[BR (OIL EXPLORATION) COMPANY OF NEW ZEALAND LiMiTED, P.O. BOX 892 WELLINGTON. NEW ZEALANDGAS CONDITIONING AND PROCESSING VOLUME 4 GAS AND LIQUID SWEETENING By ROBERT N, MADDOX Leonard F. Sheerar Professor 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 programs 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 4 GAS AND LIQUID SWEETENING Third Edition No part of the text or original figures may be reproduced in any form without written permission of the publisher, except for bona fide reviews of the book for general publication. Library of Congress Catalog Card No.: 73-91966 First Printing, April 1982 Published by: Campbell Petroleum Series 1215 Crossroads Blvd. Norman, Oklahoma 73069 Printed ané Bound in the US.AChapter TABLE OF CONTENTS INTRODUCTION... - Toxicity of hydrogen sulfide, 6; gas specifications, 7. BASIC PROCESS PRINCIPLES... 1... eee eee eee eee es B Basic dimensions, 13; mass and energy balances, 16; fluid flow, 183 pump power, 31; heat transfer, 33; vapor-liquid equilibrium, 38; absorption and stripping, 41; vessel sizing, 43; gas P-V-T behavior, 45; water content, 51. AMINE PROCESSES... . . Moncethanolamine (MEA), 625 diethanolamine (DEA), 635 triethanolamine (TEA), 63; diglycolamine (DGA), 63; diisopropanolanine (DIPA), 64; methyldiethanolamine (MDEA), 64; solution concentrations, 65; corrosion, 715 solution degradation, 71; foaming, 75; amine reclaiming, 753 filtration, 76; foam inhibitors, 78; corrosion inhibitors, 79; inlet scrubbing, 79; amine losses, 795 filtration, 79; amine~amine HEX, 61} amine regeneration, 81; piping design, 84. AMINE PROCESS CALCULATIONS . 22... eee eee ee ee ee ee 87 Shortcut calculations, 87; monoethanolamine, 945 diethanolamine, 105; factors affecting MEA performance, 1153 stripper design, 118; ethanolamine-~acid gas equilibrium, 120. CARBONATE PROCESSES ©. ee eee ee ee ee ee 129 Reactions, 129; split-stream process, 133; two-stage process, 133; other process modifications, 135; process choice, 136; corrosion, 137; CO, absorption calculations, 138; ¢atacarb process, 143; Benfield’process, 1463 DEA~~hot carbonate, 146; Gianmarco-Vetrocoke proccesses, 1473 seaboard process, 152; vacuum carbonate process, 154; tripotassium phosphate process, 155; sodium phenoline process, 157; alkazid process, 158; hot carbonate--acid gas equilibrium, 159. PHYSICAL ABSORPTION METHODS . . . . see 169 Water absorption, 1693 Fluor solvent process, 1735 equilibrium data for propylene carbonate, 176; Selexol process, 180; Rectisol~Purisol processes, 189; Estasolvan process, 198; other physical solvents, 201; power recovery turbines, 211.Chapter 7. SOLID BED SWEETENING ©... 22... eee eee ee ee ee Iron oxide (sponge) processes, 215; molecular sieves, 221; mercaptan removal, 226; EFCO process, 227; formation of carbonyl sulfide, 235; chemsweet, 237; NCA process, 239; slurrisweet, 239. LIQUID SHEETENING © oe ee eee eee ee eee ML COS removal, 241; hydrogen sulfide removal, 245; amine Process, 246; molecular sieve processes, 247; doctor treatment for mercaptans, 249; caustic wash, 249; regenerated caustic wash, 251; unisol process, 256; mercapsol process, 257; tannin solutizer process, 258; dualayer process, 258; prediction of mercaptan removal, 258; mercapex process, 261; copper sweetening, 261; solid copper treating, 263; Merox process, 263; Bender process, 265. 9, SULFUR PRODUCTION. 