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