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to Sfead, State MOdeling

01 Petroleum Processes .



f ~

r ,

A Practical Guide to Steady State Modeling of Petroleu m Processes

(Using Commercial Simulators)


First Edition

Gerald L. Kaes

Consulting Chemical Engineer Chemical Process Simulation Colbert, Georgia

The Athens Printing Company

Athens, Georgia

--_"" L__

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:

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.

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





TABLE OF CONTENTS Chapter 1 - Introduction to. Steady State Simulation


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

? ~

3 3 4 , ;:

4 5


7 10 10
; 13 13 14

2 - Composition

of Petroleum Refinery Feed Stocks

2.1 Crude Oil Properties



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


3 - Laboratory

Testing of Petroleum Streams


16 17 _ 18 19 .':

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..


19 20


'!:J:' 1

3.7 Flash Point 3.8 PourPoint


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

23 23

Pseudo-components : 25 '25 26 28

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


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


4.2 Development 4.3 Development

4.4 Pseudo-component

and Critical Propenies


5 - Limitations

of Petroleum Pseudo-components

.•...........••............•...•....... 37
: 37

.5.1 Prediction
5.2 Prediction

of Laboratory

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

5.3 Simulation 5.4 Simulation

39 40 43 43


6 - Thermodynamics K Values

for Petroleum Calculations

on K values :

6.1 Equilibrium

6.2 Effect of Non-Hydrocarbons


6.3 Hydrocarbon-Water
6.4 Enthalpies 6.5 Recommended




for Petroleum


46 48

6.6 Thermodynamic Chapter 7 - Practical

"Rules ofThumb"


. ~ ,,,

52 S3 54 56 56

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 ,. " . ,

.. 58 58 S9 64 67 71 72 72 76

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


8 - Crude Distillation

82 83 87

8.1 Crude Distillation Units' Generallnformation 8.1.1 Process Description 8.1.2 Typical Ope.ations and Controt.



8.1.3 Schemes to Increase Crude Processing Capacity Main Column Considerations . . F umace C· apaclty C onslid eratrons S.2 Crude Distillation Units: Simulation of Existing Columns 8.2.1 Definition of the Crude Oil.. Crude Assay Oata 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 Main Column Stripping Zone Main Column Flash Zone Main Column Wash Zone Pumparound Zones Side Product Draw Zones.. Top Section of Main Column Side Stripping Columns 8.2.4 Crude Column Overhead System ~.2.S Solution Techniques: Inside! Out Column Algorithm Initial Estimates Initial Model Phase Tuning the Model _ 90 90 . 93 95 95 95 98

108 109 109 110


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

Chapter 9.l

9 - Vacuum



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

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 Crude Assay Data 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 Steam Stripping Zone for Wet Vacuum Units 9 2.4.2 Boot Cooler Circuits ' Light Gas Oil Zone .. Heavy Gas Oil Zone Wash Grid and Flash Zone 9.2.5 Solution Techniques: inside! Out Algorithm 92.5.1 Initial Estimates Initial Model Building Phase ~ 92.5.3 Tuning the Model Chapter 10 - Refinery Reaction Systems




10.1 Reactor Processes- General Information 10.1.1 Catalytic Cracking 10.1.2 Hydrocracking and Hydrotreating Hydrocracking Hydrotreating 10.1.3 Reforming and Isomerization Catalytic Reforming Isomerization 10. 1.4 AI ky lation and Polymerization Alkylation Catalytic Polymerization 10.1.5 Thermal andCoking Visbreaking Coking 10.1.6 HydrogenPlants 10.1.7 Ether Processes MTBE Processes T ANtE Processes

······················· ·····.·..····· .

···· ..·······

148 150 153 153 157 160

0 •• : • .. •••••·•• .. •• .. • • .. •


··· ·

·..-..···· ..····..· ···· ·..· ··..··..··..· · · ·..··· ·:· ·· ·

· ·

164 7 16 167 172 174 174 178 181 183 183 186 188 188 i90

10.2 Reactor Processes: Simulation Techniques 10.2.1 Black Box Reactor ModeL.

· ·

·.. ·..· ·· · .. .'...... ..

10.2.2 Modified Black Box Reactor 10.2.3 Empirical Predictive Reactor 10.2.4 Free Energy Minimization Reactor (Gibbs) 10.2.5 Equilibrium Reactor 10.2.6 Stoichiometric Conversion Reactor Chapter 11 - FCC (Fluid Catalytic Cracking) Processes
11.1 FCC Processes: Genemllnformation 11.1.1 Process Description 11: 1.2 Typical Operations and Control.. FCC Reactors Main Fractionators Slurry Strippers FCC Gasoline Splitters : FCCGasPlants

196 198 200

" · ···

·····.·················· . 204 ··..·..·..· 204

205 207 208 208

··..· ·..··· ·..··· ··.. ··..· ···..··· ..· · ..···..·· ~ · ·· ..··..· ·..··

2 t2 212 217 217 220 222 223 224 225 226 227 228

11.2 FCC Processes: Simulation of Existing Units 11.2.1 Definition of the Reactor Effluent............. 11.2.2 Collection of Operating and Laboratory Data 11.2.3 Reactor Modeling ·······.···· . ..·· 1 12.4 Main Fractionator 11.2.4. 1 Quench (Desuperheating) Zone ·..· ·· 11.2 4 2 Heavy Cycle Oil Zone

. ·· Light Cycle Oil Zone 11.2.44 Heavy Naphtha Zone 11.2.4. 5 Overhead System

.... --.-- _. ---___;=.::.:.:::..._.__ ..... . ;;;;-"==" _ ..'~~;..;;_-..~-.-.

;,:!:,::_. ___;_ ........

TABLE OF CONTENTS (continued) 11.2.5 Gas Plant Columns : Primary Absorber Stripper I Secondary Absorber. Stabilizer C3! C4 Splitter 1 ] .2.6 Recycle Loops................................................................................ 11.2.6. I Recycle Estimates 11.2.7 Solution Techniques: Inside! Out Column Algorirhm Initial Estimates: Main Fractionator 1 i .2.7.2 Initial Estimates: FCC Gas Plant Columns Initial Model Phase I Tuning the Model. Chapter 229 229 230 230 23 J 23: ,)~ 2~'" 232 233 233 233 234 234

12 - Catalytic

Reforming Processes

236 237 239 241 242 242 243 243 245 246 248 248 249 249 249 250

12. I Catalytic Reforming Processes: General Information 12. I. I Process Description 12.1 ..2 Typical Operations and Control.. 12.1.3 Catalytic Reformer Reactors 12.1.4 Reformer Separator Operations 12.1.5 Stabilizer Tower Operations 12.2 Catalytic Reforming Processes: Simulation of Existing Units 12.2.1 Definition of the Reactor Effiuent... 12.2.2 Collection of Operating and Laboratory Data 12.2.3 Reactor Modeling 12.2.4 Stabilizer Modeling 12.2.5 Recycle Loops ~ Recycle Estimate 12.2.6 CCR Catalyst Systems · 12.2.7 Solution Techniques Blocked Operations


13 - Hydrogen Processes

251 252 253 255 255 256 2 56 256 258 260 262 262

13. I Hydrotreating Processes: General Information 13. 1. 1 Hydrotreating: Process Description 13.12 Typical Operations and Control 13 I 3 Hydrotreating Reactors l3.l A Separators! Gas Treating 13 1 5 Product Stabilizers (Strippers) 13 '") H\'d ~. P . S' I' f Exi . . rotr eanng rocesses. irnu anon 0 xrsting Ul1Its............................ 13.2. 1 Definition of the Reactor Emuent... 13.2 2 Collection of Operating and Laboratory Data 13.2.3 Reactor Modeling 13.24 Modeliog Separators! Gas Treating 13.2.5 Modeling Stabilizer (Stripper) Columns

- TABLE OF CONTENTS (continued) 13.2.6 Recycle I Purge Gas Calculations 13 .2.6.1. Initial Estimate for Recycle Hydrogen 13.i.7 Solution Techniques 13.2.7: 1 B locked Operations 13.3 Hydrocracking Processes: Generallnformation

264 : 265 265

13.3.1 Hydrocracking: Process Description 13.3.2 Typical Operations and Control., 13.3.3 Hydrocracking Reactors 13.3.4- Separators! Gas Treating
13.3.5 13.3.6 Quench Hydrogen Produ_ct Separation


266 266 '267 269 269 270 270 270 271 272 274 276 277 279 279

13.4 Hydrocracking Processes: Simulation of Existing units »: 13.4.1 Definition of the Reactor Effiuent. 13.4.2 Collection of Operating and Laboratory Data 13.4.3 Reactor Modeling Heat of Reaction Reactor Calculations for the Design Case....................................... 13.4.4 Modeling Separators! Gas Treating 13.4.5 \ ~odeling Fractionation Columns......... .. 13.4.6 Recycle / Purge Gas Calculations Initial Estimate for Recycle Hydrogen Recycle! Quench Hydrogen Techniques 13.4.7 Solution Techniques Blocked Operations '" 13.5 Hydrogen Plants: General Information 13.5.1 Hydrogen Plants: Process Description 13.5.2 Typical Operation and Control 13.5.3 Hydrogen Plant Reactors 13.5,4 Energy Recovery __ 13.6 Hydrogen Plants: Simulation of Existing Units 13.6.1 Collection of Operating and Laboratory Data 13.6.2 Modeling Reactors in Hydrogen Plants 13.6.3 Modeling Amine Treaters 13 .6,4 Modeling PSA Units 13.6.5 Steam! Water Systems Chapter l4.1

280 281 282 282

283 284 286


~ 289 290 .: 290 290 292 292

14 - Thermal Visbreaking:

Processes General Information

1 1 visbreaking: Process Description

294 296 296

1..: 1.2 Typical Operations and Control.. 1..:.1.3 Visbreaking Reactions 142 Product Separation Processes: Simulation of Existing Processes

14::: Visbreaking



Definition of the Soaker Outlet., Collection of Operating and Laboratory Data: 14.2.3 Reaction Modeling 14.2.4 Modeling Fractionator Columns
J 4.2.2


297 298 299 300 301 30l 302 303

~O~ ) .)

14.3 Delayed Coking: General Information 14.3.1 Delayed Coking: ProcessDescription 14.3.2 Typical Operation and Control 14.3.3 Coking Reactions " Separation · . 14.3.4 Product

14.4 Coking: Simulation of Existing Processes 14.4.1 Definition of the Coke Drum Outlet (Reactor Effluent) 14.4.2 Collection of Operating and Laboratory Data: 14.4.3 Reaction Modeling ~ 14.4.4 Modeling Main Columns , Chapter

304 304 307 308 309 311 311

15 - Alkylation Alkylation


Processes: General Information ,

15.2 Alkylation Processes: Process Description 15.2.1 Process Description: HF Alkylation Units 15.2.2

311 313

Process Description:

H2S04 Alkylation Units .

15:.; Alkylation Processes: Typical Operations and Control I 5 3. 1 Typical Operations and Control: HF Processes............. 15.3.2 Typical Operations and Control: H2S04 Processes 15'-i Alkylation Reactors ] 5.4.1 Reactors: HF Processes 15.4.2 Reactors: H2S04 Processes 15.5 Product Separation I ) 6 Al k I' • f Exrsting U' " 'y atron Processes: S· I' irnu atron 0 nits 15.6.1 Definition of the Reactor Effiuent 1 ~ 6 ') ~ II . fO peratmg an d L a boratory Data . . •. .- LO ection 0 i 5 6 3 Reactor Modeling....... 15.6.3.l HF Reactcirs.............................................. H2S04 Reactors : : 5.6.4 Modeling the Acid Systems ]56 5 Modeling of Distillation Columns.......................... I 5 6 5 I Propane HF Strippers................. r 56.5.2 Oepropanizers............................................ 156.5.3 Deisobutanizers in f'hSO,; Processes IS 6.5.4 Isostrippers in HF Processes 5 15.6.5. Debutanizers 15.6.56 Alkylate Splitters j 5 66 Modeling ofRecycles Chap[er 16 - \1' II . p. - --'''.. (see aneous rocesses

318 3I8

32 I
321 322

322 " ')~ .)_-' 323 "')6 .)_ 328 329


. ..

331 333 33::;

335 335

336 337 337 338 341



16.1 Processes That May Be Modeled with Commercial Simulators 16. I. 1 Catalytic Polymerization Catalytic Polymerization: General Information Catalytic Polymerization: Simulation Techniques 16.1.2 MTBE Processes MTBE Processes: General Information MTBE Processes: Simulation Techniques 16.1.3 TAt'vtE Processes TAME Processes: General Information TAME Processes: Simulation Techniques ..<.4 Amine Treaters 16.] .4.1 Amine treaters: General Information Amine Treaters: Simulation Techniques ~ 16.2 Processes for Which Commercial Simulators Are Inadequate 16.2.1 Asphalt Processes : 16.2.2 Lubricating Oil Processes 16.2.3 Aromatic Extraction 16.2.4 Chemical Treatment Processes 16.2.5 Diffusion! Adsorption Processes Appendix Appendix
A.. -

341 341

343 344 345 347 349 350 351 352

352 356
·.. · 358 359 359 360 360 361 363 , 379


B -Referenc-e:s

Appendix C - Subject Iadex Biography of Author ., ,'

_387 39'7


341 341 342 343 344

Chapter 1


to Steady State Simulation

347 349

350 351

The modeling. techniques in this book are for steady state simulation. 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. While ~ecenl advances in computer technology have made possible the use of dynamic simulation for large process flow sheets, steady state simulation continues to be the major tool for ana'ysis and design of chemical processes. 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. The commercial software is cost effective; however, it may represent a compromise in technology since only open-literature and vendor-developedmethods are provided. To overcome these limitations, a licensee may have a vendor incorporate proprietary methods and data into a private version of the software. A major advantage of commercial software is stanJardization of methods and data. Common software is available to both engineering contractors and operating companies, Therefore, plant design models may be constructed using the simulation program of choice for an operating company. For companies with multiple sites, 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. There are many commercial programs available that may be used to model the petroleum processes. 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.

352 352
356 358 359 359 160 )60 161



Th e Steady State Process

By definition,

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. That IS, the law of conservation of mass is perfectly upheld, and every unit of mass entering the precess in the feed stocks leaves the process in the products. Only in the C2.5eof a chemical reaction is mass transformed; however, for this case the total units of mess entering and leaving the process are still the same. For many of the petroleum reactors, some mass is converted to coke which is deposited on the catalyst. This mass leaves the reaction separately from {he other reaction products and it must be considered when calculating the mass balance jar the process,

.--,-'~' .~ ..

..j," ";',

. ...
.. ~



.' .oi

Introduction to Steady State Simulation



The heat or energy-balance is also perfect for a steady state process. That is, 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. The principle also applies to chemical reaction within the process, where the reaction heat is supplied for endothermic reactions and removed for exothermic reactions. Endothermic reaction heat is normally supplied by a heat source while exothermic reaction heat is usually removed in the products and heat sinks. For both cases, the energy must balance. perfectly across the reactor and the overall process. Time is not a variable in steady state analysis. Rather, the steady state concept is used to represent the average operation ofa process for a period of elapsed time. For example, 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. The steady state operation is defined as the 24-hour test period. In similar fashion, a steady state operation may be defined for the average operation of the plant for a longer period of time such as a month. In the petroleum industry; the steady state time is commonly expressed in terms of one twenty-four hour day. Regardless of the length of time chosen to define a steady state operation, it is likely that the process deviated from the steady state during that time period. Deviations are caused l::. feed stock composition and rate changes, changes in specifications and rates for products, set point changes in the process because of minor upsets, and start-ups and shut-downs for the process or individual unit operations within the process. Processes may deviate greatly from steady state during start-ups and shut-downs, and these time periods should never be used for steady state representation of the process. Steady state simulation is widely used for the design and analysis of chemical processes. For design it is also necessary to consider maximum and minimum limits which may occur during start-ups, shut-downs, and upset conditions for the process. Since each steady state condition represents only one point in time, the evaluation of operating dynamics requires a modified approach in which time is introduced as a variable. Time dependent simulation is called dynamic simulation and is discussed briefly in the section following.


... ~

•• '"",!:



1.2 Dynamic


The most basic form of dynamic simulation is a series of steady state simulations in ·.,·hich a process variable or variables are changed with time. For each snapshot in time, ::-:e steady state condition of perfect material and energy balance is maintained, This type of dynamic model is useful for analysis of control schemes such as those used for :istillation operations. However, 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,

True dynamic simulation requires sophisticated, time dependent models for the unit operations. The number of calculation~ req_uired for dynamic models is many that required for ste~dy. state models. Hlst?, t.he spee~ and storage ca?acltJes for computers have limited the use of dynamic simulation, particularly for modeling ?f large processes. In past years, limited-scope dynamic modules were developed for use In plant start-ups and shut-downs, process control, and operator training. . Current advances in computer technology have made possible the consideration of dynamic simulation models for large process flow sheets. It is probable that, in the future, dynamic simulation models will find widespread use in operator training and determination of optimum set points for large chemical processes. Nevertheless, the greater share of process modeling today is steady state simulation and this is the focus of this book.


Steady State Simulation Program Features

Commercial data library, physical and special flow simulation programs provide a common list of features: a pure component estimation procedures for non-library components, thermodynamic methods, transport properties, simulated laboratory tests, unit operation calculations, sheet building modules, and a user interface for program input and output.

All of the unit operation calculations are based on feed streams comprised of distinc: chemical components, for which various thermophysical properties are available Calculated results always include product streams comprised of the same chemical components (or corresponding reaction-produced components); therefore, it is convenient [0 store calculated results from the unit operations as streams. A product stream from one unit operation may become a feed stream to another and so forth. In this fashion, the process flow sheet is constructed using the streams as the connectors. The calculation platform of most interest is the personal computer (PC), and all vendors offer PC versions of their products. Ease of use is important for PC products, and all commercial simulation programs provide a graphical interface,";n which process information may be entered and retrieved via a process flow diagram (PFD). Portability is an 'important feature for engineering programs, especially for engineers who commonly visit operating plants in many locations. Laptop PC's have become very popular because of their portability.

