GAS CONDITIONING AND PROCESSING VOLUME 4: GAS TREATING AND SULFUR RECOVERYBP (OIL EXPLORATION) COMPANY OF NEW ZEALAND LiMiTED, P.O, BOX 892 WELLINGTON NEW ZEALANDGAS CONDITIONING AND PROCESSING VOLUME 4 GAS AND LIQUID SWEETENING ans | By J 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 and Bound in the U.S.A.TABLE OF CONTENTS Chapter Page 1, INTRODUCTION ...- +--+ + Toxicity of hydrogen sulfide, 6; gas specifications, 7. 2. BASIC PROCESS PRINCIPLES ©... 1 2 eee ee ee eee ee 13 Basic dimensions, 13; mass and energy balances, 16; fluid flow, 18; 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. 3. AMINE PROCESSES 2 6 1 ee ee ee ee ee 59 Monoethanolamine (MEA), 62; diethanolamine (DEA), 63; triethanolamine (TEA), 63; diglycolamine (DGA), 63; diisopropanolamine (DIPA), 64; methyldiethanolamine (MDEA), 64; solution concentrations, 65; corrosion, 71; solution degradation, 71; foaming, 75; amine reclaiming, 75; filtration, 76; foam inhibitors, 78; corrosion inhibitors, 79; imlet scrubbing, 79; amine losses, 79; filtration, 79; amine~amine HEX, 81; amine regeneration, 81; piping design, 84. 4. AMINE PROCESS CALCULATIONS . © 6-6 ee eee ee ee ee ee 87 Shortcut calculations, 87; monoethanolamine, 94; diethanolamine, 105; factors affecting MEA performance, 1153 stripper design, 118; ethanolamine--acid gas equilibrium, 120. 5. CARBONATE PROCESSES 2 2. we ee ee ee ee eee ee 19 Reactions, 129; split-stream process, 133; two-stage process, 133; other process modifications, 135; process choice, 136; corrosion, 137; CO, absorption calculations, 138; Gatacarb process, 143; Benfield“process, 146; DEA~-hot carbonate, 146; Giammarco-Vetrocoke proccesses, 147; seaboard process, 152; vacuum carbonate process, 154; tripotassium phosphate process, 155; sodium phenoline process, 157; alkazid process, 158; hot carbonate--acid gas equilibrium, 159. 6. PHYSICAL ABSORPTION METHODS. . 2. - 6 ee ee ee ee ee ee 169 Water absorption, 169; Fluor solvent process, 173; 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 a 8. LIQUID SWEETENING. 2... ee ee ee 9. SULFUR PRODUCTION. .... 2.2.20. SOLID BED SWEETENING »... 1 eee. eee Page Se ee ee ee 25 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. pee eee ee ee OAL 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. Se ee ee ee ee 267 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, 2843 Shell sulfolane process, 288; Freeport sulfur process, 288; Claus process, 288; Amoco process, 2943 summary of Claus reactions, 297; selectox process, 306. 10. TAIL GAS CONDITIONING... 2... eee ee eee eee eee 818 INDEX . . ASR sulphoxide process, 320; U. $. Bureau of Mines citrate process, 320; Westvaco process, 321; Sulfreen Process, 322; IFP process, 323; Aquaclaus process, 325; cold bed adsorption, 327; Weliman-Lord process, 328; LUCAS process, 332; Allied $0, process, 333; Pritchard "Cleanair" process, 334; Beavon process, 335; Shell Claus off-gas treating process, 336; Flue gas desulfurization (FGD), 338. APPENDIX 1 -- CONVERSION FACTORS ....... wee ee ee ee eee 840 APPENDIX 2 -- MEA, DEA and DGA PROPERTIES»... 2... ee ee ee ee (346LIST OF FIGURES Figure 1.1 Western world sulfur consumption by end use. -.-. +--+ + oe 1.2 U.S. sulfur production trends. 2... eee ee ee ee ee tee 1.3 U.S. sulfur supply/demand... 2 ee ee ee ee ee we ee 1.4 Sulfur recovery from natural gas. . 6 ee ee ee ee wee 1.5 Removal of carbon dioxide only «ee see eee ee ee ee wae 1.6 Removal of hydrogen sulfide only .....--- rary wee 1.7. Simultaneous removal of He$ and C07... eee ee ee et ee wee 1.8 Selective removal of HS 1 1 ee ee ee ee ee 2.1 Density of MEA solutions .... 2... see ee eee eee ees 2.2 Density of DEA solutions ..- 2. see ee eee see 2.3 Friction factor as a function of Reynolds Number .... + . 2.4 Viscosity of aqueous MEA solutions as function of weight percent “MEA” 2.5 Viscosity of aqueous DEA solutions as function of weight percent DEA 2.6 Nomograph for finding line pressure loss . . 6 ee ee ee eee 2.7 Density of aqueous DGA solutions «6... ee ee ee ee ee oe 2.8 Viscosity of aqueous DGA solutions «1... ee ee ee ee ee ee 2.9 Pump horsepower requirements . - ee eee ee ee ee we ae 2.10 Nomograph for estimating overall heat transfer coefficients . rrr 2.11 Generalized correlation of the fugacity function in the form of a fugacity coefficient. ....-..-- be ewes 2.12 Absorption factor chart... - +s. eee De 2.13 Compressibility factors for natural gas... 1 ee ee ee ee ee . 2.13a Compressibility factors at low reduced pressures .. --. + + + . . 2.13b Compressibility factors for gases near atmospheric pressure... .. - 2.14 Pseudo critical temperature adjustment factor, c¢, °R - + es sees 2.15 Water content of saturated natural gas (at its water dew point) . 