2. ke ee ee ee ee ee 287 Liquid oxidation chemistry, 274; Ferrox process, 275; Gluud process, 276; Manchester process, 276; Stretford A.D.A. process, 277; Takahax process, 281; Thylox Process, 281; Perox process, 283; Giammarco-Vetrocoke process, 284; Shell sulfolane process, 288; Freeport sulfur process, 288; Claus process, 288; Amoco process, 294; summary of Claus reactions, 297; selectox process, 306. 10. TAIL GAS CONDITIONING. 2... ee eee ee eee eee 8B ASR sulphoxide process, 320; U. S. Bureau of Mines citrate process, 320; Westvaco process, 321; Sulfreen process, 322; TFP process, 323; Aquaclaus process, 325; cold bed adsorption, 327; Wellman-Lord process, 328; LUCAS process, 3325 Allied $0, process, 333; Pritchard "Cleanair" process, 334; Beavon process, 335; Shell Claus off-gas treating process, 336; Flue ges desulfurization (Hep), 338. APPENDIX 1 -- CONVERSION FACTORS 2... eee ee eee ee ee eee ee 340 APPENDIX 2 -- MEA, DEA and DGA PROPERTIES... 2... 1... ee ee ee 806 INDEX Soi te cee dty Pre eet ee eee eeeeead paeeetne ett a70:LIST OF FIGURES Western world sulfur consumption by end use... . ~~~ aieeeiee U.S. sulfur production trends... . 1. U.S. sulfur supply/demand... 2. : Sulfur recovery from natural gas. . +.) eee ee ee eee te Removal of carbon dioxide only... ee eee ee eee Removal of hydrogen sulfide only... . « eS eee eae cance Simultaneous removal of HS and COp-- ++ ee eee ee Selective removal of HS ee ee ee ee eee ee ee Density of MEA solutions ©. - sll lscvseecerereee Density of DEA solutions . see... wee ee ee pee ee Friction factor as a function of Reynolds Nunber Peeieaare Viscosity of aqueous MEA solutions as function of weight percent MEA Viscosity of aqueous DEA solutions as function of weight percent DEA Nomograph for finding line pressure loss. - + eee eee ee eee Density of aqueous DGA solutions .... +. esse eee eee Viscosity of aqueous DGA solutions .....- SHEESH eH Pump horsepower requirements «s+ + ee ee ee ee eee ee Nomograph for estimating overall heat transfer coefficients . 2... Generalized correlation of the fugacity function in the form of a fugacity coefficient... eee ete tee eee Absorption factor chart . . 2. 6 ee ee ee ee ee ee Compressibility factors for natural gas 27. eee 1 Compressibility factors at low reduced pressures... ... +. += Conpressibility factors for gases near atmospheric pressure»... Pseudo critical temperature adjustment factor, c, °R see ww ee Water content of saturated natural gas (at its water dew point) . Effective water content of saturated hydrogen sulfide in natural gas” systems 2... 2... See eefeeeeettereeisteede ae teat ttetec Effective water content of saturated carbon dioxide in natural gas iiisetupestactenrte aistea tists eeu re ueiiseceistenatiscee eee area rae tee Water content of natural gas mixtures... 0. ee ee eee ee Water content of natural gas mixtures... ee ee ee ee Water content of natural gas mixtures...) ee eee eee Chemical structural formulas for alkanolamines of interest in gas sweetening. ee ee Seer eee Process flow for typical ethanolamine sweetening unit... 2... + Flow sheet of split-stream amine process «1. eee eee eee NEA process flow sheet showing typical temperatures»... 5. se DGA process flow sheet showing typical temperatures... .... : Normality of aqueous amine solutions ... +... s eee pH of MEA solutions at various temperatures... . +. + + pH of DEA solutions at various temperatures... ... - pH of DGA solutions at various temperatures... . Effect of acid gas loading on pH of MEA solutions . . . « ‘ Graded bed activated carbon filter... +--+ eee rene Deep bed activated carbon filter»... 5-2 essa 5 Series installation of filters . 