Pure Component Data Library
.-\11 commercia! simulators have large pure component libraries containing data for the various classes of chemical compounds encountered in chemica! processing plants. Vendors may develop these data for less common components, but most of the data

4 usually-come from recognized reputable sources. Common sources for pure component 2 data include the PPDS' and DIPPR libraries. Some vendors also allow the licenser to incorporate private technical libraries within their sc.ftware.

1.3.2 Non-Library


No simulator is complete without procedures to estimate thermophysical properties for non-library components. Open literature estimation procedures are commonly employed in which component properties are related to chemical structure. For petroleum streams, structural data are not available for non-library components and properties- must be estimated from such correlating parameters as normal boiling point, specific gravity, and molecular weight. The concept of pseudo-components is used, where a pseudo-component represents a certain 'boiling point range of the feed stock. 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.

1.3.3 Thermodynamic


). ,

f~ :;1 !i? h1

Thermodynamic data include vapor-liquid equilibrium ratios (K values), emhalpies, and entropies. These properties are necessary for the unit operation calculations, particularly the first two. Entropies are used for isentropic calculations such as compression and expansion. Calculation methods for K values include equations of state, liquid activity coefficients, and empirical formulae.' The accuracy of an equation of state is improved by incorporation of tuning factors based on pure component binary vapor-liquid equilibrium data. Liquid activity coefficients are calculated with standard equation forms using pre-determined coefficients. These data and other relevant parameters are kept in thermodynamic data banks in commercial simulators. Many of the thermodynamic parameters are vendor-developed; however, there are also recognized sources for data such as the DECHEhLA-\ Chemistry Data Series. The user may also supply thermodynamic parameters as program input. 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. 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.

' .. -.-.'.-~-----~_;;;;;.

=:a:C"'"'TO::"A . ....;-;:;;:_-,.:.._.. '-" ..



1.3.4 Physical and Transport Properties

It is useful to calculate physical and transport properties for the feed and product streams in a simulation model. These properties may be calculated using the individual component contributions, or determined based on the average properties for the stream Properties computed from individual component data include stream total flow in mole, weight, and volume units, and stream density. Transport properties such as viscosities, thermal conductivities, and liquid surface tension are commonly computed usmg the principle of corresponding states .


Simulated Laboratory Tests

The sped fications for petroleum' products are based on standardized laboratory tests. Most commercial simulators include methods to simulate these tests. Laboratory tests include distillations, vapor pressures, flash points, pour points, freeze points, cetane numbers, octane numbers, densities, and viscosities. Accuracy of the simulated test depends on two factors: how well actual test data can be correlated into a predictive equation, and how well the composition effect can be represented with the components and pseudo-components used in the model. Some tests such as octane, pour point, and viscosity nearly defy correlation because they are so composition dependent. More discussion on laboratory tests is given in Chapter 3.

1.3.6 Unit Operation Calculations

in chemical engineering to divide processes into a series of calculation steps called unit operations, which commonly appear in process after process. The individual unit operations have common techniques and are based o,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. Lnit operations include the following: vapor-liquid equilibrium separation, heat transfer, tluid flow. reaction, and mass transfer operations such as distillation, absorption, stripping, diffusion, and adsorption. An additional subset of unit operations is available for handling solids and inorganic processes; however, these operations are not needed for the petroleum processes and are omitted from discussion. The fundamental unit operation is vapor-liquid equilibrium separation (also known as "flash" separation). K values are used in a calculation procedure to determine the vapor and liquid portions of a mixture at a given temperature and pressure. One or two liquid

It is convenient





....-- ............ _ ••......



_._r __ .....- ..

phases are considered to be in equilibrium with one homogenous vapor phase. In plant operations. 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. The flash separation principle is used as a subset of nearly every other unit operation. Heat transfer calculations include heat exchangers, furnaces, and coolers. Fluid flow operations include pumps, compressors, pipes, and valves. A variety of reactor types may be provided, including stoichiometric, equilibrium, kinetic, and Gibbs free energy minimization. Distillation and its subsets of absorption and stripping are the most important unit operations in petroleum processes, Diffusion and adsorption seldom have application and are omitted in the discussion below.

The distillation process consists of a vertical series of inter-linked flash separations, 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. The separation steps are designated as theoretical trays and the composite group of trays is called a column. The vapor from the top tray is condensed, and some of the liquid is returned to the top tray as reflux. Reflux flows down the column, washing the heavier components down the column. 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. The stripping vapor flows upward through the column, carrying the lighter components in the feed up the column. Distillation calculations are based on steady state operation. At solution, every column has a perfect mass balance for every component for every tray as well as for the entire column. Likewise, there is a perfect energy balance for every tray and the entire column. Finally, every tray is at vapor-liquid equilibrium and has both liquid and vapor products. It is sometimes desirable to impose additional performance specifications on the solution, related to the product qualities, quantities, and the column operating conditions. Distillation calculations are iterative, 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.


Special Flow Sheet !\lodules

Severa: auxiliary modules are used in process modeling. 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. Some processes have recycles, in which a unit operation product stream is returned to an upstream operation for re-processing. The recycle stream will reach a constant

', ··t


Ipes " !rgy

Composition. rate, temperature, and pressure in the steady state. To model the recycle calculation, .the downstream product stream is directly substituted as a feed to the upstream operation. This procedure is repeated until the recycle stream reaches the steady state. Most simulators have accelerator techniques for recycle calculations, in which a new recycle stream composition is predicted, based on two or more previously calculated compositions. Other useful flow sheet modules include feed back and feed forward controllers. feedback controllers are used to adjust an upstream process variable such as temperature to produce a desired downstream result such as a product quality. Feed forward controllers are used to set downstream operating conditions based on calculated upstream results.




the as the lux

have an empirical stream separation module, in which a feed stream is separated into two streams using a defined set of individual component separation factors. This module finds utility in shortcut representation of auxiliary process flow sheets within the main process flow sheet. Another useful concept provided in many simulators is a user-defined calculation block in which special calculations may be defined. These calculations may represent proprietary technology or a unit operation not provided by the program vendor.

All simulators


1.3.8 G ra phicaJ In terrace

The graphical capabilities of PC's are useful for simulation programs. The user build a PFD visually on the screen. This reduces errors in definition of the flow sheet is also a convenient means to provide the operating data for the individual operations. The PFD may also be used to retrieve calculated results for specific operations. may and unit unit


Steady State Simulation


Over one hundred and thirty programs are listed in the A.I.Ch.E. Software Directory' -..;nder the category "Process Design/Simulation". The following listed programs are general process simulation programs with petroleum pseudo-component capabilities:



.-,--S,PD\· PLUS
10 /ot






Apsen Technology Chemstations, Inc. Windows Simulation Company Hyprotech, Ltd. Hyprotech, Ltd.



Cambridge. IvfA, USA Houston, TX, USA Houston, TX, USA Calgary, Alberta, Canada Calgary, Alberta. Canada




Deerhaven Technical Software




Simulation Sciences, Inc.

Bryan Research & Engineering

Brea, CA, USA

Bryan, TX, USA


l) HYSYS is the future replacement for HYSIM. It has both steady state and dynamic simulation capabilities.

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. The reader is encouraged to contact souware vendors directly fer

more information

on specific products.

When presented in this book, examples and simulator specific information are limited to the HYSIA1, HYSYS, and PROVISION programs for which the author has extensive experience. This is not meant to imply that other products cannot be used to produce satisfactory results.









1 PPDS (Physical Property Data Service) and the National Engineering association with the Institute of Chemical Engineers, England. 2 DIPPR Data Compilation of Pure Compound Properties, American 345 E. 47 St., New York, NY 10017.



Chemical Engineers,




3 DECHEMA , the German Society for Chemical Apparatus, Chemical Engineering, and

4 1998 CEP Software Directory, American St., New York, l\ty 10017 (January 1998).

Institute of Chemical


345 E. 4 '7 .


ii il

' I

h 1:

Chapter 2 Composition of Petroleum Refinery Feed Stocks

The primary raw material for all of the petroleum processes is crude .oi1. Crude oil is a naturally occurring liquid resource produced from wells drilled into the earth. The depth of crude oil wells and methods used to produce the oil vary widely around the world. The nature and chemical composition of crude oil also vary widely, depending on the geographical region from which it is produced. In fact, crude oil may vary widely in composition within the same producing field. It is possible to make some generalizations about the nature of crude oil. First, it is primarily a mixture of compounds containing hydrogen and carbon (hydrocarbons). Additionally, sulfur, nitrogen, and some inorganic salts are also found in most crude oil mixtures. According to Gary and Handwerk', the elementary composition of crude oil usually falls within the following ranges. Element Carbon Hydrogen Sulfur Nitrogen % by weight
84 - 87

11 - 14 0-3 0-0.6

Crude oil is classified roughly according to the predominant family of hydrocarbons it contains as paraffin base, naphthene base, aromatic base, or asphalt base. Crude oil bases vary greatly with geography. The refining scheme is dependent on the crude oil base. The relative values for crude oils depend on the processing costs and the market values for the-associated products.
.~ .;.


Crude oil is produced in all comers of the globe. However, greater than fifty percent of the world's known reserves are located in the geographical region known as the "Middle East". For this reason, this region will continue to be a strategic focal point for the nations of the world.

2.1 Crude Oil Properties

Crude oil is a very complex mixture of thousands of hydrocarbons. A.P.l. Project 6 has succeeded in isolating over 16,000 distinct hydrocarbon compounds from a single sample of Oklahoma crude oil. In general, such complete analyses are not conducted on crude oils, and no attempt is made to analyze for pure components in crude oil except for the low boiling point distilled components (or light ends). A number of simple tests are used to evaluate crude oils as potential refinery feeds.




__ '._- .._.,.,----

.. -'-.,.,





These tests include. the following: J) Gravity, API The density of petroleum oil is expressed in the United States as APr gravity, where API gravity is related to specific gravity as follows: Degrees API

(14 J.5 / ~ 131_5

The specific gravity or API gravity is relative to the density of water at 60 degrees F (15.9 degrees C). The expression for API is non-linear, and specific gravities must be used when calculating the gravity for blends. The API gravity is an inverse relationship when compared to the specific gravity, and a higher value indicates a Jess dense material. It is also useful to note as a reference point that the API gravity of water is W.O. Crude oil API gravities vary widely with the crude base, from heavy Venezuelan crude oils of 10.0 API to light paraffinic. condensates of 70 API. However, 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 0.934 specific gravity). 2) Boiling Point Range The boiling point range for a crude oil is determined with a true boiling point distillation test (TBP). 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. Results for the test are reported at one atmosphere of pressure. Unfortunately, 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. Therefore, 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. 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. According to Nelson 6 and others, [he maximum boiling point for crude oil mixtures is greater than 1400 degrees F (760 degrees C).


Factor factor is that proposed by Watson, Nelson, and

The mo~t commonly used characterization :'.1urphy·. It is defined as: K




03)3 /

sp. gr.

where T" is the mean a verage boiling point of the sample in degrees Rankine and sp. gf.



Composition of Refinery Feed Stocks

is the specific gravity at 60 degrees F relative to water. This characterization factor has been related to viscosity, molecular weight, critical temperature, etc., so that almost any laboratory data may be used to estimate it. A factor of 10.0 or less indicates an aromatic material and a factor of 15.0 indicates a paraffinic material. For most crude oil, the factor is in the range 10.5 to 12.5. Note that this factor is a rough indicator of the hydrocarbon class (or composition) for the crude oil.

.; ;


j\ .J

4) Sulfur Content, 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. High sulfur content crude oils are known as "sour" crude oils and require more extensive processing than low sulfur or "sweet" crude oils. In general, the lower the API gravity for a crude oil the higher the sulfur content. However, there are exceptions to this rule, with low API sweet crude oils and high API sour crude oils. The additional processing for sour crude oils involve hydrogen treating processes to convert the sulfur to H2S that can be removed. 5) Carbon Residue,
\\1 8

i i





;i i

@ Q


This property is determined by destructively distilling a sample to elemental carbon (coke) in the absence of air. 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. 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. In general, the higher the carbon residue for a crude oil, the lower its value as a refinery feed stock.
.i _;

i i

; '~I

6) Salt Content, pounds/1000 barrels All crude oil contains some inorganic salts, generally in the form of chlorides. 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 . 7) Metals, parts! million (ppm) by weight Numerous metals occur in crude oil, with the most common being nickel and vanadium. Metals tend to concentrate in the heavier fractions of the crude oil where they act as poisons for the catalytic and hydrogen cracking processes. Other metals include arsenic, copper, iron, and zinc. 8) Nitrogen Content,

. t;

1 I




Nitrogen compounds in crude oil reduce the activity of cracking catalysts. Most of the nitrogen in crude oil is contained in the highest boiling fractions. High nitrogen content crude oil may require special processing to remove the nitrogen.




Pour point is a measure of the paraffinicity or waxiness of a crude oil. A waxy crude oil has a high pour point; that is, it congeals at a temperature higher than room temperature. Conversely, a low pour point indicates an absence of paraffins and! Or a presence of aromatic compounds which tend to lower the pour point. All of the above mentioned properties are indicators of the composition for a crude oil. As previously stated, a true component breakdown is not usually detennined for most CI ude oil samples except for the low boiling portion. This portion includes pentanes and other light components with normal boiling points below 100 degrees_F (38 degrees C). For some iight crude oils and condensates, a complete chemical breakdown can be determined through the light naphtha portion (normal boiling point 200 degrees F) with chromatography, but such data are not typically available for most crude oil samples,

2.2 Crude Oil Composition

Three general classes of hydrocarbons are present in crude oil; paraffins, naphthenes, and aromatics. Signitlcant quantities of olefins do not naturally Occur in petroleum. In oil refineries olefins are created in the cracking processes. Paraffins in crude oil range in boiling point from methane to compounds with boiling points exceeding 1000 degrees F 8 (53 degrees C). Naphthenes have at least one saturated ring and range from cyclopentane through complicated multiple condensed-ring compounds. Aromatics have a! least one unsc.turated ring and range from benzene through multiple condensed-ring Slnlcrures with 56 carbon atoms or more. As Iong side chains are added to ring compounds they become more paraffinic in their properties and behavior. This makes it dlflicult to c1assi fy most crude oils as one particular class of hydrocarbons. Asphalt Content of crude oil is directly. related' to the concentration of aromatic compounds and asphaltenes in the heaviest portion. While there are generalizations useful for predicting asphalt production from crude oil, 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, it is necess3.ry to process the heaviest portion in allother heavy oil process such as a hydrocracking, coking, or a modified FCC operation.

CrUde Oil Assay Data
.-\ large quantity of crude oil assay data are available for the crude oils of the world. Some of the data are company proprietary; however, many of the data are available in Open literature. A typical assay contains the fOllowing information for the crude oil:

14 1) Whole crude oil average properties:

Composition of Refinery Feed Stocks

Gravity, weight percent sulfur, weight percent nitrogen, pour point, viscosities, metal contents, weight percent carbon residue, Reid vapor pressure, salt content, flash point, percent asphaltene, bottom sediment and water (8 S & W), light hydrocarbon yields (C1(\), and boiling point curve. 2) Fractional properties:

Boiling point or cut-point range and yield on crude, properties as shown above for whole crude oils, research octanes for gasoline fractions, smoke and freeze points for kerosenes, naphthene and aromatic contents for reforming stock, and cetane number for diesel fuels. It is important to note that crude oil assay data change over time for any crude oil. This is. caused by two factors. First, the crude oil itself cbanges in composition over time as it is produced from a given well. Secondly, a crude oil sample represents a mixture of the crude oil produced in many wells and possibly many crude oil fields. Therefore, as new wells and fields are brought on line, the composition of the mixture changes. For this reason it is good practice. to request a confirming sample for a crude oil mixture being used in 11. process design. A genera' rule is to be wary of crude oil assays that are more than two years old when accurate simulation work is required.

2.4 Crude Oil Blending

Many refineries process more than one crude oil. The individual crude oils may be transported to the refinery via trucks, pipelines, and ships. Since most refineries do not have sufficient crude oil storage to isolate the various crude oils as they are received. 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. This presents some problems for test runs conducted over short...tirne periods. The volumes of the individual crude oils received by the refinery are available from the refinery accounting system. However, for refineries that process multiple crude oils, 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. Choosing data for a longer time period, such as two to four weeks, is helpful in damping variations in crude oil distillation yields caused by day to day fluctuations in the crude oil mixture.




James H. Gary and Glenn E. Handwerk, Petroleum Refining Technology and Economics, 3rd edition, Marcel Dekker, Inc., New York, (1994), p.23. 6. W. L. Nelson, Oil

& Gas J; p.125,126, (March 25,1968).

7. Characterization

of Petroleum Fractions, Ind. Eng. Chem., 27, 1460 (1935).


8. James H. Gary and Glenn E. Handwerk, Petroleum Refilling Technology Economics, 3rd edition, Marcel Dekker, Inc., New York, (1994), p. 25.

Chapter 3 Laboratory

Testing of Petroleum Streams

Because they are derived from crude oil, most petroleum streams consist of a continuum of components from various hydrocarbon classes. A component by component analysis is neither practical nor oost-effec_tive and is rarely performed in the laboratory. Moreover, such analyses are net usually necessary since the qualities (compositions) of the intermediate and final products are controlled to meet simple laboratory tests. These tests are designed to be quick, inexpensive, and repeatable within a reasonable accuracy. In general, specifications for petroleum products allow a range of acceptable test results. For example, the ASTM D86 end point for a gasoline blend must be less than or equal to 432 degrees F (223 degrees C). Thus, within reason, and assuming that the other test specifications can be satisfactorily met, there is a range of end point test results that satisfy this specification . Inspection of laboratory test results for streams in a petroleum process show that the test results vary with time within some acceptable range. In fact, it is not unusual to see variances in ASTM D86 temperature points of 10 to 20 degrees F (5.6 to 11 degrees C). These variances are caused by changes in the process feed stock, set points, etc. When developing steady state simulation models, 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. In representing the steady state operation, it is often more realistic to look at average test resuits for a given time period instead of single samples.

