Di srenr onGAS CONDITIONING AND PROCESSING VOLUME 3 ADVANCED TECHNIQUES AND APPLICATIONS By ROBERT N. MADDOX Leonard F. Sheerar Professor Oklahoma State University and JOHN H. ERBAR Professor of Chemical Engineering Oklahoma State University Edited for Campbell Petroleum Series by John M. Campbell ©Copyright 1982 by Campbell Petroleum Series. This book is sold for personal or library reference use, or for regularly scheduled university classes only; use as a reference or manual for adult training program is specifically reserved for John M. Campbell and Co. No part of the text or original figures may be reproduced in any form without written permission of the publisher. All translation rights are likewise reserved. .GAS CONDITIONING AND PROCESSING Volume 3 Library of Congress Catalog Card No.: 76-157183 Printed in U.S.A., January 1982 Published By: Campbell Petroleum Series 1215 Crossroads Blvd. Norman, Oklahoma 7306910. TABLE OF CONTENTS Introduction 2. ee ee eee ew “Garbage Begats garbage" Phase Behavior of Hydrocarbon Systems... . - eee eee ot ae sree ee Pure component phase behavior, multicomponent phase behavior Thermodynamic Property Prediction Methods... 22... 2. 0 31 Basic thermodynamic property equations, equation of state solution methods, evaluation of thermodynamic property prediction procedures, selecting a thermodynamic property prediction procedure Equilibrium Calculations... 2-2... Retest ibe Hee Edd. Basic equilibrium calculations, equilibrium calculation failures Predicting the Properties of Hexanes Plus (C64) Fractions .. ~ 5-1 Cgq fraction availability Advanced Characterization Methods... -. eee ee ee eee 6-1 Data requirements, critical property estimation procedure, verification of the method, effect of proposed procedure on processing calculations Principles of Continuous Binary Distillation... 2... + 7-1 Minimum trays, minimum reflux, complex fractionators Continuous Multicomponent Distillation ©... 2... ee Bl Minimum number of trays, minimum reflux, operating reflux and plates, feed plate location, influence of feed operation Tray-By-Tray Calculations... 6... ee ceeaaenc | Lewis-Matheson method, Thiele-Geddes method, contemporary” tray-by-tray calculation procedures, thermodynamic property prediction methods and C,, characterization, reconmended procedure for distillati8a column simulation, "diagnosing" tray-by-tray output Absorption . .. Sees trees eee rec etieeea tierce eee tee teteEEdOeT Graphical calculation, how an’absorber operates, multicomponent absorption, stripping, multicomponent stripping, tray-by-tray calculations, complex absorber calculationsChapter i. 12. 13. 4. 15. 16. Column Sizing Calculations «©... ee eee ee eee Plate (tray) towers, effect of liquid hydraulics (Compressfontete susie sucaet suet etter eaeaercr decree teedgue Prediction methods, Mollier chart method, gas law methods, true polytropic method, efficiencies based on operating data, comparison of the methods, comparison of efficiencies, corrections to the predicted gas power requirements, optimum interstage pressures, thermodynamic property prediction effects on compressor evaluation, specific centrifugal compressor parameters, second level efficiency estimation Expansion Processes 6... ee ee ee ee Adiabatic expansion processes, cryogenic expander processing Natural Gas--Water System... ee ee ee ee Phase behavior, water content prediction methods, comparison of methods, hydrate prediction Dehydration et see ee csec case eee cent ee Absorber design factors, regenerator design, isotherms for molecular sieves Fluid Flw . 2-2-2222 2-0-- see eeetesee eae Gas flow equations, two phase flow calculation methods: Lockhart-Martinelli, Baker, AGA, Flanigan, Beggs and Brill ii Page 1-1 12-1 13-1 14-1 15-1 16-1ORUNnHSwe Vo oos wre & EGRES wo 4. 4 4 4 4 4 5. 5, 5, 5: 5, LIST OF FIGURES A Typical Pure Component Pressure--Temperature Design . . - A Typical Pure Component Pressure--Volume Diagram... . . Phase Envelope for a Typical Natural Gas Mixture... . . Composition--Critical Temperature Diagram for a Methane-Propane Binary... - ee ee ee ee a Composition--Critical Pressure Diagram for a Nethane-Propane Binary... eee eee ee eee Typical Pressure-Temperature Envelopes for Various Mixtures Possible Critical Point Locations Along the Pressure-Temperature Envelope... + +e ee ee eee Retrograde Behavior . . . - Bebe Ha He ae se eee Phase Envelope for Example 2.1)... . 2. rn Phase Envelope for Example 2.2... ... annie Illustration of the Path of Enthalpy Change. . . Overall Equation of State Solution Procedure . . Typical Behavior of Cubic Equations of State . . Block Diagrams for Equation of State Solution . . Typical Effect of Errors in Compressibility Factor Calculations 2. ee ee ee ee ae Block Diagram for Bubble Point Calculation .....-.- Block Diagram for Dew Point Calculation. ....- 2+. Temperature Adjustment Routines for Equilibrium Calculations . 2... ee... ee SHH une Ea Pressure Adjustment Routines for Equilibrium Calculations . . Block Diagram for a Flash Calculation. .... 2... +> Example of Difficulties in Performing Flash Calculations at Fixed Enthalpy Conditions ..... . eee Graphical Example Showing How Fixed Enthalpy/Entropy Problems Are Solved... ee eee ee ee ee Block Diagram for Enthalpy/Entropy Balancing Procedure . « Possible Trouble Points in Bubble/Dew Point Calculation Specifications ....--. ++ ee- Temperature-Pressure Diagram for Gas Shown in Table 4.1 Example of a "Needle Shaped" Phase Envelope... .. - Forbidden Regions for Bubble/Dew Point Calculations . . . Phase Diagrams for Different Hexanes Plus Characterizations Phase Envelopes Predicted by Split and Single Equation ‘of State Approaches se eee tee ee ee es Another Example of Phase Envelope Predictions by Split and Single Equation of State Approaches... .-.-.- Critical Temperature of Petroleum Fractions .. +... Critical Pressure of Petroleum Fractions ...- ++ +++ TBP Specific Gravity and Molecular Weight Data for Sample Problem Ce, Fraction... vee eee eee Effect of C., Charactérization on Predicted Liquid Formtigf... 2... se ee ee Wolecular Weight, API Gravity and Boiling Point of Petroleum Fractions... - sean wie wok BESaNNSS on Bb beeen Se f BEE SEOSample Problem Data for Converting Partial TBP Analysis to Complete TBP Analysis . . . . Relationship Between ASTM and TBP Analyses . 7 Sample ASTM Distillation Curve ....... : Plot of Calculated TSP Curve from Table 5.5... . . Empirical Correction Factor for Chromatographic TBP's Plot of a Chromatographic Based TEP Distillation . Graphical Example of Data Requirements... . . . Typical Critical Function Plots. ... 1.1... Effect of C,, Characterization on Predicted Dew Point Efvelope . . . ppaeenes Comparison of Calculated and Experimental Liquid” Formation at 70°F... 1... 2. pe tece ue Comparison of Calculated and Experimental Liquid Formation at 10°F oo. eee ee eee Comparison of Calculated and Experimental Liquid Formation at 160°F .. ee ee ee ee eee Comparison of Calculated and ‘Experimental Liquid” Formation at 220°F ...... 2... eee : Comparison of Calculated Well Bore Conditions | 2. Simplified Three Stage Separation System .. 1... Simplified Turbo-Expander Process... ae Schematic of a Continuous Distillation Colum 122111! Equi VibriuniPlabedstacsaasiasctasieiccseaeevenee ee eae Graphical Construction of Equilibrium Curve and Operating Lines... . Se oa rt Feed Plate of Distillation Colum... .. 2... tee Location of q-Line for Various Feed Conditions»... 2. Construction for Graphical Solution... .....- 7 Graphical Construction of Theoretical Plates . . McCabe-Thiele Construction for Minimum Plates... 5... McCabe-Thiele Construction for Infinite Plates»... 1. Determination of Minimum Reflux Rate on McCabe-Thiele Plot. . Distillation Colum with Side Product... ....... fe McCabe-Thiele Construction for a Column with Rectifying Section Side Draw... .. » eeesereas Schematic of a Distillation Column with Two Feeds |.) 1! NeCabe-Thiele Construction for a Column with Two Feeds . . . Construction Showing Effect of Incorrect Feed Plate location... . : Variation of Distillate Composition with Distiila Multicomponent Column at Minimum Trays... 2... 2. oe Schematic of a Complex Fractionator for Minimum Trays Calculation... 2... ee ee ee eee eto ee Colunn at Minimum Reflux 2.22 De an and Key Ratios in Feed... . eset tied Light Keys and Lighter 222. D LID DI IIIT! Light Keys and Lighter 2s. le Heavy Keys and Heavier... ee ee ee ee eee Minimum Reflux for Complex Fractionator : | eee Gilliland Graphical Correlation of Reflux and Plates |. iv Page 2 geamaqnan z 5 en RES SSURUREDe SPEEEPEe SOY wey RBESEEGNeFigure 8.11 8.12 8.13 8.14 8.15 © Reaver 10. 10. 10. 10. i il. MM. ll. il. i. DORURHOVAGS ul. 7 ll. 8 1. 9 11.10 un 11.12 11.13 11.14 11.15 42.1 12. 2 12. 3 12.4 12.5 12. 6a Martin-Brown Graphical Correlation of Reflux and Plates . . Erbar-Gray-Maddox Correlation... 2. ee ee eee Relationship Between Reflux and Trays for De-propanizer . Effect of Feed Plate Location on Required Reflux Rate ‘at Constant Separation, Feed 3% Vaporized . . . . +. + Effect of Feed Plate Location on Required Reflux Rate ‘at Constant Separation, Feed 67% Vaporized .....- Material and Energy Balance Envelopes for the Rectifying Section ..--- +--+ +. eee Logic Diagram for Rectifying Section Calculations . Overall Colum Balances... ee ee ee Material and Energy Balances for Stripping Section Logic Diagram for Stripping Section Calculations Nodels of Two Different Feed Zones... - +++ + Logic Diagram for Feed Zone Calculations ..-...- fogic Diagram... ee eee ee ee et ae Schematic Diagram of an Absorber... ssw ee ee ee Graphical Construction for Determination of Minimum Solvent Rate to Recover Specified Amount of Solute . . - Graphical Determination of Minimum Solvent Rate to Recover All of Solute... ....- Graphical Solution of Equation 10.12... ..--- 5 + Schematic of a Stripper... 1 ee ee ee ee ee ee Nomenclature Used in Tray-By-Tray Absorption Development Sketch of Absorber Process for Tray-By-Tray Calculations Typical Reboiled Absorber... +s eevee eee es Effect of Vapor and Liquid on Sieve Tray Performance Representation of Free and Active Area... - Types of Downcomers . . - + ee ee ee ee Multi Pass Trays . 0s Tray Dynamics Schematic Diagram. . 22... Correlation for Overall Efficiency of Absorbers andlieractdonacanseisteriieusioripeeeeieriarses Effect of Vapor and Liquid Load on Sieve Tray Efficiency Tower Sizing Correlation for Sieve Trays ..-- +--+ Tower Sizing Correlation for Bubble-Cap Trays... + - + Tray Sizing Correlation for Koch Flexitrays .. . Generalized Flooding Capacity for Glitsch Sailast Trays + + - Specific Surface and Voids Fraction for Tower Packings Correlation for Flooding Characteristics of Packed Towers in Gas Liquid Service «+ +s eee eee ere Nguyen Correlation for Flooding Effects... ++... Correlation to Determine Flooding Velocities in Liquid-- Liquid Contactors . . ee ee ee ee et ee Logic Diagram for Compressor Calculations»... -- ++ Compressor Calculation on Mollier Chart... 2... a+ Approximate Horsepower Requirement for Centrifugal (Compressors) ecg rer seis tint aise arrest Approximate Heat Capacity Ratios of Hydrocarbon Gases - + « Conversion of Adiabatic to Polytropic Efficiency ..-- - Logic Diagram for Compressor Horsepower Calculation . . . . . v Page 8-23 8-24 8-27 8-31 8-32 easeecaseestt caaeceeaaaaa 1l- lle i 11-10 11-12 i-14 11-15 11-16 11-18 12-4 12-5 12-7 12-9 12-10 12-12Figure 12. 12. we. 1. 6b Logic Diagram for Compressor Horsepower Calculation . 