6-0 ee eee ee ee ee Typical temperature distribution in an amine reboiler Temperature profile across the wall of an amine firetubePage Density of MEA solutions as a function of temperature and concentration 88 Nomograph for estimating MEA circulation rate... ss... eee 88 Graphical determination of amine circulation rate... 111. 10.~« (90 Amine contactor size required... .... Bie reise eee eine 3 Amine plant cost (1977 dollars). at 93 4 Equilibrium data for HyS and 15.3% MEA at 40°C with COp present...) 94 4 Equilibrium data for H2S and 15.3% NEA at 60°C with COp present |... 95 4 Equilibrium data for HS and 15.3% NEA at 100°C with COp present... 95 4 Equilibrium data for H2S and 15.3% NEA at 120°C with CO2 present... 96 4,10 Equilibrium data for C02 and 15.3% MEA at 40°C with H2S present... 96 1 Equilibrium data for COz and 15.3% MEA at 60°C with H2S present... . 97 4.12 Equilibrium data for C02 and 15.3% MEA at 100°C with HS present... 97 4.13 Equilibrium data for COz and 15.3% MEA at 120°C with H2S present 11. © 98 4.14 MEA treating limitations ....... 0... Piscreeratieree etic ia areas HH#EHOO: 4.15 Trends showing expected CO2 retention in MEA solutions... 11... 99 4.16 Typical MEA contactor temperature profile. .............. (100 4.17 Nutual solubility data for HS and C02 in 2.0N DEA at 50°C... + 106 4218 Mutual solubility data for HoS and COp in 2.0N DEA at 60°C 11... 106 4:19. Mutual solubility data for HoS and COp in 2-0N DEA at 100% ||) 1). toy 4:20 Mutual solubility data for Hs and COp in 2.0N DEA at 100°C |)... 107 4:21 Mutual solubility of Hos and/COp in 3-5N DEA at 0°... 2.1... 108 4.22 Mutual solubility of HgS and COz in 3.5N DEA at 50°C 2.222122. 108 4:23 Mutual solubility of HS and COp in 3.5N DEA at 100°C |). 109 4:24 Mutual solubility of HoS and COp in 3.5N DEA at 100°C |. 22). og 4.25 Effect of acid gas composition and temperature on the viscosity of MEA sOlutiona/jectaisesaeecienierer iets ae ee eererieteceeess ea 4.26 Effect of acid gas composition and’ temerature on the specific gravity Of MEA solutions... eee eee eee ee ee ieee eet pmereeeec) 4.27. Effect of acid gas composition and temperature on the pH of MEA SOUubsons ites terse tater eee ora ciiietecsitesidees eats tuttet yy 4.28 Kent and Eisenberg comparison of calculated and experimental data for HS - MEA equilibrium... . Pepe eorciernicne + 123 4.29 Kent and Eisenberg comparison of calculated and experimental data for Op = DEA equilibrium se ee ee ee ee ee 123 4.30 Predicted and experimental values of partial pressure of (0p... . 124 4.31 Predicted and experimental values of partial pressure of mall te 125 5.1 Equilibrium pressures of H0 vapor over KzC03 solution... ... .. I 5.2 Schematic flow diagram for a conventional hot carbonate process... . 133 5.3 Schematic flow diagram for a split-stream hot carbonate process... 134 5.4 Schematic flow diagram for two-stage hot carbonate process ...... 134 5.5 Reducing steam consumption with ejectors ..........- 2+ 1S 5.6 Equilibrium partial pressures over solutions of potassium carbonate |. 136 5.7 Nomograph for calculation of COz absorption... 2... eee ee es 139 5.8 Nomograph for calculation of COz absorption. +... 2.222... 10 5:9 Nonograph for calculation of (Op absorption |... 1... ..5552~ Ul 5:10 Nonograph for calculation of COs absorption |. 1... ssl .se 1. (ae 5.11 Selection quide to obtain specified gas purity’. . sere eens 5.12 Effect of contamination on activity of carbonate solutions | 11... 145 5.13 Activity of catalyzed carbonate solutions... +++ +e eee ee ee 145 5.14 Flow sheet for DEA-Hot carbonate process»... 