~. I








3.1 True Boiling Point Distillation (TBP)




The TBP distillation is the best representation of the true composition for a petroleum stream. Unforrunately, the time and expense required for this test restricts its use to crude oil samples. Simpler, less costly tests are used for control-of the refining processes. There are no standard test procedures for TBP distillations. The U. S. Bureau of Mines Hempel method and the ASTM D-285 test procedure are most commonly used. According to Nelson'. any equipment that accomplishes a good degree of fractionation is termed "true-boiling-point" equipment. Gal)' and Handwerk'o state that there is a trend toward using a 15:5 distillation (ASTM D-2892) instead of the TBP. This method is conducted using 15 theoretical stages and a still reflux ratio of 5: 1. Because the TBP distillation tends to separate the individual. mixture components relati·..dy sharply in order of boiling point, it is a good approximation of the separation that may be expected in an actual distillation column. Products are collected and

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 . expected qualities for the products. True boiling point temperatures are always reported al a pressure of760 rnm Hg (one atmosphere). Petroleum oils begin to thermally decompose or crack at a temperature of approximately 6~O degrees F (344 degrees C) at one atmosphere. Therefore, 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. For many TBP apparatuses, the minimum pressure obtainable is 40 mm of Hg. 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. Because of the laboratory time required and the subsequent high cost for TBP distillations, this test is often approximated using correlations that relate the TBP temperatures to temperatures measured by other types of laboratory distillation stills.


ASTI\1 D86 Distillation


The ASTM 086 distillation is the most common laboratory distillation used by petroleum refiners. It has been widely used for process unit control and finished product specifications. Application of this test is limited to the temperature at which the oil begins to decompose or crack. When the cracking temperature is reached, the temperature of the vapors from the still no longer increase since light cracked products begin exiting the still. As previously mentioned,the approximate temperature at which petroleum oils begin to crack is 650 degrees F (344 degrees C) at one atmosphere. The exact cracking temperature for an oil sample depends on its chemical composition. Paraffin base oils crack at lower temperatures than aromatic base oils, causing variances in the cracking temperature threshold. The ASTM D86 distillation is a non-fractionating distillation that is run at laboratory room temperature and pressure. Temperatures are reported at a pressure base of 760 mm Hg For high altitude laboratories the barometric pressure corrections to the observed .cmpcratures are significant and must not be ignored. Table 3. III presents temperature corrections for various laboratory barometric pressures. The DSG distillation was originally called the Engler distillation since a simple Engler distillation flask is used. All distilled vapors are removed from the still and condensed, and no liquid reflux is returned to the flask. 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 4.5 degrees C). The light components that boil at temperatures lower than the condensing temperature are lost from the distilled product.









, ~

11\ :\ , til :.,'



1"-' ---- ....



1 e:)",,~VJ

tal Vtt;uIU

._ ............

Table 3.1 Temperature

Corrections for Barometric Pressure

Laboratory Pressure, mm Hg

Observed Temp, F

12 13 14 15 16



7 8 8

5 6

698 4 4 4 5 66

724 2



ISO 200 250 300 350 400 450 500

550 600 650


12 13 14 15 16

7 7 8 8 9

3 3 J



13 14 15 16 17 18 18 19

10 11
12 12 13 14 14 15 16


21 22 . 23 24




11 12

6 7 7 7
8 8 9



22 :3


4 4 4 4 4 5 5 5

For use with ASTM D86 Distillations Temperature corrections are in degrees Fahrenheit.

One hundred milliliters of sample are distilled and the vapor temperature versus volume reco .... -ered is recorded. The initial boiling point is defined as the temperature at which the first drop of liquid leaves the condenser tube, 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. Any liquid left in the still after the end point temperature is recorded is cooled and measured as the residue. The difference between 100 milliliters and the sum of the recovery and the residue is recorded as the loss. Repeatability of the test is purported to be plus or minus 6 degrees F (3.3 degrees C) for the initial boiling point and end point. Intermediate .distillation points are reproducible within 2 ml. of distillate which corresponds to six to seven degrees F (3_3 to 3.9 degrees C)-

3.3 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. Typical samples for which 0 I 160 distillations are useful are heavy heating oils, cracker gas oil feeds, and residual oils. 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. The distillation


. most commonly selected for ASTM D1160 tests is 10 rnm Hg. All observed .tempe'ratures are pressure corrected to a basis of 760 mm Hg for reporting

At 10 mm Hg, 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. Lower pressures are sometimes used to extend this boiling point range for residual stocks. The reduced pressure used for 01160 di stillations produces a separation of components that is more ideal than that for D86 distillations, In fact, the D 1160 method closely approximates the TBP method, and the temperatures recorded for 50 percent distilled and higher are assumed to be identical to the corresponding TBP temperatures. The 0.11.60 "method is sometimes used to ex-tend the TBP distillation curve for mixtures contaimng high boiling materials, such as crude oils.

3.4 API Gravity

This property has been previously discussed. It is determined with a hydrometer corrected and reported at a basis 0[60 degrees F (15.9 degrees C). and


Reid Vapor Pressure (R.Y.P.)

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. It.correlateswell with tt~ nOfll}al butane content _~ the_§!'!.I!l.p-L~.J!Q.g".Lclin.e{S..1ypicall¥-adjust Reid vapor the pressure of gasoline blends by adding or According to Ne~for·gaso1inelifiheR:V.rrangeof8ioT4psi., the percentage of butanes in the stream is approximately the same as the. R. VP. The Reid vapor pressure is always reported in absolute pressure units of psi, kpa, bar, etc. 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, one part of chilled Iiquid sample at 3G degrees F.(2.6 degrees C) is combined with four parts laboratory air at 70 degrees F (21.4 degrees-C) in a bomb that has a pressure gauge attached to the lid. The bomb is placed in a constant temperature bath at 100 degrees F (37.8 degrees C) and when the pressure gauge reaches a constant value this reading is recorded as the Reid vapor pressure. The repeatability of the test is somewhat less than 0.5 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 3.2 below. The largest deviations occur for the samples at the highest vapor pressures. 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.

J ~')H"~

uJ ...........

__ ... ---

Table 3.2 Relationship between the True and Reid Vapor Pressure for Miscellaneous Volatile Products";
Vapor pressure, psi Ratio Reid I.!:ill< TruefReid 26_2 2~.O 1.09 20.0 1.09 21.8 18.4 20.1 1.092 17.8 20.3 1.14 16.0 1.09 17.5 14.0 15.4 1.10 1.07 12.0 12.9 12.0 12.9 1.07 1.04 10.0 10.4 8.3 9.7 1.17 8.0 8.3 1.04 6.0 6.3 1.04 5.9 v.z 1.16 5.0 5.2 1.04 3.0 3.1 1.03 2.0 2.1 1.05



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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



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. There are four standard tests currently in use by refinery test laboratories: D3710, 02887, D2887 extended, and HTSD. They are summarized in Table 3.3 below.
The most commonly used method" is as set forth in ASTM Standard D "2887-73. This method is limited to petroleum fractions with a final boiling point 1000 degrees F (538 degrees C) or lower. The sample must also have a boiling point range of no less than 100 degrees F (55 degrees C). Carbon disulfide is used for the carrier gas in this procedure. Equipment used for D2887 simulated distillations (sim-dists) has been highly automated .






H ..




I' ,~



Table 3.3 Simulated Distillation Procedures Method 03710


D2S87-ext HTSD

Application gasolines, naphthas cycle oils, gas oils heavy gas oil, crude heavy gas oil, crude

Standard Cs-C1S C5-C44 C5-C60



< 500 F <1015 F <1140 F <1382 F

Report volume weight weight weight


% % %

Note: The standard is a mixture of normal paraffins with carbon number ranges as shown. All of the methods work in similar fashion. The chromatographic column is first calibrated with a standard mixture of normal' paraffin hydrocarbons. 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. The sample in question is next introduced into the column and the retention times and the areas of the sample components are recorded. 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. Crude oils and heavy residues have such high boiling points that the column temperature cannot be increased enough to recover the highest boiling fractions. Therefore, the total area of the sample is not known and the boiling point curve for the sample cannot be determined accurately for these streams. High temperature simulated distillation, HTSD, 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 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. This modification shows great potential for analysis of heavy petroleum residues. With good laboratory technique, reproducibility of boiling point curves using chromatography is much better than that for conventional laboratory distillations. This makes the test desirable for process control. . As the technique is further developed and improved it most likely will replace the laboratory distillations, in particular, the TBP distill arion. The method has been found to have some limitations for mixtures containing aromatic compounds boiling higher than the gasoline range. These aromatic compounds have lower retention times than the normal paraffins of similar boiling points. Thus, the boiling point curve predicted using the paraffin stan.d.ard calibration curve is lower than


". .",-~' r-,



Laboratory Testing of Petroleum


the actual boiling point curve for the sample. This may be overcome by developing aromatic correction factors for the simulated distillation temperatures. Because the correction factors depend on the relative quantities of the aromatic compounds in the sample, multiple sets of correction factors are required to accurately represent the various refinery samples containing high boiling aromatic compounds.

3.7 Flash Point

The flash point test determines the temperature at which the vapors from a petroleum oil will ignite or "flash". Two basic procedures are used to determine the flash point: the '. Cleveland open Clip method (ASTM 092), and the Penskey Martens (ASTM D93) and the Tag (ASTM 053) closed cup methods. To determine the flash point, a sample is heated at a specified rate and an open flame introduced into the emitted vapors at specified time intervals. The .temperature at which the vapors ignite is recorded as the flash point. The open cup method is often used because of its simplicity. Below flash points of 51 0 degrees F (266 degrees C), the open cup flash point is approximately 10 degrees F (5.6 degrees C) higher than the closed cup flash point for the same sample, The open cup method heats the oil at a rate of 10 degrees F (5.6 degrees C) per minute with the test flame applied at 30 second intervals. Therefore, the best accuracy that could be expected from this method is plus or minus 5 degrees F (2.8 degrees C). The closed cup tester heats the oil at a rate of 1.8 degrees F per minute and is the more precise of the two methods.


3.8 Pour Point

The pour point test (ASTM D97) is useful in determining the waxiness of a petroleum oil. A sample of oil is first heated to 115 degrees F (46.4 degrees C) to ensure that all wax is in solution. It is then cooled to 90 degrees F (32.6 degrees C). The sample is now placed in a cooling bath that is maintained from IS to 30 degrees F (8.3 - 16.7 degrees C) below the pour point of the oil. The test jar containing the oil is removed from the bath at 5 degree F (2.8 degree C) intervals and tilted to determine if the oil will flow. If no movement is detected for 5 seconds the solid point has been reached. The pour point is defined as the temperature 5 degrees F (2.8 degrees C) above the solid point. The same procedure is used to detenninc the cloud point of a petroleum oil. 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. The cloud point is typically about 5 degrees F (2.8 degrees C) higher than the pour point.






The' viscosity of an oil is its internal resistance to flow and a measure of its usefulness as a lubricating substance. The Saybolt Universal viscosity test (ASTM 088) is the most common method used by refiners. 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 usual test temperatures are 100 and 210 degrees F (37.8 and 99.2 degrees C). Sayboh viscosities are 088) is a similar test viscosities are reported used to convert Saybolt reported as seconds. The Saybolt Furol viscosity test (ASTM for heavy fuel oils and uses a larger orifice. Saybolt Furol at 122 and 210 degrees F (50.3 and 99 .. degrees C). Tables are 2 viscosities to kinematic viscosities.

Viscosities at other temperatures may be determined with ASTM viscosity paper,. on which a straight line is used to connect two known viscosity! temperature points. Values for intermediate temperatures are read from this line.

The octane test is used to measure the knocking characteristics of a fuel in a laboratory gasoline engine. The engine is calibrated by measuring the knocking value for a standard material, 2-2-4 trimethyl pentane (2241MP). By definition, an octane number of 100.0 is assigned to 224TMP. The knocking value of the test sample is next determined and compared to the knocking value for the 224TMP standard to determine its octane. Two octane tests are run for gasoline: the Research method (F-I) and the Motor method (F-2). F -1 octanes are higher than F-2 octanes because of test engine differences. 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. Historically, gasoline was sold by the higher, F-l value. The current trend is to advertise the average octane from the two tests, i.e., (R + M) !2.

The cetane number is used to measure the performance of a fuel in a diesel engine. Historically it was determined in a laboratory engine (ASTM engine test D613), but today it is usually calculated with a formula that relates cetane number, API gravity, and . ASTM D86 50 percent distilled. An extensive evaluation of methods to compute cetane has been published by Collins and Unzelrnan" of the Ethyl Corporation.

In summary,

Laboratory Testing of Petroleum Streams

all of the above mentioned laboratory tests are used to evaluate the qualities processes. They are, important in simulation since they can be used to define petroleum pseudo-components to represent the streams for the unit operation calculations. This concept is discussed further in Chapter 4. .

of feed stocks and products from the petroleum

9. W. L. Nelson, Petroleum Refinery Engineering, 4th edition, Company, Inc., New York, (1958), p. 95. McGraw-Hili Book

10. James H. Gary and Glenn E_ Handwerk, Petroleum Refining Technology and Economics, 3rd edition, Marcel Dekker, Inc., New York, (1994), p.27.
i~ I i

11. G. L. Kaes from K M. Buster, Personal Communication,

12. American Society for Testing Philadelphia, PA (1982).

(1964). 23, Method D86-IP 123,






Ibid, Part 23, M(:tfiod 01 ]60.

14. Ibid, Method 0323-56.

15. W. L. Nelson, Petroleum Refinery Engineering, 4th edition, Mcfiraw-Hill Company, Inc., New York, (1958), p. 133. 16.lbJd, p. 138 for Book

17. American Society Philadelphia, PA (1982).

Testing and


Part 24, Method


18. Villalanti, D.C., Jansen and P.CoHe, "Hydrocarbon Characterization Temperature Simulated Distillation", 1995 Al.Ch.E. Spring National- Meeting, Texas, (March 19-23, 1995).

by High Houston,

19. Collins, J. ~t and Unzclman, G. H., "Better Cetane Prediction Equations Developed", Oil & GasL, p. 148.160, (Jur.e ", 1982).

apter 4 Developing Petroleum

. Pseudo-components

For the unit operation calculations, it is necessary to represent all process streams with discreet components for which thermophysical properties may be defined. Since most of the actual components are unknown for petroleum streams, 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. 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, specific gravity, and molecular weight. Open literature correlations enable the prediction of any of these three parameters from the other two. For a pseudo-component, these parameters are the weight averaged values for the TBP cut-point range of the pseudo-component. The compositions for all flow sheet streams are represented with actual components and pseudo-components. Laboratory distillations and various other properties are predicted for these streams from their compositions. 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.

4.1 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. As mentioned previously, TBP distillations are seldom' run in the laboratory because of the time required and the associated high cost. Alternately, 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. 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. However, 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. The normal boiling point for each pseudo-component defined as the weight average temperature for its cut-point range. or is



Developing Petroleum r seuao-componaos

4.1.1 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. A revision of this 21 method was published by Edmister and Okamoto in 1959 and is illustrated in Figure 4.1. This method consists of two graphs. The first graph relates the D86 50 % distilled temperature to the TBP 50 % distilled temperature. 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 %, 10-30 %, 30-50 %, 50-70 %, 70-90 %, and 90100 % distilled. The method is illustrated in Tabie 4.1 below.

Table 4.1 Conversion

of D86 to Data with the Edmiste.r and Okamoto Method (Figure 4.1) Corresponding D86 Temp. TBP Temp. DitT., DegF Diff., Deg F

% Distilled 0 0-10

D86. Dec F

TBP. Dec F



10 10-30


58 240 77

165 242 Starting Point

" {f' ~:'j

., 'I
k ...


!~. ~


50-70 70 70-90

60 300 65 365 60


75 393



90-100 100


No provision exists for conversion of other distilled percents, e.g., 5, 20, 40, 60, 80, and 95. Commercial simulators determine these points by quadratic interpolation of the predicted TBP curve. Note that the Edmister and Okamoto method always predicts a distillation curve with a positive slope. This correlation has found widespread acceptance by petroleum refiners. American Petroleum Institute (API) Technical Data Books published prior to 1987 present the Edmister, et. aI., method as Figure 3Al.1.


Figure 4.1 . Conversion of D86 Distillation to TBP Distillation 21 ' Method of Edmister and Okamoto
Figure ".18: Volumetric slope conversions Figure ".1A: 50% conversion


V /,

140 10





T8P 50 % minus 086 50 %, Deg F


10 :10

TBP Temperature Difference. Deg F

100 80








40 20


///. Ct ~ ~~ l&: ~ ", ~ ~


/., ':II-K


v..: ::6 1- :1





ASTM 086 50 %, Degrees F

of o





1;>0 140



ASTM 086 Temperature Difference, Oeg F

The 1987 API Technical Data Book introduced a new method for conversion of D86 to TBP, This method was based on work done by Riazi and Daubert=: and was based on a different approach from the earlier Edmister, correlations, The following equation form was used for all inter-conversions:

where: T "" Absolute temperature, deg R Sg "" Stream average specific gravity, API a.b,c = unique constants corresponding to 0, 10,30, 50, 70, 90, and 95 % distilled TBP,086;::: designate atmospheric TBP and ASTM 086 data, respectively Unfcrtunately, the Riazi and Daubert correlation resulted in prediction of TBP distillation curves that were inconsistent for some cases, 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. Because of these anomalies, the Riazi and Daubert method was not widely accepted by petroleum refiners and a new study was commissioned for its replacement.