2.16 Effective water content of saturated hydrogen sulfide in natural gas, systems... ee ee ee ee os 2.17 Effective water content of saturated carbon dioxide in “natural” gas” mixtures. . 2. i rs se 8 Water content of natural gas mixtures... . - eee pene 9 Water content of natural gas mixtures... eee ee eee eee 0 Water content of natural gas mixtures... +22. ee eee tee Chemical structural formulas for alkanolamines “of interest in gas sweetenimg . - -. - 2 ea ee Se ee ee te 2 Process flow for typical “ethanolamine sweetening unit... eee wae 3 Flow sheet of split-stream amine process ..... - ar we 4 MEA process flow sheet showing typical temperatures . 5 DGA process flow sheet showing typical temperatures 6 Normality of aqueous amine solutions .....+.- 7 pH of MEA solutions at various temperatures... « 8 PH of DEA solutions at various temperatures... 9 l L L 1 1 1 pH of DGA solutions at various temperatures»... + ee eee tee 0 Effect of acid gas loading on pH of MEA solutions ......-. wee 1 Graded bed activated carbon filter «6 6 eee eee ee ee 2 Deep bed activated carbon filter «2. ee ee ee ee ee 3 Series installation of filters .. « ce ee see 4 Typical temperature distribution in an ‘amine reboiler so. ee 5 Temperature profile across the wall of an amine firetube ....... iiiFigure Page 4.1 Density of MEA solutions as a function of temperature and concentration 88 4.2 Nomograph for estimating MEA circulation rate... . See eee 88 4.3 Graphical determination of amine circulation rate. .........4 90 4.4 Amine contactor size required. ...... ew et ee ee ee 92 4.5 Amine plant cost (1977 dollars)... 2... Se ee ee 93 4.6 Equilibrium data for H2S and 15.3% MEA at 40°C with CO2 present... . 94 4.7 Equilibrium data for H2S and 15.3% MEA at 60°C with COs present... . 95 4.8 Equilibrium data for HS and 15.3% MEA at 100°C with COz present .. . 95 4.9 Equilibrium data for H2S and 15.3% MEA at 120°C with C02 present .. . 96 4.10 Equilibrium data for COz and 15.3% MEA at 40°C with H2S present... . 96 4.11 Equilibrium data for CO2 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 H2S present ... 97 4.13 Equilibrium data for CO? and 15.3% MEA at 120°C with H2S present . . . 98 4.14 MEA treating limitations . rs 99 4.15 Trends showing expected C02 retention ‘in MEA solutions eee eee . 99 4.16 Typical MEA contactor temperature profile wee ee ee eee eee 100 4.17 Mutual solubility data for H2S and COz in 2.0N DEA at 50°C .. 1... 106 4.18 Mutual solubility data for HoS and CO in 2.0N DEA at 50° .. 1... 106 4.19 Mutual solubility data for HoS and C05 in 2.0N DEA at 100°C... 1... 107 4.20 Mutual solubility data for H2S and cos in 2.0N DEA at 100°C... .. . 107 4.21 Mutual solubility of HgS and COp in 3.5N DEA at 50°C ......... 108 4.22 Mutual solubility of HS and COp in 3.5N DEA at 50° 7... . wees 108 4.23 Mutual solubility of HoS and CO> in 3.5N DEA at 1007... 2... 1. 6109 4.24 Mutual solubility of Hes and toe in 3.5N DEA at 100°C... . rr) 4.25 Effect of acid gas composition and temperature on the Viscosity of MEA solutions 2. ee 15 4.26 Effect of acid gas composition “and temperature on the specific gravity of MEA solutions... 2... ee ee eee ee eee 116 4.27 Effect of acid gas composition and temperature” on the pH of MEA solutions ...... a 117 4.28 Kent and Eisenberg comparison of calculated and experimental “gata for HoS - MEA equilibrium... ... 2... see 123 4,29 Kent and Eisenberg comparison of calculated and exper imental “gata for COg - DEA equilibrium... 1... . eee soe ee ee 123 4.30 Predicted and experimental values of partial pressure of co eee) 124 4.31 Predicted and experimental values of partial pressure of 138 wee 125 5.1 Equilibrium pressures of H20 vapor over K2C03 solution ...... oe 131 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 .........- ». 135 5.6 Equilibrium partial pressures over solutions of potassium carbonate ~. 136 5.7 Nomograph for calculation of COg absorption... .. 2... 2.024 139 5.8 Nomograph for calculation of COj absorption... . 2... 2... e ee 140 5.9 Nomograph for calculation of C0j absorption... 2... ee ee eee 141 5.10 Nomograph for calculation of COp absorption. .......-..05 » + 142 5.11 Selection guide to obtain specified gas purity ............- 143 5.12 Effect of contamination on activity of carbonate solutions ...... 145 5.13 Activity of catalyzed carbonate solutions... . 2... eee eee ee) 145 5.14 Flow sheet for DEA-Hot carbonate process ......--- wees 145 5.15 Comparison of C02 absorption in G-V and hot carbonate Solutions wee ew 148 iv