7 Figure of Turboexpander Recompression Process . . . « 8 Sketch of Reinjection Compression Process... ... 9 Sketch of Process and Process Conditions for Interstage Pressure Study... 2... - eee ee 12.10 Effect of Specific Speed and Diameter on Compressor Efficiency... . . ereedieeisedieee 12.11 Comparison of Predicted and Neasured Efficiencies . | 13, 1 Typical Expansion Processes... .... +--+ 40. 13. 2 Sketch of Process Flow Diagram»... 222.102 13. 3. Phase Envelope for the Gas... es. le 13. 4 Heavy Component K-value as Function of Separator Condi 13. § Sketch of Process Flow Diagram... 2.2... 44 13. 6 P-T Envelope for Separator Feed and Off-Gas .. . . 13. 7 Process Flow for Expansion Process... . . | a 13. 8 Bubble Point-dew Point Curve for Gas After 80% Ethane Recovery... +e eee ee ee 13. 9 Process Conditions and Pressure-Enthalpy Diagram . 13.10 Block Diagram for Compressor Calculations... . +. 13.11 Process Flow Sheets... 2.2... cscs 13.12 Turbine Outlet Temperature and Liquid Formation as Function of Turboexpander Efficiency .. . ‘i 13.13 Allowable Turbine Speed (RPM based on of1 bearings) 13.14 Specific Speed Efficiency Relationship for Turbines . 13.15 Turboexpander Efficiency as a Function of (Tip Speed/Spouting Velocity)... ......5 13.16 Balje and Scheel Correlation for Expander Efficiency 13.17 Schematics of Expansion Processes... 1... 14. 14. 14. M4. 14. 14. 14. 14. 14. 1 Phase Envelope for Wet Gas... -.. ee eee ee 2 Liquid Formed... . Beccieacnci Seatac 3. Phase Envelope for Wet Gas 11.1] lll 4 Liquid Formd. . 1.2... ee eee 5 Phase Envelope ...... eee aiaesteeeiae 6 Liquid Formed... .. 0. ‘i pecieniee 7 Water Content of Lean, Sweet Natural Gas 1... 8 | Schematic Diagram of Three-Phase Separator... . . 9 Comparison of Predicted and Experimental Phase Solubilities for Nethane-Water Systen...... 14.10 Comparison of Predicted and Experimental Phase Composition for n Butane-Water ... 1. ee es 14.11a Comparison of Predicted and Experimental Vapor Phase Composition for Methane-n Butane-Water System... . . 14.11b Comparison of Predicted and Experimental Water-Rich Liquid Compositions for Methane-n Butane-Water Systems. 14,11e Liquid Phase Composition for Methane-n Butane- Comparison of Predicted and Experimental Hydrocarbon-Rich Water Systems... 2... aire eaters aineeeE 14.12 Comparison of Predicted and Experimental Phase Composition for Carbon Dioxide-hater System. . . viFigure 14.13 14.14 14.15 14.16 44.17 14.18 15. 1 15. 15. 15. 15. 15. 15. is. 15. 15.10 15.11 15.12 15.13 15.14 15.15 15.16 15.17 15.18 15.19 15.20 15.21 15.22 16. 1 16. 16. 16. 16. 16. 16. 16. OVARY ean Aen 16. 9 16.10 16.11 16.12 Comparison of Predicted and Experimental Phase Comparison for Hydrogen Sulfide-Water System 2... + Comparison of Predicted and Experimental Bubble Point Pressures for Nethanol-Carbon Dioxide System... « Comparison of Predicted and Experimental Bubble Point Pressures for Methanol-Hydrogen Sulfide Systems . . . Process Nodel .. ett te ee Effect of Methanol on Predicted C02 Solubilities in Liquid Water oe ee et ee es Effect of Methanol on Predicted Hydrocarbon Solubility in Liquid Water se ee ee Equilibrium Water Dew Point as Function of TEG Concentration and Contactor Temperature»... + + + Activity Coefficient for Water in TEG-Water Systems . . . Another Correlation for Water Dew Point of Natural Gas . WT. % Water vs. Nol Fraction Water in TEG-Water Solutions Dew Point Depression vs. Glycol Rate . +--+ + sees Dew Point Depression vs. Glycol Rate -. +. +--+ +s Dew Point Depression vs. Glycol Rate... + eee eee Nomograph for Predicting Regenerator Performance ... ~ Mater Adsorption Isotherms for Type 4A Molecular Sieves . Schematic Representatives of the Adsorption Zone Concept Equilibrium Adsorption Loading of COz on 4A Pellets . « Equilibrium Adsorption Loading of COz on 5A Pellets . . Equilibrium Adsorption Loading of C02 on 13X Pellets Equilibrium Adsorption Loading of figs on 4& Pellets « Equilibrium Adsorption Loading of H2S on 5A Pellets . Equilibrium Adsorption Loading of H25 on 13x Pellets Equilibrium Adsorption Loading of H2S on 3A Pellets « Equilibrium Adsorption Loading of H2S on 5A Pellets . . Equilibrium Adsorption Loading of H2S on 5A Pellets « Equilibrium Adsorption Loading of H2S on 13X Pellets Friction Factor... eee et ee ee Pressure Drop Coefficient... 2-1 eee eee Friction Factor for Use in Equation 16.5 .... + Roughness of Commercial Pipe... -.. + : Equivalent Length of Valves and Fittings . . - Two-Phase Flow Regimes According to Baker . . . Panhandle Pipeline Efficiency. ...----+-- Flanigan Correlation for@ «2. +... +e eee Two-Phase Flow Friction Factors for AGA Procedure . . . Liquid Holdup Correlation for Horizontal Pipe for AGA Procedure . ee eee ee eee Influence of Heat Transfer on Line Temperature... . Horizontal Line Comparison Smooth Pipe, No Heat Transfer Horizontal Line Comparison, Roughness 0.0005 ft. No Heat Transfer... eee tee ee es Horizontal Line Temperature Comparison Smooth Pipe, No Heat Transfer oe ee ee eet et vii Page 14-23 14-26 14-27 14-29 14-32 14-33 15Figure 16.13 16.14 16.15 16.16 16.17 16.18 Horizontal Line Temperature Drop Comparison. Roughness 0.005 ft., No Heat Transfer... . . Pipeline Elevation Profile Inclined Flow Pressure Drop Comparison Smooth Pipe, No Heat Transfer Inclined Flow Pressure Drop Comparison, Roughness 0.0005 ft., No Heat Transfer : Inclined Flow Pressure Drop Comparison, Smooth Pipe, is 0.5 Btu/hr-ft2-°F Vertical Flow Pressure Drop Comparison Page 16-42 16-43 16-44 16-45, 16-46 16-4710. 10. 10. ROOREREH © RO LIST OF TABLES Typical Input Required for MINI*SIM Program Flash... . + Soave-Redlich-Kwong Equations... +. 2 +--+ e- eee Chao-Seader Equations... 2. ee ee ee BWRS Equations . See ee ete aa eae Peng-Robinson Equations... ee ee Characteristics of Split and Single Equation of State Approaches... . . eee eter cate : Calculation of Lower Dew Point Temperature at 1400 psia Calculation of Upper Dew Point Temperature at 1400 psia Calculation of Lower Dew Point Pressure at 36.47°F . . Effect of Cg+ Characterization on K Value Predictions and Liquid Formation... eee ee ee Sample Analysis for Various Categories of Cg+ Analysis. Experimental Data for Illustrative Calculations... . . Effect of C74 Characterization on Predicted Sample Problem Phase Behavior... ee eee ee eee Sample Partial TBP to Complete TSP Calculations ..... ~~ Sample ASTM to TBP Conversion Calculations .......-- Sample Calculations for Converting a Chromatographic Analysis toa TBP... ee ee eet Sample Calculations to Convert Volumetric Cg+ Sub-Fraction Data to Molar Data... ees ee eee Conparison of Predicted and Experimental Results for” a Crude Oi] System oe ee ee eee ee Summary of Predicted and Experimental Liquid Formations for a Gas Condensate System... ee eee eee ee Feed Composition and (g+ Characterization... .. +--+ Effect of Characterization on Predicted Liquid and Vapor Recoveries... --- +. Ba ae Effect of Cg, Characterization on Predicted Turbo-Expander Plant Performance... 1 ee ee ee et ee ee Distillation Column Nomenclature ss eee Feed Composition and Process Conditions... ...-... Optimum Feed Plate Location... + see ee ee ee Summary of Calculations for a Sour Crude Stripping Column . Lean 011 Characterizations ... . . tte ceeeeetatteree ete Stream Compositions for Lean 0i1 Characterized as n-Heptane . . - eee dacte ttce eat eastetetet ee Stream Compositions for Lean Oil Characterized ‘as Lumped Component... eee ee ee ee Stream Compositions for Lean Oil Characterized ‘as Four Hypothetical Components... .-. +--+ e ee Reboiled Absorber Problem Definition... +++ +++ + Reboiled Absorber Comparison of Product Distributions and Heat Loads see et ee ee ee Reboiled Absorber Comparison of Tray Profiles... +. + + ix13.7 14. 4. uM. M4. 4. 9 14.10 4.11 14.12 14.13 14.14 15.1 15. 2 15. 3 1b. 4 16. 1 16. 2 16. 3 Sample Calculations for Compression Systems . : Wollier Analysis... 2... soneicrietait Ideal Gas State Equations Adiabatic |.) . Ideal Gas State Equations Polytropic. . | | | : Effect of Z, on Predicted Power Requirements |. | | Feed to Turboexpander Compression Train... 1... Summary of Results of Turboexpander Recompression Train Feed Composition for Reinjection Compression Process. Summary of Resul ts--Reinjection Compression Process . _ High Pressure Compression Horsepower Comparison. . |. Summary of Effects of Interstage Pressure on Predicted Power Requirements ......-...... Summary of Effects of C7, Characterization on Predicted Power Requirements at P= 435 psia . . . Locus of Predicted Separator Conditions to Produce a 90°F Dew Point Residue Gas at 300 psia .. . . . Summary of H, $, for Hand Calculations ... 2... MINI*SIM Turboexpander Calculations... 2... aeae Turboexpander Design Conditions... 2... 0.00 Sample Turboexpander Problem (Liquid) . 2... 1! Specified Process Conditions for Joule-Thomson Turboexpander Process Comparison... .. 2... Calculated Process Conditions for Joule-Thomson Turboexpander Process Conditions ......... Absolute Percentage Error Between Experiments and Calculated Natural Gas Water Content .... . . Peng-Robinson Equation of State Equations... 2. . Soave-Redlich-Kwong Equations... . ee. ee PFGC Equations... ee ee ee ee Summary of Comparisons of Equations Handling Water. Summary of Comparisons of Ternary Hydrocarbon- Non Hydrocarbon-Water Systems... ......-4 Experimental Multicomponent Mixture Compositions . . . Comparison of Predicted and Experimental Water Contents of Multicomponent Systems ........ Comparison of Predicted and Experimental Bubble Point Pressure for the Nitrogen-Carbon Dioxide-Hydrogen Sulfide-Methanol System at -15°C .... 2... 7 Gas Composition... . 2-2... 2 ee eee Process Pipeline Conditions... .. sss. ce eee Results Based on Dry Hydrocarbon Flash...) 1... Results Based on Wet Hydrocarbon Flash... Summary of Calculated Results for Wet Methanol - Hydrocarbon Flashes... ........-0- 7 Effect of Regenerator Pressure on TEG Concentration Physical Properties of Glycols ........0. Molecular Diameter... 2... 2 2 5 Properties of Davison Molecular Sieves +2... Three Common Gas Pipeline Equations. ...... Pipeline Calculations Using the Weymouth Equation Pipeline Calculations Using Panhandle A Equation x Page 12-15 12-15 12-17 12-18 12-19 12-19 12-19 12-20 12-21 12-23 12-29 12-30 13-6 13-17 13-19 13-23 13-24 13-38 13-39 14-10 14-13 14-14 14-15 14-16 14-24 14-25 14-25 14-28 14-28 14-30 14-30 14-31 14-31 15-2 15-4 15-22 15-22 16- 6 16-7 16-11Table 16. 16. 16. 16. 16. eras 16. 9 16.10 16.11 16.12 Pipeline Calculations Using Panhandle B Equation : Pressure Drop Calculation for Different Pipeline Segments Calculations for Vertical Line... - ee ee eee Constant "C" for Use in Equation 16.8 4... 1... @ and R as Function of X for Lockhart~1 Martinelli Correlation... se ee ee ee ee ee ee Fitted Equations for Lockhart-Nartinel]i p and” (Sereretesets Equations for Predicting Liquid Holdup for Beggs and Brill Procedure... 