.! \

.: I

, II


, 'I'


Developing Petroleum Pseudo-components


In 1994 the results of the new study were published by Professor T. E. Daubert. The D86 and TBP data used by Riazi and Daubert were refit to different equation forms. The new correlation first converts the 086 50 % distilled temperature to the TBP SO % distilled temperature. Based on the SO % distilled point, temperature increments for the following ranges are added and subtracted to develop the complete TBP curve: 0-10 %, 10-30 %, 30-50 %, 50-70%, 70-90 %, and 90-100 % distilled. Observe that this is the same approach taken by Edmister, Professor Daubert reports that the new correlation is more accurate than the older Edmister, et. al., correlation. At this writing, there is insufficient industrial experience with the new correlation to confirm this claim. However, it is likely that the new correlation is a significant improvement over the 1987 Riazi and Daubert correlation. All of the methods discussed above are in the open-literature and have been incorporated '+ into commercial simulators/ The 1987 Riazi- and Daubert method, however, should not _be used since it does not always produce satisfactory results.' Furthermore, it can result in' distillation curves with negative slopes that are a physical impossibility. 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. The correction is applied to ASTM D86 temperatures greater than 475 degrees F (246.4 degrees C) and is calculated with the following equation:
I ;


10gl0 0 :;; 0.00473 (T) - 1. 587 where: 0:;; correction to be added to observed D86 temperature, T = observed D86 distillation temperature, degrees F.

degrees F


Calculation of the cracking correction is illustrated in Table 4.2. Although the more recent versions of the API Technical Data Book no longer include ...his method, most t commercial simulators still make it available. However, this simple equation is a gross oversimplification for the cracking of petroleum stocks in which chemical class is the controlling factor. The author recommends that this cracking correction not be used. A better approach is to use distillation probability paper to adjust the portion of th::; distillation curve for which cracking is occurring.


29 Table 4.2 Cracking Corrections for Observed D86 Distillations:

Observed D86 .Temperature, F 500 550 600 650 700 Corrected D86 Temperature, F 506 560 618 6S1 753


4.1.2 Conversion of D1160 Distillations

The Edmister and Okamoto" method is used to convert ASTM Dl160 distillation data to TBP distillation data. The method is given in Figure 4.2 and has a pressure base of 10 mm Hg for the D 1160 distillation and the predicted TBP distillation. D 1160 data are nonnally reported by laboratories on a 760 mm Hg basis. Therefore, 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. Note from Figure 4.2 that no correction is applied to the D 1160 temperatures for 50 percent distilled and higher. Correction curves are given to adjust the D 1160 temperature differences for the segments o. I0 %, 10-30 %, and 30~50 % distilled. 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.

4.1.3 Conversion of Simulated Distillations

The D2887 simulated distillation is a relatively new test. ASTM Standard D 2887-73 procedure was first published in 1973. 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). 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). As previously mentioned in Sec/ion 3.6, the test has been revised to accommodate higher boiling stocks. The first method for conversion of D2887 distillation data to TBP data was published by Riazi and Daubert", This method involves two conversion steps. First, the D2887 data are converted to D86 data with the following equation:

Figure 4.2

Developing Petroleum Pseudo-components

Conversion of D1160 10 mm Hg Distillation to TBP 10 rnm Hg Distillation Method of Edmister and Okamoto'·




140 120 100


"loAN p3G-Q




:Y I 2~L'V I VY /V
0-1 ~%

-, V V~



-r /


60 700,(,

NOT ~%
















wh ere... F = 0 009524 ( T 02887 1ODA) 0

a, b,

o.oso~ (

T D2~81 500/.) 0.6147 0



D86. D2887

for 086 0, 10, 30, SO, 70, 90, and 100 % distilled. = 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. I. I. The Riazi and Daubert procedure has been made available in commercial simulators. However, results are very poor because of the inherent inconsistencies in the approach used for both the 086 and TBP temperature conversions, and the compounding of inaccuracies by the two step conversion procedure. The conversion equations shown above are also based on a limited sample base with the highest boiling point being 762 degrees F (406 C). Because of these problems and limitations, this conversion method is not recommended and should not be used,




As a part of the study to replace the Riazi and Daubert inter-conversions, Daubert also refit. the D2887 distillation data to equations similar to the Edmister, et. al. correlations. A single conversion step is used in this latest procedure to predict the TBP temperatures from the 02887 temperatures. In this procedure, the TBP 50 volume % distilled temperature is assumed to be equal to the D2887 50 weight % distilled temperature. A f:l!11ilyof curves is next used to predict the TBP temperature differences for 0-10, 10-30, 30-50, 50-70, 70-90, and 90-100 volume percents from the corresponding D2887 temperature differences for 0-10, 10-30, 30-50, 50-70, 70-90, and 90-100 weight percents. The revised procedure published by Daubert is an improvement from the earlier Riazi and Daubert method. There is little industrial experience with this method to date, and it is recommended that all predicted results from this method be carefully examined for reasonableness. As bas been discussed in Section 3.6, 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 (204.8 degrees C). Because of this characteristic, it is not likely that a single correlation can ever be developed to accurately predict TBP distillations from simulated distillations. Rather, the more accurate approach is to develop individual conversion methods for the various types of refinery streams with high aromatic contents, i.e., FCC slurry oil, coker gas oil, asphaltic crude oil, etc. The following approach is recommended when using commercial simulators. Enter the simulated distillation as if it were a TBP distillation to prevent the simulator from using an inaccurate general conversion method. Note that the 02887, D2887 extended, and HTSD are entered on a mass basis; the D371 0 is supplied on a volume basis. Modify the TBP as needed to account for the aromatic content of the stream. The aromatic boiling point correction may be estimated by comparison of the simulated distillation temperatures to another laboratory distillation such as the D 1160. If no other laboratory distillations are available, 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.


Selection ofTBP Cut-point Ranges

TB P cut -poi nt ranges are used to define the pseudo-components, with the average . temperature of the cut-point range defined as the pseudo-component normal boiling point (I--.'BP). The number of cut-point ranges (or cuts) used to define the true boiling point curve for a petroleum stock is somewhat arbitrary. 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. On the other hand, using too few cuts results in a model that does not predict a continuous, smooth distillation for the process streams such as occurs in a typical refinery distillation operation.


uevelopmg Petroleum rseuao-componeoo The following cut-point ranges are reasonable for most refining problems and are used as defaults in many commercial simulators:

Range, DegF < 100 100-800 800-1200 1200-1600

Range, Number of cuts

< 37.8

37.8-427 427-649 649-871

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. This concept win be further discussed in Chapter 7. Figure 4.3 illustrates selection of cut-point ranges for a petroleum stock.

Figure 4.3
Definition of TBP Cut-point Ranges for Petroleum Stock

Atmospheric TBP Distillation Curve

.... c
g') (l)

x ::;pseudo-component
boiling point (NBP)

average normal

c a.

u... (/) c


0= Defined Component NBP

U .-


C) Q)

Q) <;:: Q)



Liquid Volume %





4.2 . Development of Pseudo-component


Definition of the cut-point ranges establishes the normal boiling points (NBPs) and corresponding liquid volume flows for the pseudo-components. The next step is determination of the pseudo-component gravities to establish the corresponding rl!ass flows. The minimum information required in this step is the average stream density for the stream being characterized. When only the average stream density is supplied, 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 Watson-Murphy K factor is computed for the stream average boiling . point:





I .


where T,,_ ,



== stream average boiling point in degrees R and stream specific gravity at 60 degrees F, respectively.

The stream average boiling point is defined by commercial simulators in a variety of ways. Individual pseudo-component gravities are next determined with this variation of
the formula

above: [T B,]

I K'Vg

where: K." == stream average Watson-Murphy T B,


K factor


average boiling point in degrees R

Specific gravities for the known components in the stream are extracted from the pure component library. 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. Commercial simulators differ in the approach taken in this step; however, they all agree in that the needed adjustment is done to the pseudocomponent gravities only, e-: The assumption of a constant Watson-Murphy characterization factor becomes less accurate as the boiling point range for a stream increases. : For wide boiling streams such as crude oil, the characterization factor for the lighter boiling fractions is higher than the _stream average value because of the higher paraffin content of these fractions. Converse Iy, the characterization factor for the higher boiling fractions is lower than the stream average because of the greater concentration of aromatic and asphaltene compounds. Thus, a stream gravity curve developed with the stream average characterization factor tends to have a slope that is too flat.


. .

uevelop,ng r eiroteum

r .)t:uuv;.v ...y""



Most commercial simulators provide an option by which additional points on the gravity curve may be supplied. Such data are usuallyavailable for crude oils, where several fractions from the distillation test are collected and analyzed. The gravities for these fractions are entered at their mid-volume percents on the overall boiling curve to establish a gr.avity curve for the stock. Normalization is still necessary for the pseudocomponent gravities derived from the supplied curve; however, the slope of the supplied curve is held constant during the adjustment process. 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.

Figure 4.4 Relationship

of Pseudo-component

Properties to the TBP Distillation Curve

Atmospheric TBP Distillation Curve


;.\ <II


pseudo-component NBP's








, I'

, ,, ,




I I I I ,

I. I I I I I I I




, .n
1 I :. I I

1 I I I 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 ..... :

, ~: , , ,





I I , ,

• , t, ~~ I t ,

I : • ,



, I


,t ,I II

~ 't-"f , ,,

: I 1







Liquid Volume 'J.

·;u.q···.··· ...




4.3 Develo pment of Pseudo-com ponent Molecula r Weigh ts

Detennination of .the pseudo-component molecular weights is the final major step in characterization of petroleum stocks. The relationship of the pseudo-component normal boiling points, gravities, and molecular weights are shown in Figure 4.4 above. These three correlating parameters allow the accurate prediction of other needed data for the petroleu m pseudo-components. Molecular weight data are seldom available for petroleum stocks. Therefore, they are predicted by commercial simulators based on the pseudo-component normal boiling points and gravities. 'Numerous open literature correlations have been .developed and published since the 1930's that relate normal boiling point, gravity, and molecular weight. Commercial simulators allow the user a variety of methods to predict molecular weight; however, it is usually prudent to use the simulator default method since other thermodynamic data may be tuned to the default molecular weights. Similar to gravity data, most commercial simulators provide an option by which molecular weight data may be supplied. 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. If the stream average molecular weight is also given, the pseudo-component molecular weights are normalized such that the stream average is met. 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. First, any error in predicting the gravity has a direct effect on its accuracy. Second, open literature methods that relate normal boiling point, gravity,. and molecular weight have a bias toward paraffins. Thus, for highly aromatic materials, the methods may predict molecular weights more representative of paraffins than aromatics. In fact, proprietary methods not available in the open literature often ..... introduce s fourth correlating parameter such as the source of the petroleum stock; i.e., straight run; catalytic cracker, coker, hydrocracker, etc. Since these methods are based on actual experimental data they are more accurate than the open literature methods in commercial simulators. Therefore they should be preferentially used when available. Commercial simulators all have provision for the direct entry of the three correlating parameters for petroleum pseudo-components.




Developing Petroleum Pseudo-components


Pseudo-component Enthalpies and Critical Properties

The open literature abounds with accurate methods for predicting enthalpies, entropies, and critical properties for petroleum stocks from the three correlating parameters previously discussed. Enthalpies are typically computed with equations of state as deviations from the ideal gas state. Thus, it is only necessary to predict the ideal gas enthalpy curves for the petroleum pseudo-components to predict their enthalpies. Ideal gas enthalpies for hydrocarbons correlate well to polynomial expressions. Therefore, polynomial coefficients are derived for standard ideal gas enthalpy equation forms using the pseudo-component normal boiling points, gravities, andlor molecular weights. Critical properties for petroleum pseudo-components also correlate well with normal boiling point, gravity, and/ or molecular weight and the open literature abounds with such correlations. 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. for thermodynamic calculations


References: 20 Edmister, W. C. and Pollock, D. H., "Phase Relations Chem. Engr. Prog. Vol. 44, p.90S, (1948).
for Petroleum Fractions",

21 Edmister, W. C. and Okamoto, K K., "Applied Hydrocarbon ThermodynamicsPart 12: Equilibrium Flash Vaporization Correlations for Petroleum Fractions", . Petroleum Refiner, Vol. 38, No.8, p. 117 (1959). ... 22 Riazi, M. R. and Daubert, T. E., "Analytical Correlations curve Types", Oil & GasJ, p.SO-57, (August 25, 1986). 23 Daubert, T. E., "Petroleum Fraction 1994). Distillation Inter-convert Distillation-



Processing, p. 75-78, (September




I !

----- .....


pterS mitati~ns of Petroleum Pseudo-components

The concept of petroleum pseudo-cornponents is necessary and useful for calculations with petroleum feed stocks. However, the engineer must always remember that pseudocomponents are a gross oversimplification for the complex mixture of actual components found in petroleum. A typical petroleum stream characterization uses 50 to 100 library plus pseudo-components to represent full boiling range crude oil. In reality, crude oil is a continuous mixture of thousands of actual components. 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. This limits the ability of commercial simulators to predict accurate results for laboratory tests that are strongly influenced by composition, e.g., pour point, viscosity, etc. This chapter discusses the limitations inherent in petroleum pseudo-components produced by commercial simulator programs. This does not invalidate the pseudocomponent approach to solving petroleum problems; however, these limitations must be considered when interpreting the calculated results from commercial simulator programs.

5.1 Prediction of Laboratory Distillations

Commercial simulators use a discreet number of components and pseudo-components to represent petroleum oil, which is a continuum of actual components. The selection of TBP cut-point ranges for pseudo-components has been previously discussed in Section .J.!. 4. Calculations with the characterized feed stocks predict products with varying amounts of these same components and pseudo-components. The laboratory distillations for products are predicted by a procedure that is the exact reverse of the feed stock characterization procedure. For each flow sheet stream, the predicted TBP distillation is determined by volumetric integration of its components in order of normal boiling point. The next step is to predict the desired laboratory distillation; i.e., D86, D 1160, D2887, etc., using the conversion relationships presented in Sections 4.1.1-4.1.3. Some problems arise when predicting the TBP distillation by volumetric integration of [he normal boiling points for the stream components. This TBP is not smooth, and may have flat regions corresponding to blocks of discreet components and pseudoComponents. Therefore, it is necessary to smooth this rough curve to reproduce the characteristic shape of an actual TBP distillation curve. 37








. .j:....

. ~;.

.,.:' '.f'_'

"" :"·~· ...




.:',.. ';


Limitations of pseudo-components .

Prediction of the TBP initial and end point temperatures present special problems. In the real world, these points represent small quantities of light and heavy components. A typical characterization uses cut-point ranges of25 to 100 degrees F (13.9 to 55.6 degrees C) for the highest boiling fraction of the petroleum stock. The lowest boiling fraction is represented by pure component boiling points andl or pseudo-component cut-point ranges of 25 degrees F (13.9 degrees C). Thus, the first and last component may represent several percent of the distillation curve. For this reason, commercial simulators arbitrarily define the predicted TBP initial boiling point and end point temperatures as . those temperatures corresponding to 1.0 volume % and 9&.0 volume % distilled, respectively. These default percentages may be changed by the user, but this will have little effect without corresponding changes in the pseudo-component cut-point ranges.
'r ,

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. Therefore, the conversion correlations have higher errors when predicting the initial and end points corresponding to the simulated TBP temperatures. This compounds the problems caused by the discreet blocks of components, and the net result is that the predicted initial and end points for laboratory distillations are not reliable. Initial and end point temperatures are used in many petroleum product ~:ecifications. However, for simulation purposes, it is better to estimate the corresponding 5 and 95 volume percent temperatures to use for the simulation specifications. 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. If the predicted initial and end point temperatures are used for decision making, the corresponding changes in the 5 and 9S volume percent temperatures should always be reviewed as a test of reasonableness.


Prediction of True Stream Composition

Two problems arise in prediction of the true stream composition: the cut-point ranges, and inaccuracies in the open literature methods used to predict the pseudo-component properties. Unfortunately, these problems are additive. r Obviously, the cut-point width has an important effect. Users of commercia! simulation programs usually do not specify the cut-point ranges and the default ranges are used in the characterization process. Default cut-point ranges may vary from 25 to 100 degrees F (13 9 - 55.6 degrees C). In terms of actual components, a cut-point range of 2S degrees F may represent many components of different chemical class and/ or isomer structure. Table 5. 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.

Chapter 5


Table 5.1 possible Actual Components in One FCC Gasoline Pseudo-component Pseudo-component Properties; Cut-point range on TBP: 150 - 175 degrees F Average NBP, degrees F == 164 Average API Gravity = 63.4 Average Molecular Weight == 84.4 NBPt Grav., Mole r-i Wt Octane
155.7 81.6 161.3

Pure Component

n-hexane 2,2dimethylpentane methylcyclopentane l-hexene l-Mvcyclopentene 4-M-cyclopentene benzene (See note)


Class - ... -------paraffin paraffin naphthene olefin olefin olefin aromatic

deg F API

Ht of formation., btullb-mole ---_ ... -----~71,900 ~88,500 .45,900 ·17,900

174.6 77.1 56.2 146.3 72.2 158.4 48.7 167.4 48.8

176.2 28.4

86.2 100.2 84.2

82.1 82.1 78.1

24.8 92.8 91.3 83.0 >100 >100 100


Note: benzene is likely present because of azeotroping.

Four distinct classes of component are represented by the one pseudo-component shown above in Table 5.1. The average properties predicted by the simulator cannot possibly represent the unique properties corresponding to each pure component. Thus, 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. Furthermore, the average pseudo-component properties predicted by if' simulator have a definite paraffin bias. 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. Therefore, as might be expected, 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.

