Daubert". 4. the D2887 data are converted to D86 data with the following equation: . This procedure is appl icable to petroleum . fractions with final boiling points of 1000 degrees F (538 degrees C) or less and boiling ranges of at least] 00 degrees F (55 degrees C). The final step in application of this method is use of a Cox chart to convert the predicted 10 mm Hg TBP Curve to a 760 mm Hg TBP curve. the first step in using the Edmister and Okamoto method is conversion of the laboratory data to a 10 mrn Hg basis with a Cox chart. D 1160 data are nonnally reported by laboratories on a 760 mm Hg basis. F 500 550 600 650 700 Corrected D86 Temperature.3 Conversion of Simulated Distillations The D2887 simulated distillation is a relatively new test.1. the test has been revised to accommodate higher boiling stocks. This method involves two conversion steps. ASTM Standard D 2887-73 procedure was first published in 1973. First. and 30~50 % distilled.1.2 Cracking Corrections for Observed D86 Distillations: Observed D86 . 4. 10-30 %. As previously mentioned in Sec/ion 3.

However. The conversion equations shown above are also based on a limited sample base with the highest boiling point being 762 degrees F (406 C).. this conversion method is not recommended and should not be used. so " &0 .) 0. 90. D2887 for 086 0. and the compounding of inaccuracies by the two step conversion procedure.0 20 :Y I 2~L'V I VY /V 0-1 ~% / V / -. 30. The Riazi and Daubert procedure has been made available in commercial simulators. Because of these problems and limitations. V V~ V V V r-. F. F = 0 009524 ( T 02887 1ODA) 0 a. 1GO 140 120 100 1~ "loAN p3G-Q % -.. results are very poor because of the inherent inconsistencies in the approach used for both the 086 and TBP temperature conversions. l!: -r / l~ I 60 700. NOT ~% ! I . C= o. b. Q r 20 40 GO 60 100 120 140 160 180 200 220 240 ASTM 01160 TEMPERATURE DIFFERENCE.oso~ ( T D2~81 500/. 10. = designate ASTM 086 and ASTM 02887 report eO temperatures The second step is conversion of the predicted 086 temperatures to TBP temperatures with the 1987 Riazi and Daubert correlation discussed in Section 4. SO. DEG F wh ere.30 Figure 4. I.t . and 100 % distilled.(. 70.2 Developing Petroleum Pseudo-components Conversion of D1160 10 mm Hg Distillation to TBP 10 rnm Hg Distillation Method of Edmister and Okamoto'· 240 220 ::00 160 .6147 0 I Constants D86. I.

A single conversion step is used in this latest procedure to predict the TBP temperatures from the 02887 temperatures. FCC slurry oil. The following approach is recommended when using commercial simulators. As bas been discussed in Section 3. asphaltic crude oil. and 90-100 volume percents from the corresponding D2887 temperature differences for 0-10. 10-30. A f:l!11ilyof curves is next used to predict the TBP temperature differences for 0-10. 30-50.'BP). 10-30.6. the TBP 50 volume % distilled temperature is assumed to be equal to the D2887 50 weight % distilled temperature. i. correlations. Daubert also refit. Modify the TBP as needed to account for the aromatic content of the stream. etc. it is not likely that a single correlation can ever be developed to accurately predict TBP distillations from simulated distillations. Rather. 30-50. and HTSD are entered on a mass basis. with the average . the D371 0 is supplied on a volume basis. temperature of the cut-point range defined as the pseudo-component normal boiling point (I--. the more accurate approach is to develop individual conversion methods for the various types of refinery streams with high aromatic contents. distillation probability paper may be used for a "cut and try" approach until the model produces satisfactory temperatures for the products that contain the heavy aromatic compounds. The aromatic boiling point correction may be estimated by comparison of the simulated distillation temperatures to another laboratory distillation such as the D 1160. 4. "-~ . 50-70. Note that the 02887. smooth distillation for the process streams such as occurs in a typical refinery distillation operation.1.4 n 31 As a part of the study to replace the Riazi and Daubert inter-conversions. In this procedure. Enter the simulated distillation as if it were a TBP distillation to prevent the simulator from using an inaccurate general conversion method. The number of cut-point ranges (or cuts) used to define the true boiling point curve for a petroleum stock is somewhat arbitrary. 50-70. On the other hand. Using a large number of cuts is not generally justified in consideration of the accuracy ofa TBP boiling curve that is derived from an ASTM laboratory distillation of limited accuracy. coker gas oil.4 Selection ofTBP Cut-point Ranges TB P cut -poi nt ranges are used to define the pseudo-components. The revised procedure published by Daubert is an improvement from the earlier Riazi and Daubert method.e. 70-90. 70-90. Because of this characteristic. There is little industrial experience with this method to date..8 degrees C). and it is recommended that all predicted results from this method be carefully examined for reasonableness. simulated distillations are based on normal paraffin boiling points and become inaccurate for streams containing appreciable contents of aromatic compounds boiling above 400 degrees F (204. If no other laboratory distillations are available. D2887 extended. and 90-100 weight percents. al. the D2887 distillation data to equations similar to the Edmister. using too few cuts results in a model that does not predict a continuous. et.

1 .- . DegF < 100 100-800 800-1200 1200-1600 TBP Range.8 37. Number of cuts DegC < 37. c g') (l) x ::... This concept win be further discussed in Chapter 7..uevelopmg Petroleum rseuao-componeoo The following cut-point ranges are reasonable for most refining problems and are used as defaults in many commercial simulators: TBP Range. g t .:: Q) c r .8-427 427-649 649-871 Use actual components (pentanes and lighter) 28 8 4 The final selection of cut-point ranges for a model depends on the distributed components in the fractionation zones. Figure 4.. u. . ~i.3 illustrates selection of cut-point ranges for a petroleum stock..3 Definition of TBP Cut-point Ranges for Petroleum Stock Atmospheric TBP Distillation Curve . Figure 4.c: _J C» C) Q) "0 Q) <. o :: Liquid Volume % 100 . (/) c Q E 0 0= Defined Component NBP e U . 0 ! ~.pseudo-component boiling point (NBP) average normal 0 c a.

they all agree in that the needed adjustment is done to the pseudocomponent gravities only. a stream gravity curve developed with the stream average characterization factor tends to have a slope that is too flat.33 4.gr. The stream average boiling point is defined by commercial simulators in a variety of ways.gr. The next step is determination of the pseudo-component gravities to establish the corresponding rl!ass flows. iLVg == stream average boiling point in degrees R and stream specific gravity at 60 degrees F. Thus.sp. point: K •~ =[ T~_] ~~ 0333 I sp. 0<I1o'jr:. the characterization factor for the lighter boiling fractions is higher than the _stream average value because of the higher paraffin content of these fractions.. commercial simulators determine the pseudo-component gravities by assuming that the Watson-Murphy K factor is constant (or nearly constant) throughout the entire stream boiling range. The stream gravity curve must now be smoothed (or normalized) such that the weight average sum of all of the component gravities in the stream equals the supplied average stream gravity.333 sp. Commercial simulators differ in the approach taken in this step.gr .] 0. = I K'Vg - where: K. Individual pseudo-component gravities are next determined with this variation of the formula above: [T B. : For wide boiling streams such as crude oil. e-: The assumption of a constant Watson-Murphy characterization factor becomes less accurate as the boiling point range for a stream increases._ . however. The Watson-Murphy K factor is computed for the stream average boiling .2 . H~ where T. the characterization factor for the higher boiling fractions is lower than the stream average because of the greater concentration of aromatic and asphaltene compounds. When only the average stream density is supplied.. = . __ . . The minimum information required in this step is the average stream density for the stream being characterized. respectively. Converse Iy. K factor pseudo-component average boiling point in degrees R Specific gravities for the known components in the stream are extracted from the pure component library." == stream average Watson-Murphy T B. Development of Pseudo-component Gravities Definition of the cut-point ranges establishes the normal boiling points (NBPs) and corresponding liquid volume flows for the pseudo-components. .

~ . II 1I I I I I .. where several fractions from the distillation test are collected and analyzed. I I : I 1 . ~: . ..' .)t:uuv. I' I I . 34 ....b· • . The resultant pseudo-component gravities are a better representation of the chemical nature of the oil than those derived with the constant characterization factor assumption.··· . . . uevelop. Normalization is still necessary for the pseudocomponent gravities derived from the supplied curve.. . •4 .4 Relationship of Pseudo-component Properties to the TBP Distillation Curve :J Atmospheric TBP Distillation Curve . .q···. I .\ <II t C AI J pseudo-component NBP's c: 8. I . . however. ..n 1 I :.. the slope of the supplied curve is held constant during the adjustment process. : I .. I. I t' . I I I I Ie'· t 4 ~ :. ..~••- ~ I Most commercial simulators provide an option by which additional points on the gravity curve may be supplied.. Such data are usuallyavailable for crude oils. . . . "ZVt t. I I I I I I I . The gravities for these fractions are entered at their mid-volume percents on the overall boiling curve to establish a gr. II II II II II ~ " . I ~:~·f *.. . .I II ~ 't-"f .~ 4 ._1 4 4~ . ~~ I t . ..ng r eiroteum r .v . (' 'I ' I I I . ~ : : 1 I : • . .y"" .avity curve for the stock.. '.. . ·. I 't.. I I I I I I I I I I I I . I I II I ...~ i[ I' II I' ~I I 4 t I I I t I I I ~ t I I i L I I ~ y 4 ..- C. . t. • . 100 <·7 o Liquid Volume 'J.. .f. I I 1 I I I I c . Figure 4.t .. I I I I I t .u.. u § 4 .

e. they are predicted by commercial simulators based on the pseudo-component normal boiling points and gravities. \ 1\ "I I I II I II . . Commercial simulators all have provision for the direct entry of the three correlating parameters for petroleum pseudo-components.. First. Similar to gravity data.. and molecular weight. 'Numerous open literature correlations have been . gravity. introduce s fourth correlating parameter such as the source of the petroleum stock. Therefore they should be preferentially used when available. catalytic cracker.3 Develo pment of Pseudo-com ponent Molecula r Weigh ts Detennination of . Second. any error in predicting the gravity has a direct effect on its accuracy.developed and published since the 1930's that relate normal boiling point.35 4. however. Since these methods are based on actual experimental data they are more accurate than the open literature methods in commercial simulators. Commercial simulators allow the user a variety of methods to predict molecular weight. gravity. In fact. gravities. If the stream average molecular weight is also given. and molecular weights are shown in Figure 4. proprietary methods not available in the open literature often .. it is usually prudent to use the simulator default method since other thermodynamic data may be tuned to the default molecular weights. most commercial simulators provide an option by which molecular weight data may be supplied. Thus. i. Molecular weight data are seldom available for petroleum stocks. These three correlating parameters allow the accurate prediction of other needed data for the petroleu m pseudo-components. the pseudo-component molecular weights are normalized such that the stream average is met.the pseudo-component molecular weights is the final major step in characterization of petroleum stocks.. coker. The relationship of the pseudo-component normal boiling points. The slope of the supplied curve is held constant during the adjustment process and the resultant pseudo-component molecular weights will be a better representation of the chemical nature of the stream than those derived with the open literature methods A pseudo-component molecular weight predicted from only normal boiling point and gravity is the least accurate of the three correlating parameters. Therefore.. The molecular weight for stream fractions are entered at their mid-volume percents on the overall boiling curve to establish a molecular weight curve for the stock. and molecular weight have a bias toward paraffins. the methods may predict molecular weights more representative of paraffins than aromatics. hydrocracker. etc. open literature methods that relate normal boiling point.4 above. for highly aromatic materials.. straight run.

for Petroleum Fractions". for thermodynamic calculations with References: 20 Edmister. p.SO-57. C. polynomial coefficients are derived for standard ideal gas enthalpy equation forms using the pseudo-component normal boiling points.8. "Phase Relations Chem. (August 25. Engr. (September . and/ or molecular weight and the open literature abounds with such correlations. 1 f: ! i: Ii I ! . Ideal gas enthalpies for hydrocarbons correlate well to polynomial expressions. p. and Pollock. 44.4 Pseudo-component Enthalpies and Critical Properties The open literature abounds with accurate methods for predicting enthalpies. W.. K K.. andlor molecular weights. (1948). . C. 21 Edmister. T. E. H. R. E. 75-78. 23 Daubert.. T. and Daubert. Enthalpies are typically computed with equations of state as deviations from the ideal gas state. Thus. Plots of the simulator predicted pseudo-component properties should a/ways be used to make certain that the entire boiling point range is represented in a reasonable fashion Other pseudo-component properties required equations of state are discussed in Chapter 6. ----. 1986).. p. Hydrocarbon Processing. f· I' i 1 . "Petroleum Fraction 1994). Vol. p. gravity. M. Distillation Inter-convert Distillation- Inter-conversions"....90S. W. "Applied Hydrocarbon ThermodynamicsPart 12: Equilibrium Flash Vaporization Correlations for Petroleum Fractions". No.. 117 (1959). and Okamoto. . "Analytical Correlations curve Types". Oil & GasJ. and critical properties for petroleum stocks from the three correlating parameters previously discussed. Vol. Prog. entropies. 38... Therefore. it is only necessary to predict the ideal gas enthalpy curves for the petroleum pseudo-components to predict their enthalpies. 22 Riazi.36 Developing Petroleum Pseudo-components 4.. Petroleum Refiner... D. Critical properties for petroleum pseudo-components also correlate well with normal boiling point.. gravities..

