Acid Gas Removal Text by Terry Kryska, Howard R. Morrow and Rudy Gall Program by Ray McLain Paragon Engineering Services, Inc. International Human Resources Development Corporation Boston/Houston/LondonLimited Warranty THRDC warrants that: ) the material of each software disk is not defective; ) the software is properly recorded on each disk; ) the manual contains all the information IHRDC deems necessary for use of the software; and (4) the software functions substantially as described in the Software Documentation IHRDC excludes any and all implied warranties, including warranties of merchant- ability and fitness for a particular purpose, and limits your remedy to a return of a faulty disk within sixty days after your acquisition of the software. In the United States some states do not allow the exclusion or limitation of implied warranties. 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For informa: tion, address IHRDC, Publisher, 137 Newbury Street, Boston, MA 02116Contents Acknowledgements viii About the Publisher x About the Authors x4 IHRDC Production Facility Bookware Series xii Unit Systems xiv J. Introduction 1 2. Process Description 7 21 Solid Beds 7 2.1.1 Iron Sponge Process 7 © 2.12 Molecular Sieve Processes 13 2.1.3 Zine Oxide 14 2.2 Chemical Solvent Processes 15 © 2.2.1 Amine Processes 15 2.2.2 Carbonate Processes. 25 2.2.3 Specialty Batch Chemical Solvents 28 2.3 Physical Solvent Systems 30 2.3.1 Fluor Solvent Process 32 2.3.2 Sulfinol Process 34 2.3.3 Selexol Process 36 2.3.4 Rectisol Process 36 2.4 Direct Conversion Processes 37 2.4.1 Stretford Process 37 2.4.2 IFP Process 39 * 2.43 LO-CATSulferox 41 » 2.5 Distillation 44 2.6 Gas Permeation 46 2.7 Tail Gas Treating 473. Process Selection 51 4. Design Procedure 57 41° Iron Sponge 57 42 Amine System Design 61 4.2.1 Amine Absorbers 61 4.2.2 Amine Circulation Rates 63 4.2.3 Heat of Reaction 67 4.2.4 Flash Vessel 68 4.2.5 Amine Reboiler 68 4.2.6 Amine Stripper 72 4.2.7 Overhead Condenser and Reflux Accumulator 77 4.2.8 Rich/Lean Amine Exchangers 79 42.9 Amine Cooler 80 4.2.10 Amine Solution Purification 81 42.11 Amine Solution Pumps 82 4.2.12 Materials of Construction 83 4.2.13 Procedure for Sizing an Amine System 83 Nomenclature 85 Appendix A: Equations Using SI Units 89 Appendix B: Equation Derivations 93 Appendix C: Example Problems 101 Appendix D: Software Documentation 115 Appendix B: Process Listing 131 uuAcknowledgments The following companies participated as supporters of the Production Facility Bookware Series: Abu Dhabi National Oil Company AGIP Al Furat Petroleum Company Amerada Hess Arabian American Oil Company Arco Oil and Gas Corporation The Bahrain National Oil Company Chevron Corporation Cities Service Oil and Gas Corporation Conoco, Inc Corporacion Estatal Petrolera/Ecuatoriana Kerr McGee Corporation Marathon Oil Company Mobil Oil Exploration and Producing Southeast Inc. Norsk Hydro A.S. OMV Petrofina S.A. Phillips Petroleum Company QATAR General Petroleum Company Saga Petroleum A.S. Shell Oil Company Standard Oil Production Company STATOIL Sun Exploration and Production Texaco, Inc Thai Shell E&P Company, Ltd. TOTAL C.F.P. vitTurkish Petroleum Corporation UNOCAL Corporation Union Texas Petroleum Thanks are given for their financial and technical support Their support does not constitute their approval or recommendations of the methods or procedures contained herein ixAbout the Publisher THRDC is the premier petroleum industry training company— one that emphasizes the training of technical professionals. In eighteen years of integrated petroleum experience, IHRDC has gained broad industry respect for the excellence of its many products and services. Video Library for Exploration and Production Specialists Video Library for Production Operators Instructional Programs Book Libraries Bookware Series Experts Network English Language Training Efficiency, variety, and flexibility characterize all IHRDC training products and services. Industry-oriented training, in our ever- changing environment, is the key to success. For further information on any of the above products or services, please contact: IHRDC Sales Department 137 Newbury Street Boston, MA 02116 USA Telephone: (617) 536-0202; Telex: 6817117 IHRDC B Cable: HUMDEVCO Toll-free in U.S. only (800) 327-6756.About the Authors The text and software are written by the engineers at Paragon Engineering Services, Inc., Houston. Paragon is a medium-sized, full-service company devoted to engineering design, project coor- dination, and project management for the petroleum industry. Specifically, Paragon designs and executes such projects as: pro- duction facilities and platforms, waterflood facilities, gas and liquid pipelines and their related facilities, compressor and pump sta- tions, gas plants and their related facilities, electrical generation. and distribution facilities, instrumentation and control panels, and cogeneration facilities. Paragon Engineering Services has designed facilities in the Unized States, Middle East, Far East, Africa, Latin America, and Europe for over 30 major petroleum-producing clients. Paragon engineers, many of whom have contributed to this Pro- duction Facilities Bookware Series, have an average in excess of 15 years of experience in this field. With a total staff of between. 