Simulation of Refinery Reactors
This subject will be discussed in more detail later in this book. However, it is apparent from the discussion in Section 5.2 that pseudo-components from commercial simulators


Limitations of pseudo-components


cannot represent stream compositions accurately !D terms of unique classes and isomers hydrocarbons. The catalytic and thermal reactions that occur in refinery reactors, furnaces: etc., are dependent on the chemical classes and isomer structures of the' feed stock components. For example, straight chain (unbranched) hydrocarbons are easier to crack than highly branched structures. Paraffins are more easily cracked than ring structures such as naphthenes and aromatics. Unsaturated components such as ole fins and aromatic rings can be saturated with hydrogen in hydrocracking and hydrotreating reactors, etc . .. There is another complicating factor for many of the refinery reactors, namely, the number of reactions taking place. The feed stocks for fluid catalytic cracking units have hundreds of actualcomponents of various chemical classes, carbon numbers, and isomer structures. These pure components are involved in thousands of reactions that include cracking, hydrogen transfer, condensation, isomerization, and coking (carbon formation). Thus, simulation of the catalytic cracking reactions is an impossible task, both from the standpoint of representing the feed stock with discreet components, and in definition of the reactions that occur. This is also true of many of the other refinery reactor units, such as reformers, hydrocrackcrs, cokers, etc. Prediction of the heat of reaction is also a problem. 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. However, 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. As Table 5.1 illustrates, the heats of formation for hydrocarbons vary significantly with the chemical class.


I i




I' ,.
I· i




Simulation of Laboratory Tests

in prediction of the laboratory distillations, particularly the initial and end point temperatures, have been previously discussed in Section 5.1. 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. 1) Octanes It is apparent from the illustration in Table 5.1 that this property cannot be predicted accurately with pseudo-components. Not only is octane highly dependent on the class of component, it is also highly dependent on the isomer structure of the component. For example, normal heptane has an F-l octane of 0.0. The other seven-carbon atom paraffins have the following octanes: 2-methylhexane 3-methylhexane
= =

42.4 52



= 92.8.

In addition to anomalies because of hydrocarbon class and structure, there are synergistic octane effects when one class of hydrocarbon is blended with another. For example, olefins blended with aromatics exhibit blending octanes that are several numbers higher [han the pure olefin values. 2) Pour Point, Cloud Point These tests are a measure of the wax content of a petroleum stream. Waxes are primarily paraffins with long side chains, or long paraffin side chains attached to other hydrocarbon structures. Pseudo-component TBP cut-point ranges in the temperature range for wax are typically SO to 100 degrees F (27.8 - 55.6 degrees C). Wax properties are well disguised within a pseudo-component of this boiling point range . . 3) Viscosities Viscosity is a nemesis to correlate for actual petroleum stream data. Many of the open literature relationships in commercial simulators are based on pure component data. The viscosities for petroleum streams with large numbers of components are difficult to correlate. Some of the early attempts such as Watson, Nelson, and Murphy" are still state of the art. Watson, Nelson, and Murphy correlated whole stream viscosity with API gravity and the Watson-Murphy characterization factor. 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, Nelson, and Murphy which predict the average stream viscosity. The controlling factor in viscosity is chemical composition. Paraffins have higher viscosities than aromatics in the same boiling point range, etc. Moreover, good chemical anal yses for heavier refinery streams are virtual! y non-existent. The best indicators of the actual product viscosities are the laboratory viscosities of the corresponding crude oil fractions for the straight run products. 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. ... Predicted viscosities from commercial simulators are order of magnitude accuracy for light oils, such as light diesel fuel, kerosene, naphtha, and gasoline.· However, predicted viscosities for heavier petroleum fractions and whole crude oil are highly inaccurate and should not be used for process design and decision making. Rather, actual viscosity tests should be run for the stocks in question, and a viscosity blending method used to predict the blend stream viscosities. Some commercial simulators provide for input of stream viscosity blending indices,




4) Flash Point

Limitations of pseudo-components

The flash point is a measure of the volatile components in a petroleum middle distillate. Therefore, the accuracy of predictions is dependent on the predicted solubility for light hydrocarbons in the middle distillate hydrocarbons. 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. Flash point tests have limited accuracy because of the procedure itself, even assuming perfect sampling techniques. Therefore, a predicted flash point within plus or minus} 0 to 15 degrees F (5.6 to 8.3 degrees C) to the laboratory test value is reasonable. . 5) Vapor Pressure and Reid Vapor Pressure Real components have the largest effect on vapor pressure and Reid vapor pressure predictions for petroleum streams. Nearly all of'the contribution to the vapor pressure for a petroleum stream is from hydrocarbon components with five carbon atoms or fewer. This makes it very important that chromatographic data be used to define the light hydrocarbons in petroleum streams. Note that the ASTM D86 distillation for a stream is inadequate to pseudo-components to represent hydrocarbons witu fewer than five carl.on atoms. As described in .\'1' . '(jon 3.2, the 086 distillation test does not condense hydrocarbons with normal boiling points lower than the specified condensing temperature of 32 - 40 degrees F (0 - 45 degrees C). Therefore, a characterization based solely on the D86 distillation does not properly represent the light components that exert the highest vapor pressures. 6) Cetanes

. =..t one time; cetane number was determined in a laboratory test engine. However, it correlates with the API gravity and average boiling pc.r.t for petroleum streams and is now calculated with a standard formula. Since the API gravity and average boiling point may be accurately simulated, the accuracy of the predicted cetane number is good.
7) Sulfur and Metals Commercial simulator programs cannot predict these properties. However, when the distillate fractions for an actual stream have been analyzed in the laboratory to determine 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. Stream average properties may then be calculated with a reasonable degree of certainty using the pseudo-component blending values, since these properties tend to distribute in petroleum streams as an increasing function of normal boiling point.


, . ,


24 Watson, Nelson, and Murphy, Ind. Eng Chem., 27, p. 1460, (l93 5).

~_ .....





Chapter 6
Thermodynamics for Petroleum Calculations
For most petroleum processes, the thermodynamics are relatively uncomplicated. Hydrocarbon systems tend to behave ideally, and component relative volatilities are nearly independent of pressure. Hydrocarbon water solubilities are small, and hydrocarbon/water systems may be approximated with simplifying assumptions. The focus of this chapter is practical, working thermodynamics, A standard textbook in thermodynamics may be consulted for theoretical derivations. It is also important to remember that the thermodynamics for petroleum calculations are affected by the feed stock pseudo-component characterizations, and no thermodynamic correlation can compensate for inaccuracies in the pseudo-component properties.

6.1 Equilibrium K Values


K values, i.e., (yJ :v)'s, are the fundamental

building blocks for nearly all

unit operation calculations. The K values for any given system of components are a function of the temperature, pressure, and composition of the system. Before (he age of computers, K values were predicted based on temperature and pressure only, with various concepts such as convergence pressure and multiple charts used to account for composition effects. The computer age has permitted more sophisticated prediction of K values using equations of state. Equations of state based on the Redlich-Kwongi equation have proven to be the most useful for petroleum systems. The most widely used Redlich26 Kwong equations are the modifications of Soave and of Peng-Robinson". These equations are similar and give equivalent results when properly calibrated or "tuned" to the system in question. Two methods are used to tune the above equations of state: fitting of binary interaction parameters (kts), and adjusting the pure component acentric factors'io accurately predict the pure component vapor pressures. The k..'s are determined by regression fitting of ~ binary vapor-liquid equilibrium data to the equation of state. They represent the nonideal interactions between pairs of components. For an ideal pair of components such as methane and ethane, k,j is equal to zero. For a non-ideal pair of components such as C02 and propane, k'J is approximately 0.15. A highly non-ideal interaction a hydrocarbon may have a k. greater than 0.5.


such as water and

The literature] abounds with equations of state. 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. Vendors of simulation programs of parameters to represent operating data for various 43



Thermodynamicsjor Petroleum Calculations

processes. However, 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, or when highly accurate results are required. Pseudo-components present some special problems when using the modified RedlichKwong equations of state. For these components, it is not possible to tune the acentric factors to match pure vapor pressure data. Furthermore, experimental binary vapor-liquid equilibrium data are not available to regression fit the kiJ's. Predictive methods based on known systems must be used to estimate these parameters. These predictive methods are a source of differences when comparing results from commercial simulators. 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, alcohols, ketones, etc. 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. However, for most petroleum calculations these specialized modifications are not needed. While there are numerous other methods to predict K-vatues for petroleum systems, 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. 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. The method has approximate limits of 800 degrees F ( 427 degrees C) and 3000 psia ( 207 bar), but has been extrapolated to higher temperatures with reasonable results.





Effect of Non-Hydrocarbons

on K values

Non-hydrocarbon light gases are often present in petroleum processes. These gases include H2• N2, CO, CO2, Sal, H2S, and NIh The non-ideal mixture behavior attributable to these gases is predicted accurately by the modified Redlich-Kwong equations when using ~;s relating them to the hydrocarbon components. In the case of hydrogen, a modified acentric factor is also used to improve predictions of the hydrogen solubility in the hydrocarbon liquids.







Hydrocarbon-Water Systems
Hydrocarbons are only slightly soluble in water and for most petroleum calculations rigorous three-phase calculations are not necessary. A simple model may be used as shown in Figure 6.1 below.


Figure 6.1 Simple Hydrocarbon-Water



For the above model, the vapor is saturated with water vapor and the hydrocarbon liquid is saturated with water according to a solubility relationship. The aqueous phase consists of pure water. Water K-values are computed as:



pO::: water vapor pressure

Xs ::: water solubility in the hydrocarbon liquid phase


= 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.



Thermodynamics for Petroleum Calculations


Enthalpies are typically calculated with thermodynamic relationships that relate the actual mixture enthalpy

to the mixture enthalpy in the ideal gas state. That is,



where: H. H* == mixture enthalpy and mixture ideal gas enthalpy 6.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. Pseudo-component ideal gas enthalpies are predicted as described in Section 4.4. The enthalpy deviation term is calculated as: p

6H ==


T (dV/dT) - V]r dp
and pressure

where: T, 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. Enthalpies calculated in this fashion using the modified Redlich-Kwong expressions have proven to be more accurate for petroleum mixtures than older, empirical methods.



Methods for Petroleum Systems

!.: ..

It is impossible to recommend specific methods without identifying specific commercial simulators. The recommendations given below are based on the author's experience with the Hyprotech, Ltd. HYSIM and HYSYS programs and the. SimSci, -Inc. PROVISION""" program. The first method listed is the author's preferred method. 1) Heavy Hydrocarbon This includes crude Systems: and vacuum distillation, FCC main fractionators and coker


HYSIMI HYSYS: Peng-Robinson with Lee-Kesler enthalpies, PROVISIO/"; : Grayson-Streed, Soave RK


Chapter 6
2) Light Hydrocarbon Systems:

This category includes gas recovery plants, fractionators and splitters __


3) Hydrogen-Rich Included plants. Systems: are reformers, hydrocrackers, hydrotreaters-, .andhydrogen

in this category

HYSIMI HYSYS: Peng-Robinson, Grayson-Streed PROVISION: Soave RK (with SimSci alpha), 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

6) Aromatic Extraction Hexamer Method Systems: Check with the


vendor for applicable

A liquid phase activity coefficient model is necessary for these systems. system and necessary parameters.


7) Super-fractionators: These columns include C2, C3, C4, C5, splitters, etc. HYSIMI HYSYS and PROVISION have special k ~ parameters for C2 and C3 splitters. Check with vendors for other super~ fractionators_ When separating close boiling isomers, it is probably necessary to supplement the vendor supplied k.ts,



8) Light Hydrocc.rbuns

Dissolved in Water: considerations. Check with the

These calculations may be needed for environmental \-endor for applic.ability and specific recommendations.

HYSIMI HYSYS: Kabadi-Danner

PROVISfO:V: Kabadi-Danner

SRK, Henry Constants SRK, Henry Constants


Thermodynamics for Petroleum Catcutauons

6.6 Thermodynamic "Rules of Thumb"

The following guidelines are based on the author's experience with calculations for hydrocarbon ·systems in general. There is no particular significance to the order in which they are presented. 1) It is necessary to use the Peng-Robinson or Soave RK methods to locate t be true critica! points of light gas mixtures. They may also be used to predict the phase diagrams. Pseudo-critical calculations are inaccurate because of mixture non-ideal ities. 2) Large heat capacities may indicate that the mixture critical point is being approached. Heat capacity becomes very large and the latent heat becomes zero at the critical point. 3) The vapor density approaches the liquid .density as the critical point is approached. This may be used as a quick check of distillation column conditions. Large vapor densities indicate that the column is operating too close to the critical pressure. The maximum pressure for typical deethanizers is about 475 psia (32.8 bars). 4) Water has an important heat effect with hydrocarbons. The heat capacity is approximately twice that of hydrocarbons and the latent heat is five times as large as hydrocarbons. For FCC main fractionators it is important to have an accurate rate for the reactor steam. 5) Water has an important partial pressure effect with hydrocarbons in columns with steam stripping. An accurate steam flow is necessary to match nash zone temperatures. 6) For hydrogen-rich systems such as hydrocrackers and reformers, the heat capacities of the feeds and products are nearly identical in the feed/effluent exchangcr s. 7) The duty versus temperature lines for mixtures containing hydrogen are curved and not straight. 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," method. 8) A Joule-Thompson expansion across a valve results in a temperature drop for most mixtures. Mixtures containing hydrogen may show a temperature increase. 9) Benzene forms azeotropes with nearly every light hydrocarbon. Accurate prediction of the benzene distribution in a light-ends column may require use of a liquid activity coefficient model. 10) Hydrogen sulfide causes large non-idealities in hydrocarbon mixtures by shifting the critical point of the mixture.


-.-~-- •..

--:--- ....-.. -~---.-.--

11) Carbon dioxide fractionators.

forms an azeotrope with ethane.

It may also solidify in cryogeriic

12) Hydrogen has strange phase behavior. It cannot be condensed, but it can be dissolved in hydrocarbons at high pressures. The Peng-Robinson and Soave RK methods predict better hydrogen solubilities in hydrocarbon liquids than the Grayson-Streed method. 13) It is not possible to calculate bubble points for systems containing hydrogen.

14) Alcohol-hydrocarbon systems hive highly non-ideal behavior and must be calculated using liquid phase activity coefficients. 15) When applicable to the system, equations of states are always more accurate than empirical and semi-empirical methods. They also are more thermodynamically consistent than liquid activity coefficient methods. 16) The relative volatilities of hydrocarbons 17) Hydrocarbons are nearly insoluble water phase as pure water. are nearly independent of system pressure. of the liquid

in water, allowing approximation

18) In general, hydrocarbon systems composed of the same chemical class behave very ideally. Thus, an aromatic stream from an extraction process behaves very ideally for distillation purposes. 19) Small

non-idealities for close boiling isomers are very important for superThese may be represented with k.s in the modified Redlich-Kwong


While the k's are very small they are necessary for accurate calculations.
') I)


example, the k. for propane and propylene is approximately

0.0089. and should never

20) The Grayson-Streed method cannot predict critical point behavior be used for systems that may approach the critical point.

21) The Braun KIO K value. method and Johnson-Grayson enthalpy method superceded long ago by more accurate methods and are not recommended. 22) Commercial simulators often tune thermodynamic data to the default weight correlation. Therefore, it is usually not advisable to select another weight correlation unless absolutely necessary.

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. The methods produce equivalent results. when properly tuned to the system being calculated.

24) Design Generalities:

Thermoaynamtcs Jur r~uVU;l.m.

~ ... _-_

•• - •. -

The modified Redlich-Kwong equations are more conservative for design than the Grayson-Streed method. . Lower molecular weight lean oils absorb more light gases than heavier oils. Absorbers are very poor recovery devices because ofthe low tray efficiencies. Equilibrium vapor or liquid can be re-circulated to an equilibrium stage in any quantity with no change in the separation. Thermodynamics are almost never the cause for distillation calculation failures, assuming an appropriate method is selected.
The higher the column pressure, the more non-ideal the separations.

Liquid viscosity is usually the controlling property for overall tray efficiency .

. -__,~..,.__..

Chapter 6 References:
2S Redlich, 0., and Kwong,


J. N. s. Chem. Rev., 44, 233 (l949).

equation of

26 Soave, Giorgio, "Equilibrium constants from a modified Redlich-Kwong state", Chern. Engr. Sci., Vol. 27, p. 1197-1203, (1972). 27 Peng, Ding- Yu, and Robinson, Donald B., "A New Two-Constant Ind. Eng. Chern. Fund., Vol. IS, No. I, p. 59-64, (1976). 28 Grayson, H. G., and Streed, C. W. , "Vapor-Liquid Equilibria High Pressure Hydrogen-Hydrocarbon Systems", 6th World FrankfurtlMain, Sect VII, Paper 20, (1963).

Equation of Stale",

for High Temperature Petroleum Congress,

29 Chao, K. C. and Seader, 1. D., "A General Correlation of Vapor-Liquid Equilibria Hydrocarbon Mixtures", A. I. Journal, Vol. 7, No.4, p. 598-605, (1961).



30 Kabadi, V. N. and Danner, R. P., " A Modified Soave-Redlich-Kwong Equation of State for Water-Hydrocarbon Phase Equilibria", Ind. Eng. Chem., Vol. 24, No.3, p. 537541, (1985).