1.. i. etc. pour point... .. which is a continuum of actual components. The laboratory distillations for products are predicted by a procedure that is the exact reverse of the feed stock characterization procedure. D 1160.:.:'. viscosity. '. Pseudo-components derived by commercial simulator programs do not represent the composition effect very well because of limitations in the open literature correlations that are used to predict the thermophysical properties.g. The selection of TBP cut-point ranges for pseudo-components has been previously discussed in Section . 4. it is necessary to smooth this rough curve to reproduce the characteristic shape of an actual TBP distillation curve. In reality.!..:- :~.. Therefore. . . however. However..e.j:.J. . 5. This limits the ability of commercial simulators to predict accurate results for laboratory tests that are strongly influenced by composition.... '... the predicted TBP distillation is determined by volumetric integration of its components in order of normal boiling point.. crude oil is a continuous mixture of thousands of actual components. D86..:' '. and may have flat regions corresponding to blocks of discreet components and pseudoComponents.'... This chapter discusses the limitations inherent in petroleum pseudo-components produced by commercial simulator programs. these limitations must be considered when interpreting the calculated results from commercial simulator programs. For each flow sheet stream... . .1-4. tc~·' ' .. This TBP is not smooth. D2887. ~.pterS mitati~ns of Petroleum Pseudo-components The concept of petroleum pseudo-cornponents is necessary and useful for calculations with petroleum feed stocks.f'_' "" :"·~· . using the conversion relationships presented in Sections 4.1. This does not invalidate the pseudocomponent approach to solving petroleum problems. ~. e. Calculations with the characterized feed stocks predict products with varying amounts of these same components and pseudo-components. A typical petroleum stream characterization uses 50 to 100 library plus pseudo-components to represent full boiling range crude oil.. ~. the engineer must always remember that pseudocomponents are a gross oversimplification for the complex mixture of actual components found in petroleum. Some problems arise when predicting the TBP distillation by volumetric integration of [he normal boiling points for the stream components.1 Prediction of Laboratory Distillations Commercial simulators use a discreet number of components and pseudo-components to represent petroleum oil. 37 i II 1\ Ii i! ._.. etc.. -'.3. The next step is to predict the desired laboratory distillation.

.55. those temperatures corresponding to 1. Thus. and inaccuracies in the open literature methods used to predict the pseudo-component properties.2 Prediction of True Stream Composition Two problems arise in prediction of the true stream composition: the cut-point ranges.6 degrees C) for the highest boiling fraction of the petroleum stock.9 degrees C). the cut-point width has an important effect.9 to 55. These default percentages may be changed by the user. In the real world. respectively. This compounds the problems caused by the discreet blocks of components. r Obviously. it is better to estimate the corresponding 5 and 95 volume percent temperatures to use for the simulation specifications. Prediction of the TBP initial and end point temperatures present special problems. In terms of actual components. It is also noteworthy to remember that the distillation curve slopes for the initial and final portions of all types of laboratory distillations are much steeper than those for the middle portions.6 degrees C). If the predicted initial and end point temperatures are used for decision making. commercial simulators arbitrarily define the predicted TBP initial boiling point and end point temperatures as . Users of commercia! simulation programs usually do not specify the cut-point ranges and the default ranges are used in the characterization process. the conversion correlations have higher errors when predicting the initial and end points corresponding to the simulated TBP temperatures. and the net result is that the predicted initial and end points for laboratory distillations are not reliable. For this reason. Therefore. but this will have little effect without corresponding changes in the pseudo-component cut-point ranges. these problems are additive. However. the corresponding changes in the 5 and 9S volume percent temperatures should always be reviewed as a test of reasonableness. I below illustrates the actual components that may be present in the cut-point range of a pseudo-component developed for FCC gasoline with a commercial simulator.0 volume % distilled. Initial and end point temperatures are used in many petroleum product ~:ecifications. 'r . for simulation purposes. Unfortunately.0 volume % and 9&. these points represent small quantities of light and heavy components.38 Limitations of pseudo-components . 5. a cut-point range of 2S degrees F may represent many components of different chemical class and/ or isomer structure. the first and last component may represent several percent of the distillation curve. It is doubtful that commercial simulators can accurately predict the true magnitude of end point and initial poi nt temperature changes that occur in operating plants when productcut-points are changed. . Table 5. Default cut-point ranges may vary from 25 to 100 degrees F (13 9 . A typical characterization uses cut-point ranges of25 to 100 degrees F (13. The lowest boiling fraction is represented by pure component boiling points andl or pseudo-component cut-point ranges of 25 degrees F (13.

the average pseudo-component properties predicted by if' simulator have a definite paraffin bias. prediction of pseudo-component properties for streams rich in paraffins (such as straight run gasoline) will be more accurate than those for streams rich in ring structures and unsaturated compounds. Thus.2 158.2 100. Cut-point range on TBP: 150 .1..3 Simulation of Refinery Reactors This subject will be discussed in more detail later in this book.4 86. btullb-mole ---_ . a property such as F-1 octane that is highly dependent on both component class and isomer structure cannot possibly be predicted for the above pseudo-component with any measure or accuracy.. it is apparent from the discussion in Section 5.2 84.4 48..7 167. as might be expected.. Four distinct classes of component are represented by the one pseudo-component shown above in Table 5. However.8 92.700 Note: benzene is likely present because of azeotroping.1 82. The open literature correlations used to predict pseudo-component properties have a bias toward paraffins since much of the data used in their development are for paraffins..1 24. 5.2 that pseudo-components from commercial simulators .6 161.900 174. -----~71.175 degrees F Average NBP.8 176. degrees F == 164 Average API Gravity = 63.2 82.2 28.500 ..2dimethylpentane methylcyclopentane l-hexene l-Mvcyclopentene 4-M-cyclopentene benzene (See note) ---~------------- Class ..3 83.1 56.2 146.4 Average Molecular Weight == 84.4 48. Mole r-i Wt Octane 155.4 NBPt Grav.0 >100 >100 100 35. Furthermore.900 ·17.3 72.6 77.1 possible Actual Components in One FCC Gasoline Pseudo-component Pseudo-component Properties. -------paraffin paraffin naphthene olefin olefin olefin aromatic deg F API - Ht of formation. The average properties predicted by the simulator cannot possibly represent the unique properties corresponding to each pure component.900 ~88. Therefore.1 78.3 Pure Component n-hexane 2.2 84.7 81.Chapter 5 39 Table 5.8 91.45.

carbon numbers.0. :! I i j i: i 1 :1 1 . Prediction of the heat of reaction is also a problem.40 Limitations of pseudo-components of cannot represent stream compositions accurately !D terms of unique classes and isomers hydrocarbons. namely. However. isomerization. These pure components are involved in thousands of reactions that include cracking.. Several other laboratory tests present difficulties because of their dependence on the chemical composition of the stock and the inability of petroleum pseudo-components to accurately represent true chemical class and structure. hydrogen transfer. I· i Ii 1 : [: I I 5. For example. furnaces: etc. the heats of formation for hydrocarbons vary significantly with the chemical class. hydrocrackcrs. the number of reactions taking place. straight chain (unbranched) hydrocarbons are easier to crack than highly branched structures. and coking (carbon formation). it is not possible to predict accurate heat of formation data fer the pseudo-components since they represent a mixture of pure components of various classes and structures. condensation. cokers. both from the standpoint of representing the feed stock with discreet components. are dependent on the chemical classes and isomer structures of the' feed stock components. For example. . have been previously discussed in Section 5. Thus. normal heptane has an F-l octane of 0. Classic reactor calcu lations compute the standard heat of reaction as the difference in the sum of the heats of formation for the products and the reactants. This is also true of many of the other refinery reactor units. simulation of the catalytic cracking reactions is an impossible task. etc . The feed stocks for fluid catalytic cracking units have hundreds of actualcomponents of various chemical classes. and isomer structures. Unsaturated components such as ole fins and aromatic rings can be saturated with hydrogen in hydrocracking and hydrotreating reactors. 1) Octanes It is apparent from the illustration in Table 5. it is also highly dependent on the isomer structure of the component. Paraffins are more easily cracked than ring structures such as naphthenes and aromatics. The other seven-carbon atom paraffins have the following octanes: 2-methylhexane 3-methylhexane = = 42. There is another complicating factor for many of the refinery reactors.4 52 . and in definition of the reactions that occur.. such as reformers. As Table 5. particularly the initial and end point temperatures..1.1 illustrates.1 that this property cannot be predicted accurately with pseudo-components.. Not only is octane highly dependent on the class of component.4 Simulation of Laboratory Tests Difficulties in prediction of the laboratory distillations. etc. 'I I' . The catalytic and thermal reactions that occur in refinery reactors.

Paraffins have higher viscosities than aromatics in the same boiling point range.6 degrees C). . Predicted viscosities from commercial simulators are order of magnitude accuracy for light oils.. Many of the open literature relationships in commercial simulators are based on pure component data. The best indicators of the actual product viscosities are the laboratory viscosities of the corresponding crude oil fractions for the straight run products.. In addition to anomalies because of hydrocarbon class and structure.8 . Pseudo-component TBP cut-point ranges in the temperature range for wax are typically SO to 100 degrees F (27.· However. Wax properties are well disguised within a pseudo-component of this boiling point range . Predicting pseudo-component viscosities and weight averaging them to determine the average stream value has not been any significant improvement over simple correlations such as Watson. and a viscosity blending method used to predict the blend stream viscosities. For example. Cloud Point These tests are a measure of the wax content of a petroleum stream. Some of the refining processes for lubricating oils preferential Iy extract a particular class of hydrocarbon to give the lubricating oil a peculiar viscosity! temperature relationship. . 3) Viscosities Viscosity is a nemesis to correlate for actual petroleum stream data. The controlling factor in viscosity is chemical composition. Nelson. Watson. there are synergistic octane effects when one class of hydrocarbon is blended with another. kerosene. Nelson.4] 2-4-dimethylpentane = 92. and Murphy correlated whole stream viscosity with API gravity and the Watson-Murphy characterization factor. Some of the early attempts such as Watson. naphtha. and gasoline. etc. Some commercial simulators provide for input of stream viscosity blending indices. . Moreover. 2) Pour Point. The viscosities for petroleum streams with large numbers of components are difficult to correlate. good chemical anal yses for heavier refinery streams are virtual! y non-existent. Nelson.55. such as light diesel fuel. and Murphy" are still state of the art. Waxes are primarily paraffins with long side chains. Rather. olefins blended with aromatics exhibit blending octanes that are several numbers higher [han the pure olefin values. actual viscosity tests should be run for the stocks in question. and Murphy which predict the average stream viscosity. predicted viscosities for heavier petroleum fractions and whole crude oil are highly inaccurate and should not be used for process design and decision making. or long paraffin side chains attached to other hydrocarbon structures.8.

t for petroleum streams and is now calculated with a standard formula. Since the API gravity and average boiling point may be accurately simulated. Therefore. .t. l. =." . Stream average properties may then be calculated with a reasonable degree of certainty using the pseudo-component blending values. 27. 1460. However.. a characterization based solely on the D86 distillation does not properly represent the light components that exert the highest vapor pressures.ie pseudo-components to represent hydrocarbons witu fewer than five carl.. 5) Vapor Pressure and Reid Vapor Pressure Real components have the largest effect on vapor pressure and Reid vapor pressure predictions for petroleum streams. j ...r. . 7) Sulfur and Metals Commercial simulator programs cannot predict these properties. these data may be supplied to the simulator at the mid-volume percents of the fractional products and used to develop average blending values for the pseudocomponents. This makes it very important that chromatographic data be used to define the light hydrocarbons in petroleum streams.45 degrees C).40 degrees F (0 .6 to 8.. 6) Cetanes .. the accuracy of the predicted cetane number is good. Therefore.. '(jon 3. Numerous attempts have been made to correlate flash points for petroleum distillates. and all attempts use the predicted ASTM 086 10 percent distilled temperature as a correlating parameter. I' ~_ . . (l93 5). the 086 distillation test does not condense hydrocarbons with normal boiling points lower than the specified condensing temperature of 32 .t one time. Eng Chem. the accuracy of predictions is dependent on the predicted solubility for light hydrocarbons in the middle distillate hydrocarbons. it correlates with the API gravity and average boiling pc. L L I l .. . 42 4) Flash Point Limitations of pseudo-components ~ The flash point is a measure of the volatile components in a petroleum middle distillate. cetane number was determined in a laboratory test engine.3 degrees C) to the laboratory test value is reasonable. '"'--. Flash point tests have limited accuracy because of the procedure itself. even assuming perfect sampling techniques. However. since these properties tend to distribute in petroleum streams as an increasing function of normal boiling point. Note that the ASTM D86 distillation for a stream is inadequate to defi.' '~'< > . Nearly all of'the contribution to the vapor pressure for a petroleum stream is from hydrocarbon components with five carbon atoms or fewer.2. Therefore. j! J lt. and Murphy. ~· References: 24 Watson. p. As described in .. Ind.. when the distillate fractions for an actual stream have been analyzed in the laboratory to determine these properties. a predicted flash point within plus or minus} 0 to 15 degrees F (5. ~-~:. Nelson..\'1' .on atoms.