50 and 100 engineers and draftsmen, Paragon is one of the largest engineering firms in Houston specializing primarily in production facilities and offshore platform design. Carlton T. Sikes, Lew Skaug and Kenneth E. Arnold act as series editors. Individual con- tributions are identified on the title page of each module. Inquiries to Paragon may be made to: Paragon Engineering Services, Inc. 13939 Northwest Freeway, Suite 201 P.O. Box 41207 Houston, TX 77241-1207 (713) 462-8828 * ‘TWX 9108817268 xiIHRDC Production Facility ) Bookware Series The JHRDC Production Facility Bookware Series consists of twenty-three modules grouped into six major topical areas. Each module consists of a manual, which by itself is a stand-alone reference to production equipment and its design, and an applica- tion software program for a microcomputer. These materials are published as both training and design tools for practicing engineers at all levels. Oilfield Systems and Equipment 101 Two-Phase Separators 102 Three-Phase Separators 103 Oil Treaters 104 Desalting 105 Crude Stabilization Gas Systems and Equipment 201 Acid Gas Removal Water Systems and Equipment 301 Treating Oil from Produced Water 302 Removing Solids and Dissolved Gases from Produced Water Utility Systems and Equipment 401 Fuel Systems 402 Fired Heaters and Hydrate Control 403 Heat Transfer Systems 404 Waste Heat Recovery 405 Heating, Ventilating, and Air Conditioning (HVAC) xxiiInstrumentation 501 502 503 504 505 506 507 508 Controllers and Control Theory (manual only) Pressure Instrumentation ‘Temperature Instrumentation Flow Instrumentation Level Instrumentation Control Valves Safety Shutdown Systems Wellhead Shutdown Systems Platform and Structural Design Considerations 601 602 Offshore Facilities Layout Living Quarters Layout tttUnit Systems Two systems of units are used throughout the Production Facility Bookware Series. They are the former English system of oilfield units common to the United States and the International System (SI units). In the manual, units ‘within the text are expressed as oilfield units first and as SI units second in parentheses, Numbered equations are expressed in oilfield units. The corresponding SI unit for each term in these equations is found after the correct term in the Nomenclature. The SI equation (with appropriate constants) ap- pears in Appendix D: Equations Using ST Units. Nominal values in oilfield units that are used by the American Petroleum Institute (API or by equipment manufacturers (¢.g., standard vessel dimen- sions) have not been converted The software program asks the user to specify English or SI units as its first prompt with sequential input and output appearing in the system specified. The Software Documentation expresses English units first and SI units second in parentheses. xivAcid Gas RemovalProduction Facility Bookware Series Series editors: Kenneth 8. Arnold, Lew Skaug & Carlton T. SikesL. Introduction In addition to heavy hydrocarbons and water vapor, natural gas often contains other contaminants which may have to be removed. Carbon dioxide (CO,), hydrogen sulfide (H,$), and other sulfur compounds such as mercaptans may require com- plete or partial removal for acceptance by a gas purchaser. These contaminants are known as “‘acid gases". H,S and CO, combined with water form sulfuric acid and carbonic acid, respectively, thus the term “acid gas’. Natural gas with HS or other sulfur compounds present is called “sour gas”, while gas without H,S or sulfur compounds is called “sweet”. Both H,S and CO,are undesirable, as they cause corrosion, and reduce the heating value and thus, the sales value of the gas. In addi- tion H,$ is poisonous and may be lethal, eyen in very small quantities. Table I shows physiological effects of very small concentrations of H,$ in air.Table 1 Effects of HS Concentrations in Air Percent Paris por Grains per Miligrame oy ‘iition 100 Stancerd por ube Physiological Volume by Volume __Cubie Feet™ ierer Effects ons OT 3008 O18 Obvious and wapleant odor genealy percep Shleat0 13 ppm and quite notable 46 pm AS the concenvaion increta, the sense of Smet fatigues andthe gs ean 90 longer be Seteced by odor oo 20 26 2883 Aceptabeceling concentration permied by Feder Sta standards e005 so 31s 7207 Acceptable maximum penk above the OSHA a0 ceptable ceiling concentration permite! once for TO minutes per egnehour si cre tmeasuable exposure occs oot 300 630 14414 Coughing, ex ination, fst cf sens of mel after 10115 minutes Altered respiration, pista tyes and drowsiness ater 1510 0 mines {allowed by thom ration ater one ovr ro Tonged expocore resus in a ical increase fa the eeveiy ofthese symptoms 002 200 239 268.06 Kile sense of smell py, buns eyes ane thos 00s 500 ne 72049 Dizznes, os of sense of ressoning and balance Breathing problems ina few minutes Vitis teed prompt arictlrestscation 007 700 $408 1008 55 Unconscious qulcly Breathirg wil stop and desis wil eave I not rescued promptly At- til estseaton fs needed o10+ 000+ esa 1440984 Unconsciousness at once Permanent brain “Based on 1 per = 629.77 gr!100 SCF at 14 696 psia and 59" gamage or death may result unless rescued promptly and given acificial resuscitation (or 101 325 KPa and 15%Gas sales contracts for natural gases often limit the concentra- tion of acid compounds. In the United States, typically, gas sales contracts will permit up to two or three percent carboa dioxide, and % grain per 100 SCF (approximately 4 ppm) of hydrogen sulfide. The actual requirement for any sales con- tract may vary, depending upon negotiations between seller and purchaser. Besides sales contract restrictions, several other reasons exist for the removal of acid components from natural gas streams. Among these are personnel safety, odor reduction, fuel BTU improvement and recovery of CO, components for enhanced oil recovery projects. Corrosion protection ranks high among the reasons for the removal of acid gases. The partial pressure of the acid gases may be used as a measure to determine whether treatment is required. The partial pressure of a gas is defined as the total pressure of the system, times the mole fraction of the gaseous component. Where CO, is present with water, a partial pressure of 30 psia or greater would indicate that CO, corro- sion should be expected. Factors which influence CO, corro- sion are those directly related to solubility, ic. temperature, pressure and the composition of the water. Pressure increases solubility while increased temperature decreases solubility. If CO, is not removed, inhibition and special metallurgy may be required. Below 15 psia partial pressure of CO, corrosion is not normally a problem, although inhibition may be required. The presence of H,S may cause sulfide stress cracking due to hydrogen embrittlement in certain metals. An H,S partial pressure greater than 0.05 psia necessitates treating. Figures 1 and 2 show the H,S concentration at which the National Association of Corrosion Engineers (NACE MR 01-86) recom- mends special metallurgy to guard against