2 ee eee er eee Two-Phase Flow Calculation Summary. sss eee ee ee Gas Composition Used for Two-Phase Flow Comparison . . - xi Page 16-11 16-13 16-15 16-16 16-18 16-18 16-31 16-35 16-38INTRODUCTION ‘Today most designievaluation calculations in the gas processing industry are done by computer. Even the simplest and most routine calculations have been programmed for computer solution. The ability to perform calculations that are free from arithmetic error with the blinding speed of computers should produce higher quality results. Unfortunately, in the opinion of many engineering supervisors lower, not higher, quality results are being obtained. ‘This paradox can be partially explained by examining the way some engineers approach utilization of the computer. They expect to stand beside a computer with only a vague idea of the problem to be solved. The computer is to develop the program, prepare the input, use the appropriate segment of accumulated knowledge of mankind to solve the problem, produce answers of unquestioned integrity and write the final report. Of course, all of this work is to be performed instantly for no charge. Unfor- tunately, computers have not yet reached this stage of development. While the preceding statement may be somewhat exaggerated, it does point out two growing problems — the engineer has less and less per sonal involvement with the problem he is attempting to solve, more is expected from the computer than it can possibly produce. Reduced personal involvement with the problem has many consequences. Two of the major ones are: 1, The engineer does not develop that “sixth sense" variously defined as engineering judgement, background or know how. 2. The engineer becomes less critical when analyzing the results of calculations or the data requi to get a solution to the problem. The expectation that the computer can produce high quality results from Inadequate Information is a human frailty; we all want something for nothing. An international law should be passed that requires each page of computer output to be headed: “GARBAGE BEGATS GARBAGE” Perhaps this subtle warning would alert engineers to question all computer results, to spend more time acquiring more and better information about the problem and, finally, to critically analyze the answers from any computer calculation. Stated another way, a person can only use a computer effectively if he (or she) possesses a basic knowledge of the physical principles involved AND understands the mechanical and physical constraints of the specific system being analyzed. The computer can so out-compute the knowledge of the user that he cannot interpret meaningfully the output. Remember . . . calculations only yield answers in the academic sense; in the real world calculations yield numbers which are merely a portion of the input into final decisions, There is no simple solution to the problems outlined here. Part of the solution will come from the educational processes — improved formal education and on-the-job training, professional level educa- tional programs, etc. However, the major part of the solution must come from the individual engineer — his contribution will be the development of his own professional talents by expanding his technical 4-4capabilities through self study, developing the ability to raise the “right questions” about any calcula: tional result and becoming involved with the problem, One of the things that may help with the problem of the detachment of the engineer from his problem solution via computer is the development of mini computers. These are small desk top units that have amazing capabilities for engineering problem solution (|-1). They offer the same kind of step function im- provement in engineering process calculations that the programmable pocket calculator did. The mini ‘computer brings to the desk of the engineer the capability to perform major process calculations. In addi- tion, the involvement of the engineer through his keyboard input is such that he again becomes a part of the problem solution. Table 1.1 shows typical input for the MINI*SIM program (I-2} that will be used to pro- vide examples of many of the calculations and sample problems in this book. The interactive capabilities of mini computer programs seem to give promise for increasing engineer involvement in the computer solution of his problems. the third volume of the Gas Conditioning and Processing series is a logical extension of the first two volumes. Those two volumes presented the basic fundamentals and applications for the most common equipment and systems used in the producing/processing segment of the Petroleum industry. For the most part the calculations presented are useful for manual calculation and should give reliable results. Some yield answers that are as good as those obtainable on a computer, either by virtue of the quantity or quality of data normally available, or by the very nature of the calcula. tion itself, Many of these equations, in fact, have been programmed for convenience. In other cases only the computer can be used effectively. Examples of these are unsteady state and two-phase flow, certain fractionation and absorption processes, expansion of fluids across chokes and expanders, PVT and flash calculations, etc. These involve repetitive andlor trial-and-error calculations which are not feasible timewise by manual calculation methods. ‘Some recapitulation of information in the first two volumes is presented in this volume to make it ‘somewhat self-standing for training purposes. However, the user of this volume must be familiar with the content of these preceding volumes in order to use this one effectively. The course using this volume is entitled “Advanced Gas Conditioning and Processing” to denote this situation. The purpose of this volume is to assist you, the engineer, in this development process. Selected specific technical information, (the best available at the time of writing) along with some guidelines for analyzing computer predicted results will be presented. The quality of the specific technical facts will deteriorate with time. New knowledge will become available to replace the information given here. We believe the guidelines for analyzing the results will be pertinent for years to come; they have served the authors and many of our colleagues in the gas processing industry for many years. Some ideas about pro- ‘gram organization, and the logical framework of typical computer programs will be given. We don't teach Programming. The programs that we will discuss are programs written and used extensively by the authors and others in the petroteum industry. The techniques presented are not recipes. They are principles which must be supplemented by the good judgment and intelligence of the user. The programs you use may be different from those presented. This Is not important if you realize the limitations of the program used, have feedback on how it has worked in past applications and then interpret the results in a manner which reflects the non- mathematical factors affecting system performance. In the tinal analysis our goal is to improve man- machine interaction. References (1-1) Moshteghian, M.. J. H. Erbar and R. N. Maddox, “Applications of MiniComputers in Chemical Engineering”, Proceedings of First International Conference on Micro and Mini Computers, Houston, November 1979, (12), Etbar,J.H., MINISIM Documentation, Chemical Process Consultants, nc, Stillwater, June, 1978 (13) Campbell, John M., "Gas Conditioning and Processing." Vol. , Campbell Petroleum Series, Norman, Oklahoma (1976). 1-2TABLE 1.1 Typical Input Required for MINI*SIN Program Flash -MNT 0 RUN MINI*SIM ENTER DRIVE 0 ENTER TITLE ?DEMO PROBLEM ANY HYPO*S? ENTER CALC OPTION?5. ENTER PRINT OPTION?1 ENTER FEED OPTION?1 ENTER UNIT OPTION?1 ENTER H/S OPTION? ENTER SPEC TEMP?-60 ENTER SPEC PRES?200 ENTER ESTM L/F? ENTER COMP ID AND FEED RATE FOR COMP( 1)?2,200 COMP( 2)?3,50 coMP( 3)24,30 coMP( 4)25,10 COMP( 5)?6,5 CONP( 6)?7,2 CONP( 7)78,1 comP( 8)? CPC MINI*SIN PAGE He DEMO PROBLEM FLASH: VARY L/F FIX. 11;P1 TEMPERATURE = -60.00°F PRESSURE = 200.00 PSIA COMPONENT FEED Liquip VAPOR NAME Hols MOL. FR. MOLS MOL. FR, MOLS MOL. FR. chy 200.00 0.6711 -11.11—0.1498 188.890.8440 Coe 50.00 0.1678 21.13 0.2847 «(28.87 0.1290 CH 30.00 01007 24.70 0.3328 «= 5.30 (0.0237 iGgtyg «+1000» 0.0396. 9.45 (0.1274 550.0024 nC qHyg 5.00 0.0168 4.88 0.0652 16 0.0007 iGgty 2.00 0.0067 «1.98 0.0267 .02 0.0001 ely 1,00 0,003 = «990.0138 -01 0,000 TOTAL «298.001.0000 74.27 «*1.0000 223.791.0000 HjKBTU 428.42 «1.438 -282.22 3.264 670.64 2.997 S;KBTU/R 11.76 0.039 3.000.040 8.76 0.039 MOL WT 23.987 40.007 18.675 p3LB/FT? 30.724 960 kK VALUE 5.63614 +45302 0714 01915 +01130 00300 +01882 PHASE BEHAVIOR OF HYDROCARBON SYSTEMS The pressure-volume-temperature (phase) behavior of hydrocarbon systems is a complex and di ficult subject common to many sub-branches of the petroleum and natural gas industry. The P-V.T inter. relations are usually presented graphically and show the amount of liquid or vapor present for various combinations of temperature and pressure. Hence they are called phase diagrams. Those concerned with predicting the performance of reservoirs must account for the evolution of gas andlor liquid from the reservoir fluid and its subsequent effect on the production from the reservoir. The design engineer must ‘select operating conditions for the process that are consistent with good engineering practice on the basis of the phase behavior of the hydrocarbon streams being processed. The engineer in operations can use the phase diagram of his process streams to recognize the causes of poor performance of his pro- cess equipment. Improved design and operation of field separation equipment and pipelines can be achieved through proper utilization of the phase diagram for the fluids processed. Proper interpretation of the phase diagram is critical to all aspects of gas processing. Phase diagrams for hydrocarbon systems either may be measured experimentally or predicted using One of the thermodynamic property prediction procedures to be discussed later. Prediction will never replace experimental determination of phase diagrams. in some instances, predicted phase diagrams may be as accurate or more accurate than experimentally determined diagrams; rarely is this true for naturally occurring systems. However, experimental data on a given system for a narrow range of temperature andior pressure may be extended to a much broader range of temperature-pressure condi- tions through effective use of thermodynamic property prediction methods coupled with “proper” description of the system. These techniques will be described in subsequent chapters. While accurate description of the phase diagram of a hydrocarbon system is usually desirable, qualitative description of the phase diagram is frequently adequate, The objective of this chapter is to review the basic principles of hydrocarbon phase behavior and give some illustrations of the use of phase diagrams in solving designioperating problems. These examples by no means cover all of the possible applications but are intended to give a philosophy of the use of phase diagrams. We challenge you to find additional applications for phase diagrams in your daily practice of engineering. This chapter parallels the presentation in Chapter 4, Volume 1, for the convenience of the reader. PURE COMPONENT PHASE BEHAVIOR Pure component systems are not frequently encountered in natural gasipetroleum industrial prac- tice. The possible exceptions would be in refrigeration systems using propane, ammonia or some other Pure component. Since pure component phase behavior is a limiting case of multicomponent phase be- havior, it will be used to introduce the subject of phase behavior. The pressure-temperature diagram for a pure component is shown in Figure 2.1. The lines HF, HD, and HC are shown as separating the various phases. In addition to this separation of phases, these lines represent the temperature-pressure conditions at which