It is also important to remember that the thermodynamics for petroleum calculations are affected by the feed stock pseudo-component characterizations. The focus of this chapter is practical.j is equal to zero.1 Equilibrium K Values Equilibrium K values. (yJ :v)'s. and composition of the system. k'J is approximately 0. i. and no thermodynamic correlation can compensate for inaccuracies in the pseudo-component properties. Hydrocarbon water solubilities are small. 'I 'J such as water and The literature] abounds with equations of state.15.. The k. A standard textbook in thermodynamics may be consulted for theoretical derivations. pressure. The most widely used Redlich26 Kwong equations are the modifications of Soave and of Peng-Robinson".'s are determined by regression fitting of ~ binary vapor-liquid equilibrium data to the equation of state. A highly non-ideal interaction a hydrocarbon may have a k. with various concepts such as convergence pressure and multiple charts used to account for composition effects. Equations of state based on the Redlich-Kwongi equation have proven to be the most useful for petroleum systems. Hydrocarbon systems tend to behave ideally. For an ideal pair of components such as methane and ethane. 6. working thermodynamics. Before (he age of computers.Chapter 6 Thermodynamics for Petroleum Calculations For most petroleum processes. K values were predicted based on temperature and pressure only. For a non-ideal pair of components such as C02 and propane. These equations are similar and give equivalent results when properly calibrated or "tuned" to the system in question. It is important data having definite temperature also provide extensive libraries fitted parameters for the Soave and Peng-Robinson to note that these parameters are based on experimental and pressure ranges. and hydrocarbon/water systems may be approximated with simplifying assumptions. Two methods are used to tune the above equations of state: fitting of binary interaction parameters (kts). the thermodynamics are relatively uncomplicated.e. greater than 0. They represent the nonideal interactions between pairs of components. are the fundamental building blocks for nearly all unit operation calculations. k..5. and adjusting the pure component acentric factors'io accurately predict the pure component vapor pressures. The K values for any given system of components are a function of the temperature. The computer age has permitted more sophisticated prediction of K values using equations of state. and component relative volatilities are nearly independent of pressure. Vendors of simulation programs of parameters to represent operating data for various 43 .

s relating them to the hydrocarbon components. but has been extrapolated to higher temperatures with reasonable results. The modifications involve use of a different mixing rule for calcu lation of the "a" term in the equation of state and usc of a different equation form to predict the component "alpha" term that is related to the pure component acentric factor. A variety of modifications have been made to the S·oaveand Peng-Robinson equations to improve predictions for systems of non-polar hydrocarbons and polar compounds such as water.~ ! . H2S. CO. Grayson and Streed extended the range of the Chao-Seader liquid fugacities and added specific curves for hydrogen and methane that were based on experimental hydrocracking data. These predictive methods are a source of differences when comparing results from commercial simulators. Predictive methods based on known systems must be used to estimate these parameters. ~ 44 Thermodynamicsjor Petroleum Calculations processes. for most petroleum calculations these specialized modifications are not needed. The method has approximate limits of 800 degrees F ( 427 degrees C) and 3000 psia ( 207 bar).2 Effect of Non-Hydrocarbons on K values Non-hydrocarbon light gases are often present in petroleum processes.I 6._. CO2. a modified acentric factor is also used to improve predictions of the hydrogen solubility in the hydrocarbon liquids. or when highly accurate results are required.. etc.___ __ •• . and NIh The non-ideal mixture behavior attributable to these gases is predicted accurately by the modified Redlich-Kwong equations when using ~. the older Crayson-Strced" method is the most useful and worthy of further mention. This is 9 an ext ension of the Chao-Seade/ method and is a semi-empirical approach that uses the Redlich-Kwong equation of state to determine the vapor fugacity and a corresponding states model to compute the liquid fugacity. For these components.: ~ .. experimental binary vapor-liquid equilibrium data are not available to regression fit the kiJ's. ketones. it is prudent 'for the user of a commercial simulator to ascertain that appropriate tuning parameters are available in the software when calculations are required for unusual systems. Sal. However. Pseudo-components present some special problems when using the modified RedlichKwong equations of state. it is not possible to tune the acentric factors to match pure vapor pressure data. - . These gases include H2• N2. While there are numerous other methods to predict K-vatues for petroleum systems. ~~_c __ • . However. Furthermore. In the case of hydrogen. alcohols.

1 below. A simple model may be used as shown in Figure 6. Water K-values are computed as: . .1 Simple Hydrocarbon-Water Model VAPOR FEED He LIQUID For the above model. the vapor is saturated with water vapor and the hydrocarbon liquid is saturated with water according to a solubility relationship.45 Hydrocarbon-Water Systems Hydrocarbons are only slightly soluble in water and for most petroleum calculations rigorous three-phase calculations are not necessary. The aqueous phase consists of pure water. where: pO::: water vapor pressure Xs ::: water solubility in the hydrocarbon liquid phase Il = system pressure such as the When more YJ rigorous treatment is required for the water phase. an equation Kabadi-Danner modification of the Soave equation may be used..3 Figure 6. 6..

SimSci. Enthalpies calculated in this fashion using the modified Redlich-Kwong expressions have proven to be more accurate for petroleum mixtures than older. HYSIM and HYSYS programs and the. : Grayson-Streed. The enthalpy deviation term is calculated as: p 6H == o {[ T (dV/dT) .4. H=H* -~H _. 6. PROVISIO/". Soave RK Grayson-Streed . -Inc.4 Enthalpies Enthalpies are typically calculated with thermodynamic relationships that relate the actual mixture enthalpy to the mixture enthalpy in the ideal gas state. That is. HYSIMI HYSYS: Peng-Robinson with Lee-Kesler enthalpies. The recommendations given below are based on the author's experience with the Hyprotech. Pseudo-component ideal gas enthalpies are predicted as described in Section 4.~' I~ 46 Thermodynamics for Petroleum Calculations I· 6. H* == mixture enthalpy and mixture ideal gas enthalpy 6. empirical methods.: . PROVISION""" program. P = mixture temperature V == mixture volume {= Integral An equation of state is used to evaluate the V and (dV/dT) tenus in the above expression. Ltd.5 Recommended Methods for Petroleum Systems !. 1) Heavy Hydrocarbon This includes crude Systems: and vacuum distillation.. The first method listed is the author's preferred method.V]r dp and pressure where: T. j It is impossible to recommend specific methods without identifying specific commercial simulators.H = deviation of the mixture enthalpy from the ideal gas enthalpy The ideal gas enthalpy for the mixture is computed as the mote average of the component and pseudo-component ideal gas enthalpies. where: H. FCC main fractionators and coker fractionators.

ability and specific recommendations. system and necessary parameters. Henry Constants SRK. it is probably necessary to supplement the vendor supplied k. C5. hydrocrackers. C4. Check with vendors for other super~ fractionators_ When separating close boiling isomers. Check with the These calculations may be needed for environmental \-endor for applic. .rbuns Dissolved in Water: considerations. HYSIMI HYSYS: Kabadi-Danner PROVISfO:V: Kabadi-Danner SRK. Grayson-Streed PROVISION: Soave RK (with SimSci alpha). splitters. hydrotreaters-.Chapter 6 2) Light Hydrocarbon Systems: This category includes gas recovery plants. etc. Systems: are reformers. C3. HYSIMI HYSYS and PROVISION have special k ~ parameters for C2 and C3 splitters. Ii d 7) Super-fractionators: These columns include C2. IJ ii' I' !I J 8) Light Hydrocc. Henry Constants . Grayson-Streed 4) Sour Water Systems: HYSIA1! HYSYS: Peng-Robinson (Sour option) PROV/SIOV: Sour Method (modified Soave RK) 5) Hydrofluric Acid Systems: HYS1Ali HYSYS: Check with vendor PROVISION: 6) Aromatic Extraction Hexamer Method Systems: Check with the / !I !: vendor for applicable A liquid phase activity coefficient model is necessary for these systems.andhydrogen in this category HYSIMI HYSYS: Peng-Robinson. fractionators and splitters __ HYS1MI HYSYS: Peng-Robinson PROVISION: Soave RK 3) Hydrogen-Rich Included plants.ts.

Heat capacity becomes very large and the latent heat becomes zero at the critical point.8 bars).. This may be used as a quick check of distillation column conditions. The heat capacity is approximately twice that of hydrocarbons and the latent heat is five times as large as hydrocarbons.•.-- . 8) A Joule-Thompson expansion across a valve results in a temperature drop for most mixtures. 1) It is necessary to use the Peng-Robinson or Soave RK methods to locate t be true critica! points of light gas mixtures. 10) Hydrogen sulfide causes large non-idealities in hydrocarbon mixtures by shifting the critical point of the mixture. -~---..-. This can result in system pinches requiring at least one more heat exchanger shell in series versus calculations which are based solely on the exchanger "F. An accurate steam flow is necessary to match nash zone temperatures. They may also be used to predict the phase diagrams. the heat capacities of the feeds and products are nearly identical in the feed/effluent exchangcr s..-~-." method. There is no particular significance to the order in which they are presented.. --'----.48 Thermodynamics for Petroleum Catcutauons 6. For FCC main fractionators it is important to have an accurate rate for the reactor steam..6 Thermodynamic "Rules of Thumb" The following guidelines are based on the author's experience with calculations for hydrocarbon ·systems in general. The maximum pressure for typical deethanizers is about 475 psia (32. 3) The vapor density approaches the liquid . 2) Large heat capacities may indicate that the mixture critical point is being approached. 7) The duty versus temperature lines for mixtures containing hydrogen are curved and not straight. Mixtures containing hydrogen may show a temperature increase. Pseudo-critical calculations are inaccurate because of mixture non-ideal ities.density as the critical point is approached. 6) For hydrogen-rich systems such as hydrocrackers and reformers.-- -. Large vapor densities indicate that the column is operating too close to the critical pressure.. Accurate prediction of the benzene distribution in a light-ends column may require use of a liquid activity coefficient model. 5) Water has an important partial pressure effect with hydrocarbons in columns with steam stripping..-. 9) Benzene forms azeotropes with nearly every light hydrocarbon.. 4) Water has an important heat effect with hydrocarbons. --:--. .

and should never 20) The Grayson-Streed method cannot predict critical point behavior be used for systems that may approach the critical point. Thus. have been molecular molecular 23) The Peng-Robinson and Soave RK methods are as accurate as the tuning data supplied by the simulation program vendor. Therefore. ') I) For example. The methods produce equivalent results.s in the modified Redlich-Kwong ') equations. 22) Commercial simulators often tune thermodynamic data to the default weight correlation. non-idealities for close boiling isomers are very important for superThese may be represented with k. It may also solidify in cryogeriic 12) Hydrogen has strange phase behavior. 16) The relative volatilities of hydrocarbons 17) Hydrocarbons are nearly insoluble water phase as pure water. it is usually not advisable to select another weight correlation unless absolutely necessary.0089. 13) It is not possible to calculate bubble points for systems containing hydrogen. 19) Small fractionators. but it can be dissolved in hydrocarbons at high pressures. of the liquid in water. method and Johnson-Grayson enthalpy method superceded long ago by more accurate methods and are not recommended.49 11) Carbon dioxide fractionators. equations of states are always more accurate than empirical and semi-empirical methods. It cannot be condensed. They also are more thermodynamically consistent than liquid activity coefficient methods. allowing approximation 18) In general. While the k's are very small they are necessary for accurate calculations. an aromatic stream from an extraction process behaves very ideally for distillation purposes. hydrocarbon systems composed of the same chemical class behave very ideally. forms an azeotrope with ethane. . are nearly independent of system pressure. 21) The Braun KIO K value. the k. 15) When applicable to the system. for propane and propylene is approximately 0. 14) Alcohol-hydrocarbon systems hive highly non-ideal behavior and must be calculated using liquid phase activity coefficients. when properly tuned to the system being calculated. The Peng-Robinson and Soave RK methods predict better hydrogen solubilities in hydrocarbon liquids than the Grayson-Streed method.

. the more non-ideal the separations. - The modified Redlich-Kwong equations are more conservative for design than the Grayson-Streed method.•..m.__. ~ . Equilibrium vapor or liquid can be re-circulated to an equilibrium stage in any quantity with no change in the separation. Absorbers are very poor recovery devices because ofthe low tray efficiencies... -__. The higher the column pressure. _-_ •• . .. .. Lower molecular weight lean oils absorb more light gases than heavier oils. Liquid viscosity is usually the controlling property for overall tray efficiency .so 24) Design Generalities: ( Thermoaynamtcs Jur r~uVU.l. Thermodynamics are almost never the cause for distillation calculation failures. assuming an appropriate method is selected.~..