HS corrosion.00'001 ao (SL-10-EW (FOWN) SsoourSuy uotsoss0D fo uoprors0ssy jouoymn fo dsa1snoD) ‘warsds sv8 Suraooun ssoass apsfins | aanSpq 000'01 oot oot on 1 829 UI SH Wedd L L to" boo tooo” sep ui s*H % 10% ty ‘@NSSOId [101 YISd SOI 008 < 2 ojOay BunjaeI9 s80118 SpLiNs § oor ‘o00'0 ooo oo OL t 08 OOL Jad S*H SURED“(SL-10-UW (ADEN) Ssvour8uz uojsoss0D fo uotwrossy pouonwy fo Ksa1nop) masts pinbyysw8 Surqov.9 ssoays apifins & aanSpy 00'001 o00'ot ooo ot on 4+ Se UI SH add OL 4 4 bo 100 000" $29 Ul S*H % IOW ‘iMisSaig (EOL ViSa S92, Total Pressure PSIA woiBay Bupyaeu9 ssaNg epyInS | o00'0t ooo} oot on 1 JOS 001 48d S*H SUIEIIn the 1930’s a commercial process was developed using basic organic compounds to react with these acid components. The initial compound promoted for this use was triethanolamine (TEA). Over the years many other processes have been de- veloped to treat these acid gases. This guideline discusses the amine processes as well as several other common types of processes that have been developed. Additional processes are likely to become available with time.2. Process Description Numerous processes have been developed for acid gas removal and gas sweetening based on a variety of chemical and physical principles. These processes can be categorized by the principles used in the process to separate the acid gas from the other natural gas components. This is illustrated in Table IL The list, although not complete, represents many of the common available commercial processes. 2.1 Solid Beds A fixed bed of solid particles can be used to remove acid gases either through chemical reactions or ionic bonding Typically, in solid bed processes the gas stream must flow through a fixed bed of solid particles which remove the acid gases and hold them in the bed. When the bed is spent, the vessel must be removed from service and the bed regenerated or replaced. Since the bed must be removed from service to be regenerated some spare capacity is normally provided. There are three commonly used processes under this category: Iron Sponge Process, Molecular Sieve Process and Zinc Oxide Process. 2.1.1 Iron Sponge Process The Iron Sponge Process utilizes the chemical reaction of ferric oxide with H,S to sweeten gas streams. This process is economically applied to gases containing small amounts of H,S. Carbon dioxide is not removed by this process.Table 2 Acid Gas Removal Processes Chemical Solvent Physical Solvent Direct Conversion MEA Selexol Iron Sponge DEA Rectisol Stretford TEA Purisol Unisulf MDEA Sapasolv Takahax DIPA/Shell ADIP Propylene Carbonate LO-CAT DGA/Flour Estasolven Lacy-Keller Econamine Propietary Amine —_—Alkazid Townsend Benefield Sulfint (Hot Carbonate) Catacarb (Hot Carbonate) Giammarco- Vetrocoke (Hot Carbonate) Diamox Dravo/Still Speciality Solvent Sulfinol Amisol Flexsorb PS Selefining Ucarsol LE 711 Optisol Zinc Oxide Sulfa Check Slurrisweet Chemsweet Merox Distillation Gas Permentation Ryan Holmes Membrane Cryofrac Molecular Sieve‘The reaction of hydrated colloidal iron oxide and H,S pro- duces iron sulfide and water as follows: Fe,0, + 3H,S > Fe,S, + 3H, FeO + HS > FeS + H,0 The reaction requires the presence of water and a temperature below 120°F When temperatures exceed 120°F, careful con- trol of pH must be maintained. If the gas does not contain sufficient water vapor, water may need to be injected into the inlet gas stream. A pH level of 8-10 can be maintained through the injection of caustic soda, soda ash, lime, or ammonia with the water. pH control should be avoided whenever possible Although the presence of free alkalies enchances H,S removal, it creates potential safety hazards, promotes formation of undesireable salts and adds to capital costsManway w/Davit Platform. | Pressure Gauge Gas Inlet Relief Valve: Internal Cone Gas Outlet Manway ioe Figure 3. Iron oxide acid gas treating unit. 10 Caged Ladder‘The ferric oxide is impregnated on wood chips which pro- duce a solid bed with a large fetric oxide surface area. Several grades of treated wood chips are available, based on iron oxide content. They are commonly available as 6.5, 9.0, 15.0 and 20 Ib iron oxide/bushel. The chips are contained in a vessel and sour gas flows downward through the bed and reacts with the ferric oxide. Figure 3 shows a vessel for the iron sponge process. The ferric sulfide can be oxidized with air to produce sulfur and regenerate the hydrated ferric oxide. The regeneration step must be performed with great care as the reaction with oxygen is exothermic (i.c., gives off heat). Air must be in- troduced slowly so the heat of reaction can be dissipated. If air is introduced quickly, the heat of reaction may ignite the bed. For this reason spent wood chips should be kept moist when removed from the vessel. Otherwise, the reaction with oxygen in the air may ignite the chips and cause them to smolder. ‘The reactions for oxygen regeneration are as follows: 2Fe,8, + 30, + 2H,O > 2Fe,0,(H,0) + 6S + Heat 4FeS + 30, + 2xH,O > 2Fe,0,(H,O), + 48 + Heat S, + 20, > 280, Some of the clemental sulfur produced in the regeneration step remains in the bed. After several cycles this sulfur will cake over the ferric oxide which decreases the reactivity of the bed and causes excessive gas pressure drop. Typically, after 10 cycles the bed must be removed from the vessel and replaced with a new bed. ilIt is possible to operate an iron sponge with continuous regeneration by the introduction of small amounts of air in the sour gas feed. The oxygen in the air regenerates the iron sulfide and produces elemental sulfur. Although continuous regeneration decreases the amount of operating labor, it is not as effective as batch regeneration and it may create an ex- plosive mixture of air and natural gas. Because of the added costs associated with an air compressor, continuous regenera- tion generally does not prove to be the economic choice for the typically small quantities of gas involved. Cooler operating temperatures of the natural gas during the winter creates the potential for hydrate formation in the iron sponge bed. This can cause high pressure drop, bed compac- tion and flow channelling. Where the potential for hydrates exists, methanol can be injected to inhibit their formation; however, if insufficient water is present to absorb the methanol it may coat the bed, forming undesirable salts. Hydrocarbon liquids in the gas tend to accumulate on the iron sponge media which inhibits the reactions. The use of a gas scrubber upstream of the iron sponge and a gas temperature slightly less than that of the sponge media may prevent | significant quantities of liquids from condensing and fouling the bed. There has been a recent revival in the use of iron sponges to sweeten light hydrocarbon liquids. The sour liquids flow through the bed and are contacted with the iron sponge media and the reaction proceeds as above. 