Chapter 7
Practical Distillation Principles
The unit operation of most interest for petroleum calculations is distillation. This is an energy intensive operation and the economic benefits of an improvement can be substantial. Furthermore, 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, that is, product qualities. Thus, improving an operation by lowering the operating cost (while achieving the same objective) results in a direct increase in the profitability of the operation. There are also improvements in energy efficiency that may be attained in the process -. design phase with simulation. Simulation permits easy exploration of the entire anticipated range of operations and selection of a design that has flexibility for future operations. However, most of the discussion in this chapter focuses on simulation of existing operations, since this is the usual case in petroleum refining operations today. While there is some design work being done, most calculations today are conducted for improvement, debott!enecking, and troubleshooting of existing columns


7.1 Theoretical


The theoretical basis for distillation calculations has been established for many decades. Distillation columns consist of a series of inter-linked vapor-liquid equilibrium stages or theoretical {rays. The liquid and vapor leaving each tray are in vapor-liquid equilibrium and the vapor enters the next higher tray, where it establishes a new equilibrium with the liquid on this tray. TIl(; liquid flows to the next lower tray where it establishes a new equilibrium with the vapor entering this tray and so on. The lightest components in tbe feed mixture exit with the overhead product and the heaviest components exit with the bottom product. A column typically has a heat source or reboiler at the bottom. and a heat sink or condenser at the top. Some condensed liquid is returned to the top tray of the column as reflux. Solution of distillation calculations is a trial and error procedure. Temperature and flow profiles are assumed for all trays in the column and vapor-liquid equilibrium and heat balances are calculated for each tray. All calculation procedures keep the column pressures constant. The results from the assumed profiles are used for the next series of calculations and so forth. Calculations are further complicated by the fact that the equilibrium K values for the components on each tray are affected by the tray cornposit.on as well as the temperature and pressure. 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, the vapor-liquid equilibrium relationships for every tray. {he component mass balances for every tray, and the heat and mass balances for the entire operation. It is also desirable to add equations to the above matrix


to define process conditions or specifications that must be met by the solution. Since the calculations are based on steady state operation. all of the above conditions must be satisfied by the solution. High-speed computers have made possible the rigorous solution of the large matrices describing distillation columns. A converged solution is defined as a set of independent variables for the column, e.g., tray temperatures, flows, heat inputs, etc., which produce a solution for all of the column equations within certain defined tolerances or errors. Tolerances are prescribed for the component material balances, the tray heat balances, the tray equilibrium relationships (usually expressed as the tray liquid bubble point condition), the performance specifications, and the tray equilibrium K values. Note that the latter tolerance is required since the K values are dependent on composition. Thus, it is also necessary to converge the K values in addition to all of the column equations. Several methods have been devised to solve distillation problems and the literature abounds with descriptions of these procedures .. All of the methods are iterative in nature, and produce steady state solutions within prescribed tolerances. The most useful method for solution of petroleum distillation columns is the inside-out method. This method is further described in the discussion below.

7.1.1 Inside-out

Distillation Algorithm

The Newton-Raphson method was the first method used by commercial simulators to solve distillation problems. 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. in 1970. Richard Russell adapted this method to the rapid solution of alI types of distillation columns, including multi-draw columns with side-strippers and pumparounds such as are used in the petroleum refining industry. 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 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. Consequently, the Russell method has proven ideal for commercial simulators . .As implied in the name, the I/O algorithm consists of two iterative loops: an inside calculation loop and an outside calculation loop. The inside loop calculations use simple models for the K values and enthalpies and converge the tray heat and material balances, and the performance specifications. By using stripping factors and side-stream withdrawal factors as independent variables, the distribution of components within the column for any 'trial solution is always in perfect mass balance. This is an important feature when performing calculations for columns in which trace component flows in the products are important, such as super-fractionators.


Practical Distillation Principles


In the outside loop, the K values and enthalpies are recalculated with the newly predicted compositions. If the component relative volatilities have changed by more than the convergence tolerance, the inner loop calculations are repeated with the new K values and enthalpy data. 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,

The 110 method is not dependent on accurate column flow profile estimates for convergence; however, it is always good practice to estimate flows as accurately lIS possible. Convergence of this method can be enhanced significantly when an accurate estimate of the column temperature profile is supplied. Temperature data ore usually
easier to estimate than flow data, particularly for complex refinery columns.


Colun1n Conventions
The conventions used by all commercial simulators are very similar. Figure 7.1 shows typical representation of column features. It is important to note that all distillation
calculation methods are derived for theoretical/rays, that is, trays in which perfect vapor\iquiJ equilibrium is achieved between the exiting liquid and vapor.

',," 1


Referring to Figure 7.1, the conden«r and overhead accumulator drum aCCconsidered to be the first tray. A net liquid product from this tray is returned to the column as reflux. Liquid water, if present, is decanted as an aqueQus phase. Liquid and vapor products are
withdrawn from the reflux drum. For some columns, only a liquid product is withdrawn from the reflux drum and the condenser is not truly a theoretical tray. In fact, for many

petroleum columns, the liquid product is sub-cooled below its bubble point. The same
convention condenser. is followed, however, and the overhead system is still considered This tray always receives the reflux liquid. as the first

tray. The top tray of the column is considered to be the second tray for a column with a

The reboiler, if present, is normally considered to be the highest tray number, N+ 1. From

Figure 7.1. this convention represents the reboiler as a kettle reb oiler. Most commercial
simulators However,

provide ways to represent other types of reboilers such as thermo siphons. for simulation purposes the kettle rebotler assumption is adequate for most


columns. Columns may have side liquid and vapor draws and side water draws. Side-stripping columns may also be attached to a column. Side columns of all types are solved simultaneously with the main co\umnby the VO method. pump~around side draws are used to remove heat from the column and pump~downs (not illustrated) may be used for side heaters. Finally, note that columns may have multiple feeds .

: ~ I

.i 'I

ii, iii



:~ ;



Figure 7.1 Column Conventions



r~-------------~ , ,








TrCly N




Theoretical tray numbering conventions vary from simulator to simulator. The most common convention is to number trays from the condenser down to the reboiler starting with tray one for the condenser (when present). 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. For columns with no condenser-reflux drum, e.g., a reboiled stripper, the top tray of the column is designated as tray one by all simulators. For columns with no reboiler, e.g., an absorber, the bottom tray of the column is designated as tray N by all simulators.


Practical Distillation Principles

7.1.3 Initial Solution Estimates

Commercial simulators require the user to supply flow estimates for all column products except one, either one of the top non-aqueous products, or the bottom liquid product. The reflux quantity must also be estimated, either by the user or by using a program default value. The first and last tray temperatures are also required for most simulators. It is good practice to always supply the temperature for the physical top of the column, i.e.• second tray for columns with condensers, since there is usually a substantial temperature grad.ient from the second tray to the first tray in most columns. While not required, temperature estimates for side draw trays enhance convergence. Commercial simulators do not vary the tray pressures during the I/O calculations. The user is required to supply values for the first and last trays in the column model. A linear pressure profile is assumed for the intermediate trays. Note that for columns with condensers, a pressure should always be supplied for the second tray, since there is a substantial pressure gradient between the column top tray and the condenser. The condenser pressure drop may be as higb or higher than the total pressure drop across all of the other trays. For crude and vacuum columns, 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.

Non-converged Column Solutions
A non-converged column solution is one in which all of the mathematical equations describing the column were not satisfied, Therefore, the results are not valid and should 1101 be used for engineering design and analysis. 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 causes for calculation failures when using the algorithm may be grouped in the following categories: '" 1) Improper characterizati on of the feed stock:


This can be avoided by careful analysis of the stream characterizations before column calculations are attempted. However, the feed checking step is often omitted in the haste to secure calculated results for a project. Poor feed stock characterization can result in unexplainable behavior in the column calculations. 2) Impossible Specifications:

A COIUffilL may be over-constrained and hence all of the performance specifications cannot be met. This is the most common type of convergence failure when using the





----........ ...


57 algorithm and it is signaJed by failure. of the inside loop to converge. Section 7.2.4 gives reasonable suggestions for column specifications that are likely to convergence.

3) Poor Initial Estimate:

This is seldom the problem when using the I/O method, since it is relatively insensitive to initial estimates. It is still good practice to provide the best initial estimates possible. In particular, failure to supply an estimate for the physical top tray for columns with condensers can be a problem, especially if this causes free water to condense on the ·column trays for the initial trial solution.

4) Free-Water on the Trays:

Most petroleum processing columns are operated such that water is carried overhead as a vapor, condensed, and decanted at the accumulator drum. However, 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. Commercial simulators are not consistent in their handling of free water on trays other than the condenser. Some simulators "force" a solution by assigning a large K value to the water to carry it overhead in the column. 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. In either case described above, the column results are invalid and should not be used. 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. 5) Thermodynamics: Assuming an applicable method has been selected for the calculations, this is almost never the reason for column non-convergence. For columns in which the K values are highly dependent on the tray compositions, it may be necessary to use a damping factor to prevent oscillation of the trial solutions. Oscillation caused by thermodynamics is evidenced by failure of the outside loop calculations to converge. III-chosen process conditions can also cause problems. The most common problem is using a column pressure that is too high, resulting in the tray mixtures in some parts of the column being above their critical points. As the critical point is approached for any mixture, the liquid and vapor compositions become identical, and the component K values approach unity. Under these conditions fractionation ceases, both in the real world and in the simulation calculations. It is usually easier to check for this condition by inspecting the liquid and vapor densities for the trays. If the vapor densities become large, i.e., exceed an approximate value of 4.0 lbs/cu ft (64 kgs/cu rn), it may be necessary to lower the column pressure to avoid supercritical conditions.





Practical Distillation Principles


Simulation of Existing Columns

While this section focuses on existing columns, the same principles may be applied to column design. Certain steps are always necessary in the setup, solution, and interpretation of results for column models.

7.2.1 Gathering the Information

While this step may seem obvious, 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. Good calculated results depend on good information about the column, including the feed stock and its conditions. Several categories of information are needed for simulation of a distillation column: 1) Accurate Representation of the Feed Stock: This cannot be over emphasized, particularly for complex column calculations such as crude and vacuum columns. For some columns it is better to combine the products to characterize the feed. For example. FCC main fractionators have a very hot vapor feed which is difficu1t to analyze accurately (if at all). It is usually better to build the feed for these columns from the analyses and rates of the products.
! ...

2) Column Operating Conditions: These include pressures, temperatures, and internal flows such as reflux. It is good to have redundant measurements when possible, since it is usually necessary to reconcile plant data. There are many sources of inaccuracies in measured data, and data must . always pass a test for reasonableness when building simulation models. Accurate measurements of the feed and product conditions are necessary if accurate calculation of the column duties is desired. Note that is usually best for simulation purposes to calculate the column duties such that performance specifications are met. Needless to say, it is reassuring to have duties from the operating data as a validity test for the model. 3) Product Compositions: Product compositions may be direct determinations such as a component by component breakdown from a chromatograph, or indirect determinations such as laboratory test results. Some of the laboratory tests that are useful in defining product compositions are density, laboratory distillation, and vapor pressure.

59 '4) PFD Information:

It is critical to have a current process flow diagram (PFD) for the column operation.

This provides information on feed and product draw locations, the column tray confi~~ation, condenser, reboiler, other duty arrangements, and so forth. For example, 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). Without an accurate PFD, the engineer may not be aware of this flow. Some information is available on the PFD regarding the column size and internals. It is usually necessary to supplement this information with tray drawings, downcomer details, etc., when rating calculations are desired to test the column operating point for possible flooding conditions. The rating calculations in commercial simulators are useful for preliminary analysis of existing columns.


Defining the Separation Zones

The concept of separation zones is useful in column analysis. A separation zone IS defined as a column section in which a split between two products occurs. Multi-draw columns such as crude and vacuum distillation columns have multiple separation zones. Simple columns with only overhead and bottom products have only a single separation zone. Note that both rectification of heavy components and stripping oflight components may occur in a separation zone.
It is important to represent the distributed components in a separation zone accurately. Distributed components are those components that exit in both products leaving the separation zone. These are the components that fractionate or split. The other components are non-distributed components, with the heavy non-distributed components exiting in the bottom product and the light non-distributed components exiting in the overhead product. Non-distributed components have almost no influence on the separation, and they may be combined or averaged as desired with little effect on the calculated results for the column.

Within the distributed components, the split may be accurately defined by proper selection of the key components. The fractionation is based on a desired split between the key components. The light key is a light distributed component for which a small, but definite quantity is present in the bottoms product The heavy key is a heavy distributed component for which a small, but definite quantity is present in the overhead product. Note that trace components do not meet these criteria. The key component concept is most useful for column sections in which the distributed components are defined as real components. Some manipulation of plant data is useful in determining key components. Table 7.1 gives some typical plant data as reponed for a fractionator, The compositions and rates






-Practical Distillation Principles

have been tabulated for the overhead and bottom products. From these data as reported, the separation key components are not apparent. 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. In fact. an incorrectly defined separation may result in multiple solutions for the column simulation model. Note that the separation zone contains only four significant distributed components. 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. In fact, the C7 plus component may represent several actual components. These nondistributed components have little effect on the calculated separation.

Table 7.1

!!.!.; iii ~ I)

Distillation Plant Data

Products Overhead Product LV Percent 2.48 11.07 Bottoms Product



I!' ~I"







Componem i-pentane n-pentane cyclopentane 2,2 dimethyl butane 2,3 dimethyl butane 2 methylpentane 3 methyl pentane n-hexane methylcyclopentane 2,2 methyl pentane benzene cyclohexane C7 plus Total Flow, Bblslday

LV Percent

1.17 1.34 46.73 25.58 trace

2.16 23.98 10.13 0,25 3.97 9,20

0.11 trace

2442 7558







The data from Table 7.1 have been transformed to a component recovery basis in Table 7.2. In a recovery table, the percent of each component in the feed that is recovered ir the overhead and bottom product is tabulated. Note that it is relatively easy to see when the separation is occurring upon inspection of the recovery table. Two methylpentane i dearly the light key component and n-hexane is the heavy key component. These tw components define a unique separation for the column. This column has split fa components, that is. the light and heavy key components are not adjacent. with 3 rnethy pentane lying between them. Components lighter. than the light key do not define



:'Il ;,/





'-. '-_ _.L __ • _._


61 unique operation for the column nor do components heavier than the heavy component. The component that appears between the separation keys also fails to define_ a unique operation. 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, it is very important to find where the separation is occurring when modeling existing column operations.

Table 7.2 Distillation Column Recovery Table Overhead Product RecoveD'.% Bottoms Product Recovery. %

Component i-pentane n-pentane cyclopentane 2,2 dimethylbutane 2,3 dimethylbutane 2 methyl pentane

100.00 100.00 100.00 97.50


3 rnethylpentane
n-hexane methylcyclopentane 2,2 methylpentane benzene cyclohexane C7 plus

3.90 0.35

100.00 100.00 2.50 20.71 96.10 99.65 100.00 100.00 100.00 100.00

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". This useful for revamp modifications at a new operating point.

keys when identified. by Kister" approach is

Many of the columns in petroleum refineries have separation zones for which the components are not clearly identified. For example, consider the separation zone for light naphtha and heavy naphtha in a splitter column. Some composition data are available for the combined naphtha stream; however, it is usually for the light components which do not distribute to both products and are totally recovered in the light naphtha product. The distributed components are represented in the simulation model as pseudo-components, and a reasonable definition is necessary for an adequate column model. Definition of too few distributed pseudo-components results in a model that predicts step changes when the operating point is changed. This is a poor representation of the actual operation in which the petroleum components are a continuum and step changes in the products rarely, if ever, occur when the operating point is move'!:


.r« "



:rr {'

62 Figure 7.2 presents the AsTM D86 distillations

Practical Distittauon rnw.;zpu:,,)

for light and heavy naphthas from a splitting operation. The splitter is being operated to produce a 5-95 gap of 20 degrees F. The separation zone appears to be small on a D86 basis. being equal to approximately 20 degrees F. However. 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.

Figure 7.2 Naphtha Splitting Column ASTM D86 Distillations
350 300








--- ~Eii






~I---50 60

NZf ~E

- ~-.L

4 f
·c; •• ;













" I'


In Figure 7.3 the Edmister-Okamoto'lmethod has been used to convert the light and heavy naphtha distillations to a TBP basis. The normal boiling points for the petroleum
pseudo-components correspond to the TBP distillations. On a TBP oasis, the separation zone is from 140 to 245 degrees F. or 105 degrees F. It is important that an adequate .number of pseudo-components be used to model the feed stock in this boiling range. Note that pseudo-components boiling below 140 degrees F or above ~45 degrees F have little effect on the separation in the column.


j' .1






"; :I





Figure 7.3 Naphtha Splitting Column TBP Distillations

400 350 300 250 DEGREES F 200 150 100

1/ - ... - ~-V V. -__..


-V V




_.. V ~


r- -


- - ~}_
roo -















Simulation programs are convenient for analysis of pseudo-component separation zones. A preliminary case can be calculated in which the simulator default cut-point ranges are used for the pseudo-components. As described in Section 4.1.4, typical cut-point ranges for the naphtha feed stock to this splitting column would be 25 degrees F. Thus, at least five pseudo-components would be defined for the separation zone between light and heavy naphtha. 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. Rather, the D86 data for the column feed stock may be supplied to the simulator for translation into pseudo-components and the column calculations performed. 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. If a detailed engineering study were being performed for the naphtha splitting column described above, the simulator default cut-point ranges would be inadequate and more pseudo-components should be used in the separation zone. In fact, it is also desirable to



It 'J


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. A guideline is to have at least six to eight significant pseudo-components in a separation zone.