Vol. N. H. Vol. "A New Two-Constant Ind. 29 Chao. Chern. p... D. 24. "Equilibrium constants from a modified Redlich-Kwong state". 0. P. 537541. (1976). C. p. No. Ding. and Robinson. s. 1197-1203.Yu. C. and Kwong. I. " A Modified Soave-Redlich-Kwong Equation of State for Water-Hydrocarbon Phase Equilibria". V. 44. 233 (l949). Vol. and Danner. Journal... Paper 20.. Eng.. 28 Grayson. and Seader. 59-64. A. 27 Peng. . Vol. I. for High Temperature Petroleum Congress. and Streed. equation of 26 Soave. No. IS. (1972). Sect VII. K. G. (1963). 7. Chern. Ind. ell. "Vapor-Liquid Equilibria High Pressure Hydrogen-Hydrocarbon Systems". Giorgio. Engr. p.3. 51 J. Donald B.. in 30 Kabadi. R. p. Rev. Chem. Eng. 27. W. N.4.Chapter 6 References: 2S Redlich. No. 1.. 598-605. . Equation of Stale".. (1961). Fund. Sci. "A General Correlation of Vapor-Liquid Equilibria Hydrocarbon Mixtures". 6th World FrankfurtlMain. Chem. (1985).

the vapor-liquid equilibrium relationships for every tray. improving an operation by lowering the operating cost (while achieving the same objective) results in a direct increase in the profitability of the operation. Temperature and flow profiles are assumed for all trays in the column and vapor-liquid equilibrium and heat balances are calculated for each tray.on as well as the temperature and pressure. All calculation procedures keep the column pressures constant. While there is some design work being done. and troubleshooting of existing columns 'j. distillation is somewhat unique in that for most columns there are hundreds of sets of operating conditions that may be used to achieve the same desired results. and a heat sink or condenser at the top. 7. that is. liquid flows to the next lower tray where it establishes a new equilibrium with the vapor entering this tray and so on. Simulation permits easy exploration of the entire anticipated range of operations and selection of a design that has flexibility for future operations.Chapter 7 Practical Distillation Principles The unit operation of most interest for petroleum calculations is distillation.1 Theoretical Considerations The theoretical basis for distillation calculations has been established for many decades. The liquid and vapor leaving each tray are in vapor-liquid equilibrium and the vapor enters the next higher tray. most of the discussion in this chapter focuses on simulation of existing operations. and the heat and mass balances for the entire operation. Some condensed liquid is returned to the top tray of the column as reflux. The results from the assumed profiles are used for the next series of calculations and so forth. Distillation columns consist of a series of inter-linked vapor-liquid equilibrium stages or theoretical {rays. Furthermore. Solution of distillation calculations is a trial and error procedure. The lightest components in tbe feed mixture exit with the overhead product and the heaviest components exit with the bottom product. product qualities. All of the "tray to tray" calculations may be inter-linked into a large set of equations which describe the heat balances for every tray. However. debott!enecking. A column typically has a heat source or reboiler at the bottom. This is an energy intensive operation and the economic benefits of an improvement can be substantial. {he component mass balances for every tray. It is also desirable to add equations to the above matrix 52 . TIl(. where it establishes a new equilibrium with the liquid on this tray. since this is the usual case in petroleum refining operations today. Thus. design phase with simulation. There are also improvements in energy efficiency that may be attained in the process -. most calculations today are conducted for improvement. Calculations are further complicated by the fact that the equilibrium K values for the components on each tray are affected by the tray cornposit.

the tray heat balances.al. which produce a solution for all of the column equations within certain defined tolerances or errors.. and the performance specifications. Richard Russell adapted this method to the rapid solution of alI types of distillation columns. All of the methods are iterative in nature. By using stripping factors and side-stream withdrawal factors as independent variables. This method is further described in the discussion below. the Russell method has proven ideal for commercial simulators . A description of this technique has been published by 3l Goldstein and Stanfield • The inside-out method (UO) for solution of distillation 33 14 problems was devised by Boston32. e. the I/O algorithm consists of two iterative loops: an inside calculation loop and an outside calculation loop. Several methods have been devised to solve distillation problems and the literature abounds with descriptions of these procedures . Note that the latter tolerance is required since the K values are dependent on composition. Consequently. including multi-draw columns with side-strippers and pumparounds such as are used in the petroleum refining industry. tray temperatures. . all of the above conditions must be satisfied by the solution.. it is also necessary to converge the K values in addition to all of the column equations.g. Since the calculations are based on steady state operation. Tolerances are prescribed for the component material balances. The Russell modification offers significant advantages in calculation speed and lower storage requirements versus the Newton-Raphson approach which makes it ideally suited to use on personal computers as reported by Morris. the tray equilibrium relationships (usually expressed as the tray liquid bubble point condition). High-speed computers have made possible the rigorous solution of the large matrices describing distillation columns. the distribution of components within the column for any 'trial solution is always in perfect mass balance. such as super-fractionators. the performance specifications. and produce steady state solutions within prescribed tolerances. This is an important feature when performing calculations for columns in which trace component flows in the products are important.As implied in the name. 7. flows. . in 1970. The inside loop calculations use simple models for the K values and enthalpies and converge the tray heat and material balances.1.S3 to define process conditions or specifications that must be met by the solution. and the tray equilibrium K values.. Thus. heat inputs. et. A converged solution is defined as a set of independent variables for the column. The most useful method for solution of petroleum distillation columns is the inside-out method.1 Inside-out Distillation Algorithm The Newton-Raphson method was the first method used by commercial simulators to solve distillation problems. etc." The Russell method also has a great advantage over the older Newton-Raphson algorithms in that the calculations are not highly dependent on an accurate initial estimate of the solution for convergence.

Referring to Figure 7. Side-stripping columns may also be attached to a column. Most commercial simulators However. The 110 method is not dependent on accurate column flow profile estimates for convergence." 1 I'. :~ . pump~around side draws are used to remove heat from the column and pump~downs (not illustrated) may be used for side heaters. for simulation purposes the kettle rebotler assumption is adequate for most . It is important to note that all distillation calculation methods are derived for theoretical/rays. iii .1. only a liquid product is withdrawn from the reflux drum and the condenser is not truly a theoretical tray.2 Colun1n Conventions The conventions used by all commercial simulators are very similar. '. is followed. A damping factor may also be applied in the outer loop to avoid osciHation for systems in which the K values are strongly dependent on composition. Temperature data ore usually easier to estimate than flow data. is decanted as an aqueQus phase. columns. Columns may have side liquid and vapor draws and side water draws. however. From Figure 7.1 shows typical representation of column features. For some columns.'. if present.". Finally. is normally considered to be the highest tray number. The top tray of the column is considered to be the second tray for a column with a The reboiler. if present..i 'I ii. The same convention condenser. for many petroleum columns. . I• provide ways to represent other types of reboilers such as thermo siphons. as the first tray. . :. particularly for complex refinery columns. note that columns may have multiple feeds . 1.! : ~ I . ~. it is always good practice to estimate flows as accurately lIS possible.. the K values and enthalpies are recalculated with the newly predicted compositions. that is.·'. and the overhead system is still considered This tray always receives the reflux liquid. Liquid and vapor products are withdrawn from the reflux drum. N+ 1. this convention represents the reboiler as a kettle reb oiler.r- Practical Distillation Principles 54 In the outside loop. trays in which perfect vapor\iquiJ equilibrium is achieved between the exiting liquid and vapor. II! . the inner loop calculations are repeated with the new K values and enthalpy data. Convergence of this method can be enhanced significantly when an accurate estimate of the column temperature profile is supplied. 7.1. however. '. Side columns of all types are solved simultaneously with the main co\umnby the VO method. If the component relative volatilities have changed by more than the convergence tolerance. Figure 7. the conden«r and overhead accumulator drum aCCconsidered to be the first tray.1. the liquid product is sub-cooled below its bubble point. Liquid water. In fact. A net liquid product from this tray is returned to the column as reflux.

e.55 Figure 7. . the top tray of the column is designated as tray one by all simulators. The most common convention is to number trays from the condenser down to the reboiler starting with tray one for the condenser (when present). an absorber. a reboiled stripper. the bottom tray of the column is designated as tray N by all simulators.g. For columns with no reboiler. For columns with no condenser-reflux drum...g. . e. I : OVHO VAPOR COI'fOENSER FEED SIDE FEED STRIPPER PRODUCT PUMPAROUND ---y~ TrCly N ~ LIQUID DRAW VAPOR BOTTOMS LIQUID Theoretical tray numbering conventions vary from simulator to simulator. HYSYS designates jhe condenser-reflux drum tray as the Condenser and the second tray as tray number one. This simulator also designates the reboiler (when present) as the Reboiler and tray N as the highest tray number in the column model.1 Column Conventions r- ---''-+i I I I I r~-------------~ .

.1.. either by the user or by using a program default value. the feed checking step is often omitted in the haste to secure calculated results for a project.4 Non-converged Column Solutions A non-converged column solution is one in which all of the mathematical equations describing the column were not satisfied. since there is a substantial pressure gradient between the column top tray and the condenser. Note that for columns with condensers. 7.ient from the second tray to the first tray in most columns. The causes for calculation failures when using the algorithm may be grouped in the following categories: '" 1) Improper characterizati on of the feed stock: va This can be avoided by careful analysis of the stream characterizations before column calculations are attempted. either one of the top non-aqueous products. The cause for the non-convergence must be determined and a fully converged solution developed so a trustworthy analysis of the column operation is possible.. ------ . The reflux quantity must also be estimated. it is especially important that the pressure of the flash zone of the column be accurate and an additional pressure should be supplied for this purpose. Therefore. However... or the bottom liquid product.. The first and last tray temperatures are also required for most simulators. a pressure should always be supplied for the second tray. since there is usually a substantial temperature grad.• second tray for columns with condensers. It is good practice to always supply the temperature for the physical top of the column.. For crude and vacuum columns.e. While not required.. 2) Impossible Specifications: A COIUffilL may be over-constrained and hence all of the performance specifications cannot be met. The condenser pressure drop may be as higb or higher than the total pressure drop across all of the other trays...1. i. This is the most common type of convergence failure when using the va . -~ ~-~------ ----. A linear pressure profile is assumed for the intermediate trays. Poor feed stock characterization can result in unexplainable behavior in the column calculations. the results are not valid and should 1101 be used for engineering design and analysis.3 Initial Solution Estimates Commercial simulators require the user to supply flow estimates for all column products except one. temperature estimates for side draw trays enhance convergence.. The user is required to supply values for the first and last trays in the column model.56 Practical Distillation Principles 7. Commercial simulators do not vary the tray pressures during the I/O calculations.

As the critical point is approached for any mixture. exceed an approximate value of 4. ~~ . it may be necessary to lower the column pressure to avoid supercritical conditions. it may be necessary to use a damping factor to prevent oscillation of the trial solutions. It is usually easier to check for this condition by inspecting the liquid and vapor densities for the trays. Under these conditions fractionation ceases.0 lbs/cu ft (64 kgs/cu rn). Commercial simulators are not consistent in their handling of free water on trays other than the condenser. since it is relatively insensitive to initial estimates. 3) Poor Initial Estimate: This is seldom the problem when using the I/O method. resulting in the tray mixtures in some parts of the column being above their critical points. especially if this causes free water to condense on the ·column trays for the initial trial solution. the liquid and vapor compositions become identical. 4) Free-Water on the Trays: Most petroleum processing columns are operated such that water is carried overhead as a vapor.4 gives reasonable suggestions for column specifications that are likely to result. the column results are invalid and should not be used. This procedure is accompanied by a warning message that free water would occur at trays other than the condenser. Calculations with other simulators may simply fail because no forcing technique is used and therefore a material balance for water in the column cannot be attained. The most common problem is using a column pressure that is too high.. and the component K values approach unity. some columns may have free water on some of the trays because of process conditions and it may be necessary to include water draw-off trays for its removal.2. of the inside loop to converge. In either case described above. If the vapor densities become large. For columns in which the K values are highly dependent on the tray compositions.57 algorithm and it is signaJed by failure. 5) Thermodynamics: Assuming an applicable method has been selected for the calculations. Oscillation caused by thermodynamics is evidenced by failure of the outside loop calculations to converge. failure to supply an estimate for the physical top tray for columns with condensers can be a problem.. this is almost never the reason for column non-convergence.in convergence. condensed. i. .e.' . Section 7. However. The column process conditions must be revised andlor a water draw-off tray added to the column model and the model re-calculated to attain a true solution. It is still good practice to provide the best initial estimates possible. In particular. III-chosen process conditions can also cause problems. and decanted at the accumulator drum. Some simulators "force" a solution by assigning a large K value to the water to carry it overhead in the column.. both in the real world and in the simulation calculations.

It is good to have redundant measurements when possible. There are many sources of inaccuracies in measured data. Good calculated results depend on good information about the column. For some columns it is better to combine the products to characterize the feed.2 Simulation of Existing Columns While this section focuses on existing columns. and interpretation of results for column models. or indirect determinations such as laboratory test results. including the feed stock and its conditions.. it is reassuring to have duties from the operating data as a validity test for the model. and internal flows such as reflux. laboratory distillation. Needless to say. always pass a test for reasonableness when building simulation models.1 Gathering the Information While this step may seem obvious. FCC main fractionators have a very hot vapor feed which is difficu1t to analyze accurately (if at all).2. temperatures. !:.58 Practical Distillation Principles 7. Note that is usually best for simulation purposes to calculate the column duties such that performance specifications are met. Certain steps are always necessary in the setup. Several categories of information are needed for simulation of a distillation column: 1) Accurate Representation of the Feed Stock: This cannot be over emphasized. since it is usually necessary to reconcile plant data.. particularly for complex column calculations such as crude and vacuum columns. and data must . and vapor pressure. 2) Column Operating Conditions: These include pressures. ! . 3) Product Compositions: Product compositions may be direct determinations such as a component by component breakdown from a chromatograph. some engineers expect simulators to solve problems with little or no information: It is helpful to remember that the calculated results from simulators are no better than the information on which they are based. . solution. the same principles may be applied to column design. For example. It is usually better to build the feed for these columns from the analyses and rates of the products. Accurate measurements of the feed and product conditions are necessary if accurate calculation of the column duties is desired. Some of the laboratory tests that are useful in defining product compositions are density. 7.

Some manipulation of plant data is useful in determining key components. Note that trace components do not meet these criteria. The fractionation is based on a desired split between the key components. the column tray confi~~ation. Note that both rectification of heavy components and stripping oflight components may occur in a separation zone. etc. The key component concept is most useful for column sections in which the distributed components are defined as real components. r' Within the distributed components. reboiler. other duty arrangements. Multi-draw columns such as crude and vacuum distillation columns have multiple separation zones. The light key is a light distributed component for which a small. the split may be accurately defined by proper selection of the key components. Distributed components are those components that exit in both products leaving the separation zone.59 '4) PFD Information: It is critical to have a current process flow diagram (PFD) for the column operation. but definite quantity is present in the overhead product. It is important to represent the distributed components in a separation zone accurately.2 Defining the Separation Zones The concept of separation zones is useful in column analysis. For example. A separation zone IS defined as a column section in which a split between two products occurs.2. condenser. The other components are non-distributed components. Non-distributed components have almost no influence on the separation. 7. The rating calculations in commercial simulators are useful for preliminary analysis of existing columns. and they may be combined or averaged as desired with little effect on the calculated results for the column.1 gives some typical plant data as reponed for a fractionator. These are the components that fractionate or split.. This provides information on feed and product draw locations. downcomer details. but definite quantity is present in the bottoms product The heavy key is a heavy distributed component for which a small. It IS not uncommon for FCC main fractionators to have a small jumper line which injects quench directly into the bottom of the column to prevent coking (carbon formation). Table 7. Some information is available on the PFD regarding the column size and internals. and so forth. Simple columns with only overhead and bottom products have only a single separation zone. Without an accurate PFD. It is usually necessary to supplement this information with tray drawings. The compositions and rates . the engineer may not be aware of this flow. with the heavy non-distributed components exiting in the bottom product and the light non-distributed components exiting in the overhead product. when rating calculations are desired to test the column operating point for possible flooding conditions.