122.1.2 Molecular Sieve Processes Molecular Sieve Processes use synthetically manufactured crystalline solids in a dry bed to remove gas impurities. The crystalline structure of the solids provides a very porous material having uniform pore size. Within the pores the crystalline structure creates a large number of localized polar charges called active sites. Polar gas molecules such as H,S and water vapor which enter the pores form weak ionic bonds at the active sites. Nonpolar molecules such as para‘fin hydrocarbons will not bond to the active sites. Molecular sieves are available with a variety of pore sizes. 4 molecular sieve should be selected with a pore size that will admit H,S and water while preventing heavy hydrocarbons and aromatic compounds from entering the pores. Carbon dioxide molecules are about the same size as H,S molecules, but are nonpolar. Thus, CO, will enter the pores but will not bond to the active sites. Small quantities of CO, will be removed by becoming trapped in the pores by bonded H,S or H,O molecules blocking the pores. More importantly CO, will obstruct the access of H,$ and H,O to the active sites which decreases the overall effectiveness of the molecular sieve. Beds must be sized to remove all H,O and provide for interference from other molecules in order to remove all H,S The adsorption process usually occurs at moderate pressure. Jonic bonds tend to achieve an optimum performance near 450 psig but the system can be used for a wide range of pressures. The molecular sieve bed is regenerated by flowing hot sweet gas through the bed. The hot stripping gas breaks the ionic bonds and removes the H,$ and H,O from the sieve. Typical regeneration temperatures are in the range of 300-400°F. 13Molecular sieve beds can suffer chemical and mechanical degradation. Care should be taken to minimize mechanical damage to the solid crystals as this may decrease the bed’s effectiveness. The main cause of mechanical damage is the sudden pressure and/or temperature changes that may occur when switching from adsorption to regeneration cycles. Proper instrumentation can significantly extend bed life. Molecular sieves are generally limited to small gas streams operating at moderate pressures. Due to these operating limita- tions, molecular sieve units have seen limited use for gas sweetening operations. They are generally used for polishing applications following one of the other processes. 2.1.3 Zine Oxide This process is similar to the iron sponge process in the type of equipment used. The zinc oxide process uses a solid bed of granular zinc oxide to react with the H,$ to form zinc sulfide and water as shown below. ZnO + H,S > ZnS + H,O The rate of reaction is controlled by the diffusion process, as the sulfide ion must first diffuse to the surface of the zinc oxide to react. High temperature (250°F and above) increases the diffusion rate and is normally used to promote the reac- tion rate. The strong dependence on diffusion means that other variables such as pressure and gas velocity have little affect on the reaction. Zinc oxide is usually contained in long thin beds to lessen the chances of channeling. Pressure drop through the beds is low. Bed life is a function of gas sulfide content and can vary from 6 months to over 10 years. The beds are often used in series to increase the level of saturation prior to change out of the catalyst. The spent bed is discharged by gravity flow through the bottom of the vessel. The process has seen decreasing use due to increasing disposal problems with the spent bed which is classified as a heavy metal salt 142.2 Chemical Solvent Processes Chemical solvent processes use an aqueous solution of a weak base to chemically react with and absorb the acid gases in the natural gas stream. The absorption driving force is a result of the partial pressure differential between the gas and the liquid phases. The reactions involved are reversible by changing the system temperature or pressure, or both. Therefore, the aqueous base solution can be regenerated and circulated in a continuous cycle. The majority of chemical solvent processes utilize either an amine or carbonate solution. 2.2.1 Amine Processes Several processes have been developed using the basic action of various amines. These amines can be categorized by the number of organic groups bonded to the central nitrogen atom, as primary, secondary or tertiary. For example: H | HOCH,CH,-N-H Monoethanolamine (MEA) Primary amine H HOCH,CH,-N-CH,CH,OH Diethanolamine (DEA) Secondary amine CH,CH,OH HOCH,CH,-N-CH,CH,OH ‘Triethanolamine (TEA) ‘Tertiary Amine 5Acid Gas Condenser ®) e| | Reflux Drum Acid Free. Gas Liat Rich-Lean Circulation — Sone Pump Exchanger Reflux Pump Stripper Charcoal Fitter fe Absorber Reboiler Reclaimer Inlet Scrubber = UCN Flash Tank :) Booster A Sock Filter Figure 4 Gas sweetening process flow schematic amine sweetening. (Note: Filter locations vary) 16Primary amines form stronger bases than secondary amines which form stronger bases than tertiary amines. Amines with stronger base properties will be more reactive toward CO, and HLS gases and will form stronger chemical bonds. This implies that the acid gas vapor pressure will be lower for 2 given loading as amine reactivity increases and a higher equilibrium loading may be achieved. A typical amine system is shown in Figure 4. The sour gas enters the system through an inlet scrubber to remove any en- trained water or hydrocarbon liquids. Then