1... te 2. M5 5.15 Comparison of COz absorption in G-V and hot carbonate solutions... . 148 ivFigure Page 5.16 G-V process with steam regeneration... 2. ee ee ee eee ee 150 5.17 G-V process with air regeneration... . . anaes ate 5.18 Basic flow sheet for the Seaboard process». +... ee eee ee 183 5.19 Basic flow sheet for vacuum carbonate process... 2... ++ + 185 5.20 Basic flow sheet for tripotassium phosphate process... . 2... ++ 186 5.21 Equilibrium vapor pressure of HS over 50% and 20% tripotassium phosphate solutions»... ee ee ee tt ee ee . 187 5.22 Schematic flow diagram for Alkazid process... 1... D158 5.23 Equilibrium partial pressures of HS and CO over Alkazid solutions . . 160 5.24 Rate of absorption of HS and CD2 in Alkazid solutions ........ 162 5.25 Partial pressure of CO over 20% equiv. Kp003.---- +--+ e+e e+ 163 5.26 Partial pressure of C02 over 30% equiv. K3C0}.-- +. 1 ee 163 5.27 Partial pressure of C02 over 40% equiv. K2003..... 6. sae 164 3128 Partial pressure of COs over 30% equiv. KsC03 with total loading | |) lea 5.29. Partial pressure of COS over 40x equiv. KoC03 with total loading... 165 5130 Partial pressure of Hos over 30% equiv. KSCO3 with total loading |. . 165 5.31 Partial pressure of HpS over 40% equiv. KsCOy with totai loading | | 166 6:1 Typical water wash flow sheet. ss swe S peepee) 6.2 Calculated performance of water wash unit)... eee eee ee ee 122 6.3 Typical fluor solvent process for synthesis gas treating ....... 174 6.4 Equilibrium constants for carbon dioxide in propylene carbonate... . 179 6.5 Equilibrium constants for hydrogen sulfide in propylene carbonate... 179 8.6 Solubility of C0 in DMTES containing 1.5, 2.5 and S% Hgd . . .. . «180 6.7 Solubility of CO2 in DMPEG containing 1.5%H20 .........+.. 180 8-8 Pikes Peak carbon dioxide renoval plant... Peeeone eee alist 6.9 Selexol process for a gas with a high C02 to HzS ratio. pene 183 6-10 Selexol process for a gas with a low COz to H25 ratio . tee 188 GO greene eae teeeosa tic teesteitatie east EC aa eee eS e 6.12 Gas solubiiities in Seiexol 1112 T IIIT I! see 6.13 Flow sheet for Selexol plant treating Sour gas with high HS... . 186 6.14 Mitchell plant selexol unit... see ee ee eee eee ee ee 188 6.15 Equilibrium constants for carbon dioxide in selexol ss... ee ee 188 6.16 Equilibrium constants for hydrogen sulfide in selexol......... 189 6.17 Basic flow sheet of Purisol process... see eee eee 190 6.18 Vapor-liquid equilibrium diagram for M-Pyrol-water system at atmospheric Presa iseeeditisescre cress gereeise uate ateeeatictCateeteatteietatsareadasteesteeO? 6.19 Solubility of sulfur compounds and COg in M-Pyrol ss... eee ee 193 6.20 Solubility of paraffin hydrocarbons in M-Pyrol «es. ee ee ee. 193 6.21 Vapor-liquid equilibrium values for sulfur compounds and COg in M-Pyrol at atmospheric pressure . 2... . See ceite lier eee eeeeie 19m 6.22 Vapor-Viquid equitibrium values for paraffin hydrocarbons in M-Pyrol at atmospheric pressure... 2... : secaie tiered 6.23 Correlation of equilibrium values for ethane and heavier hydrocarbons in M-Pyrol at atmospheric pressure... eee eee eee ee 195 6.24 Relationship between "Kk" values and solute vapor pressures in M-Pyrol . 195 6.25 Flow sheet of Rectisol process for HgS and C07... .- +. +++ ++ 196 6.26 Equilibrium curves for COz in various washing agents ......... 197 6127 Basic Estasolvan process for renoving H2S . sss «ss cvs ts 199 6.28 Estasolvan process for simultaneous recovery of hydrocarbons and sweetening. 