(Natural Gas can be either a wellhead stream from natural reservoir or associated to a crude production) INERT GASES Nitrogen (N2), Helium (He) ACID GASES Hydrogen Sulfide (H2S), Carbon Dioxide (CO2) PURE HYDROCARBONS Light Ends Methane (C1) Ethane (C2) Propane (C3) Butanes (C4) PETROLEUM CUTS Heavy ends or C5+ CONTAMINANTS mercaptans, COS, CS2 WATER under liquid form MERCURY metallic formWHY GAS FIELD PRODUCTION PROCESS FACILITIES? — To: @ Satisfy Export Gas Specifications e Satisfy downstream specific Specifications e Dispose of extracted contaminants with minimal environmental impact (sustained development) © Optimize hydrocarbon production (either gas side or hydrocarbon liquid side) Radial DevelopmentDevelopment with intermediate stations and trunk lines Collector Test line Central Processing Facilities Intermediate station (cluster) GAS PROCESSING COMPOUNDS PROBLEMS WATER Hydrates (with free water) Gas Water Dew Point ACID GASES Corrosion (with free water) (H2S and/or CO2) Safety (H2S content) Gas Calorific Value (CO2 content) HEAVY COMPONENTS Condensation (Transportation line) (C5+) Gas Hydrocarbon Dew Point Gas Calorific Value (too high C5+ content)CONTENTS | « GAS WATER CONTENT « HYDRATE FORMATION ¢ GAS DEHYDRATIONINTRODUCTION Water is a conspicuous component of natural gas in all steps of gas handling from its initial production until its ultimate consumption. Presence of water vapor in the natural gas is especially troublesome because it condenses when the temperature decreases. Pressure favors the combination of condensed water with natural gas to form solid hydrates even though the temperature is above the freezing point of water. These hydrates can plug pipe lines then interrupting the steady flow of gas. In addition, should the gas contain acid gas (CO2 and/or H2S), the condensed water would promote all forms of corrosion. Definition of the GAS GRAVITY (AIR Gas Gravity (Air = 1) = Gas Molecular Weight (dry basis¥28.97 with Air Molecular Weight = 28.97 (can be rounded to 29) Remark: Some call it “density”, a misleading simplificationGAS WATER CONTENT Water Dew Point of Natural Gas McKETTA PlotNatural Gas Water Content (W) by the BUKACEK Equation W=(AIP)+B Aand B constants are function of the temperature t W (Ib/MMSCF wet gas) P Operating Pressure (psia) Operating Temperature (deg.F) ~ or: W (mg/Sm3 wet gas) P Operating Pressure (bar abs.) Operating Temperature (deg.C) ~ Eegeuapeaeanyyyaa EEGSORSEEINE jaa HF GAZ de FRANCE Equations for the calculation of the BUKACEK A and B Coefficients ‘Between -40 dea.C and 40 dea. A= 4926.5878 x @ (00797581 -0.0000873012«) |B = 44,8739 x 0 (0.059970027 «1-0 ocot9e8041 «2 ‘Botwoen 40 deg.G and 90 deg.C A= 6186.961 1 x0 00620808 1-0 015066945. 2) 1B = 40.5058 » 9 0085012700 1-ocoressa7s3.2) Between 90 dea.C and 130 dea.C A= 6156.9611 x 9 m%0s86 1-0 0t2HED4942) 1B = 70.0737 x 9 00ces7e04xt ‘(temperature in the above equations) is expressed as deg.C. P (pressure in the BUKACEK correlation) must be in bar abs, W (Water content) = (A/P) + 8 is expressed as mg/Nm* wet gas 6bar x 14.5 = PSI Some Conversion Factors atm x 14.7 = PSI Ib x 0.4536 = kg m3 x 35.3147 = CF (Ib water/MMSCF) x 379.495/18.02 = ppm volume (mg water/Nm3) x 22.414/18.02 = ppm volume (Ib water/MMSCF) x 16.9076 = mg water/Nm3 (Ib water/MMSCF) x 16.0187 = mg water/Sm3 Standard (S) Conditions: 1.013 bar abs (101.3 kPa) and 15 deg.C Normal (N) Conditions: 1.013 bar abs (101.3 kPa) and 0 deg.C Sm3 = Nm3 x (15 + 273.15¥273.15 1 kgmole of gas fills a volume of 22.414 Nm3 1 kgmole of gas fills a volume of 23.645 Sm3 1 Ibmole of gas fills a volume of 379.495 SCF NATURAL GAS WATER DEW CURVE [Water saturated gas PandT |) Pressure (bar a) vu T Temperature (deg.C)Water Content of COz ‘water MMscl wet gas os Sexo Sour Gas Water Content CORRECTIONS DUE TO THE ACID GAS CONTENT Mc Ketta Plot or BUKACEK correlation applies to natural gas with low acid gas content. (C02 and/or H2S) content lower than § mole % Should the gas be loaded with high CO2 and/or H2S concentrations, a correction must be included to cater for the high acid gas content Two (2) Methods: CAMPBELL GASUNIEEffective H2S Water Content (Campbell