the gas enters the bottom of the amine absorber and flows countercurrent to the amine solution. The absorber can be either a trayed or packed tower with conventional packing usually used for 20 inch or smaller diameter towers, and trays or structured packing for larger towers. The sweetened gas then leayes the top of the tower. An optional outlet scrubber may be included to recover entrained amine from the sweet gas. Since the natural gas leaving the top of the tower is saturated with water, the gas will require dehydration before entering a pipeline 17The amine solution leaves the bottom of the absorber, carry- ing with it the acid gases. This solution containing the CO, and H,S is referred to as the rich solvent. From the absorber the rich solvent flows to the flash tank to remove most of the dissolved hydrocarbon gases or entrained hydrocarbon con- densates. A small amount of the acid gases will also flash to the vapor phase in this vessel. From the flash tank the rich amine proceeds to the rich amine/lean amine heat exchanger. This heat exchanger recovers some of the sensible heat from the lean amine stream to decrease the heat duty on the amine reboiler and the solvent cooler. The pre-heated rich amine then enters the amine stripping tower where heat from the reboiler breaks the bonds between the amine and acid gases. The acid gases are removed overhead and lean amine is removed from the bottom of the stripper. The hot lean amine flows to the rich amine/lean amine heat exchanger and then to additional coolers, typically aerial coolers, to lower its temperature to approximately 10°F above the inlet gas temperature. This reduces the amount of hydrocarbons con- densed in the amine solution when the amine contacts the sour gas. Typically, a side stream of approximately 3% of the amine flow rate is taken off after the rich/lean amine heat ex- changer and is flowed through a charcoal filter to clean the solution of contaminants. The cooled Jean amine is then pumped up to the absorber pressure and enters the top of the absorber. As the amine solution flows down the absorber it absorbs the acid gases. The rich amine is then removed at the bottom of the tower and the cycle is repeated 18The most common amine processes are monoethanolamine (MBA) and diethanolamine (DEA). Both processes will remove CO, and H,S to pipeline specifications. Among the newer pro- cesses which have been developed is methyldiethanolamine (MDEA). It can be used for selective removal of H,S in the presence of CO, and significantly reduces treating costs when CO, reduction is not necessary. a. Monoethanolamine Systems Monoethanolamine (MEA) is a primary amine which has had wide spread use as a gas sweetening agent. This process is well proven, can meet pipeline specifications, and has more design/operating data available than any other system. MEA is a stable compound and in the absence of other chemicals suffers no degradation or decomposition at temperatures up to its normal boiling point MEA reacts with CO, and H,S as follows: R= HOCH,CH, MEA = RNH, low tem] 2(RNH,) + HS Z————~ (RNH,),S high temp. low temp. (RNH,),S + HS Z 2 2(RNH,)HS high temp. low temp, 2(RNH,) + CO; RNHCOONH,R high temp. ‘These reactions are reversible by changing the system temperature. 19The reactions with CO, and HS shown above are reversed in the stripping column by heating the rich MEA to approximate- ly 245°F at 10 psig. The acid gases evolve into the vapor and are removed from the still overhead. Thus the MEA is regenerated. A disadvantage of MEA is that it also reacts with carbonyl sulfide (COS) and carbon disulfide (CS,) to form heat stable salts which can not be regenerated at normal stripping column temperatures. At temperatures above 245 °F a side reaction with CO, exists which produces oxazolidone-2, a heat stable salt, which consumes MEA from the process. The normal regeneration temperature in the still will not regenerate heat stable salts or oxazolidone-2. Therefore, a reclaimer is often included to remove these contaminants. A side stream of from 1% to 3% of the MEA circulation is drawn from the bottom of the stripping column. This stream is then héated to boil the water and MEA overhead while the heat stable salts and oxazolidone-2 are retained in the reclaimer, The reclaimer is periodically shut in and the col- lected contaminants are cleaned out. Although contaminants are removed from the system, any MEA bonded to them is also lost MEA is usually circulated in a solution of 15% to 20% MEA by weight in water. From operating experience it has been found that the solution loading should not be greater than 0.3-0.4 moles of acid gas per mole of MEA. Both the soluti strength and the solution loading are limited to avoid ex- cessive corrosion. The solution concentration and loading is largely determined by the H,S/CO, ratio. The greater the ratio (ie., the higher the concentration of H,S relative to CO,), the higher the allowable loading and amine concentration. This is due to the reaction of H,S and iron (Fe) to form iron sulfide (Fe,8; and FeS), which forms a protective barrier on the steel surface. This barrier can be stripped away by high, fluid velocities and may lead to increased corrosion on the exposed steel. 20‘The acid gases in the rich amine are corrosive, but the above concentration limits may hold corrosion to acceptable levels. The corrosion commonly shows up on areas of carbon steel that haye been stressed, such as heat affected zones near welds, in areas of high acid gas concentration, or at a hot gas and liquid interface. Therefore, stress relieving all equipment after manufacturing is necessary to reduce corrosion, and special metallurgy is usually used in specific areas such as the still overhead or the reboiler tubes. MEA systems foam rather easily resulting in excessive amine carryover from the absorber. Foaming can be caused by a number of foreign materials such as condensed hydrocarbons, degradation products, solids such as carbon or iron sulfide, excess corrosion inhibitor, valve grease, etc. One of the more effective methods of foam control is to use a coalescing filter separator at the gas inlet to the MEA contactor. This removes many of the contaminants before they enter the system. Hydrocarbon liquids are usually removed in the flash tank. Degradation products are removed in a reclaimer as described above. MEA storage tanks and surge vessels must have an inert blanket gas system to prevent the oxidation of MEA. Sweet natural gas or nitrogen can be used as the blanket gas. MEA has the lowest boiling point and the highest vapor pressure of the amines. This results in MEA losses of 1 to 3 Ibs/MMSCE of inlet gas. In summation, MEA systems can effectively treat sour gas to pipeline specifications. However, care in the design and material selection of MEA systems is required to minimize equipment corrosion. 