2... eee ee see ieee saree dates ele etiart Pedieren 99Figure Page 6.29 Equilibrium chart for natural gas components in MCA... . 2... ++ 202 6.30 Equilibrium chart for natural gas components in MCA... 2.12] pgp 6.31 Equilibrium chart for natural gas components inMCA... 2... 1.) (202 6.32 Equilibrium chart for natural gas components in MCA . Bee eee eee e202 6.33 Equilibrium chart for natural gas components in MCA... 1.1. (303 6.34 Equilibrium chart for natural gas components in MCA... +.) 203 6.35 Equilibrium chart for natural gas components in MCA... 2... 2. (203 6.36 Equilibrium chart for natural gas components in MCA... 2+... (203 6.37 Equilibrium chart for natural gas components in MCA. >>)... ) (203 6.38 Equilibrium chart for natural gas components in MCA... 2) 11) 2 (204 6.39 Equilibrium chart for natural gas components in MCA... 11... (208 6.40 Equilibrium chart for natural gas components in MCA... 1... 204 6.41 Equilibrium chart for natural gas components in MCA... 11). 204 6.42 Graphical solution of absorption factor equation... +... 2... .~« 206 6.43 Solubility characteristics of physical and chemical solvents |...) 207 6.44 Solubilities of several gases in SepasolvMPE...........~, + 208 6.45 Vapor pressure for several physical solvents»... 211. 208 6.46 Equilibrium water partial pressure over Sepasolv MPE.. 7...) 1) 209 6.47 Sepasolv MPE schematic flow sheet... 1... ee el) 209 6.48 Characteristic curves for constant inlet and outlet pressures of turbine SING BMD recedgece cette die eee et ates eee eee te eee eae 6.49 Application ranges for power recovery turbines 12.1... 10«: 212 6.50 Comparative performance of power recovery turbine and pump... ... 212 7.1 Typical iron oxide process flow sheet... 2... eee sll 217 1.2 Progress of stain front through iron oxide bed»... 2... 2.2. (219 2.3 Oxygen content of regenerating streams ......- Geeetaetee eee 220) 7.4 Temperature profile for iron oxide tower»... sl 220 7.5 Adsorptive capacity of molecular sieves at 25°... 2.211111) be 7.6 Adsorptive capacity of molecular sieves at 25°C... 11 1 lll) 222 7.7 Effect of temperature on adsorptive capacity of molecular sieves at atmospheric pressure... eee ee ee ee ee ee ee eBeD: 7.8 Effect of contact time on adsorptive capacity of molecular sieves a atmospheric pressure... ee ee ee 222 7.9 Effect of pressure on adsorptive capacity of molecular sieves at 25°C . 223 7.10 Schematic representation of the adsorption process .......... 224 7.11 Schematic flow diagram for a simple molecular sieve adsorptive process. 224 7.12 Adsorption of sulfur compounds on 13X molecular sieve during First Vee sie rerrecteiiiare ee tea teectisieereteliie nits Retains tutea Ee itig2g: 7.13 Desorption characteristics of sulfur from 5A molecular sieves .. 1. 2 226 7.14 One system used for removal of mercaptans....... 4. +00... 227 7.15 EFCO closed cycle sweetening process... 2. 1 et 288 7.16 Equilibrium adsorption loading of COz on 4A pellets. 2... 12. 229 7.17 Equilibrium adsorption loading of COz on 5A pellets... .......~ 230 7.18 Equilibrium adsorption loading of COp on 13X pellets... 111. 230 7.19 Equilibrium adsorption loading of Ho$ on 4A pellets... 2.2... .~ 231 7.20 Equilibrium adsorption loading of HpS on 5A pellets... ... 2... 231 7.21 Equilibrium adsorption loading of H2S on 13X pellets. 1.) 1111. 232 7.22 Adsorption equilibrium loading of Hp0 on 4A pellets... 1 1s 232 7.23 Equilibrium adsorption loading of H20 on SA... . 22.7 238 7.24 Equilibrium adsorption loading of H90 on 13X21. 