the adjacent phases are in equilibrium, or saturated. The line HC represents the vapor pressure of the saturated liquid from the triple Point (point H) to the critical point (point C) while the tine HF represents the vapor pressure curve of the 2-4suBCOOLED Liovip PRESSURE, TRIPLE POINT TEMPERATURE, Figure 2.1 A Typical Pure Component Pressure — Temperature Design, saturated solid. Consider a quantity of fluid contained in a constant pressure container at any point along the line FHC. Changing the energy content of the system, with no change in temperature, will cause a change in the relative amounts of saturated vapor and liquid or saturated vapor and solid. It energy is removed from the system vapor will be “condensed” to liquid or solid. Energy addition will cause the ‘amount of vapor to increase. Should the amount of energy transferred to or from the system be large enough to cause complete vaporization or condensation, the system will move into either the superheated vapor or subcooled liquid region. The final temperature will be higher (energy added) or lower (energy removed) than the saturation point temperature, [An understanding of the critical point Is of vital importance if one is to properly understand hydro- ‘carbon behavior as demonstrated by phase diagrams. For a pure component the critical temperature is defined as that temperature above which liquid cannot exist. The eritical pressure Is the vapor pressure ‘exerted by the pure component at its critical temperature. At the critical point (or within very close prox- imity) the “vapor” and “liquid” phases have identical properties — density, molar refraction, enthalpy, etc. ‘One cannot use properties differences to distinguish between the two phases. The optical properties of hydrocarbons near the critical point change dramatically: fluorescence is observed; the materials become opalescent; a beam of light (like a laser) is scattered. Properties like these can be used to deter- mine the critical point for pure hydrocarbons. However, for most of the higher molecular weight hydro- ‘carbons the critical point is calculated (by one of several methods) not measured. The higher molecular weight hydrocarbons will decompose {thermally crack) at temperatures well below the critical temperature. Consider now the effect of moving from point E to point A as shown in Figure 2.1, i.e., moving from Te to Ta at constant pressure. Point E is located such that the material will be solid at Te. As the temperature is increased, the solid-liquid equilibrium line will be crossed. At the pressure-temperature conditions 2-2described by the solid-liquid equilibrium line and line E-A, (Point G) the substance will become liquid. If the temperature Is increased further along the line EA, the vapor-liquid equilibrium curve will be reached (Point 8). At the temperature-pressure condition described by Point B, the liquid will be transformed fo ‘the vapor state, Further increases in temperature will produce a superheated vapor, '1.a constant temperature process is considered (such as defined by the line J-K-L) the system will in- itially be in the superheated vapor region. When the pressure Is increased to Px vapor will begin to condense, the dew point. As energy is femoved to maintain a constant temperature, more and more liquid will form. During this two-phase time beriod one has both a saturated liquid and saturated vapor present. Finally, ail of the vapor will condense and only saturated liquid Is present. Further increase toward P, will produce a sub-cooled liquid. For a pure component system line HC is both the bubble point curve and dew point curve of the system (as well as the vapor-liquid saturation and vapor pressure curve). For a pure component all four terms are synonymous. Figure 2.2 shows another form of the phase diagram, the Pressure-Volume diagram. This particular diagram does not show the solid region, but lines of constant temperature are shown. CRITICAL POINT SATURATED VAPOR PRESSURE TWO PHASE REGION VOLUME Figure 2.2 A Typical Pure Component Pressure — Volume Diagram,‘The two paths described earlier are shown on this diagram to illustrate the effect of crossing the vapor-liquid equilibrium curve, points G -B, -B, -A and J - K, - K, «L. As the temperature is increased to Tx the saturated liquid curve is encountered at point B,. From points B, to B, the phase and volume of the system change at constant temperature and pressure. This change in volume corresponds to point A shown in Figure 2.1. Similarly moving along path J - K, - Kz - L causes a constant temperature and pressure phase and volume change in the region Ky - K:- While not shown or evaluated in this discussion, energy must be transferred to or from the system to accomplish the pressure-temperature-volume changes. Methods for evaluating these energy changes will be discussed later. MULTICOMPONENT PHASE BEHAVIOR Multicomponent phase behavior is much more difficult to describe than pure component phase behavior. The pressure-temperature diagram for a multicomponent system depends on the molecular species present and the relative concentration of each species. A pressure-temperature diagram for a typical natural gas is shown in Figure 2.3. The nomenclature used to describe multicomponent phase behavior is also shown. DENSE PHASE CRICONDENBAR 2 | suacoouo RETROGRADE 2) view REGION \\ | g 1 Z SUPERHEATED CRITICAL POINT N VAPOR CONSTANT, SATURATED LIQUID hKcRICONDENTHERM SATURATED TWO PHASE REGION VAPOR ‘TEMPERATURE, Figure 2.3 Phase Envelope For A Typical Natural Gas Mixture. Notice the differences between Figures 2.1 and 2.2: (a) for the multicomponent system the saturated vapor pressure-temperature curve does not coincide with the saturated liquid pressure-temperature curve; the dew point (or saturated vapor) temperature is different from (greater than) the bubble point (or saturated liquid) temperature. For the pure component system, the saturated liquid and vapor temperatures were identical at a given pressure; (b) a saturated vapor (liquid) can exist above the critical point of a multicomponent mixture. This phenomenon infers that at least a part of the mixture can be li- ‘quefied (vaporized) at temperatures above the critical temperature. This is impossible in pure component systems, 2-4The ericondenbar of a mixture.is the maximum pressure that the dew point envelope reaches. Mathematically, this maximum pressure can be described as( @ Pay! 27) = 0.. The cticondentherm is the maximum temperature that the dew point curve reaches. It can be defined as a( 8Typ! @P) = 0. The loca- tion and magnitude of the cricondenbar and cticondentherm are dependent on the molecular species pre. sent and the relative concentration of each species. The cricondentherm for natural gas systems can range between -140°C (230°F] and about 400°C [700°F]. The magnitude and location of the criconden- therm can be important in engineering calculations depending on the product quality specifications. For example, if the product specifications call for the maximum hydrocarbon dew point temperature to be less than a designated temperature at any pressure, the cricondentherm will have to be located. The loca- tion of the cricondentherm can be predicted quite reliably using modern methods for predicting ther- modynamic properties. Other than for the examples cited, location of the cricondenbar and criconden- therm may need only to be qualitative for establishing process conditions and determing the method of performing equilibrium calculations. The classical definition of the critical point for a pure component — the temperature above which the system cannot be liquefied at any pressure — clearly does not hold for multicomponent mixtures. In- stead of using this definition, the critical point is defined as that temperature-pressure combination at which the properties of the dew point vapor and bubble point liquid phases become identical. (it also can be considered as that temperature-pressure combination above which all of the mixture cannot be quetied.) The properties considered are the optical, thermodynamic, compositional and transport proper- ties. Experimental determination of the critical point of mixtures is difficult. However, the approximate critical point (15°F, 10°C; #30 psia, 200kPa) can be predicted using the thermodynamic property prediction methods available today, ‘The true critical point of a mixture cannot be predicted by using Kay's mole fraction average (pseudo- critical) value rules: (2.1) PL = zy; P (2.2) Values of the critical temperature and pressure predicted by these equations are not the true critical Point. In tact, the critical point predicted by Equations 2.1 and 2.2 is not in any way related to the true Critical properties of the mixture. Critical temperatures and pressures predicted by Equations 2.1 and 2.2 are valuable in that they permit convenient determination of selected thermodynamic properties from generalized correlations. Further, the true critical point, as predicted by the thermodynamic property cor- Felations, must not be used with generalized correlations of thermodynamic properties, since most of the correlations are based on critical temperatures and pressures predicted using Kay's rule, Kay's rule is one of many so-called combination rules used to combine the properties of each molecular species in a mixture in an attempt to find some overall characteristic of that mixture. The values obtained are called pseudocriticals and are denoted by a prime in this book to denote it is not a true critical. Remember .. . he word “pseudo” means “fake.” Figure 2.4 compares the value of pseudocritical temperature calculated. by Equation 2.1 with ex- perimental values of the true critical 2.7. The differences do not seem drastic, particularly on an absolute temperature basis for comparison. Figure 2.5 shows the same comparison for critical pressure and Equa- tion 2.2. The compositional effects on critical pressure are significant and clearly show that Equation 2.2 does not come close to predicting the true critical pressure of the mixture. in general, the further apart the boiling points of the components in the binary mixture, the more dramatic the differences between the pseudo critical values predicted by Equations 2.1 and 2.2 and the true critical values for the mixture. 2-5200 Critical Temperature, °F 3 ° 8 * 8 -200 ° 20 40 60 80 100 Mole Fraction Propane Figure 2.4 Composition — Critical Temperature Diagram For A Methane — Propane Binary. 