In fact.73 25. Note that the separation zone contains only four significant distributed components.2 methyl pentane benzene cyclohexane C7 plus Total Flow. hi. These nondistributed components have little effect on the calculated separation.-.39 2. iii ~ I) Distillation Plant Data Products Overhead Product LV Percent 2.2 dimethyl butane 2. - -~~------~ '-.46 1.34 46.!. than the light key do not define :'. Bblslday LV Percent 8. !II .20 3. In a recovery table.01 0. Two methylpentane i dearly the light key component and n-hexane is the heavy key component. the percent of each component in the feed that is recovered ir the overhead and bottom product is tabulated..~-I I i i r i.58 trace 0. Components lighter._ f{! .3 dimethyl butane 2 methylpentane 3 methyl pentane n-hexane methylcyclopentane 2.. 60 -Practical Distillation Principles have been tabulated for the overhead and bottom products.16 23..97 9.93 2442 7558 f~1 iii 1[ i! 11 f! Ii :1/ j{ f il The data from Table 7./ . the separation key components are not apparent. il.25 3.':1 :'Il . Table 7.98 10.if! Ii' 'i Ii IL r/': r Ji Componem i-pentane n-pentane cyclopentane 2. From these data as reported.l. Arbitrary selection of a heavy component concentration in the overhead and a light component concentration in the bottoms may result in an incorrect definition of the separation that takes place in the column.L __ • _.07 Bottoms Product Li..2. that is. This column has split fa components. In fact. the C7 plus component may represent several actual components.~•.13 0.. Omission of any of these components in the analysis would result in disastrous results and conclusions. Observe that there are five non-distributed light components in the overhead product and four non-distributed heavy components in the heavy product.17 1..48 11. with 3 rnethy pentane lying between them. '~! I!' ~I" y. These tw components define a unique separation for the column. the light and heavy key components are not adjacent. r: !.11 trace 49. '-_ _.- . Note that it is relatively easy to see when the separation is occurring upon inspection of the recovery table.1 . an incorrectly defined separation may result in multiple solutions for the column simulation model..1 have been transformed to a component recovery basis in Table 7.1 ._ ~~'./ !fru !!.

The distributed components are represented in the simulation model as pseudo-components.71 96. % Component i-pentane n-pentane cyclopentane 2. by Kister" approach is Many of the columns in petroleum refineries have separation zones for which the components are not clearly identified..00 100. however.35 trace 100.61 unique operation for the column nor do components heavier than the heavy component.2 Distillation Column Recovery Table Overhead Product RecoveD'._----= !'_ .29 - 3 rnethylpentane n-hexane methylcyclopentane 2.50 20. This is a poor representation of the actual operation in which the petroleum components are a continuum and step changes in the products rarely.00 97. consider the separation zone for light naphtha and heavy naphtha in a splitter column. Some composition data are available for the combined naphtha stream.r« " .00 100. it is usually for the light components which do not distribute to both products and are totally recovered in the light naphtha product. and a reasonable definition is necessary for an adequate column model. keys when identified.50 79.00 100. This useful for revamp modifications at a new operating point. occur when the operating point is move'!: j'j .00 The procedure described above is usually adequate for determining separation modeling existing columns for which the distributed components are clearly A more rigorous approach to definition of key components has been suggested in which diagrams are constructed using the method of Hengstebeck". The component that appears between the separation keys also fails to define_ a unique operation. For example.10 99.3 dimethylbutane 2 methyl pentane 100.90 0.00 100.2 methylpentane benzene cyclohexane C7 plus 3.00 100.% Bottoms Product Recovery.00 100.2 dimethylbutane 2. Definition of too few distributed pseudo-components results in a model that predicts step changes when the operating point is changed. Table 7. it is very important to find where the separation is occurring when modeling existing column operations.00 2. if ever. Any separation defined by non-key components is not necessarily unique and there may be a myriad of column operations that can be used to obtain it Thus.65 100.

1 Ii /11 I. 1[.3 the Edmister-Okamoto'lmethod has been used to convert the light and heavy naphtha distillations to a TBP basis. The separation zone appears to be small on a D86 basis. . Note that pseudo-components boiling below 140 degrees F or above ~45 degrees F have little effect on the separation in the column. the separation zone is from 140 to 245 degrees F. The splitter is being operated to produce a 5-95 gap of 20 degrees F. ..~Eii -" ~ ~ R~I( ~ ~ fo"""" 100 50 V o ~ . I ii j' . :I _--- """ "\" . or 105 degrees F. However.2 presents the AsTM D86 distillations Practical Distittauon rnw.. It is important that an adequate . the limitations of the D86 test in determining the true initial point for the heavy naphtha and the true end point for the light naphtha hinder the analysis.2 Naphtha Splitting Column ASTM D86 Distillations 400 350 300 'f C f .) ".. On a TBP oasis. The normal boiling points for the petroleum pseudo-components correspond to the TBP distillations.AVY NAP!- V" j ·C 4 250 DEGREES F 200 150 E~ --.~-. --..number of pseudo-components be used to model the feed stock in this boiling range.L " ~ 4 f ·c. V V ·4 I • 100 t~T NAPh THA o 10 20 30 40 70 80 90 lV.#" ~ ~I---50 60 NZf ~E . if I. In Figure 7.:rr {' 62 Figure 7. being equal to approximately 20 degrees F. f Figure 7.) for light and heavy naphthas from a splitting operation..PERCENT " I' I. •• .zpu:./ H:.

Rather. As described in Section 4.~-V V. This permits a reasonable representation of the fractionation between these products and for many engineering studies this would be adequate.. When using a si rnulator program it is not necessary to perform the exercise of converting the-product distillations to a TBP basis. In fact. . at least five pseudo-components would be defined for the separation zone between light and heavy naphtha. -__... Thus.1. the simulator default cut-point ranges would be inadequate and more pseudo-components should be used in the separation zone. typical cut-point ranges for the naphtha feed stock to this splitting column would be 25 degrees F. EAV'I NAP ~THA :::..4.. the D86 data for the column feed stock may be supplied to the simulator for translation into pseudo-components and the column calculations performed. V ~ L V ~ L -~ r. .3 Naphtha Splitting Column TBP Distillations 400 350 300 250 DEGREES F 200 150 100 ~ 1/ . .- '. The light and heavy naphtha component flows may be printed side by side and the number of significant pseudo-components that distribute between these products may then be easily determined. A preliminary case can be calculated in which the simulator default cut-point ranges are used for the pseudo-components.- _...~}_ roo - ~ ~ fGH' NAP ~THA 50 a V a V 10 20 30 40 50 60 70 80 90 100 LV PERCENT Simulation programs are convenient for analysis of pseudo-component separation zones..- . SE ARA.. If a detailed engineering study were being performed for the naphtha splitting column described above.63 Figure 7.. it is also desirable to . ION ONE I" - L -V V ..

the vapor and liquid • . C • .3 Translation of Actual trays to Theoretical Trays All rigorous column calculation methods are based on theoretical trays. Actual {rays C C 0:. all trays in the column model are perfect vapor-liquid equilibrium stages for the distillation calculations.It 'J 64 Pracucal Distillation Prtncipies increase the separation zone range accordingly when the distillation ranges for the light and! or heavy naphtha products are being changed for the new operation. however. Unfortunately. Then a second step is performed for each tray in which the compositions for the tray products are modified through application of a tray efficiency expression. r. in which the vapor and liquid leaving the tray are in perfect vapor-liquid equilibrium.:i = No. not theoretical trays. The trays in the column are first calculated as if they were theoretical trays. The overall efficiency usually concerns the entire column and is defined as follows: Overall efficiency I . A guideline is to have at least six to eight significant pseudo-components in a separation zone. Murphree developed the following tray efficiency model: I! . real operating columns are filled with actual trays. The Murphree" tray efficiency model is a popular model available in many commercial simulators and is presented as an illustration.2. Fractional trays are not considered with this efficiency model and the efficiencies are expressed on a percentage basis..1. The perforrnance of an actual tray compared to the performance of the corresponding theoretical tray is designated as the tray efficiency. These models are not overall efficiency models and they all generally take a similar approach when used for rigorous column calculations. the overall efficiencies are less than 100 percent and the column has fewer theoretical trays than actual trays. Thus. • c C ~ leaving (he tray for which the efficiency has been applied are no longer in equilibrium. There have been many mathematical expressions derived to represent tray efficiency. complicating the translation process. Theoretical trays INc. The relationship between actual trays and theoretical trays is not straightforward. the actual trays in a real column must be represented by theoretical trays in the model. the most useful concept in distillation problems is the overall efficiency. It is important to note that with this definition of efficiency. 7. Various tray efficiency models have been developed and published which refer to single trays or locations on a single tray. '~\1 Overall efficiencies may be defined for entire columns or zones within columns and enable a direct translation of the column actual trays into theoretical trays. For nearly all columns. Therefore.

since distillation theory will always predict an answer that is directionally correct for a new operating point. i. the column overhead vapor is not saturated and may be superheated or subcooled. since the user can supply the actual trays from the column PFD to a simulator program and use tray efficiencies to reduce the tray performances such that the actual column operation is replicated. Moreover. The non-equilibrium liquid and vapor leaving the trays cause uncertainties in heat transfer calculations. Therefore. they are not the worst problems related to using local tray efficiency models. one can argue that the model no longer corresponds to rigorous distillation at all. Manipulation of local tray efficiencies in a distillation model is analogous to the regression fitting of data to an equation form. if a tray efficiency model is applied to the top tray of the column. This approach to tray efficiency is both convenient and appealing. Commercial simulators encouragethis line of thinking by providing a variety of tray efficiency models. Consequently. In fact.e. no "typical" individual tray efficiencies have been calculated and reported for petroleum columns. For example. On the other hand. While the above-mentioned considerations are troublesome. These models may be used in predictive mode. models based on overalt efficiencies always correspond to rigorous distillation.65 where: Y. since the principle of equilibrium vapor and liquid leaving each tray has been violated. the column mode! is useless for engineering studies in which other operating points are of interest. tray efficiency models such as Murphree are too simplistic for petroleum columns. = actual composition actual composition of vapor leaving tray n of vapor entering tray n to Yn+1 Yn = = vapor equilibrium composition corresponding the liquid leaving tray n Notc that after application of the Murphree efficiency. The rigorous distillation theory that is capable of predicting results other than the current column operating point is thoroughly masked and violated by local tray efficiency models. and the user must take a cut and try approach with the efficiencies to match the actual column. Unfortunately. since the liquid and vapor leaving every tray are in equilibrium.. Thus. it is strongly recommended that tray efficiency models never be used when modeling petroleum columns. There are few open . the vapor leaving a tray is no longcr in vapor-liquid equilibrium with the liquid leaving the same tray. in which there are a large number of components and widely varying process conditions. Nothing is ever as simple as it seems and using tray efficiency models other than overall efficiencies can cause serious problems for column models. This has a direct effect on [he condensing requirement. many engineers do not understand that the tray efficiency models provided by commercial simulators are not overall efficiency models. the tray no longer corresponds to a theoretical tray in the distillation model. The worst consequence of using local fray efficiencies is that the simulation model is rendered useless for prediction mode.

. 0.' . . ~ . While the methods presented in Figures 7. efficiency. 40 30 .5 1.such correlation based 19 for 54 refinery columns was published by Drickamer and Bradford and is in Figure 7...2 0. f 10 I· o : 1~' : " if' ie. The efficiency is for the key components and the is the average of the feed as liquid at the top and bottom temperatures for the For absorbers.ie'1:. petroleum columns by matching models to operating data.. Fortunately..I . ' . typical overall efficiencies for various columns used in petroleum refineries. such as absorbers. they are probably the most reasonable open literature correlations to date for overall tray...... II'" II Figure 7. The O'Connell correlation is shown in Figure 7..'... 1.3 presents sorne.4 and 7. typical overall efficiencies have been determined for nearly all types of.3 0..1 0.. ~ 80 70 r-. Practical Disuttauon rTl''''''I''~ correlations _for prediction of overall efficiencies.••. H . Ove ratl Tray Effi:. the relative volatility of the key components and the feed liquid viscosity are evaluated at column average conditions. O'Connell based his work on commercial and laboratory column data. I ~.05 0. . i . I I r-. While these values have been derived from typical operating data. ! . % 60 50 <.5.Y. For this method. One . Table 7. the rich oil exit temperature is used.4 below.4 Overall Tray Efficiencies: Refinery Columns 39 Correlation of Drickamer and Bradford 100 90 .. cp The Drickamer and Bradford correlation was subsequently modified by O'ConneU<4/)to improve the predictions for columns with high relative volatilities.n~ r 66 literature on data presented viscosity column..0 Feedstock Avg Viscosity. I " -. they are usuatly conservative and I '/ I i ! /.S may seem overly simplistic.