21b, Diethanolamine Systems Diethanolamine (DEA) is a secondary amine also used to treat natural gas to pipeline specifications. As a secondary amine, DEA is less alkaline than MEA. DEA systems do suffer the same corrosion problems, but are not as severely as MEA. Solution strengths are typically from 25-35 percent DEA by weight in water. DEA reacts with CO, and H,S as follows: DEA = RNHR = R,NH jow temp. 2(R,NH) + H,S 27 (R,NH,),S high temp. low temp. j (R,NH,),8 + H,S Z————* 2(R,NH,)SH high temp. low temp. 2(R,NH) + CO, Z_* R,NCOONHLR, high temp. These reactions are reversible. DEA has significant advantages over MEA when COS or CS; are present. DEA reacts with COS and CS, to form compounds which can be regenerated in the stripping column. Therefore, COS and CS, are removed without a loss of DEA. High CO, levels have been observed to cause DEA degradation to oxazolidones. Typically, DEA systems include a carbon filter but do not include a reclaimer. 22The stoichiometry of the reactions of DEA and MEA with CO, and H,$ are the same. The molecular weight of DEA is 105 compared to 61 for MEA. The combination of molecular weights and reaction stoichiometry means that approximately 1.7 lbs. of DEA must be circulated to react with the same amount of acid gas as 1.0 Ib. of MEA. The solution strength of DEA ranges up to 35 percent by weight compared to 20 per- cent for MEA. Loadings for DEA systems range from 0.35 to 0.65 moles of acid gas per mole of DEA without excessive corrosion. The result of this is that the circulation rate of DEA solution is slightly less than in a comparable MEA system ‘The vapor pressure of DEA is approximately 1/30th of the vapor pressure of MEA. Therefore, amine losses are much lower than in an MEA system, typically between 4-Y% Ib/MMSCE of gas processed. ¢ Dighycolamine Systems The Fluor Econamine process uses diglycolamine (DGA) to treat natural gas. The active DGA reagent is 2-(2-aminoethoxy) ethanol which is a primary amine as follows: DGA = HOCH,CH,OCH,CH,NH, The reactions of DGA with acid gases are the same as those for MEA. Unlike MEA, degradation products from reactions with COS and CS, can be regenerated in a reclaimer. DGA systems typically circulate a solution of 50-70 percent DGA by weight in water. At these solution strengths and a loading of up to 0.3 moles of acid gas per mole of DGA, cor- rosion in DGA systems is slightly less than in MEA systems. The advantages of a DGA system are that the low vapor pressure decreases amine losses, and the high solution strength permits lower circulation rates. 234. Diisopropanolamine Systems Diisopropanolamine (DIPA) is a secondary amine used in the Shell “ADIP" process to sweeten natural gas. DIPA = (CH;CHOHCH,),NH DIPA systems are similar to DEA systems but offer the follow- ing advantages: * Carbonyl sulfide (COS) can be removed and the DIPA solu- tion regenerated easily. * The system is generally noncorrosive. * Lower energy consumption. One feature of this process is that at low pressures DIPA will preferentially remove H,S. As pressure increases the selectivity of the process decreases and DIPA removes increasing amounts of CO,. Therefore, this system can be used either to selectively remove H,S or to remove both CO, and HS e. Methyldiethanolamine Systems Methyldiethanolamine is a tertiary amine which, like the other amines, is used to treat acid gas streams. The major advantage which MDEA offers over other amine processes is its selectivi- ty for HS in the presence of CO,. If the gas is contacted at pressures ranging from 800-1000 psig, pipeline quality gas may be obtained. At the same time 40 to 60% of the CO, pre- sent flows through the contactor, unreacted. In cases where a high CO,/H,S ratio is present, MDEA can be used to improve the quality of the acid gas stream to a Claus recovery plant, however, the higher CO, content of the treated residue gas must be tolerated. Solution strengths typically range from 40 to 50% MDEA by weight. Acid gas loading varies from 0.2 to 0.4 or more moles of acid gas per mole of MDEA depending on supplier. MDEA has a molecular weight of 119. MDEA solution makeup is dependent upon the sup- Plier. It can be adjusted to optimize treatment for a particular gas inlet compositionHigher allowable MDEA concentration and acid gas loading results in reduced circulation rates. Significant capital savings are realized due to reduced pump and regeneration require- ments. MDEA has a lower heat requirement due to its low heat of regeneration. In some applications, energy require- ments for gas treating can be reduced as much as 75% by changing from DEA to MDEA. ff Inhibited Amine Systems These processes use standard amines that have been combined with special inhibiting agents which minimize corrosion. This allows higher solution concentrations and higher acid gas loadings. This reduces required circulation rates and energy requirements. 2.2.2 Carbonate Processes a. Hot Potassium Carbonate Systems Carbonate processes generally utilize hot potassium carbonate to remove CO, and H,S. As a general rule, this process should be considered when the partial pressure of the acid gas is 20 psia or greater. It is not recommended for low pressure ab- sorption, or high pressure absorption of low concentration acid gas, The main reactions involved in this process are: Potassium Carbonate = K,CO, high CO, press. K,CO, + CO, + H,O 2KHCO, low Ci 2 press. high H,S press. K,CO, + HS KHS + KHCO, low H,S press. ‘These reactions are reversible based on the partial pressures of the acid gases. Note that potassium bicarbonate (KHCO;) solu- tions are not readily regenerable in the absense of CO,, so that these processes are only employed for H,S removal when quantities of CO, are present. Potassium carbonate also reacts reversibly with COS and CS,. 