2-6Critical Prescure, peia 1400 8 1000 800 600 20 Figure 2.5 Equation 2.2 40 60 80 100 Mole Fraction Propane Composition — Critical Pressure Diagram For A Methane — Propane Binary.Better selection of processing conditions is the only justification for locating the true critical point of the mixture. imagine the difficulty of trying to separate a liquid phase from a vapor phase if the den- sities of the two phases are equal — gravitational effects cannot be used. In a few high temperature 200°C (400°F] high pressure 3000kPa [400 psia] distillation columns, true critical point conditions can be ‘approached. If the true critical point ever actually occurs in a column, the column will not operate because vapor and liquid phases have the same density. Consequently, knowledge of the true critical point of a mixture can be important in analysis of operational equipment and selection of design condi tions. The authors have encountered several situations in which process conditions were quite near or at the critical point of the multicomponent stream being processed. For these cases, pseudocritical condi- tions would have led to completely erroneous conclusions. Notice that a dense phase region is shown above the critical in Figure 2.3. This is a region where the mixture has the visual properties of gas but possesses physical properties somewhere between a liquid and gas. if one increases the pressure on a liquid (at constant temperature) there is no evident phase change as one begins to enter the dense phase region. The liquid just begins to lose its usual visual pro- perties and then becomes invisible (like a gas). What one is witnessing is a molecular rearrangement, AS a consequence, correlations for ordinary liquids and gases do not apply rigorously. Significant effects on the shape of the pressure-temperature envelope can be observed for varying concentrations and types of molecular species present in mixtures. Some envelopes for typical process and reservoir fluids are shown in Figure 2.6. Recognize that the pressure-temperature envelopes shown are only representative shapes to Illustrate the range of pressure-temperature envelopes that can be ob- tained. Small changes in the composition or molecular species present can dramatically alter the shape of any of the illustrations in Figure 2.6. These illustrations must not be used to estimate the shape of the pressure-temperature envelope for any given mixture. The pressure-temperature envelope for a specific mixture can be accurately constructed from careful analysis, and a combination of high quality ex- perimental data using a reliable method for predicting thermodynamic properties. ‘The location of the critical point along the pressuretemperature envelope is a function of the molecular species present and the relative concentration of the individual species. Figure 27 shows the potential range of critical point locations along the pressure-temperature envelope. The theoretically possible range for the critical is from Point A to Point D. The practical possible range Is from Point A to Point C for naturally occurring mixtures. Relatively lean natural gas reservoir systems (mol percent methane greater than about 80%) and typical natural gas process streams will have critical points located between Points A and B. As the reservoir fluid becomes richer (i.e. contains more propane, bu- tanes, pentanes and condensate or crude oil) the critical point will shift from Point A toward Point B or C. Point C probably would be representative of most crude oil reservoir fluids. One of the most poorly understood phenomena in vapor liquid phase behavior is that of retrograde condensation and/or retrograde vaporization. “Retrograde” simply means backwards, or the reverse of normal. Retrograde behavior in a multi-component system comes about because of the location of the true critical point for the mixture and the manner in which the bubble point and dewpoint lines are separated from each other. A typical multi-component system phase envelope with a retrograde region is shown in Figure 2.8. The retrograde region in Figure 2.8 is that section of the pressure-temperature diagram which falls to the right of the true critical point for the mixture. In this region changes in pressure and temperature do not yield the same type behavior as described for pure components. Increasing the temperature at constant pressure may cause liquid to condense. Increasing the pressure at constant temperature may cause liquid to vaporize. This cannot happen for pure component. Consider the constant pressure process described by line 1-2 in Figure 2.8. At point 1 the mixture is sub-cooled (undersaturated). At Point A the first liquid begins to vaporize (bubble point). Between Points Aand G a two-phase mixture exists. At Point G all liquid has vaporized. As one continues toward Point 2 the vapor becomes super-heated. 2-8ROCE: UID: Bor pia for pia 45 700 100 1500 8 sl j i & = g Ny-CHy CHa Cos Hg" Cole MIXTURES C3Hg mixtures co ~ 200 TEMPERATURE ~80°F - 2 TEMPERATURE 50°F rio 80° 10° ¢ Bars sia remperature Envelopes $40 2000 For Various Mixture: ¥ g CHy-nC gH.» MIXTURES 2 Lats 200 ‘TEMPERATURE 200° F - BO 100° c RESERVOIR FLUIDS Bor paid | wixrupes Bor pia 400 6000 | CONTAINING 180 3000 60% CHg 18% C74 ¢ g 28% Coy To 8 BI cols 3 = &| ey TEMPERATURE - ° Fi00 TEMPERATURE (450° F 71380 240ec 2-9PRESSURE PRESSURE Figure 2.7 ‘TEMPERATURE Possible Critical Point Locations Along The Pressure — Temperature Envelope. RETROGRADE, REGION ‘TEMPERATURE. Figure 2.8 Retrograde Behavior. 2-10This is the general situation so long as line 1-2 is above the critical and below the cricondenbar. The specific behavior between Points A and G will depend on the position of line 1-2 with relation to the quality lines. These represent a condition where the ratio of vapor to liquid is constant. Four such quality lines are shown dashed in Figure 2.8, The closer the line is to the dew point curve the more the amount of vapor. Ii line 1-2 is above where the quality lines exhibit reversed curvature (as shown), consider what will happen between Points A and G. AS one proceeds to the right of A, the line intersects the first quality line shown. When one reaches B, the intersection with the second quality line, more liquid is present in the two-phase system. Thus liquid was produced by heating — the reverse of normal. As one proceeds to the. right of B the liquid formed will be revaporized. W line 1-2 ts low enough in the phase envelope this retrograde behavior will not occur. Another manner in which retrograde behavior can occur is shown by line 3-4 on Figure 2.8, The ‘material is originally in the single phase dense fluid region at Point 3. As the pressure is reduced isother- mally, condensation will begin when the two-phase envelope Is reached at Point D. Further decreases in Pressure will cause increasing amounts of liquid to form until some point between D and F is reached, After this further decreasing the pressure to Point F will cause vaporization of the liquid that had been formed. Further decreasing pressure to Point 4 will result in the formation of a super-heated vapor. This type of behavior is frequently found in condensate reservoirs and in gas gathering lines. Retrograde behavior can be accurately predicted using a judicious combination of high quality ex- Perimental data for the system and any of the better thermodynamic property prediction correlations available today. The type and amount of experimental data required and effective use of the thermo- dynamic property correlations will be discussed and justified in later chapters. For now, accept the state- Ment that thermodynamic property prediction correlations can be used with a limited amount of experi- mental data to predict retrograde/phase envelope behavior over a wide range of temperature-pressure Conditions. The key to this is the proper amount of data and a proven technique. Application Of Phase Behavior To Practical Problems ‘Two problems from the authors’ experience are given here to illustrate the use of phase envelopes in the solution of problems in natural gas processing. Example Problem 2.1 ‘A natural gas is being planned for re-injection. Two different plans are being considered. One plan involves. locating a compressor station near the source of the gas and recompressing the gas to some intermediate pressure for transmission to the final reinjection site where the gas will be compressed to the final ‘e-injection pressure. The second plan involves using only the compressor station near the source of the gas, but the gas will be compressed to a pressure that delivers the gas to the re-injection site at required re-injection pressure. The phase envelope and pressure-temperature profiles of the two pipelines for the two plans are shown in Figure 2.9, What are the advantages/disadvantages of either plan? Obviously, the “plan 1 — pipeline” will be in two-phase flow throughout the length of the pipetine, while the “plan 2 — pipeline” will be in single phase flow throughout the length of the pipeline. The “plan 1 — pipeline” is a lower pressure pipeline while the “plan 2 ~ pipeline” is a small diameter pipeline. Which alternative is the “best”? Only a detailed analysis of the ‘economics and risks associated with each plan can give the final answer. However, if the “plan 1 — pipeline” had been designed dry, without knowledge of the phase envelope, the line would have been severely undersized, Example Problem 2.2 ‘The fuel gas for a set of gas turbines is being transported from a field separator to the location of the tur- bines via a pipeline. The pipeline is about 15 miles (25 km) long. The separator operates at about 4.0 MPa [580 sla] and 50°C{120°F}; the pressure drop in the pipeline and associated control equipment is about 2.7 MPa [390 sia]. A small scrubber to remove pipeline scale, dust, etc, is located just upstream of the gas turbines. The gas turbines have a terrible maintenance record; the blades are being burned out with high frequency. What Is the problem? ‘The phase diagram for the fuel gas and the pressure:temperature profile of the pipeline are shown in Figure 2.10. Clearly, the fuel gas is in the two-phase region at the inlet to the gas turbines. Gas turbine blades may be burned if the fuel gas has too high a Btu content, or if the gas contains liquids, The gas turbines must be receiv- ing entrained liquids and the small scrubber must be replaced with a more effective separator. 2-11PRESSURE PRESSURE Figure 2.9 Figure 2.10 PLAN 2 PLAN I ‘TEMPERATURE, Phase Envelope For Example 2.1. PIPELINE PROFILE ‘TEMPERATURE Phase Envelope For Example 2.2. 2-12‘SUMMARY Summarizing this subject is risky. Many hours could be spent discussing the nuances, theory and practical application of phase behavior to natural gas systems. The information presented here only scratches the surface of the complete subject. However, we believe that you have been given a reasonable overview of the subject and sufficient exposure to the value of knowledge about phase behavior to provide a basis for further discussion. REFERENCES (14) Katz, 0.L, 0. Cornel, R. Kobayashi, F.H. Poetiman, J.A. Vary, J.P. Elenbaas and C.F. Weinaug, “Handbook of Natural Gas Engineering”, McGraw-Hill, 1959, 2-133 THERMODYNAMIC PROPERTY PREDICTION METHODS Thermodynamic property prediction methods are among the most basic tools of engineers practic- ing in the gas processing industry today. Most, if not all, of the calculations pertormed, whether manually or by computer, are based on some method of predicting one or more of the thermodynamic properties — volume, Gibbs free energy (fugacity), enthalpy, and/or entropy. As a result, many have said that the thermodynamic property prediction methods represent the heart of process simulation, regardless of the manner of calculation. A good understanding of the methods of predicting thermodynamic properties is required to be able to fully utilize, and properly interpret, results of the calculations. A part of the understanding must deal with how the various properties are predicted, some of the potential hazards of using various correlation methods, and some of the problems encountered in solving the various equations. In the following discussion, major emphasis will be placed on current computeriz- ed methods of predicting thermodynamics. Campbell -1 has an excellent review of the hand calculation methods and their application to gas processing problems. BASIC THERMODYNAMIC PROPERTY EQUATIONS. The thermodynamic properties of most interest to gas processing engineers are volume, K values (fugacity, Gibbs free energy), enthalpy changes and entropy changes. All of these properties can be predicted from equations of state with varying degrees of accuracy. The equilibrium constants, or K values, are simply defined as the ratio of vapor and liquid composi- ions: Ke yy (3.1) ‘The Gibbs free energy is a property of particular importance because it can be related to the equilibrium state and at the same time can be expressed as a function of temperature and pressure: 4G, = -SdT + VP (3.2) If Equation 3.2s applied to an ideal gas it becomes: dG; = RTdInP (3.3) It we now define a property such that Equation 3.3 will apply for all gases under all conditions of temperature and pressure: dG, = RTd(In (3.4) f, is called the fugacity of component “i” and has the units of pressure. If Equation 3.4 is integrated for an ideal gas: f, = oP (3.5) is aconstant and for an ideal gas is equai to 1.0. For real gases the only condition under which the gas will behave ideally is at zero pressure. This can be expressed as: 3-11000 100 10 Figure 3.1 Illustration of the Path of Enthalpy Change. 