-. Figure 7. The resultant model may be used for predictive purposes when a new operating point is investigated.may be used for preliminary design. <. This requires the simulation model builder to become familiar with the actual column operation.5 2 3 Relative Volatility of Key times feed viscosity -------------------------------------------------------------------When modeling existing columns it is recommended that a typical overall efficiency be used to translate the actual trays to theoretical trays..5 Overall Tray Efficiencies . the predicted results will always be directionally correct. ( "N.67 . I . I' ~ Overall Tray Efficiency.3 0. calculations based on information specific to his trays to finalize the design. % 50 40 30 r-~ ------ r-- ---r-5 10 20 10 o 0.4 Defining Performance Specifications For successful simulation models.1 0. The tray vendor will likely perform more specific. I . specifications for the column model should be the same or similar to those used to control the actual operation.2 0.. it is imperative that column performance specifications be chosen wisely. Poorly chosen specifications are the cause for nearly all convergence failures when solving distillation problems with the VO algorithm. The model may be tuned to the plant operating data by adding or subtracting theoretical trays._.. While some tuning of the model may be necessary for the new operating point. Correlation of O·ConneU· 100 90 60 o 10 60 -. 7.2. <.. In general...

10 3-5 5-7 For every specification imposed on a column model.Top 24 .: l: it ! Quench Zone Quench .70 70 -75 25 .O.90 Alky DeiC4 (reflux) 55 .90 70 .12 SO-60 30 30 45 .40 Reboiled Absorber ·6S .:.3rd Draw Top Draw to Reflux 3S .~: .30 2 1-2 3-5 3-5 Crude Distil12tion: Stripping Zone Flash Zone.SO 50 . of Th~r~tiQ!l:t TnlSS 2 3-4 4-5 9 . Side Stripper 40 . .3 Overall Tray Efficiencies .!i F "Ii 1 Ii r .100 200 . This degree of freedom is allowed to se_e~ the level rcquir_cd_t? satisfy the performance specification equation in the solution.250 C3 Splitter 85 .3 3-5 HGO Section 3 -5 LGO Section 1 1-2 2 2 SO .30 20 .65 Alky DeiC4(no reflux) 5S .·90 7S .S5 20 .17 2 2-3 FCC Main Fract.70 2S .10 10 .30 Simple Absorb/Strip S-7 Steam Side Stripper 7 .70 6-8 Vacuum Column (G.80 C4 Splitter 20 .35 5-7 3 -5 6-S 7 . ·.2nd Draw 2nd Draw . of A~tYSlJ r~ys Ovcra\l Effici~ncy T Column S~rvic~ 20 .24 Amine Stripper Typical No.60 13 .1 ::1 Typical Typical No.35 Deethanizer 70 .12 20 . Zone to HGO Draw 2 .45 Debutanizer 85 .1st draw 1st Draw .35 Naphtha Splitter 9S ..24 Amine Contactor 4S .100 110 .90 38 .40 Depropanizer 8S .1 .HGO Draw HGO-LCGO LCGO .50 5-7 3-7 7 .to Reboil.55 60 .10 7 .SO 20 .80 35 .r 68 Practical Distillation Principles Table 7. there must be a corresponding degree of freedom or parameter that is not specifled. Operation): 2-4 Stripping Fl.130 C2 Splitter 95 .

'I . ". It is important to recognize performance specifications that are equivalent to avoid overspecifying a column model. « . the column reflux rate cannot also be used as performance specification since it is a needed degree of freedom for the calculations. Therefore.1' I. .&~~~~t1WJ~~~:'H~~i~.:~~..$J'. '{ -.~. the reflux rate may be determined indirectly by selecting the condensing duty as a degree of freedom for the column calculations. Furthermore.'i. either directly or indirectly. musl have an effect on the performance specification. the following equivalent specifications could be used to control the bottom product: Reid vapor pressure. -' =t- ':1 i ~h. Thus. Only one of these specifications should be chosen for the model.. n-butane recovery in the overhead product. n-butane content of the bottom product. or the dew point temperature of the column overhead vapor.. A logical specification for this column is the isopentane loss in the overhead product. the isopentane recovery in the bottom product. For distillation models. any pair of specifications that define the light keyJ heavy \.. For example. For example. and bubble point temperature of the bottom product.5 psi: The plant operator adjusts the reboiler heat input until the desired Reid vapor pressure is met. the isopentane loss in the debutanizer model may be specified as the actual isopentane content in the overhead product."'. the operator of a debutanizer column controls the top temperature of the column by setting the reflux rate to control the isopentane loss...~V.~E.. and the side product draw rates. and condenser has two possible degrees of freedom and may therefore have two performance specifications. an additional speci-fication may be added and the condensing duty calculated as the corresponding degree of freedom. The simulation approach is equivalent to the plant approach in controlling the isopentane loss.:!. the condensing duty is directly controlled as a degree of freedom in the calculations. it is known that the isopentane loss is controlled by the column reflux.::. For the debutanizer column example given above. the logical choices for degrees of freedom are the column heat sources. Li 1\ I Ii . a conventional column with two products.i . For the simulation model.. the Reid vapor pressure is the performance specification and the reboiler heat input is the degree of freedom. successful simulation of the debutanizer column depends on selection of performance specifications that define the separation of the light and heavy key components. Only one of these specifications may be used for the model.. i:! " . Furthermore. The Reid vapor pressure is a measure of the n-butane content in the bottom product. As stated above.".:i!jj~'~'w£r. Therefore the model replicates the plant behavior accurately. In reality. column heat sinks.'. a reboiler. Note that equivalent specifications are also possible for the debutanizer bottom product. The condensing duty is indirectly changed as reflux is returned to the column...:9 ..ci.'~t. adebutanizer column is operated such that the Reid vapor pressure of the stabilized product is 6.69 implies that the degree of freedom. The light and heavy key components are nbutane and isopentane.p~tt#'4~~. Thus. a In reality.. For this column. Therefore. it is necessary to have the reboiling duty as a degree of freedom for the calculations to meet the bottom product specification.

As previously discussed in Section 5. In fact. the D86 end point cannot be modeled accurately.95 percent gap for the products. Thus. the key components cannot be identified as known components. Therefore. " ~I I 70 Practical Distillation Pnnciptes key separation results in a successful simulation model that corresponds to the actual column operation. they may not be used as light key components for the split.6. a gap specification for the splitting column is equivalent to a specification of the light key separation component. For example. i. both liquid and vapor products are withdrawn from the reflux drum as illustrated below in Figure 7. Note that the gap specification is an ir:c:irect way to define the 086 five percent distilled temperature of the heavy product. consider a naphtha splitting column. The five percent distilled temperature of a stream is determined by the lightest components in the stream.II. For some petroleum columns. i . The liquid! vapor split on the condenser drum provides another degree of freedom and performance specification for the column model. This principle is true for any column and this is why it is so important that the column key components be identified before the simulation model is attempted. I I I' ' I Top Tray Reflux liquid Product . since the D86 end point of a stream is controlled by its heaviest components. Naphtha splitters are often controlled to produce a desired ASTM D86 5 . the planl operator controls the ASTM 086 end point of the overhead product to limit the heavy components in this product.6 Mixed Phase Condenser Condenser Overhead Vapor r: I. for this column. For these columns. the light key! heavy key separation is defined by the D86 ninety-five percent distilled point for the overhead product and the D86 5-95 gap for the bottom product.•. for the naphtha splitter. It is also necessary column discussed to choose a light key specification to solve the naphtha splitting above. therefore the 086 95 percent distilled is chosen as the specification for the heavy key component for the column model. . The gap is defined as the D86 five percent distilled of the heavy product minus the DS6 ninety-five percent distilled fer the light product. Figure 7. The ligh. This is equivalent to a heavy key component specification. hence. the concept of equivalent specifications is very important in selecting the performance specifications. components that are identified in the feed characterization are _ usually all recovered in the overhead product.L / For some columns.

the condenser side liquid draw is available as a degree of freedom for the calculations. 44 and Nutter .some of the problems encountered when relying on simulator hydraulic calculations for design. they are still useful for troubleshooting and preliminary sizing work. downcomer backups. For condensers with significant vapor product flows. In other words.if it is planned to explore alternate operations that may alter the composition of the overhead vapor to the condenser. with the liquid product flow. with its rate calculated to meet a performance specification. some commercial simulators approximate the performance for non-valve type trays by applying factors to valve tray ratings. Apparent flooding factors. Thus. Kister)6 discusses. such as the design manuals of Glitsch 42. Tray Rating Commercial simulation programs provide various correlations for tray rating. Since the reflux drum is a theoretical tray. Therefore it is good to know what methods are being used in the program for rating and design calculations. It is doubtful that the generalized tray rating methods in commercial simulators can adequately rate specially designed trays. Correlations are also provided in commercial simulators for packed columns. the actual column calculations are always based on theoretical trays which means that 7. For condensers with small vapor product flows.71 Simulation programs define the liquid product from the condenser drum as a side liquid draw and the vapor product as the overhead product for this arrangement. More rigorous methods must always be used to finalize tray calculations for revamps and designs. ratings from commercial simulators may not be applicable or accurate for your column. It is always good practice to allow the condenser side liquid draw rate to be a degree of freedom for the calculations. the condenser temperature may be used for the performance specification and the vapor product flow calculated to satisfy the equilibrium balance. While the correlations in commercial simulators are not accurate enough for design of trays. and tray pressure drops are estimated by most of the commercial simulators when tray and downcomer details are supplied. The above three chart methods are all for valve trays.5 . Koch 4). However. These are typically vendor supplied chart methods. it is best to specify the vapor flow and allow the condenser drum temperature to be calculated. Under these conditions. the liquid and vapor products leaving the drum must be in vapor-liquid equilibrium. These results arc useful for checking purposes to indicate possible operational problems within a column.2. These methods are generalized and not necessarily the same as those used by the same suppliers when guaranteeing equipment. No such chart methods exist for older type trays such as bubble caps. there is only one temperature that satisfies any given liquid! vapor product split from the condenser drum. This produces the most stable model. In fact. particularly ·.

some special techniques are necessary and these are discussed in Chapters 8 and 9.3. and depend on packing type and size. The accuracy of packing cakulations is dependent on the quality of the packing data and the applicability of the pressure drop methods used in the commercial simulator. and a variety of other operating parameters. It is further necessary to have column models that can be used in predictive mode for troubleshooting. product properties. Differences between the model and the plant are commonly reflected in the column temperatures.1 . column loadings.3 .". Therefore. top reflux rates. Surprisingly.3. 7. 7. product compositions. it is assumed that the column is operating normally and there are no operational problems. column diameter.! ! Troubleshooting Actual Columns All troubleshooting with computer simulation must be based on mathematically converged column solutions. the necessity of representing petroleum mixtures with pseudo-components has not been a serious hindrance to the development of accurate models. A step-wise approach is always best when reconciling models to plant data. Some general guidelines for feed characterization are as follows: .Practical Distillation Principles 72 HETP (height equivalent to theoretical tray) must be assumed for the packed sections in the initial setup of the simulation modeL' HETP's vary for packings. As with tray ratings. In this section. product rates.2 discusses problems attributable to column operational problems. when a computer model does not match the actual operation. models based on local tray efficiency models are of no value for troubleshooting because they cannot reliably predict an alternate operating point. It is not possible to reach valid conclusions using simulation models for which the column mathematical constraints are unsatisfied.1 Difficulties Matching Real Column Operations Computer simulation has been successfully applied to petroleum distillation problems for many years. the first and necessary step when troubleshooting must always be to obtain converged results with the column model. internal liquid flow rates.n operation and using models 1.J help troubleshoot operational problems. This section discusses troubleshooting from two perspectives: difficulties in replicating the real COlUI. Several suggestions are listed below. I) Feed Characterization: This is the most important step in any modeling project. it is important to know the limitations and accuracy of the methods and data being used for the packing calculations. Section 7. Thus. there must be an explainable reason. Therefore. and heat duties. Great care should be used to model the column feed stock as accurately as possible. For crude and vacuum systems.