7.2.3 Translation of Actual trays to Theoretical Trays

All rigorous column calculation methods are based on theoretical trays, in which the vapor and liquid leaving the tray are in perfect vapor-liquid equilibrium. Unfortunately, real operating columns are filled with actual trays, not theoretical trays. Therefore, the actual trays in a real column must be represented by theoretical trays in the model. The relationship between actual trays and theoretical trays is not straightforward, complicating the translation process. The perforrnance of an actual tray compared to the performance of the corresponding theoretical tray is designated as the tray efficiency. There have been many mathematical expressions derived to represent tray efficiency; however, the most useful concept in distillation problems is the overall efficiency. The overall efficiency usually concerns the entire column and is defined as follows: Overall efficiency




No. Theoretical trays INc. Actual {rays



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. Fractional trays are not considered with this efficiency model and the efficiencies are expressed on a percentage basis. For nearly all columns, the overall efficiencies are less than 100 percent and the column has fewer theoretical trays than actual trays. It is important to note that with this definition of efficiency, all trays in the column model are perfect vapor-liquid equilibrium stages for the distillation calculations. Various tray efficiency models have been developed and published which refer to single trays or locations on a single tray. These models are not overall efficiency models and they all generally take a similar approach when used for rigorous column calculations. The trays in the column are first calculated as if they were theoretical trays. 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. Thus, the vapor and liquid

• , • c

leaving (he tray for which the efficiency has been applied are no longer in equilibrium.
The Murphree" tray efficiency model is a popular model available in many commercial simulators and is presented as an illustration. Murphree developed the following tray efficiency model:



where: Y;

actual composition actual composition

of vapor leaving tray n of vapor entering tray n to


= vapor

equilibrium composition corresponding the liquid leaving tray n

Notc that after application of the Murphree efficiency, the vapor leaving a tray is no longcr in vapor-liquid equilibrium with the liquid leaving the same tray, i.e., the tray no longer corresponds to a theoretical tray in the distillation model. This approach to tray efficiency is both convenient and appealing, 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. Commercial simulators encouragethis line of thinking by providing a variety of tray efficiency models. Unfortunately, many engineers do not understand that the tray efficiency models provided by commercial simulators are not overall efficiency models. Nothing is ever as simple as it seems and using tray efficiency models other than overall efficiencies can cause serious problems for column models. The non-equilibrium liquid and vapor leaving the trays cause uncertainties in heat transfer calculations. For example, if a tray efficiency model is applied to the top tray of the column, the column overhead vapor is not saturated and may be superheated or subcooled. This has a direct effect on [he condensing requirement. Moreover, tray efficiency models such as Murphree are too simplistic for petroleum columns, in which there are a large number of components and widely varying process conditions. Consequently, no "typical" individual tray efficiencies have been calculated and reported for petroleum columns, and the user must take a cut and try approach with the efficiencies to match the actual column. While the above-mentioned considerations are troublesome, they are not the worst problems related to using local tray efficiency models. The worst consequence of using

local fray efficiencies is that the simulation model is rendered useless for prediction mode. Manipulation of local tray efficiencies in a distillation model is analogous to the
regression fitting of data to an equation form. 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. Thus, the column mode! is useless for engineering studies in which other operating points are of interest. In fact, one can argue that the model no longer corresponds to rigorous distillation at all, since the principle of equilibrium vapor and liquid leaving each tray has been violated. Therefore, it is strongly recommended that tray efficiency models never be used when modeling petroleum columns. On the other hand, models based on overalt efficiencies always correspond to rigorous distillation, since the liquid and vapor leaving every tray are in equilibrium. These models may be used in predictive mode. since distillation theory will always predict an answer that is directionally correct for a new operating point. There are few open

n~ r

literature on data presented viscosity column.

Practical Disuttauon rTl''''''I''~

correlations _for prediction of overall efficiencies. One .such correlation based 19 for 54 refinery columns was published by Drickamer and Bradford and is in Figure 7.4 below. 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, the rich oil exit temperature is used.



Figure 7.4 Overall Tray Efficiencies: Refinery Columns 39 Correlation of Drickamer and Bradford
100 90
,I ;

80 70




Ove ratl Tray'1:;Y. %



40 30






' .••... 1. .



1~' : "









Feedstock Avg Viscosity, cp

The Drickamer and Bradford correlation was subsequently modified by O'ConneU<4/)to improve the predictions for columns with high relative volatilities. such as absorbers. The O'Connell correlation is shown in Figure 7.5. For this method, 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. While the methods presented in Figures 7.4 and 7.S may seem overly simplistic, they are probably the most reasonable open literature correlations to date for overall tray. efficiency. Fortunately, typical overall efficiencies have been determined for nearly all types of. petroleum columns by matching models to operating data. Table 7.3 presents sorne, typical overall efficiencies for various columns used in petroleum refineries. While these values have been derived from typical operating data, they are usuatly conservative and



67 .may be used for preliminary design. The tray vendor will likely perform more specific. calculations based on information specific to his trays to finalize the design.

Figure 7.5 Overall Tray Efficiencies .

Correlation of O·ConneU·
100 90


-. -.


I' ~

Overall Tray Efficiency, %

40 30

r-~ ------


---r-5 10

20 10

0.1 0.2



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. The model may be tuned to the plant operating data by adding or subtracting theoretical trays. The resultant model may be used for predictive purposes when a new operating point is investigated. While some tuning of the model may be necessary for the new operating point, the predicted results will always be directionally correct.

7.2.4 Defining Performance


For successful simulation models, 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. In general, specifications for the column model should be the same or similar to those used to control the actual operation. This requires the simulation model builder to become familiar with the actual column operation.

( "N.


Practical Distillation Principles

Table 7.3 Overall Tray Efficiencies




r .~: ;

·.:.1 ::1

Typical Typical No. of A~tYSlJ r~ys Ovcra\l Effici~ncy T Column S~rvic~ 20 - 30 20 - 30 Simple Absorb/Strip S-7 Steam Side Stripper 7 - to Reboil. Side Stripper 40 - SO 20 - 40 Reboiled Absorber ·6S - 70 2S - 35 Deethanizer 70 - 80 35 - 40 Depropanizer 8S - 90 38 - 45 Debutanizer 85 - ·90 7S - 90 Alky DeiC4 (reflux) 55 - 65 Alky DeiC4(no reflux) 5S - 70 70 -75 25 - 35 Naphtha Splitter 9S - 100 110 - 130 C2 Splitter 95 - 100 200 - 250 C3 Splitter 85 - 90 70 - 80 C4 Splitter 20 - 24 Amine Contactor 4S - S5 20 - 24 Amine Stripper

Typical No. of Th~r~tiQ!l:t TnlSS 2 3-4

4-5 9 - 12 20 - 30 2 1-2 3-5 3-5

Crude Distil12tion:
Stripping Zone Flash Zone- 1st draw 1st Draw - 2nd Draw 2nd Draw - 3rd Draw Top Draw to Reflux

3S - 50 5-7 3-7 7 - 10
7 - 10

10 - 12

SO-60 30 30 45 - SO 50 - 55 60 - 70


Vacuum Column (G.O. Operation):

2-4 Stripping Fl. Zone to HGO Draw 2 - 3 3-5 HGO Section 3 -5 LGO Section

1 1-2 2 2 SO - 60 13 - 17 2 2-3

FCC Main Fract.:



Quench Zone Quench - HGO Draw HGO-LCGO LCGO - Top

24 - 35 5-7

3 -5
6-S 7 - 10


For every specification imposed on a column model, there must be a corresponding degree of freedom or parameter that is not specifled. This degree of freedom is allowed to se_e~ the level rcquir_cd_t? satisfy the performance specification equation in the solution.

69 implies that the degree of freedom. musl have an effect on the performance specification. For example, adebutanizer column is operated such that the Reid vapor pressure of the stabilized product is 6.5 psi: The plant operator adjusts the reboiler heat input until the desired Reid vapor pressure is met. For this column, the Reid vapor pressure is the performance specification and the reboiler heat input is the degree of freedom. For distillation models, the logical choices for degrees of freedom are the column heat sources, column heat sinks, and the side product draw rates. Thus, a conventional column with two products, a reboiler, and condenser has two possible degrees of freedom and may therefore have two performance specifications. For the debutanizer column example given above, an additional speci-fication may be added and the condensing duty calculated as the corresponding degree of freedom. A logical specification for this column is the isopentane loss in the overhead product.

In reality, the operator of a debutanizer column controls the top temperature of the column by setting the reflux rate to control the isopentane loss. The condensing duty is indirectly changed as reflux is returned to the column. For the simulation model, the condensing duty is directly controlled as a degree of freedom in the calculations. The simulation approach is equivalent to the plant approach in controlling the isopentane loss. Therefore the model replicates the plant behavior accurately.
It is important

to recognize performance specifications that are equivalent to avoid overspecifying a column model. For example, the isopentane loss in the debutanizer model may be specified as the actual isopentane content in the overhead product, the isopentane recovery in the bottom product, or the dew point temperature of the column overhead vapor. Only one of these specifications may be used for the model. Furthermore, it is known that the isopentane loss is controlled by the column reflux. Therefore, the column reflux rate cannot also be used as performance specification since it is a needed degree of freedom for the calculations. As stated above, the reflux rate may be determined indirectly by selecting the condensing duty as a degree of freedom for the column calculations. Note that equivalent specifications are also possible for the debutanizer bottom product. The Reid vapor pressure is a measure of the n-butane content in the bottom product. Therefore, the following equivalent specifications could be used to control the bottom product: Reid vapor pressure, n-butane recovery in the overhead product, n-butane content of the bottom product, and bubble point temperature of the bottom product. Only one of these specifications should be chosen for the model. Furthermore, it is necessary to have the reboiling duty as a degree of freedom for the calculations to meet the bottom product specification. In reality, successful simulation of the debutanizer column depends on selection of performance specifications that define the separation of the light and heavy key components, either directly or indirectly. The light and heavy key components are nbutane and isopentane. Thus, any pair of specifications that define the light keyJ heavy


Li 1\




-.i ..

. « ..... -'




","',.,:9 .;~;,::,,";'~t.,,$J',,'i;:~~;&~~~~t1WJ~~~:'H~~i~,;:i!jj~'~'w£r.~V,:!;';p~tt#'4~~,

i:! "

II.•. "


Practical Distillation Pnnciptes

key separation results in a successful simulation model that corresponds to the actual column operation. 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. For some petroleum columns, the key components cannot be identified as known components. For these columns, the concept of equivalent specifications is very important in selecting the performance specifications. For example, consider a naphtha splitting column. The ligh. components that are identified in the feed characterization are _ usually all recovered in the overhead product; hence, they may not be used as light key components for the split. In fact, for this column, the planl operator controls the ASTM 086 end point of the overhead product to limit the heavy components in this product. This is equivalent to a heavy key component specification, since the D86 end point of a stream is controlled by its heaviest components. As previously discussed in Section 5. i, the D86 end point cannot be modeled accurately, therefore the 086 95 percent distilled is chosen as the specification for the heavy key component for the column model.

It is also necessary
column discussed

to choose a light key specification to solve the naphtha splitting above. Naphtha splitters are often controlled to produce a desired ASTM D86 5 - 95 percent gap for the products. 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. Note that the gap specification is an ir:c:irect way to define the 086 five percent distilled temperature of the heavy product. The five percent distilled temperature of a stream is determined by the lightest components in the stream. Therefore. a gap specification for the splitting column is equivalent to a specification of the light key separation component. Thus, for the naphtha splitter, 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 some columns, both liquid and vapor products are withdrawn from the reflux drum as illustrated below in Figure 7.6. The liquid! vapor split on the condenser drum provides another degree of freedom and performance specification for the column model.

Figure 7.6 Mixed Phase Condenser



I. ,


Top Tray Reflux liquid Product

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. Thus, the condenser side liquid draw is available as a degree of freedom for the calculations. Since the reflux drum is a theoretical tray, the liquid and vapor products leaving the drum must be in vapor-liquid equilibrium. Under these conditions, there is only one temperature that satisfies any given liquid! vapor product split from the condenser drum. It is always good practice to allow the condenser side liquid draw rate to be a degree of freedom for the calculations, with its rate calculated to meet a performance specification. For condensers with small vapor product flows, it is best to specify the vapor flow and allow the condenser drum temperature to be calculated. This produces the most stable model, particularly ·.if it is planned to explore alternate operations that may alter the composition of the overhead vapor to the condenser. For condensers with significant vapor product flows, the condenser temperature may be used for the performance specification and the vapor product flow calculated to satisfy the equilibrium balance. with the liquid product flow.

Tray Rating
Commercial simulation programs provide various correlations for tray rating. These are typically vendor supplied chart methods, such as the design manuals of Glitsch 42, Koch 4), 44 and Nutter . These methods are generalized and not necessarily the same as those used by the same suppliers when guaranteeing equipment. The above three chart methods are all for valve trays. No such chart methods exist for older type trays such as bubble caps. It is doubtful that the generalized tray rating methods in commercial simulators can adequately rate specially designed trays. In fact, some commercial simulators approximate the performance for non-valve type trays by applying factors to valve tray ratings. In other words, ratings from commercial simulators may not be applicable or accurate for your column. Therefore it is good to know what methods are being used in the program for rating and design calculations. Kister)6 discusses.some of the problems encountered when relying on simulator hydraulic calculations for design. While the correlations in commercial simulators are not accurate enough for design of trays, they are still useful for troubleshooting and preliminary sizing work. Apparent flooding factors, downcomer backups, and tray pressure drops are estimated by most of the commercial simulators when tray and downcomer details are supplied. These results arc useful for checking purposes to indicate possible operational problems within a column. More rigorous methods must always be used to finalize tray calculations for revamps and designs. Correlations are also provided in commercial simulators for packed columns. However, the actual column calculations are always based on theoretical trays which means that


Practical Distillation Principles

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, and depend on packing type and size, column loadings, column diameter, and a variety of other operating parameters. 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. As with tray ratings, it is important to know the limitations and accuracy of the methods and data being used for the packing calculations.

.1 .!


Actual Columns

All troubleshooting with computer simulation must be based on mathematically converged column solutions. It is not possible to reach valid conclusions using simulation models for which the column mathematical constraints are unsatisfied. Therefore, the first and necessary step when troubleshooting must always be to obtain converged results with the column model. It is further necessary to have column models that can be used in predictive mode for troubleshooting. Thus. models based on local tray efficiency models are of no value for troubleshooting because they cannot reliably predict an alternate operating point. This section discusses troubleshooting from two perspectives: difficulties in replicating the real COlUI;",n operation and using models 1.J help troubleshoot operational problems.


Difficulties Matching Real Column Operations

Computer simulation has been successfully applied to petroleum distillation problems for many years. Surprisingly, the necessity of representing petroleum mixtures with pseudo-components has not been a serious hindrance to the development of accurate models. Therefore, when a computer model does not match the actual operation, there must be an explainable reason. In this section, it is assumed that the column is operating normally and there are no operational problems. Section 7.3.2 discusses problems attributable to column operational problems.

Differences between the model and the plant are commonly reflected in the column temperatures, product compositions, product rates, product properties, top reflux rates, internal liquid flow rates, and heat duties. A step-wise approach is always best when reconciling models to plant data. Several suggestions are listed below.

I) Feed Characterization:

This is the most important step in any modeling project. Great care should be used to model the column feed stock as accurately as possible. For crude and vacuum systems, some special techniques are necessary and these are discussed in Chapters 8 and 9. Some general guidelines for feed characterization are as follows:

73 a. Use the best current data available for the feed stock.
b. The feed to reproduce for the feed agree, it will stock analysis can always be checked by blending the characterized products the feed stock. It is especially helpful to superimpose the TBP distillations stock and the feed stock as derived from the product blend. If they do not be impossible to match the column material balance with the model. pseudo-components to represent petroleum streams such as virgin (uncracked) materials and reaction

c. Use multiple sets of petroleum with different chemical make-ups products.

d. Use intelligent methods to extrapolate all laboratory distillations to 100 percent distilled. Never rely on mathematical techniques in commercial simulators to properly extrapolate a laboratory distillation. e. Always compare the characterized feed stock to the original data.


It is imperative that a light-ends analysis of the carbon number hydrocarbons be provided for the characterization when accurate predictions are needed.

five and lighter

vapor pressure

g. Choose pseudo-component cut-point ranges wisely. The simulator default ranges are not always satisfactory. In particular, it is always necessary to include additional pseudocomponents to accurately represent narrow, "heart-cut" products from distillation columns. h. Analyze the component splits in each separation zone of the column to ascertain that a sufficient number of pseudo-components have been defined. When the column temperatures and/or side product rates change in a step-wise manner, this is usually a sure indication of an insufficient number of components in a separation zone. Actual petroleum columns change in a gradual, continuous fashion when operating changes are made. 2) Temperature data: caused by faulty instruments and/or poor

a. Be wary of poor temperature measurements placement of temperature measuring devices.

b. Incorrect simulated temperatures may result from incorrect column pressures. Be sure to include top and bottom tray pressures in each column model, as well as a condenser drum pressure. c. A pressure that is toohigh results in a predicted temperature that is too high and viceversa. 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.


Practical Distillation Principles:

d. Always supply pressures for flash zones, especially for crude and vacuum units. e. Make certain the feed temperature is accurate. results in a reboiler duty that is too high. A feed temperature that is too low

f. Bubble point and dew point' calculations may be used to check the reported temperatures for column products that are saturated liquids and vapors. g. Reponed temperatures and pressures for columns that generate steam such as amine regenerators are easily reconciled by using the steam tables. h. 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. The true top tray temperature must be the dew. point temperature of the top tray vapor at the top tray pressure, This simple model may be used to test the effect of stearn, light gases, and the top tray pressure on the top tray temperature. i. It is not uncommon for simulated top tray temperatures for crude distillation columns, FCC main fractionaiors, and coker main fractionators to be higher than the measured ;)lant values. The best indication of top temperature agreement with the plant data is the simulated distillation of the liquid overhead product. If the 95 - 100 percent distilled temperatures of this product are in reasonable agreement with the plant data, the simulated top tray temperature should equal the plant value. If it does not, there is another problem with the plant data which may be inaccurate top tray pressure measurement, incorrect steam flow in column, differences in light cracked gas rates, or the effect of liquid entrainment on the temperature measurement.