3-4Entropy calculations are handled in exactly the same fashion as enthalpy caiculations. A two-step procedure involving the isobaric effect of temperature on entropy and the isothermal effect of pressure on entropy is utilized. The isobaric effect of temperature on entropy is assumed to occur at a low pressure (zero, one atm) and is calculated by: bea (3.20) The isothermal effect of pressure on entropy can be calculated by: - Si (2A ov (3.21) s Equation 3.21 is equivalent to: s-s° ql Po St rtyyin (FE /Pyg) - aH/RT ~ o[p2| (3.22) re Equation 3.22 is more convenient if K value and enthalpy departure calculations are being carried out at the same time the entropy calculations are being performed, One other term must be considered, the en- tropy of mixing: Six = “PY 8 Y4 (3.23) Combining all these terms in proper algebraic fashion yields the entropy change of the system in going from the ideal gas to the real gas state. The mathematical manipulations required to transform a given equation of state into the appropriate equations for predicting a specific thermodynamic property are beyond the scope and intent of this, manval, These techniques can be found in any one of several good mathematicsithermodynamics texts. However, we have summarized the pertinent equations for four of the currently available methods in Tables 3.1 through 3.4. The basic equation of state plus appropriate equations for predicting fugacity and enthalpy departures along with the mixing rules are given in these tables. Review of the fugacity and enthalpy departure prediction equations in Tables 3.1 through 3.4 indi- cates that the volumetric properties of the mixture must be known before the property can be calculated. Consequently, the basic equation of state must be solved for the appropriate volumetric property (either molar specific volume, or density, or compressibility factor) before predicting the requisite thermody: namic property. This means that the property prediction calculation consists of a two-step procedure: (1) solution of the appropriate equation of state; (2) prediction of the requisite thermodynamic property. Ob- viously, the solution of the basic equation of state must be reliable if thermodynamic properties are to be predicted. EQUATION OF STATE SOLUTION METHODS, ‘The objectives of any equation of state solution method are the reliable and acourate prediction of the volumetric properties of the fluid mixture under consideration. As simple as these objectives may seem, there are many pitfalls and hazards in these solution techniques. Among these pitfalls are: (1) de- termination of the “wrong” solution; (2) imprecise solution of the equation. Consequently, we feel that a good understanding of the solution methods and some of the problems that can occur during the solu- tion of the equations is necessary to be able to recognize, diagnose and correct improper results, 3-5 oseTABLE 3.1 Soave — Redlich — Kwong Equations L i 2 i bi ing, = BL (Z-1)-in(Z-B)-- [ Seah 2] in (1+ 8) Z>-Z? + (A-B-B*)Z-AB = 0.0 a= tacalP Bzebl; beDy,b; R272 T i RTci_ i RTE b= &, “Bs ays 042747 “BH Qy= 0.08667 ; a28= 1+ m; (1-799) = 0.5 ,0.5 ,0.5 .0.5()_ (aca) = LEK agi® ag? af® af? (1-k;;) 0.5 0.5 Po? (1-k;)) n & Xj) Goi Ae] Si (aca),=TABLE 3.2 chao — Seader Equations K = YN ee Vv ey log u, = do+ 7 +d2Ty +a3T? +agT? + (ds +g Ty +a,77)P + (Ag+ Tr) - log Py + w, fayot SE + yeT +049 (P; -0.6) | gt g Ir) Fe ~ log Fr + Wi [Gio* “FE— * Gia Ir tig thr “VU. Iny, 2 ythicbnl Sm)° In g¥ = (Z-1) =e - in(Z-BP)- = — el Az lh 2° 3h aa) n= Ps asDAy;s B= DBY A2 [ 28 Bi a, =| 04278. ]°°. 9 . 0.08667 : Pei Tit 4 Tri PeiTABLE 3.3 BWRS Equations RT + (B,RT- A, ~CyfT? + Do/T?~E,JT*) 0 +@RT-a-d/T)p? + a(e+djT) p* tep?/T* (1 +0?) exp (07). B, * Ex;Byy b= EEE ab 00," : We, eee aan Aer BER A Mo Mky) a9 BEES a Sees CBE CNC yt ky? am BEES, 30,1! 0y Pay a the sh, Bx,3,7)! Px EEX, x x4 1h pee Pe 7 Cepia oo Dy = BEX a Day! Dy! Mk Fd = BEE yd)" pte thay ys Beaty Mey M4) Hen? p (BRT A, -4C,/T*# $0,/7° -66,)7*) 411298 (20RT 3a 4a) #11508 a(6a + Tal) sett? (3-6 +12 veh Ow) $59 -Z5jRln 7px) - pB,R + 2C,/7?-30,/7* +48 /75)- 1/29" (oR + 4/7?) + 1iSpSad/T? + 2efyT? (1-1 +1/26*7] exp 70" RT laf, = RT In (DRT) + 9B, * BRT Pop? A-kyp ego? a re ag sh ag yu 2244p") ah (sage 1M T 5 f T + (o£) way (seat a ( an r wt 4) & )"f-nlo-r7TABLE 3.4 Peng — Robinson Equations RY a Pe Sob” Vierbyeb Ob) 2 ~ (1-p)224(acb?-25)2-(AB-B*-3*) = 0.0 > 20 x,a 4 A Pk bay gg HR AB, and, = GE @-D = tnl2-B) - Ey MS) ne Tda a ail he eae > naxx 5 ae risa a..oja,)(i-k,.) Ae ei8ei i") 45 ja b= tx,b Be 0.45724 Eeteh Pe rt 7 0:07780 5 iThe overall solution procedure used to determine the volumetric properties of a fluid system is il- lustrated in Figure 3.2. These steps are summarized below: 1. Fix the system state (vapor or liquid) com- position, temperature and pressure. select the 2. Calculate constants for the equation of composition, phase state. 1, P to use 3. Solve the equation for the volumetric prop- erty. When dealing with two phase systems, the equation of state must be solved twice - once for the liquid and once for the vapor, The com- Select prover constants position of the two phases will be different (ex- caleulate the cept in the case of pure components or multi- Paraneters of the component systems at their critical point) so equation of state the equation of state constants will have to be evaluated for both the liquid and vapor phases. Most equations of state are, or can be, rearranged into a cubic equation. The excep: tion is the BWR equation of state and Its deriva- tive equations (BWRS, SHEWR, Orye BWR, etc.), However, as far as can be determined, the of state for the BWR equation behaves as a cubic equation in proper value the P-V-T plane of interest. Those equations which are cubic equations can be solved by either direct cubic solution procedures or by Figure 3.2 Overall Equation of State trial and error approaches. The BWR based equations can be solved only by trial and error. Solution Procedure There is no direct solution procedure for the BWR equation of state. solve the equation Cubic equations of state will yield the behavior shown in Figure 3.3a when the system under consid. eration is in the two phase region and that shown in Figure 3.3b when in the single phase region. The ‘sketches shown are independent of the equation of state being considered. If the system is in the single phase region, there is no possibility of determining the wrong value of the compressibility factor (or the molar volume). Solution techniques for the single phase region are relatively straightforward and not prone to error. However, when the system is in the two phase region, there are three values of the ‘compressibility factor that will satisfy the equation of state. Which of these values is correct? The answer, of course, depends upon whether you are dealing with ‘a vapor phase or liquid phase system. The value of Z at the compressibility factor equal to S (in Figure 3.3a) is a spurious root (solution) and is of no practical value. Consequently, the solution procedure must be told which root is being sought and must be constrained to totally eliminate the possibility of deter- mining either of the other roots. Direct cubic equation solution procedures offer this reliability. Trial and error methods do not unless special provisions are programmed into the solution procedure. Selection of a method of solution for equations of state depends on many factors. If the speci ‘equation of state is a cubic equation either a direct cubic equation procedure or atrial and error approach can be used. If the equation of state is not a cubic equation, only the trial and error approach is effective. ‘The major asset of the direct cubic solution is that the procedure will always yield a proper solution to the ‘equation. The liability of the direct cubic solution is that it witl occasionally yield bad solutions for the liq ‘quid phase compressibility factor on certain computer systems. (This comes from the manner of solution of certain trigonometric relations within the computer.) Consequently, we recommend a trial and error solution for cubic equations of state. In addition to being more reliabte (when properly programmed) than the direct cubic solutions, the trial and error solution procedures are usually about 5% faster than the direct cubic solution procedures. 3-10£(2) £(2) > ‘Two Phase Region Single Phase Region Figure 3.3 Typical Behavior of Cuble Equations of State. Throughout this book we will represent calculation procedures by logic (block) diagrams similar to Figure 3.4. These diagrams are a simple representation of the different steps involved. The nomenclature: in this book is as follows: — an instruction in the algorithm ‘Caaaeae> — a decision step @ —_~ vos (an answer toa decision ster) ® ~ no (an answer to a decision step) The word algorithm refers to the mathematical representation of the system being examined. Thus in Figure 3.4 one has a series of instructions starting at the top. Finally, one solves the equation of state. Then a test is made (in the first decision step). Subsequent steps then depend on whether the answer is yes or no. A logic diagram for a trial and error solution procedure for cubic equations of state is given in Figure 3.4, This diagram shows a traditional Newton-Raphson arpoach with an interval halving limiting pro- ‘cedure superimposed on it. We have used this approach successfully on several cubic equations of state with excellent success. Incorrect or inappropriate values of the compressibility factor have never been calculated. Several of-the steps in the procedure deserve additional comment, particularly the pro- ‘cadures for locating the boundaries of the liquid and vapor phase compressibility factor in the two phase tegion, For purposes of this discussion, assume that the equation of state is given by Equation 3.24 and that we do not know if we are in the single or two phase region. Bitte: Z +A +82+C=0.0 (3.24) where A, B, are arbitrary constants. From Figure 3.3 in the two phase region the equation of state will have a maximum and a minimum or two points at which the stope of the equation is zero. The value of the compressibility factor at the maximum defines the largest possible value for the liquid phase compressibility factor. If