25Figure 5 shows a typical hot carbonate system for gas treating The gas to be treated enters the bottom of the absorber and flows countercurrent to the potassium carbonate. The sweet | gas then exits the top of the absorber. The absorber is typical- ly operated at 230°F. Therefore, a gas/gas exchanger may be included to cool the sweet gas, recover sensible heat, and decrease the system's utility heat requirements. Acid Gas Outlet Condenser Retlex Drum Absorber Stripper Sweet Sour Gas | | Reboller Co Flash Drum Figure 5 Gas sweetening flow schematic bot carbonate process. 26The rich potassium carbonate solution from the bottom of the absorber flows to a flash drum where much of the acid gas is removed. The solution then proceeds to the stripping columa which operates at approximately 245°F and near atmospheric pressure. The low pressure, combined with a small amount of heat input, strips the remaining acid gases. The lean potassium carbonate from the stripper is pumped back to the absorber. The lean solution may or may not be cooled slightly before entering the absorber. The heat of reaction from the absorption of the acid gases causes a slight temperature rise in the absorber. The solution concentration for a potassium carbonate system is limited by both the solubility of potassium carbonate in the lean stream and the solubility of the potassium bicarbonate (KHCO)) in the rich stream. The reaction with CO, produces two moles of KHCO, per mole of potassium carbonate reacted. For this reason the KHCO, in the rich stream normal- ly limits the lean solution potassium carbonate concentration to 20-35 percent by weight. Potassium carbonate works best on gas streams with a CO, partial pressure of 30-90 psi. When CO, is not present, Hz§ removal will be limited because the regeneration of the potassium carbonate requires an excess of KHCO;. The presence of CO, in the gas provides a surplus of KHCO, in the rich stream. Note that pipeline quality gas often requires secondary treating using an amine or similar system to reduce the HLS level to 4 ppm. The entire system is operated at high temperatures to increase the solubility of carbonates. Therefore, the designer must be careful to avoid dead spots in the system where the solution could cool and precipitate solids. If solids do precipitate the system may suffer from plugging, erosion, or foaming. 27The hot potassium carbonate solutions are corrosive. All carbon steel must be stress relieved to limit corrosion. A varicty of corrosion inhibitors, such as fatty amines or potassium dichromate, are available to decrease corrosion rates. ’. Proprietary Carbonate Systems Several proprietary processes have been developed based on the hot carbonate system with an activator or catalyst. These activators increase the performance of the hot potassium car- bonate system by increasing the reaction rates both in the ab- sorber and the stripper. In general, these processes also decrease corrosion in the system. The following are some of the proprietary processes for hot potassium carbonate: (1) Benfield: Several activators (2) Girdler: Alkanolamine activators (3) Catacarb: Alkanolamine and/or borate activators (4) Gimmarco-Vetrocoke: Arsenic and other activators 2.2.3 Specialty Batch Chemical Solvents Several batch chemical processes have been developed and have specific areas of application. Among these processes are Zinc Oxide slurry, caustic wash, Sulfa-Check, Slurrisweet, and Chemsweet. In general, gas is flowed into a vessel and con- tacted with the solvent. The acid components are converted to soluble salts which are non-regenerable, limiting the life of the solution. Once saturation levels are reached the solution must be replaced. This has created problems as some of the spent solutions have been labeled hazardous and, if used, must be disposed of as Class IV materials. 28‘These units have a wide operating range with acid gas con- centrations as low as 10 ppm to as high as 20%. Operating pressures range from near atmospheric to greater than 1000 psig. Units have been designed to handle from several thou- sand cubic feet per day to more than 15 MMSCFD. ‘Typical among these processes is the Sulfa Check process This is a single step process that converts H,$ to sulfur in a bubble tower filled with a proprietary solution of oxidizing and buffering agents. The oxidizing agent is a proprietary for- mulation of chelated nitrite ions. The reaction chemistry in- volved is as follows: 3H,S + NO, > NH, + 38 + OH” + H,0 Reaction rate is independent of the concentration of the oxi- dizing agent. Although there is no limit to the concentration of H,S treated, the process is most economical for acid gas streams containing from 1 ppm to 1 percent of H,S. It is im- portant to hold pH above 7.5 to control selectivity and op- timize H,S removal. One gallon of oxidizing solution can remove up to 2 pounds of H,$ when the system is operated at ambient temperatures (less than 100°). If gas temperatures exceed 100°F, the solubility of sulfur in the oxidizing agent decreases, An operating pressure of at least 20 psig is required for proper unit operation to maintain bubble flow through the column. Bubble flow is necessary to produce intimate mixing of the gas and liquid. The oxidizing solution will eventually become saturated and require replacement. Disposal of this slurry poses no en- vironmental problem, as the reaction produces an aqueous slurry of sulfur and sodium salt. 292.3 Physical Solvent Systems Physical solvent systems are very similar to chemical solvent systems but are based on the gas solubility within a solvent in- stead of a chemical reaction. The partial pressure of the acid gases and the system temperature both affect the acid gas solubility. Higher acid gas partial pressures increase the acid gas solubility. Low temperatures have a similar