2) Temperature data: caused by faulty instruments and/or poor a. this is usually a sure indication of an insufficient number of components in a separation zone. The feed to reproduce for the feed agree. Use the best current data available for the feed stock. . b. Use intelligent methods to extrapolate all laboratory distillations to 100 percent distilled.73 a. c. as well as a condenser drum pressure. In particular. If all simulated temperatures in a column are too high or too low but the column products are satisfactory there is likely a problem with the column pressure profile. continuous fashion when operating changes are made. Incorrect simulated temperatures may result from incorrect column pressures. "heart-cut" products from distillation columns. f. It is imperative that a light-ends analysis of the carbon number hydrocarbons be provided for the characterization when accurate predictions are needed. The simulator default ranges are not always satisfactory. it will stock analysis can always be checked by blending the characterized products the feed stock. five and lighter vapor pressure g. It is especially helpful to superimpose the TBP distillations stock and the feed stock as derived from the product blend. When the column temperatures and/or side product rates change in a step-wise manner. Never rely on mathematical techniques in commercial simulators to properly extrapolate a laboratory distillation. it is always necessary to include additional pseudocomponents to accurately represent narrow. Actual petroleum columns change in a gradual. Use multiple sets of petroleum with different chemical make-ups products. Analyze the component splits in each separation zone of the column to ascertain that a sufficient number of pseudo-components have been defined. A pressure that is toohigh results in a predicted temperature that is too high and viceversa. Choose pseudo-component cut-point ranges wisely. pseudo-components to represent petroleum streams such as virgin (uncracked) materials and reaction c. Be wary of poor temperature measurements placement of temperature measuring devices. h. Be sure to include top and bottom tray pressures in each column model. e. If they do not be impossible to match the column material balance with the model. b. Always compare the characterized feed stock to the original data. d.

or the effect of liquid entrainment on the temperature measurement. If it does not. It is not uncommon for simulated top tray temperatures for crude distillation columns. and the top tray pressure on the top tray temperature. the bottoms subcooling circuit must be incorporated into the model.~~. -- '. steam rates are seldom metered accurately.1 ':':'-"~' . The simulated bottom product temperature is normally the bubble point temperature and will be higher than the subcooled temperature. results in a reboiler duty that is too high.100 percent distilled temperatures of this product are in reasonable agreement with the plant data. point temperature of the top tray vapor at the top tray pressure. especially for crude and vacuum units. An increase in the stripping of the product below a side product lowers its draw temperature. The best indication of top temperature agreement with the plant data is the simulated distillation of the liquid overhead product. When the relationship of side draw rate to side draw temperature is step-wise instead of continuous. k. T : Simulated liquid side draw temperatures are true bubble points. j. This simple model may be used to test the effect of stearn. For coiumns with thermosiphon reboilers. Column top tray (second theoretical tray for columns with condensers) temperatures may be easily checked by reconstructing the top tray vapor from the condenser products. I. The number of pseudocomponents used to represent the feed stock also affects the side draw temperatures. The normal convention for commercial simulators is to represent the reboiler as a heat source on the bottom tray of the column. e. This . Column bottom steam has an important effect on the flash zone temperature for crude and vacuum columns.. there is another problem with the plant data which may be inaccurate top tray pressure measurement. A feed temperature that is too low f.)lant values. the simulated top tray temperature should equal the plant value. If the 95 . As such. The true top tray temperature must be the dew. Always supply pressures for flash zones. and coker main fractionators to be higher than the measured . they are influenced by the light components in the separation zones. h. the bottom product temperature is lower than the reboiler outlet temperature. light gases. Make certain the feed temperature is accurate. Some columns such as FCC main fractionators and vacuum columns have bottom circulation systems which subcool the liquid bottom product. Unfortunately. i. FCC main fractionaiors. there are not enough pseudo-components in the separation zone._ ----~. differences in light cracked gas rates. Bubble point and dew point' calculations may be used to check the reported temperatures for column products that are saturated liquids and vapors. g.74 Practical Distillation Principles: d. Reponed temperatures and pressures for columns that generate steam such as amine regenerators are easily reconciled by using the steam tables. For agreement between the model and the plant.: . incorrect steam flow in column.I .

columns and FCC main fractionators. since the rate is rarely. b. The calculated reboiler duty is determined by the light key performance specification and is not dependent on the reboiler configuration used in the model. Feed preheat temperature has an important effect 00 the reboiler duty. Therefore it is best to let the duties be calculated to meet column performance specifications. 3) Reflux Rates: a Plant top reflux rates are seldom measured accurately. A safety factor of at leas! 2S degrees F (13.9 degrees C) should a/ways be maintained in any proposed new operation . if ever.7S configuration corresponds to a kettle reboiler.. Free water should never occur in complex columns such as crude columns and FCC main fractionators. and the simulated bottom product temperature corresponds to the reboiler outlet temperature. c. It is usually necessary to increase the intermediate heal removal at the heavy gas oil draw when increasing the column charge to keep the column in heat balance. For crude column pumparounds. 2) Heat Duties: a. The pumparound cooler duty should always be cross checked by calculating the duty for the other side of the exchanger. This is especially true far crude d . it may be necessary to model additional exchangers in the train to reconcile the pumparound duties. The duty for a pumparound circuit is difficult to calculate using the pumparound rate. e It is best to specify pumparound duties for crude column and FCC main fractionator models. It is easy to cross check the duty for feed-bottoms exchangers since the bottom stream is liquid and the temperatures can be accurately measured. It is difficult to calculate most reboiler and condenser duties accurately from typical plant data. f The heat balance for FCC main fractionators becomes a critical bottleneck upon expansion of the column charge rate. The condenser and quench duties for FCC main fractionators should always be degrees of freedom for the calculations. n. metered accurately. and it is not necessary to model the reboiler as a thennosiphon reboiler unless design or revamp work is being done. This simplification in the column model has no significant effect on the column results. Incorrect steam rates can have a significant heat effect for columns such as FCC main fractionators because of the high heat capacity of water versus hydrocarbons. The water dew point temperature can be easily computed by calculating the water partial pressure in the column overhead and reading the corresponding temperature from the steam tables. Most columns are over-sized and column diameter is usually not as important as the heat balance.

Simulation can be a useful tool when adjusting test run data.• ---~-- . Heat optimized columns operating at low reflux rates are more sensitive to changes in the reflux rate than changes to the number of theoretical trays used in the model.ing such drastic action as shutting down and opening up columns..-' . the number of theoretical trays in the column model should be increased and vice versa. Chemical engineering theory is a powerful tool when it is necessary to make adjustments to the test data to r" reconcile the heat and material baJances. 47. -1! a. 4) Test Run Data. this model before the operational problems occur since a crisis situation is seldom a . The most accurate product rates are based on tank gauges.f_-. A model which is based on the average operation for a two or three week period may be better than one based on a test run of short duration..- ~~... e. d. Many good artic._. Real world problems are not always easy to diagnose. Kister ~5 has published a technique to determine theoretical trays and minimum top reflux for multi-component distillation.49. 46. 7. and it is wise to explore as many facets as possible to confirm probable causes before i..S() iste ---. It is always helpful to talk with the test engineer and revisit the original test data when reconciling differences between the test and simulation results.. When the column separation is met satisfactorily and the top reflux rate is higher than the plant. -. Orifices should always be re-calibrated for test runs. 36 trou bl es hoori ooung an d several are li d as fu rt h er rererec:e mareria 1 ..::. d.3. C. J~ i 76 Practical Distillation Princtptes h. The Underwood method predicts the minimum reflux at an infinite number of theoretical trays. . This is the best way to determine the column actual overall efficiency when accurate data are available for the column operating conditions and products.4& .--. c. The best simulation models are those which represent the most typical operation.od time for model development. - .. Significant differences should be explored in more depth .. Shortcut" methods are sometimes useful in finding the boundary for top reflux rate.. It is much better to develo. The Fenske method predicts the minimum number of trays at infinite reflux.2 Ii Diagnosis of Column Operational Problems The necessary pre-requisite for troubleshooting with simulation is a good model for the normal column operation. The column operating point must lie between these extremes.es have been written on column '" . It is sometimes helpful to compare test results to typical operating data for the column. ~._ . b. AU test run data have been adjusted to show perfect heat and material balances.

i i . When using column rating data.. Tray rating calculations are useful in indicating possible poor performance due to flooding of the trays. not how it is performing. As previously discussed. Operations personnel almost always suspect column flooding when problems occur. This is because liquid is leaking from the draw tray to the next section below and acting as reflux.77 column models to diagnose operating problems is sometimes more art than science. . the rating calculations can only be used as an indication of possible flooding for the actual column.3 are typical for normal column operations. therefore. Zones of relatively constant temperature in the column indicate tray damage or missing trays. this is always the first issue to resolve when troubleshooting column operations. do not neglect to check the predicted downcomer backups and tray pressure drops. Calculated flooding factors greater than IOU percent may indicate tray flooding problems. 2) The Column Temperature Profile: The column temperature profile is a direct indication of the separation occurri ng. In this respect. The leak may be a hole in the draw tray or a bad seal between the draw tray and the column wall. The separation predicted by a column model is not degraded by flooding. there may be tray damage or missing trays. Therefore. the model becomes an indicator of how the column may be expected to perform. The product below the draw tray is al so lighter than normal. the flooding calculations in commercial simulators are approximate methods and not the final authority. I . However. Chimney tray damage always results in a greatly lowered draw temperature and difficulty in maintai n i ng a desired draw rate. If it is necessary to lower these values significantly to match a column operation. 3) Low Tray Efficiencies: The tray efficiencies presented in Table 7. In the author's experience with petroleum columns. tray mechanical problems are far more likely than flooding problems. several techniques for using the simulation data for troubleshooting are suggested below.1 ' . It is not an uncommon occurrence to have tray manways left open during construction or turnarounds. open manways are the same as missing trays. I) Checking for Column Flooding: l I dI I. High pressure drops and! or downcomer backups greater than 50 percent may also indicate possible flooding in the actual operation. The latter can be caused by a thermal upset in the column. Backflow through the column during startup is an effective way to move all of the trays to the bottom of a column. Again. Real world problems such as shoes and hard hats in column downcomers are not easy to simulate. . resulting in a greatly reduced separation zone. since model results are based on theoretical conditions being satisfied.

regardless of how the duty is distributed over the column. .n 18 Practical Distillation Principles . 5) Abnormally High Reflux Requirements: f. Reflux is generated by increasing the reboiler duty and so on. i Too much feed preheat is a likely cause for this condition. . the necessary heat removal to produce a given set of products is always the same. 4) Heat Balance Problems These occur for complex columns with side draw products and are usually diagnosed by plant personnel as flooding problems. This is not always apparent since plant reflux measurements are often inaccurate. Remember that separations are accomplished with a combination of trays and reflux.. overloading the top section of the column. ----------- .. Correcting the side cooler operation will correct the apparent flooding problem. These materials must be washed down to the bottom of the column by increased reflux. This results in a big increase in the top reflux for the column. ! I r i ! ~. Thus when side coolers are not operating properly. For these columns._ . condensing duty is shifted to the overhead condenser. I Don't neglect to check for reboiler problems when tray efficiencies seem to be low for an actual column operation. A problem reboiler may not be generating the reflux needed for the separation. . . When the feed is too hot there is too much carry up of heavy materials into the rectification zone. The column model can be used to reproduce the plant operation and determine the optimum feed temperature..

and Smith. Henry Z. 42 Glitsch. Progr. J. L. "Flexible Method for the Solution of Distillation Design Problems using the Newton-Rhapson Technique". No. 52. p. Thesis. Multicomponent 1981). Engr. (1925). Robert P. Bulletin 4900. F. 36 Kister. Chern. Vysniauskas. 32 Boston. Revision 2. Vol. 1989). Private Communication. (Nov. Chem. Vol 9.. W. "A Flexible and Reliable Method Solves Single-Tower Crude-Distillation-Column Problems". T.. "Troubleshoot 75.. 71-80.. (988). R. Am. c. G. 1983).. Chern. Develop. 1. 53-59. Engr. p. 42.. E. Engrs. and Tower Chern.. 63-68. ' A New Class of Quasi-Newton Solution Methods for Multicornponent. F. 43 Koch. "Crude Simulation on a Personal Computer". J. 39. Am. Multistage Separation Processes". p. p. Eng. D. (1943). F. (June 1995). Engr... "Successfully Distillation Towers".. and Stanfield. 41 G. Jr. Eng.. I. 63-72. p. Engrs. J. p. 1985). Chem. "An Improved Shortcut for Calculating Distillations".19 31 Goldstein. Progr.. 44 Nutter. (1970). Y. 1969). G. Can. and Bradford. 35 Morris. Chern. Henry Z. Eng. 78-84. Chem. Ind.. 747. Process Des. Engr. p. Kunesh. 741. and Svrcek. 319. W.. Float Valve Design Manual. and Sullivan. J.. E. 46 Hasbrouck. Trans. . 38 Murphree.. 13. Kaes. p. Distillation Simulations".IlS. Distillation". P.. 63- 37 Hengstebeck. (Oct... (August 45 Kister.. S. Trans. "Complex (May 13. Troubleshoot . 5th Edition.. 1974). Chern. Chem. Difficult Multicomponent v. Eng. (Febr. Vol. (Jan. Flexitray Design Manual. V. Vol. Chem. 39 Drickarner 40 O'Connell.. Ind. Ballast Tray Design Manual. C. D... L. Sirn.. p. (I946).. Richard A. " A New Class of Solution Methods for Multicomponent. Tulane University. J. (1982). 33 Boston. H. Robert B. p. 17. Chern. (1970). (Dec. Inst. Inst. (March (993). Engr. Progr. Multistage Separation Processes". Bulletin 960-1. Ph. 17. 34 Russell..

H. H. "Solve Process Column Problems.• p. F. (June 1996). ~ ~ . and Seibert. S. 1. R.. Progr. Hydrocarbon Pr .. Chem. SO Kister. C. (Sept." . . p. 83-87. H. T. 89-91. T. Z.. C.Part 2". 1990) . f .. Engr.. p. . ' Practical Distillation Principles 80 47 Kister. ~-!I . 48 Kister. Z. E. 42-48. Chern... 63-69. 49 Fair.• and Hower. and Hower..II!!ITT··. "Understand Distillation-Column Debottlenecking Options". "Predict Entrainment Flooding on Sieve and Valve Trays".. (June 1991). C. (May 1991). Engr. and Haas. "Solve Process Column Problems- r r ... Z .. Progr. Part 1". p. Hydrocarbon Pr.