Equation 3.24 is differen- tiated and set equal to zero, the following equation results: 3-11Enter with T, ?, y phase specified Set up necessary constants Solve for equation of state constants Set temporary limits for 2(2, zl) three root condition Single or three root condition Select proper Z limits & reset temporary value (zh, 2U) one root. condition ‘Assume start value of ZI Solve equation of state for £(z) & £7(2) culate and tore required constants Replace lower limit Figure 3.4 Block Diagrams for Equation of State Solution.7 +s B- 0.0 (3.25) Solving Equation 3.25 for the values of Z at the maximum and minimum gives: (3.26) {f the algebraic expression under the square root sign is negative or zero, only one real value of the com- pressibility factor will satisfy the equation of state. If however, the value of the expression under the radical is positive, three real roots exist and limits for the vapor and liquid phase compressibility factors can be determined from Equation 3.26. The solutions to Equation 3.26 represent the value of Z at the max- Imum and minimum points of Figure 3.a. The value of the maximum will represent the largest possible value for the liquid compressibility factor and the value at the minimum represents the smallest possible value of the vapor compressibility factor. These limits can then be used with arbitrary values for the other limit to assure that the root obtained is the valid one. The limits thus set up are adjusted at the end of each iteration to narrow the interval of search. ‘These limits are used only if the Newton-Raphson procedure attempts to predict a next trial value of the compressibility factor that is beyond the limits. When this occurs, the average value of the limits is used. This procedure may seem redundant and unnecessary. However, our experience has shown that in exceptional cases this boundary limitinglinterval halving procedure is required to get the proper solution to the equation of state. If an equation of state like one of the versions of the BWR equation is being used, direct solutions are impractical and trial and error calculations (usually Newton Raphson approaches or modifications of the Newton Raphson) are used. Further, the limits of the liquid and vapor roots of the equation in the two phase region cannot be conveniently determined. An implicit approach can be used to determine if the correct root is being determined. The sign of the first derivative can be checked. If the first derivative of the equation of state is negative, the solution procedure is probably searching in the area of the spurious, root and will yield the spurious root as a solution. This slope determination procedure can be used in con- junction with a boundary limits procedure to qualitatively fix the limits for acceptable solution but the protection against finding the wrong root is not as positive as the approach described earlier. ‘Why all this concern about such a mundane item as finding the correct root of the equation of state? ‘The answer is very simple ~ if an incorrect or imprecise root is found, the predicted thermodynamic pro- periy will contain substantial errors. Figure 3.5 gives some qualitative examples of the errors that we have observed when using direct cubic solutions on one of the Rediich Kwong equations of state. At some temperature, pressure, composition conditions spikes in the K value and enthalpy curves were observed. If the calculations in the regions of the spikes had been buried in a process simulator, no one would have observed the faults and serious errors could have been made in a process designievaluation, Changing to the trial and error approach of solving the equation of state completely eliminated the spikes in the predicted thermodynamic properties. Fortunately, we encountered this problem early in our evalua: tion of the equation of state and have used what we believe to be sound procedures for determining the roots of equations of state. Another factor that is usually ignored in the programmingisolution of equations of state is the effect of the equation of state parameters on the predicted thermodynamic properties. Most of the current equa tions of state use at least two of the critical properties (To, Po, Zc, Pe, Va) and the acentric factor to predict the parameters for the equation of state. Changing any one of these parameters slightly can cause significant variation in the quality of the predicted results, A recent proprietary K value prediction evalua- tion study showed that simply changing from one program version of the Soave Redlich Kwong to other versions caused a 10% - 18% variation in the predicted amount of liquid formed in a series of flash calculations. Certainly, differences in programming techniques used in the equation of state solutions contributed to these discrepancies, but there were also small differences in the critical properties and 3-13og K log P IN Figure 3,5 Typical Effect of Errors In Compressibility Factor Calculations. log P ah acentric factors used in the solution. As a result, when someone says that his company is using the XXX method of predicting thermodynamic properties, you have no guarantee that the quality of results Predicted by that method in their specific program will be similar to programs developed by other com. Panies or individuals. You must know the details of the solution procedure and the parameters use the solution procedure to completely assess the expected quality of predicted thermodynamic properties from any program. Other Thermodynamic Property Predictions Very few problems are encountered in the prediction of the various other thermodynamic properties if the proper roots to the equation of state are found. This statement is contingent on three qualifications. 1, The mathematical manipulations on the basic equations have been correctly performed. 2. The programming of the equations is correct and the proper parameters are used. 3. The particular method is not being extrapolated beyond its range of applicability. The most probable cause for the breakdown of any thermodynamic property prediction procedure is the last item above, extrapolation beyond the range of applicability of the equation of state. To define Precisely the range of applicability of a given correlation is difficult. Too many factors — mainly composi- tion, temperature and pressure — have a high level of interaction which preclude citing the correlation limits as being X-Y °C [°F] and Q-Z kPA [psial. Consequently, we always recommend that you thoroughly evaluate any thermodynamic property prediction procedure before using it or adopting it as a company standard. EVALUATION OF THERMODYNAMIC PROPERTY PREDICTION PROCEDURES Campbell (97) has expressed the problems faced by the users of thermodynamic property prediction ‘methods most eloquently: “Those who specialize in the K value (thermodynamic property prediction) area generally have a favorite method (often theirs) which they promote with all the fervor of a religious zealot. The net result is a somewhat chaotic series of claims that might (and does) confuse more than help.” To- day, there are about five methods of predicting thermodynamic properties that are in wide spread usage. Each method has its own list of devotees. All of the methods have their liabilities and assets and only 3-14you, the user, can determine which method best suits your requirements. Two avenues are available for your evaluation of a thermodynamic property prediction procedure. 1. Perform the evaluation yourself (or by the appropriate group within your company). 2. Rely on the evaluations performed by an unbiased by trusted individual outside your company (If that animal exists in captivity). Evaluation of thermodynamic property prediction procedures is an expensive, time consuming operation. However, compared to the potential losses through poor designs, inefficient operations, etc., the evalua~ tlon costs become trivial. When evaluations are performed within a company, specific regions of interest can be defined and properly explored — while the individual outside the company can evaluate only the data available to him. By performing your own evaluation you get information specific to your regions of interest, while the outside evaluator provides you with general information only. The author or purveyor of a thermodynamic property prediction method is probably the poorest individual to rely on for an unbiased evaluation of a method. That individual is seeking to publish or sell a method. What would you do? Publicize the shortcomings of your method? Certainly not. Consequently, we always recommend in- house evaluations of thermodynamic property prediction methods coupled with judicious use of outside evaluations. 4. What is the response of the proposed method around the regions of interest, i.e., critical point, cri- condenbar, cricondentherm, etc.? What is the form of the equations in the method? 2. Are you concerned with an extremely good agreement between experimental and predicted re- sults (fit) over a narrow range of temperature-pressure conditions? 3. Are the component parameters for the equation of state readily available? 4, How far can the procedure be extrapolated and still yield reliable results? 5. Are the size of the program, rel concern to you? bility of the method and execution time of the program of any 6. What accuracy of fit do you expect and will the particular method yield that accuracy? Since no one method can simultaneously be fast, require minimum amount of core, predict extremely ac- Curate thermodynamic properties, offer good prediction around the critical, etc., you will always be faced with compromises. The following discussion offers some guidelines that we have tound successful in answoring the above questions. Let us first consider the form of the thermodynamic property prediction method. Is the same equa- tion of state applied to both the liquid and vapor phase (a single equation of state approach), or are there separate (and different) equations of state for the liquid and vapor phase (a split equation of state ap- proach)? Erbar (2.12;has summarized the characteristics, and attributes of the single and split equation of state approaches. This summary is presented in Table 3.5. To better define the semantics of split and single equations of state, let us use an example of each approach. The Chao Seader method (Table 3.2) is a split equation approach. The Soave Redlich Kwong (Table 3.1), Peng Robinson (Table 3.4) and BWRS (Table 3.3) are examples of the single equation of state approach which yield relatively slow running times but reliable and reasonably accurate methods of predicting thermodynamic properties over a broad range of temperature-pressure-composition condl- tions. The accuracy of the single equation of state is generally limited by the number of parameters that can be adjusted to fit the avallable data. (On the other hand, the split equation of state can yield a relatively fast method without convergence problems that can be quite accurate for a limited range of temperature-pressure-compcsition, The major impact of the equation of state form will be on the anticipated accuracy requirements and reliability! extropolatability of the correlation. The number and availability of the required component parameters (To, Po. Ze. & » 816.) required to use a particular equation of state is critical in gas processing calculations. Most of the systems to be considered will involve a fraction heavier than n-pentane called the Cg.