effect but in general, temperature is not as critical as pressure. Various organic solvents are used to absorb the acid gases based on partial pressures. Regeneration of the solvent is ac- complished by flashing to lower pressures and/or stripping with solvent vapor or inert gas. Some solvents can be regenerated by flashing only and require no heat. Other : solvents require stripping and some heat, but typically the heat requirements are small compared to chemical solvents. Physical solvent processes have a high affinity for heavy hydrocarbons. If the natural gas stream is rich in C;, hydrocarbons, then the use of a physical solvent process may result in a significant loss of the heavier mole weight hydro- carbons. These hydrocarbons are lost because they are re- leased from the solvent with the acid gases and cannot be economically recovered. Under the following circumstances physical solvent processes should be considered for gas sweetening: © The partial pressure of the acid gases in the feed is 50 psi or higher. ° The concentration of heavy hydrocarbons in the feed is low. * Only bulk removal of acid gases is required. © Selective H,$ removal is required. 30‘A physical solvent process is shown in Figure 6. The sour gas contacts the solvent using countercurrent flow in the absorber. Rich solvent from the absorber bottom is flashed in stages to near atmospheric pressure. This causes the acid gas partial pressures to decrease, the acid gases evolve to the vapor phase and are removed. The regenerated solvent is then pumped back to the absorber. Acid Free Gas Lean Solvent Acid Gas Acid e Gas fea ) Rich Solvent i Figure 6 Typical flow schematic physical solvent process. 31The example in Figure 6 is a simple one where flashing is suf- ficient to regenerate the solvent. Some solvents require a strip- ping column just prior to the circulation pump. Some systems require temperatures below ambient, thus refrigeration using power turbines replaces the pressure reducing valves. These turbines recover some of the power from the high pressure tich solvent and thus decrease the utility power requirements for refrigeration and circulation The majority of the physical solvent processes are proprietary and are licensed by the company that developed the process. Four typical processes are discussed below. 2.3.1 Fluor Solvent Process The Fluor Solvent process uses propylene carbonate as a physical solvent to remove CO, and H,S. Propylene carbonate also removes C3+ hydrocarbons, COS, SO2, CS, and H,O from the natural gas stream. Thus, in one step the natural gas can be sweetened and dehydrated to pipeline quality. In general this process is used for bulk removal of CO, and is not used to treat to less than 3 percent CO, as may be re- quired for pipeline quality gas. The system requires special design features, larger absorbers and higher circulation rates to obtain pipeline quality and usually is not economically applicable for these outlet requirements. 32Propylene carbonate has the following characteristics which make it suitable as a solvent for acid gas treating: © High degree of solubility for CO, and other gases. © Low heat of solution for CO,. © Low vapor pressure at operating temperature. © Low solubility for light hydrocarbons (C,, C2) © Chemically non-reactive toward all natural gas components. © Low viscosity. © Non-corrosive toward common metals. These characteristics combine to yield a system that has low heat and pumping requirements, is relatively noncorrosive, and suffers only minimal solvent losses, (less than 1 Ib/MMSCE). Solvent temperatures below ambient are usually used to in- crease solvent gas capacity and therefore, decrease circulation rates, The expansion of the rich solvent and flash gases through power turbines can provide the required refrigeration. Alternately auxiliary refrigeration may be included to further decrease circulation rates. 332.3.2 Sulfinol Process The Sulfinol process, developed and licensed by Shell, employs both a chemical and a physical solvent for the removal of H;S, CO., mercaptans, and COS. The Sulfinol solu- tion is 2 mixture of tetrahydrothiophene dioxide (Sulfolane) which is the physical solvent, a secondary amine, diisopropanolamine (DIPA), and water. DIPA, previously discussed, is the chemical solvent. Typical solution concentra- tions range from 25-40% Sulfolane, 40-55% DIPA, and. 20-30% water, depending on the conditions and composition of the gas being treated. The presence of the physical solvent, Sulfolane, allows higher acid gas loadings compared to systems based on amine only. Typical loadings are 1.5 moles of acid gas per mole of Sulfinol ) solution. Higher acid gas loadings, together with a lower energy of regeneration, can result in lower capital and energy costs per unit of acid gas removed as compared to the ethanolamine processes. Other features of the Sulfinol process include: e Essentially complete removal of mercaptans © High removal rate of COS © Lower foaming tendency ° Lower corrosion rates © Ability to slip up to 50% CO, 34The process design of a sulfinol unit is similar to that of the ethanolamines. However, the degradation of DIPA to oxazo- lidones (DIPA-OX) usually necessitates the installation of a reclaimer for their removal. As with the ethanolamine pro- cesses, aromatics and heavy hydrocarbons in the feed gas should be removed prior to contact with the Sulfinol solution to minimize foaming. Although the relative merits of the Sulfinol process as com- pared to the ethanolamine processes appear many, there are other factors which must be considered before selecting t appropriate gas treating process for a particular application. The payment of a licensing fee, while not necessary for the ethanolamine processes is required for the Sulfinol process. In addition, solvent costs are generally higher for Sulfinol than they are for DEA. A less tangible disadvantage of the Sulfinol process, is that operators are more familiar with DEA and the typical problems associated with this process. Finally, in cases of low acid gas partial pressure, the advantage of a lower cir- culation rate for the Sulfinol process diminishes as compared to DEA. 35