1) lll 233 7.25 Comparison of experimental and calculated breakthrough times for HS on SA molecular sieve... ee ee ee ee ee 284 viFigure Page 7.26 Effluent gas concentration of COS and HyS during a cycle... . .. + 236 7.27 Perfornance of one molecular sieve product in the laboratory at 90°F amie BO seat ee reeeeeaaeeaetn eee tet eeeree eae eee ieee Hea eg) 7.28 Trisiv adsorbent... 2. ee ee ee eae ce eects 238) 7:29 Chemsweet contactor. 2). ee ee 288 7.30 Flow diagram for Slurrisweet unit 2. ee ee ee ee ee 240 &!1 Flow sheet for COS renoval with KOH and methanol | 2.2. +2. 1.2 282 8.2 Flow sheet for Malaprop process... ee ee sees eee eee es 28 813 Tarnish of copper strip as function of HS concentration |. +... + + 245 8.4 Schematic flow sheet for amine treating process ...-.-- ere seer 2NG, 8.5 Schematic flow sheet for molecular sieve process». +--+ +++ +++ 247 8.6 Flow sheet for removal of HyS with dilute caustic»... se... + + 208 8.7 Schematic flow sheet for caustic wash process... 2... + eee 251 8.8 Schematic flow sheet for regenerated caustic wash system... . REST eo2 8.9 Schematic flow sheet for a solutizer process. e+ + ee eee eee + 255 8.10 Schematic flow sheet for methanol (Unisol) process... ++... ++ + 256 B.ll Schematic flow diagram for Mercapsol process. +--+ +++ +--+ + 257 8.12 Schematic flow diagram for Dualayer process... ++ se ee ees + 259 8.13 Stripping coefficient in normal mercaptan ... +--+ +++ ++ +++ 260 8.14 Extraction coefficient in normal mercaptan. ...----- +++ +++ 260 8:15 Schenatic flow sheet for copper sweetening process «=. 6 + ss +: 262 8.16 Solid copper treating process... eee ee ce te ee ees 263 8.17 Schematic flow sheet for Merox process»... +e e+ eee see ees 264 8.18 Schematic flow sheet for Bender process... es ee eee ee ees 265 9:1 Equilibrium composition of various sulfur species in sulfur vapor at different temperatures... ee ee ee ce 268 9.2a Density of liquid sulfur in region of transition temperature... +. + 272 9.25 Density of liguid sulfur... - . - See ene anette 9.3 Viscosity of liguid sulfur... . - pees ete eee et a7e 9.4 Flow sheet for Ferrox process. ee ee eee ee ee ee es 2 9.5 Flow sheet of Manchester process 2. 0+ et ee eee eet es 276 916 Flow sheet for Peabody-Holmes-Stretford process... +++ +++ tes 280 9:7 Flow sheet of Thylox process. ee tee eee ee ee fs 283 9:8 Giammarco-Vetrocoke flow sheet for HzS removal from gases also containing C07 .. +... ++ pee eee pe ceiee eae cee ne 9.9 Giammarco-Vetrocoke flow sheet for HS removal when no C02 is available 285 9:10 Claus “once through" process flow scheme... ++ seer vee eee = 290 9.11 Typical reaction furnace and waste heat boiler... +... +++ +++ 290 9:12 Claus "split stream" process flow scheme... -- +--+ eee ees 291 9:13 Claus flow sheet using in-line burner ss ee ee ee ee ee es 292 9.14 Claus flow sheet using gas-to-gas exchanger se cea eee de ene oie 202 9.15 Claus flow sheet using two steam heaters... 2 12 ee ee + 293 9116 Claus flow sheet using gas-fired indirect heater»... ++ e+ 22s 293 9:17 Sulfur burning Claus flow sheet... . - ee see Aue Eeee Een a2) 9:18 Variation of sulfur vapor composition with temperature at one atmosphere pressure... 1. poate aerees aise s eeeeeetiate eters etetieteo 1209) 9.19 Equilibrium constant for reaction 21 ee ee ee 300 9.20 Vapor pressure of Sp(g) in equilibrium with St) aerate + 300 9:21 Vapor pressure of Sg(g) in equilibrium with S(1) 2... + +++ ++ + 301 9.22 Vapor pressure of Sg(g) in equilibrium with S(1) 6... ee eee eee 301 vii