(or C7) fraction. The informa tion usually available for this fraction does not include such exotic properties as dipole moments, critical 3-15oe Characteristic Approach to the Mixture Critical Discontinuities of Pre~ dicted K Values Programming Attributes Number of Parameters required Sensitivity to initial estimates, Calculational Problems Introduction of New Components Flexibility in Fitting Data Accuracy Execution Time TABLE 3.5 Characteristics of Split and Single Equation of State Approaches. Single Equation of State Response usually good, may approach ‘too East! Properly programmed, none easy to program, generally requires wore sophisticated equilibrium cal- culation convergence routine depends on method, if generalized three or four parameters required initial phase composition usually required, very sensitive to initial estimates if generalized usually quite easy; not generalized, data required Rot much ~ restricted to single equation with binary system adjustment parameters generally good, including critical region generally slow ~ depends on number of constants, number of roots in equation of state Split Equation State Response usually poor, will overshoot critical point will occur in region of critical, 1£ liquid State described by two different equations frequently occurs at break point for equation wore difficult to program, generally requires simpler equilibrium calculation convergence routines depends on method, generalized methods usually require five or more parameters initial phase composition not needed, usually not too sensitive to initial estimates if generalized, may be easy or not depending on required parameters, not genetalized data required as much as required - number of constants can be varied as needed generally excellent, except critical region depends on region of fit, number of parameters, ete. generally fast, depends on nunber of constants and vapor phase equation of stateproperties, etc. These properties must be estimated from the known properties of the fraction. If a large umber of parameters is required, the equation of state is essentially useless in gas processing calcula. tions since the Gg + fraction can have a profound effect on the predicted thermodynamic behavior of a natural gas stream. As a consequence of these problems we prefer generally to use equations of state based on a minimum number of pure component parameters, but we are willing'to predict certain para- meters such as the critical properties. Size, reliability and running speed of the program are usually not of much concern in well conceived, properly constrained programs, These factors may be of concern when implementing a particular proce- dure on a mini computer or if a large number of components (greater than about 30) is to be considered. Generally speaking, the single equations of state will be slower but require less core space than the split equation of state approach. The final consideration is the accuracy of the thermodynamic property prediction procedure. The ac- curacy must be assessed by comparing the predicted results with high quality experimental data, Unfor- tunately, most of the literature thermodynamic property data available for the light hydrocarbon com- ponents are of doubtful quality. Consequently, one of the evaluation steps must include an assessment of the quality of the data that are available — a difficult and frustrating problem since there are no magical or mathematical methods which say that a given data set is good or bad. This assessment step requires experience, intuition and judgment. ‘The second step in the evaluation of thermodynamic property prediction procedures is the actual evaluation step itself. K value evaluations can be carried out in one of two ways 4. Use the experimental composition in the appropriate equations and predict the K values directly. 2. Perform a flash calculation on a feed mixture at the specific experimental conditions. K values will be predicted on the basis of the predicted phase compositions rather than the experimental compositions. ‘The first method of evaluating K values is quite common. It is a convenient and economical evaluation method. However, the procedure does not yield a fair basis of comparison since the phase compositions are not unknowns as they are in real life applications of the procedure. The second approach is the most ‘expensive and difficult method of evaluation. However, itis the most representative of the actual applica- tion of the thermodynamic property prediction procedure. In our opinion, the second method of evalua- tion is the only one that should be used in spite of the problems involved in performing the evaluation, Based on our experience, the second approach usually gives larger errors in the predicted-experimental K value comparison than will be found in the first method, The magnitude of the relative errors between the two methods will depend on the temperature-pressure-composition range and is Impossible to generalize. Evaluation of the other thermodynamic properties of interest — volume, enthalpy, entropy — is not particularly difficult once the requisite experimental data are available. These comparisons simply re quire the composition-temperature-pressure and experimental value. The appropriate values are “plugg- ed" into the appropriate equations and a direct comparison can be made. In any evaluation of the thermodynamic property prediction procedure, we do not recommend that you use plant data or systems containing Gg + fractions. Plant data are always of doubtful quality be- cause of carry over, non-equilibrium conditions, etc., plus the profound effect that the C,+ fraction can have on the predicted thermodynamic property (particularly K values). We certainly recommend an overall evaluation of the thermodynamic property prediction procedure on operating systems after the quality of the procedure has been established using good experimental data. However, we would not attempt to use plant based K values or enthalpies to establish the quatity of the correlation, Interpretation of the results of thermodynamic property prediction procedure evaluations also re- quires some judgment. Large errors (+ 50%) can usually be expected for the heavier components in a system and in multicomponent systems (more than three components). The very lightest components (nitrogen andlor methane) can be expected to have errors as large as 20-30%. The middle boiling range ‘compounds (like ethane to pentane) can be expected to have errors ranging trom 6 to 10%. The reasons for the large errors in the lower and higher boiling components go back to experimental problems — thedifficulty of measuring the concentration of the high boiler in the vapor phase and the low boiler in the li- quid phase. Carbon dioxide and hydrogen sulfide concentrations are particularly difficult to measure by gas chromatography. We normally expect that a good correlation will yield errors in the predicted versus experimental K values of about § to 10% for most of the components between methane and decane but are not surprised if the errors approach 15 to 20% for the heavier components. Enthalpy and entropy comparisons usually are best carried out using enthalpy or entropy departure comparisons. Compare the predicted and experimental isothermal effects of pressure on the desired pro: perty, The comparison should be carried out in single phase regions to avoid the complicating effects of phase behavior on the enthalpy or entropy. We normally expect differences between experimental and predicted isothermal enthalpy departures of 2.3-5.8 kJikg [1.0-2.5 Btu/Ibm] and about 0.04 kJ/kg K [0.01 Blu/Ibm -°R] for entropy departures. In the region of the critical point, larger enthalpy errors are to be ex- pected 12-35 kJ/kg [5-15 Btu! Ibm). In summarizing this section, we must emphasize the necessity for evaluation of any thermodynamic property prediction technique; that the evaluation be carefully and properly done using the best available data and finally compared with plant performance. These evaluations are not cheap, but the potential return on a reduction of errors, etc., far outweigh the cost of performing the evaluation. Evaluations per- formed by others outside your company should always be considered suspect until you have verified the particular work. ‘SELECTING A THERMODYNAMIC PROPERTY PREDICTION PROCEDURE Some companies and engineers select a thermodynamic property prediction procedure with all the feason and forethought exhibited by a child selecting a piece of candy or a new toy. A new correlation should be capable of predicting all the requisite thermodynamic properties. Further, a variety of correla- tions should not be used in a given process simulation unless there is good justification for switching Correlations. The main objective here is to maintain consistency in thermodynamic property predictions. Not maintaining thermodynamic consistency can lead to inadequate designs or improper analysis of operating problems, A further recommendation is that when changing thermodynamic property predic- tlon procedures, always determine the impact of that change on the estimated distillation/absorber co! umn tray efficiences, compressor, pump and turbo-expander efficiencies. We encourage the develop- ment of a bank of operating data for distillation/absorber columns, compressors, etc., to be used in establishing a revised set of “standard” efficiencies for use with the new correlation, Remember that as you use a correlation, you develop a sixth sense about the reliability of the correlation, where to adjust its results, etc. When you change correlations, the entire learning process must be repeated. We always recommend against capricious change of thermodynamic property prediction pro- cedures for the reasons outlined above, Change only when you have thoroughly evaluated the correlation and the consequences of the change. We are not against change for valid reasons, but be sure the reasons are valid. ‘SUMMARY In this chapter, we have attempted to lay the foundation for the development of thermodynamic pro- erty prediction procedures and some of the problems in the use, application and evaluation of the tesulting correlation. Many pages could be, and have been, written regarding these procedures, conse- quently only an overview has been provided. We are firmly convinced that only by understanding the origin of the equations, the problems involved in using the equations and overall techniques can you ef- fectively use or interpret the results of any thermodynamic property prediction procedure. Recognize that these comments are applicable to the currently available correlations. They may be, but are unlikely to be, invalidated by future correlations or improvements in computer systems.NOMENCLATURE LIST pressure absolute units molar volume, or moles of vapor temperature, absolute units vapor liquid equilibrium constant for any component defined by Eq. 3.2 ‘mole fraction of any component in the vapor phase mole fraction of any component in the liquid phase molar enthalpy molar specific heat of a fh orle tt) {gas constant in appropriate units moles of fluid molar entropy compressi arbitrary constants critical temperature, absolute units 'y factor critical pressure, absolute units critical compressibility factor Greek Symbols o P= Subscripts 4i= 1425 abe = ref = mix = Superseripts en 2 (@ 90 oa o

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