Simulated liquid side draw temperatures are true bubble points. As such, they are influenced by the light components in the separation zones. An increase in the stripping of the product below a side product lowers its draw temperature. The number of pseudocomponents used to represent the feed stock also affects the side draw temperatures. When the relationship of side draw rate to side draw temperature is step-wise instead of continuous, there are not enough pseudo-components in the separation zone. k. Column bottom steam has an important effect on the flash zone temperature for crude and vacuum columns. Unfortunately, steam rates are seldom metered accurately.
I. Some columns such as FCC main fractionators and vacuum columns have bottom

circulation systems which subcool the liquid bottom product. The simulated bottom product temperature is normally the bubble point temperature and will be higher than the subcooled temperature. For agreement between the model and the plant, the bottoms subcooling circuit must be incorporated into the model. For coiumns with thermosiphon reboilers, the bottom product temperature is lower than the reboiler outlet temperature. The normal convention for commercial simulators is to represent the reboiler as a heat source on the bottom tray of the column. This



----~.~~.. --






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


i 76

Practical Distillation Princtptes

h. 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. c. Shortcut" methods are sometimes useful in finding the boundary for top reflux rate. The Underwood method predicts the minimum reflux at an infinite number of theoretical trays. The Fenske method predicts the minimum number of trays at infinite reflux. The column operating point must lie between these extremes. Kister ~5 has published a technique to determine theoretical trays and minimum top reflux for multi-component distillation. d. When the column separation is met satisfactorily and the top reflux rate is higher than the plant, the number of theoretical trays in the column model should be increased and vice versa. This is the best way to determine the column actual overall efficiency when accurate data are available for the column operating conditions and products. e. The most accurate product rates are based on tank gauges. Orifices should always be re-calibrated for test runs.
4) Test Run Data.


a. AU test run data have been adjusted to show perfect heat and material balances. 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. b. It is sometimes helpful to compare test results to typical operating data for the column. Significant differences should be explored in more depth .
C. Simulation can be a useful tool when adjusting test run data. Chemical engineering theory is a powerful tool when it is necessary to make adjustments to the test data to


reconcile the heat and material baJances. . d. The best simulation models are those which represent the most typical operation. 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.

Diagnosis of Column Operational


The necessary pre-requisite for troubleshooting with simulation is a good model for the normal column operation. It is much better to develo; this model before the operational problems occur since a crisis situation is seldom a .f_-..od time for model development. Real world problems are not always easy to diagnose. and it is wise to explore as many facets as possible to confirm probable causes before such drastic action as shutting down and opening up columns. Many good have been written on column '" . 36 trou bl es hoori ooung an d several are li d as fu rt h er rererec:e mareria 1 . 46. 47,4& .49.S() iste



-.- ..•





column models to diagnose operating problems is sometimes more art than science, since model results are based on theoretical conditions being satisfied. In this respect, the model becomes an indicator of how the column may be expected to perform, not how it is performing. Real world problems such as shoes and hard hats in column downcomers are not easy to simulate. However, several techniques for using the simulation data for troubleshooting are suggested below. I) Checking for Column Flooding:

l I


Operations personnel almost always suspect column flooding when problems occur. Therefore, this is always the first issue to resolve when troubleshooting column operations. Tray rating calculations are useful in indicating possible poor performance due to flooding of the trays. Calculated flooding factors greater than IOU percent may indicate tray flooding problems. As previously discussed, the flooding calculations in commercial simulators are approximate methods and not the final authority. The separation predicted by a column model is not degraded by flooding; therefore, the rating calculations can only be used as an indication of possible flooding for the actual column. In the author's experience with petroleum columns, tray mechanical problems are far more likely than flooding problems. When using column rating data, do not neglect to check the predicted downcomer backups and tray pressure drops. High pressure drops and! or downcomer backups greater than 50 percent may also indicate possible flooding in the actual operation.
2) The Column



The column temperature profile is a direct indication of the separation occurri ng. Zones of relatively constant temperature in the column indicate tray damage or missing trays. It is not an uncommon occurrence to have tray manways left open during construction or turnarounds. Backflow through the column during startup is an effective way to move all of the trays to the bottom of a column, resulting in a greatly reduced separation zone. Chimney tray damage always results in a greatly lowered draw temperature and difficulty in maintai n i ng a desired draw rate. The product below the draw tray is al so lighter than normal. This is because liquid is leaking from the draw tray to the next section below and acting as reflux. The leak may be a hole in the draw tray or a bad seal between the draw tray and the column wall. The latter can be caused by a thermal upset in the column. 3) Low Tray Efficiencies: The tray efficiencies presented in Table 7.3 are typical for normal column operations. If it is necessary to lower these values significantly to match a column operation. there may be tray damage or missing trays. Again, open manways are the same as missing trays.

,.1 '



Practical Distillation Principles


r i

Don't neglect to check for reboiler problems when tray efficiencies seem to be low for an actual column operation. Remember that separations are accomplished with a combination of trays and reflux. A problem reboiler may not be generating the reflux needed for the separation. This is not always apparent since plant reflux measurements are often inaccurate. 4) Heat Balance Problems These occur for complex columns with side draw products and are usually diagnosed by plant personnel as flooding problems. For these columns, the necessary heat removal to produce a given set of products is always the same, .regardless of how the duty is distributed over the column. Thus when side coolers are not operating properly, condensing duty is shifted to the overhead condenser. This results in a big increase in the top reflux for the column, overloading the top section of the column. Correcting the side cooler operation will correct the apparent flooding problem. 5) Abnormally High Reflux Requirements:


Too much feed preheat is a likely cause for this condition. The column model can be used to reproduce the plant operation and determine the optimum feed temperature. When the feed is too hot there is too much carry up of heavy materials into the rectification zone. These materials must be washed down to the bottom of the column by increased reflux. Reflux is generated by increasing the reboiler duty and so on.





31 Goldstein, Robert P. , and Stanfield, Robert B., "Flexible Method for the Solution of Distillation Design Problems using the Newton-Rhapson Technique", Ind. Eng. Chern. Process Des. Develop., Vol 9, No. I, p. 78-84, (1970). 32 Boston, J. F... ' A New Class of Quasi-Newton Solution Methods for Multicornponent, Multistage Separation Processes", Ph, D. Thesis, Tulane University, (1970). 33 Boston, J. F. and Sullivan, S. L. Jr., " A New Class of Solution Methods for Multicomponent, Multistage Separation Processes", Can. J. Chern. Eng., p. 52, (Febr. 1974). 34 Russell, Richard A., "A Flexible and Reliable Method Solves Single-Tower Crude-Distillation-Column Problems", Chem. Engr., p. 53-59, (Oct. 17, 1983). 35 Morris, C. G, Sirn, W. D., Vysniauskas, T., and Svrcek, W. Y., "Crude Simulation on a Personal Computer", Chem. Engr. Progr., p. 63-68, (Nov. (988). 36 Kister, Henry Z., "Troubleshoot 75, (June 1995). Distillation Simulations", and


Chern. Engr. Progr., p. 63-

37 Hengstebeck, R. J., "An Improved Shortcut for Calculating Distillations", Chern. Eng., p.IlS, (Jan. 13, 1969). 38 Murphree, 39 Drickarner 40 O'Connell, E.

Difficult Multicomponent

v., Ind. Eng.

Chem., Vol. 17, p. 747, (1925).

and Bradford,

Trans. Am. Inst. Chem.

Engrs., Vol. 39, p. 319, (1943).

H. E., Trans. Am. Inst. Chem. Engrs., Vol. 42, p, 741, (I946).

41 G. L. Kaes, Private Communication. 42 Glitsch, Ballast Tray Design Manual, Bulletin 4900, 5th Edition, (Dec. 1989). 43 Koch, Flexitray Design Manual, Bulletin 960-1, (1982). 44 Nutter, Float Valve Design Manual, Revision 2, (August 45 Kister, Henry Z., "Complex (May 13, 1985). Multicomponent 1981).


Chern. Engr., p. 71-80,

46 Hasbrouck, J. F., Kunesh, 1. G., and Smith, V. c., "Successfully Distillation Towers", Chern. Engr. Progr., P. 63-72, (March (993).





Practical Distillation Principles 80

47 Kister. H. Z .• and Hower. T. C., "Solve Process
Column Problems-

r r

Part 1",

Hydrocarbon Pr., p. 89-91, (May 1991).

48 Kister, H. Z., and Hower, T. C., "Solve Process Column Problems- Part 2",

Hydrocarbon Pr .• p. 83-87, (June 1991).

49 Fair, 1. R., and Seibert, F. S., "Understand
Distillation-Column Debottlenecking

Options", Chem. Engr. Progr., p. 42-48, (June 1996).

SO Kister,

H. Z., and Haas, C. E., "Predict Entrainment


on Sieve and Valve

Trays", Chern. Engr. Progr., p. 63-69, (Sept. 1990) .

~ ~

., .

~-!I ,."

Chapter 8.0

Crude Distillation

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






. Crude Distillation

The first section of this chapter provides general background information on the crude distillation process. Typical flow sheets and operating procedures are discussed. Some of the typical schemes used to increase unit capacities are also discussed in this section. The second section presents a stepwise procedure for modeling existing columns. These techniques may also be applied to development of design models for new columns.

8.1 Crude Distillation Units: General Information

Crude distillation columns and the associated auxiliaries are large when compared to most other refinery processing units. This book has devoted a separate chapter to vacuum distillation. However, 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. Crude oil distillation columns come in a variety of sizes, with capacities ranging from 5,000 to 10,000 barrels! day (700 to 1400 Metric tpd) to 400,000 barrels! day (56,000 Metric tpd). Process economics today favor large units, and many columns processing less than about 50,000 barrels/ day (7000 Metric tpd) have been taken out of service. The separations achieved with crude columns are independent of size and the operating strategies are similar for columns of all sizes. There is no industry-wide nomenclature standard for crude distillationcolumns or their products This can be confusing for new engineers. For example, crude distillation columns may be called: crude distillation units (COU's), crude topping units (CTUs), topping units, atmospheric units, atmospheric pipe-stills, and so forth. The light gasoline product is called: light straight run (LSR), light gasoline. light naphtha, etc. The heavy gasoline product is usually reformed to improve its octane and may be . named: naphtha, heavy naphtha, heavy gasoline, reforming naphtha, jet fuel (military JP4), etc., depending on its end use. Light fuel distillate is most commonly called kerosene, . but it may also be known as light distillate, jet fuel (commercial JET 50), virgin distillate, • etc. Middle distillate is referred to as diesel fuel, light gas oil (LGO), etc. The heaviest. distillate may be designated as: atmospheric gas oil (AGO), heavy gas oil (HGO), heavy distillate, gas oil, etc. And, finally, the crude column bottoms product is called: reduced. crude, topped crude oil, atmospheric residue, residuum, atmospheric bottoms, pipe-still . bottoms, etc. In this book, the products described above will be designated as light·



•.. e


straight run, heavy naphtha, kerosene, diesel, atmospheric gas oil, and topped crude.
Crude distillation is accomplished in multi-draw columns for which all of the heat is supplied in the feed. 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. Ref1ux is provided at the top of the column by pumpi some of the condensed liquid back to the top tray. Reflux is also provided at intermediate locations in the column with.p!lmparound cooling circuits. The hot liquid portion of

J j

83 oil feed is stripped with steam to remove dissolved light hydrocarbons before the bottom of the column. W. L. Nelsen" presents four fundamental principles for the operation of crude columns and other multi-draw columns that are worthy of repetition:
1.: The yield of a given product is primarily a function of the composition of the

feed mixture, not the degree of separation. 2. The number of trays only slightly alters the boiling range of the products as defined by ASTM initial boiling points and end points.

The initial boiling point of side draw products is always corrected by either steam stripping or reprocessing.


ami' it must be

4. The end point of a side draw product is primarily controlled by opening or closing the draw valve to change the yield.

8.1.1 Process Description

A general crude unit is depicted in Figure 8.1. 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 oil is heated to 250 to 300 degrees F (120 to 150 degrees C), five to six liquid volume percent water is injected, and the resultant emulsion is fed to an electrostatic desalter. In the desalter, the salts (primarily chlorides) selectively migrate to the aqueous phase and are withdrawn as a brine solution.

After desalting, the crude oil contains from 0.25 to 0.5 liquid volume percent water from
solubility and emulsion effects. 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. Upon exit from the last preheat exchanger the oil is heated to the desired column inlet temperature in the crude furnace. Furnace outlet temperatures typically range from 630 to 725 degrees F (333 to 385 degrees C), depending on the crude oil composition. The hot oil mixture from the furnace flows through a transfer line into the flash zone of the main crude column. Here it mixes with the steam and light hydrocarbons from the column stripping zone. 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 lower panial pressure for the hydrocarbons lowers the temperature required to distill the overhead products from the column feed.




Crude Distillation




The hot liquid from the flash zone drops through the column stripping section. where it is stripped by steam injected into the bottom of the column. The hot vapors from the flash zone rise and are contacted by colder reflux flowing down the column. The reflux condenses the side liquid 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. The cooled pumparound liquid is typically returned to the column a few trays above the draw tray. Pumparound flow rates are high, because heat is being exchanged with crude oil that is at a high flow rate.

Figure 8.1 Typical Crude Distillation Unit


Wet Gas


'---------.. Topped Crude



The pumparound cooling circuits accomplish three objectives. First, they remove latent heat from the hot flash zone vapors and help condense the side products. Secondly, they improve the efficiency of the crude preheat train by enabling heat recovery at higher
temperature levels than the overhead condenser. This decreases the required crude furnace duty. Finally, they reduce the vapor flow rate through the column which reduces the required size of the column. Since crude column sizes are primarily determined by the vapor tlow rates, the pumparound cooling is important when designing and expanding these columns. Unfortunately, the pumparound circuits degrade the fractionation between side products by reducing the internal liquid flows between side products.


-!,: i.i
















85 liquid side draw products are usually stripped in steam strippers or reboiled strippers light materials and control their flash points. Thus. the composition of the , portion of a liquid side product is controlled by a side stripper. not the main ...:"column. In the case of the gas oil side product, stripping is used to remove diesel boiling ' ?:",'-"'~-.-- range materials from the cracking stocks for fluid catalytic crackers (FCC's). . The end points for the liquid side products are controlled on the main column by their draw rates. For example, to increase the end point of the kerosene product in Figure 8.1. it is necessary to decrease the flow of the diesel product and increase the flow of the kerosene product. This adjustment allows heavier components to travel up the column to the kerosene draw tray, increasing the end point of the kerosene product. There may also be a small decrease in the lightest portion of the diesel product because of this adjustment, but this effect is small when compared to the effect of the diesel steam stripper. The unit depicted in Figure 8.1 recovers a combined light straight run! heavy naphtha overhead product. The separation between these products is accomplished with an auxilliary splitter column. An alternate processing scheme to separate light and heavy naphtha is shown below in Figure 8.2. .

Figure 8.2 Alternate Light! Heavy Naphtha Separation





_____~ L,

LPG Li ght

L - ---

r---- ~

Stripper ,---_.,.

Straight RurY Heavy Naphtha

Note that for this scheme, an additional liquid side draw product is located on the main column above the kerosene side draw. The heavy naphtha product is withdrawn at this location and stripped with steam. The light straight run gasoline is removed as the overhead liquid product from the condenser and stabilized. The separation of light and heavy naphtha with a splitter column as depicted in Figure 8.1 has at least three advantages over the flow sheet shown in Figure 8.2. The use of naphtha strippers has been widely abandoned by refiners for these reasons.

Crude Distilkuion First, recovering the heavy naphtha with the column overhead products- provides a better measure of operating safety by substantially raising the water dew point for the overhead vapor from the main column. 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.
The other reasons concern the qualities of the light straight run and heavy naphtha products. 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. Hence, light materials (five carbon number compounds) may be minimized in the heavy naphtha reformer feed, and good reforming stocks (carbon number six and higher) may be minimized in the light straight run gasoline. This improves the profitabi lity of the naphtha reformer operation. Nearly all of the steam introduced into the main column and the side strippers leaves the top of the main column as steam. It is condensed and withdrawn as an aqueous phase frcn: the condenser accumulator drum. Chemicals are injected into the main column overhead vapor line to minimize corrosion caused by hydrolization of salts in the condensed water. A small amount of water leaves the process dissolved in the topped crude and side stripper liquid products. Refiners sometimes use reboiled side strippers to control the flash points of side liquid products while keeping the products dry. 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. The separations between side products are not precise, 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. Main crude columns typically have 30 to 50 actual trays, depending on the number of side products being withdrawn. Seven to ten trays are commonly used between adjacent side products. Purnparound cooling zones may have two to four trays for heat transfer purposes; however, these trays do not accomplish any signi ficant fractionation. The column section between the flash zone and the heaviest side product is of particular interest. 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. This protects the quality of the heaviest side product and prevents carbonization or coking of the trays in the wash zone. 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. The quantity of overf1ash that is necessary depends on the unit design 2nd the characteristics of the crude oil being processed. Current design philosophy is to use six to eight trays in the wash zone and an overflash rate of 3.0 to 5.0 liquid volume percent based on fresh crude charge. Older column designs (prior to 1970) were based on two t? four wash trays and overflash design rates of 10.0 to 15.0 volume percent of fresh crude charge. .





Typical Operations and Control

There is wide variation in the operating conditions used for crude distillation. In general, 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. Thermal decomposition of a crude oil is dependent on its chemical makeup. A paraffin base crude oil cracks more readily than an aromatic or asphalt base crude oil. Therefore, it is necessary to process a paraffin base crude oil at a lower temperature than an asphalt base crude oil. The decomposition (cracking) of crude oil produces light gases, tar-like substances, and elemental carbon (coke). As might be expected, a paraffin base crude produces more cracking gas than an aromatic or asphalt base crude oil. The pressure of the crude column is controlfed by holding a back-pressure on the reflux accumulator drum. 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. Figure 8.3 presents a typical pressure control scheme used for crude column accumulator drums. A double control valve arrangement is used to bleed external gas into the accumulator drum as needed to maintain a desired pressure. When sufficient gas is produced from the crude oil, the external gas flow is zero. The pressure of the accumulator drum is usually in the range 3.0 to 5.0 psig (l.22 to 1.36 bar absolute), although some refiners operate at pressures as high as 30 psig (3.1 bar). A higher pressure reduces vapor loading, but increases the flash zone temperature. The top tray pressure for the main column is 6 to 10 psi (0.4 to 0.7 bar) higher than the accumulator drum, depending on the drop through the overhead vapor line and coolers. The flash zone pressure is usually 5 to 8 psi (0.34 to 0.55 bar) higher than the top tray, with the furnace transfer line pressure about 5 psi (0.34 bar) higher than the flash zone.

Figure 8.3 Typical Pressure



Fuel Gas

•. "j

Column Overhead

• I


Ret1ux to Column Water Overhead Liquid