For example. crude oil distillation units throughout the world operate in similar fashion and achieve similar results. Crude distillation models are also useful for investigating the effect of revised crude oil slates or product requirements on the current operation. many crude distillation units have been designed with the flexibility to process a wide variety of crude oil types. Simulation of crude distillation units is important for many reasons. the most profitable use of simulation models is often in the improvement of the current operation.globe. For a successful effort. In fact. refineries in the Netherlands purchase crude oil from tankers on an available basis and may process entirely different types of crude oil on a short term basis. The laboratory TBP distillation is conducted at a higher reflux ratio than the plant operation and the separations between the adjacent products are sharper. it is imperative that the model builder has a good understanding of crude oil distillation and the unit being modeled. This translates to larger equipment (especially furnaces) and larger utility costs than for the downstream processing units. a small improvement in efficiency produces a significant reduction in the unit operating cost. However. Data reconciliation is very important when developing crude distillation models. ..Chapter 8. Nevertheless. Because crude oil distillation is the first step in the refining process. any proposed expansion of a refinery begins with ~ serious evaluation of the current crude distillation capacity and the steps necessary to expand it. Crude oil qualities vary widely around the . The crude oil is heated and distilled at low pressure into several products with overlapping boiling point ranges. This is accomplished by developing models for the current and proposed expanded operations and using the models to identify and resolve equipment bottlenecks for the proposed operation. 81 " "" '. However. the charge rate to this process is the highest of all the refinery process units. Most of these products are further refined in downstream processing units. Because of the large scale of this operation.0 Crude Distillation Crude distillation is the first step in the refining process. especially in the separations between adjacent side products. The product separations in a crude distillation column approximate the product separations in a TBP laboratory still with one exception. e. this does not negate the value of the laboratory TBP distillation in predicting the product yields and product properties which may be expected in a crude distillation column for a given crude oil. This improves the profitability of the entire refinery. Since this is the first step in the refining process. i. It is not unusual that some of the necessary operating data are not available and must be estimated for the model. there are fewer distributed components in the separation zones. First. Subsequently.' there are often many questions to resolve regarding the operating data. the crude oil feed stock must be represented as accurately as possible.

heavy gas oil (HGO). heavy naphtha. kerosene. atmospheric pipe-stills. atmospheric bottoms. crude topping units (CTUs).f • f <. gas oil. The second section presents a stepwise procedure for modeling existing columns. The hot liquid portion of ! 1 J J j . depending on its end use. etc.000 to 10. This book has devoted a separate chapter to vacuum distillation. Reflux is also provided at intermediate locations in the column with. Some of the typical schemes used to increase unit capacities are also discussed in this section. with capacities ranging from 5. light gas oil (LGO). •. it can be argued that vacuum distillation is also part of crude distillation since it is a continuation of the crude oil distillation process for the heaviest portion of the crude oil.000 barrels/ day (7000 Metric tpd) have been taken out of service. These techniques may also be applied to development of design models for new columns. reforming naphtha. The products are successively condensed and withdrawn as side products as the hot vapor portion of the feed rises and is contacted with colder liquid reflux flowing down the column. atmospheric units.. And. 8. In this book.000 barrels! day (700 to 1400 Metric tpd) to 400. etc.000 Metric tpd).000 barrels! day (56. Middle distillate is referred to as diesel fuel. atmospheric gas oil. etc. Light fuel distillate is most commonly called kerosene. The heaviest. Typical flow sheets and operating procedures are discussed. named: naphtha.82 . and topped crude. virgin distillate.p!lmparound cooling circuits. There is no industry-wide nomenclature standard for crude distillationcolumns or their products This can be confusing for new engineers. jet fuel (military JP4). bottoms. residuum. 4 straight run. heavy distillate. the products described above will be designated as light· . crude. pipe-still . etc. light gasoline. but it may also be known as light distillate. etc. Crude distillation is accomplished in multi-draw columns for which all of the heat is supplied in the feed. The heavy gasoline product is usually reformed to improve its octane and may be . crude distillation columns may be called: crude distillation units (COU's). jet fuel (commercial JET 50). and many columns processing less than about 50. Crude oil distillation columns come in a variety of sizes. Ref1ux is provided at the top of the column by pumpi some of the condensed liquid back to the top tray. diesel. . the crude column bottoms product is called: reduced. atmospheric residue. heavy naphtha.1 Crude Distillation Units: General Information Crude distillation columns and the associated auxiliaries are large when compared to most other refinery processing units. distillate may be designated as: atmospheric gas oil (AGO). heavy gasoline. The separations achieved with crude columns are independent of size and the operating strategies are similar for columns of all sizes. e I. Crude Distillation The first section of this chapter provides general background information on the crude distillation process. and so forth. • etc. Process economics today favor large units.. topping units. For example. However. finally. The light gasoline product is called: light straight run (LSR). topped crude oil. light naphtha.

25 to 0.---------- ' .1 Process Description A general crude unit is depicted in Figure 8. Upon exit from the last preheat exchanger the oil is heated to the desired column inlet temperature in the crude furnace.1. The pressure of the desalted crude oil is raised in a booster pump and it continues through a preheat train where its temperature is raised by exchange with hot intermediate streams from the crude and vacuum columns. In the desalter. Here it mixes with the steam and light hydrocarbons from the column stripping zone. 3. not the degree of separation. five to six liquid volume percent water is injected. Furnace outlet temperatures typically range from 630 to 725 degrees F (333 to 385 degrees C). Nelsen" presents four fundamental principles for the operation of crude columns and other multi-draw columns that are worthy of repetition: 1. the salts (primarily chlorides) selectively migrate to the aqueous phase and are withdrawn as a brine solution. L. After desalting. The oil is heated to 250 to 300 degrees F (120 to 150 degrees C). The hot oil mixture from the furnace flows through a transfer line into the flash zone of the main crude column. Sufficient steam is heated and introduced into the stripping zone to strip the lightest hydrocarbons from the topped crude product The stripping steam also lowers the partial pressure ofthe hydrocarbons in the column flash zone. The number of trays only slightly alters the boiling range of the products as defined by ASTM initial boiling points and end points. the crude oil contains from 0..83 oil feed is stripped with steam to remove dissolved light hydrocarbons before the bottom of the column.1. 8. depending on the crude oil composition. The lower panial pressure for the hydrocarbons lowers the temperature required to distill the overhead products from the column feed. 2. ami' it must be 4. 10\'-/.5 liquid volume percent water from solubility and emulsion effects. Cold crude oil from storage is pumped through a series of exchangers where it is preheated by exchange with intermediate products from the crude and vacuum distillation columns. - The initial boiling point of side draw products is always corrected by either steam stripping or reprocessing. W. and the resultant emulsion is fed to an electrostatic desalter. .: The yield of a given product is primarily a function of the composition of the feed mixture. The end point of a side draw product is primarily controlled by opening or closing the draw valve to change the yield.

•. . 1'1 t. Secondly. Since crude column sizes are primarily determined by the vapor tlow rates. The reflux condenses the side liquid products. ' .. !f !i The hot liquid from the flash zone drops through the column stripping section. they reduce the vapor flow rate through the column which reduces the required size of the column. Unfortunately..:i .. Finally. -~ ---~- Ii ii I! 'j J i"i.! -!. ".1 Typical Crude Distillation Unit Condenser Wet Gas C • • ~ Desalter . Pumparound flow rates are high.. The hot vapors from the flash zone rise and are contacted by colder reflux flowing down the column. the pumparound cooling is important when designing and expanding these columns. because heat is being exchanged with crude oil that is at a high flow rate. Topped Crude Charge Pump C • The pumparound cooling circuits accomplish three objectives.84 Crude Distillation J. where it is stripped by steam injected into the bottom of the column. . f J f 4 i'i I. ...i I.. the pumparound circuits degrade the fractionation between side products by reducing the internal liquid flows between side products. Reflux is provided by the overhead condenser and by pumparound circuits in which side draw liquid is pumped through exchangers and cooled by exchange with crude oil in the preheat train. This decreases the required crude furnace duty.. they improve the efficiency of the crude preheat train by enabling heat recovery at higher temperature levels than the overhead condenser.i . ' /. ~ '---------. Figure 8. they remove latent heat from the hot flash zone vapors and help condense the side products.: !: J /.: i.i. First. The cooled pumparound liquid is typically returned to the column a few trays above the draw tray.

The end points for the liquid side products are controlled on the main column by their draw rates. The separation between these products is accomplished with an auxilliary splitter column. ... The separation of light and heavy naphtha with a splitter column as depicted in Figure 8. This adjustment allows heavier components to travel up the column to the kerosene draw tray. increasing the end point of the kerosene product.. to increase the end point of the kerosene product in Figure 8. The unit depicted in Figure 8. stripping is used to remove diesel boiling ' ?:". ... but this effect is small when compared to the effect of the diesel steam stripper. Straight RurY Heavy Naphtha Note that for this scheme. Stabilizer LPG Li ght L . There may also be a small decrease in the lightest portion of the diesel product because of this adjustment.'-"'~-. Thus.85 liquid side draw products are usually stripped in steam strippers or reboiled strippers light materials and control their flash points. For example. an additional liquid side draw product is located on the main column above the kerosene side draw.2.-.2. the composition of the .2 Alternate Light! Heavy Naphtha Separation Condenser Scheme r--·WetGas "------... The heavy naphtha product is withdrawn at this location and stripped with steam..~ : Stripper . not the main .range materials from the cracking stocks for fluid catalytic crackers (FCC's). Figure 8.1 has at least three advantages over the flow sheet shown in Figure 8. portion of a liquid side product is controlled by a side stripper.1. it is necessary to decrease the flow of the diesel product and increase the flow of the kerosene product...------. .. In the case of the gas oil side product.:"column. The light straight run gasoline is removed as the overhead liquid product from the condenser and stabilized. An alternate processing scheme to separate light and heavy naphtha is shown below in Figure 8.1 recovers a combined light straight run! heavy naphtha overhead product. . . The use of naphtha strippers has been widely abandoned by refiners for these reasons.--- r---.---_. _____~ L.

recovering the heavy naphtha with the column overhead products. It is condensed and withdrawn as an aqueous phase frcn: the condenser accumulator drum. Current design philosophy is to use six to eight trays in the wash zone and an overflash rate of 3.0 to 15. Purnparound cooling zones may have two to four trays for heat transfer purposes. A small amount of water leaves the process dissolved in the topped crude and side stripper liquid products. There must be significant liquid wash (overflash) and contact area (trays) to wash metals and coke forming materials down the column into the bottoms product. 86 Crude Distilkuion First. these trays do not accomplish any signi ficant fractionation. This improves the profitabi lity of the naphtha reformer operation. The other reasons concern the qualities of the light straight run and heavy naphtha products.0 volume percent of fresh crude charge. Thesplitter column provides both better stripping and rectification than the side stripper and top trays in the crude column used in the heavy naphtha side draw scheme. The separations between side products are not precise. The quantity of overflash should not be larger than necessary since it represents heat supplied in the furnace in addition 10 that needed to distill the overhead products. Chemicals are injected into the main column overhead vapor line to minimize corrosion caused by hydrolization of salts in the condensed water. .V -~---------. A safety margin of25 to 35 degrees F (14 to 20 degrees C) should always be maintained between the main column overhead temperature and the dew point of water in the overhead vapor to prevent water condensation in the main column trays. depending on the number of side products being withdrawn. however. Seven to ten trays are commonly used between adjacent side products.. Nearly all of the steam introduced into the main column and the side strippers leaves the top of the main column as steam. and there are regions of overlap where the heaviest components in one side product also OCC~lr as the lightest components in the next lower side product. .provides a better measure of operating safety by substantially raising the water dew point for the overhead vapor from the main column. This protects the quality of the heaviest side product and prevents carbonization or coking of the trays in the wash zone. and good reforming stocks (carbon number six and higher) may be minimized in the light straight run gasoline. Older column designs (prior to 1970) were based on two t? four wash trays and overflash design rates of 10. The quantity of overf1ash that is necessary depends on the unit design 2nd the characteristics of the crude oil being processed. The column section between the flash zone and the heaviest side product is of particular interest. Hence. Main crude columns typically have 30 to 50 actual trays. Reboiled side strippers reduce the vapor load for the main column versus steam side strippers since the stripping vapor returning to the main column does not contain steam. Refiners sometimes use reboiled side strippers to control the flash points of side liquid products while keeping the products dry.0 to 5.0 liquid volume percent based on fresh crude charge.~ . light materials (five carbon number compounds) may be minimized in the heavy naphtha reformer feed.

3 Typical Pressure Control Scheme I· Fuel Gas •. Asphalt base crude oils produce little cracking gas and it may be necessary to use an external gas source to maintain a desired positive pressure on the accumulator drum. A paraffin base crude oil cracks more readily than an aromatic or asphalt base crude oil. In general. it is necessary to process a paraffin base crude oil at a lower temperature than an asphalt base crude oil. As might be expected. a paraffin base crude produces more cracking gas than an aromatic or asphalt base crude oil.1 bar).34 bar) higher than the flash zone. A double control valve arrangement is used to bleed external gas into the accumulator drum as needed to maintain a desired pressure. with the furnace transfer line pressure about 5 psi (0. The decomposition (cracking) of crude oil produces light gases.22 to 1. Figure 8. When sufficient gas is produced from the crude oil. The pressure of the accumulator drum is usually in the range 3. but increases the flash zone temperature.)8. tar-like substances. A higher pressure reduces vapor loading.7 bar) higher than the accumulator drum. the distillation takes place at low pressure and the furnace outlet temperature is controlled to keep thermal decomposition of the crude oil at an acceptable level.0 psig (l. Ret1ux to Column Water Overhead Liquid .55 bar) higher than the top tray. "j Column Overhead 1 • I I. the external gas flow is zero.36 bar absolute). depending on the drop through the overhead vapor line and coolers. The pressure of the crude column is controlfed by holding a back-pressure on the reflux accumulator drum. Therefore. and elemental carbon (coke).4 to 0.3 presents a typical pressure control scheme used for crude column accumulator drums. although some refiners operate at pressures as high as 30 psig (3.1. The top tray pressure for the main column is 6 to 10 psi (0. Thermal decomposition of a crude oil is dependent on its chemical makeup.0 to 5. Figure 8.34 to 0.87 <·. The flash zone pressure is usually 5 to 8 psi (0.2 Typical Operations and Control There is wide variation in the operating conditions used for crude distillation.

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