Method) = 10000 ° aD = = 1000 =< 2 = 100 oO 3 s = 10 ae 100 1000 10000 Pressure (psia) a Effective CO2 Water Content (Campbell Method) a 10000 =F =——S o a = a 1000 = 160 deg.F = 100 190 deg.F oO 100 deg.F s 80 deg.F & = 10 —— 100 1000 10000 Pressure (psia)CAMPBELL’s METHOD FOR THE WATER CONTENT OF WET SOUR GAS Wet Sour Gas mole % Hydrocarbons 21 H2s Z2 co2 z3 Total 100 Sweet Gas Water Content (Bukacek or McKetta) Wey H2S Water Content (Campbell curve) Whos CO2 Water Content (Campbell curve) Weos Wet Sour Gas Water Content Weg Weg = (Z1 X Weya + Z2 X Wyzg + Z3 X Weog)/100 Water Content of Natural Gas!Correction Factor for Acid Gas/GASUNIE Chart ‘mole % C02 x 0.75 = mole % H2S mg m3 (n) 400 300 200 100 0 cenecton act's based Oe er Suet Sac Water Caran 1 — — tapatet ' nes ymietineedas ao -20—«N0 40 NARHA I 30 | sto - ‘Temperature (des.C) 20 40 60 80 100 120 wo Pressure (bar a)Water Content of a Wet (saturated) Sour Natural Gas Pressure 100 bar a (1450 psia) - Temperature 40 deg.C (104 deg.F) Coz content S mole % H2S content 5 mole % 1. Sweet Gas Water Content (Bukacek) = 50800 B= 167 Sweet Gas Water Content = (50800/1450}+ 16.7 = 51.7 Ib/MMMSCF 2. CAMPBELL method H2S water content = 160.2 LB/MMSCF (C02 water content = 70.8 Ib/MMSCF ‘Sour Gas Water Content = 51.7x0.9 + 160.2x0.05 + 70.8x0.05, Sour Gas Water Content = 58.1 Ib/MMSCF 3. GASUNIE Graph "H28" gas content = § + 5x0.75 = 8.75 mole % Correction for "2S" compound = 77 mg/Nms or Correction for "2S" compound =77/16.9076=4.6 Io/MMSOF ‘Sour Gas Water Content = 51.7 + 4.6 = 56.3 Ib/MMSCF 4. Conclusion The difference between the two results is 3.2 % ‘This small difference shows a good consistency between the two methods. COMPUTER AND MANUAL CALCULATIONS OF NATURAL GAS WATER CONTENT (LOW ACID GAS CONTENT) Aguada Pichana Field (Argentina) Component mole % WATER CONTENT at 158 bar a and 67 deg.C coz 0.21 (expressed as kg water/MSm3 wet Gas) Ne ont Manual | Computer methods (PROT) ot 86.76 method |SRK — |SRKKD | SRKM ce 6.74 Bukacek | (GPA (Kabis cs 2.68 Campbett | option) —_{Dannner) C4 1.28 os 050 2045 | 2060 | 2044 | 2282 ce 0.16 7 1.26COMPUTER AND MANUAL CALCULATIONS OF NATURAL GAS WATER CONTENT (HIGH ACID GAS CONTENT) Uch Field (Pakistan) ‘Component H2S coz N2 a1 c2 c3 C4 cé cer mole % 39.40 19.84 39.28 0.90 0.26 0.15 0.03 0.07 WATER CONTENT at 142 bar a and 88 deg.C (expressed as kg water/MSm3 wet Gas) Manual Computer methods (PRO) method | SRK ISRKKD SRKM Bukacek | (GPA (Kabi/ Campbell | option) _|Dannner) 5299 3421 5854 5246 On-Site Natural Gas Moisture Analyzers Color indicator tubes (for rough or quick moisture measurement) aChilled mirrors giving water dew point (Bureau of Mine Dew Scope) uElectrolytic sensor (use of Phosphorus pentoxide P205):slow process uPiezoelectric sorption (complex and not always accurate due to H2S) mDielectric Layers (Metal oxide, Silicon-optic-):reliable at beginning Absorption Spectroscopy (danger of overlapping by gas components) Same as above + Tunable Diode Laser (TDL):very accurate uKarl-Fisher Reagent (Methanol solution of iodine, pyridine, S02) All are susceptible to liquids (water, methanol, glycols, hydrocarbons)Bureau of Mine Dew Point Tester Chilled Mirror Process SOLUBILITY OF NATURAL GAS IN WATER (SCF/B) x 0.000135 = mole gas/mole water and (SCF/B) x 0.1781 = Sm3 gas/m3 water Seas 8 TIP TTTT Soyo ae gate, t/t 3 on sao a TTat HYDRATE DEFINITION SOLUTION OF GASES IN CRYSTALLINE SOLIDS Hydrate density is around 0.88-0.9 kg/l Large hydrocarbon molecules break the crystal structure of the hydrate. Therefore, hydrates can form only with light hydrocarbons but also with acid gases (H2S and/or co2)HYDRATE FORMERS E S 48—__ cH4,H2S & 9 2 g & 2 ie |— co2 = | a Ls sa— wo 5 ge |— C2H6 x eu a Se = © © 6A__| g 38 | = ae |— css, ic4H10 = 5 7A 2 3 NO HYDRATE By, | ncano Large hydrocarbon molecules do not form hydrates i€5, NCS do not form hydrate However, Cyclopentane can form hydrates CONDITIONS FOR HYDRATE FORMATION * FREE WATER * HIGH PRESSURE * LOW TEMPERATURE * CRYSTALS OF HYDRATEPRESSURE-TEMPERATURE CURVES FOR PREDICTING HYDRATE FORMATION 4000 Temperature (deg.0) 35 CORRELATION FOR NATURAL GAS HYDRATE FORMING POINTS th (deg.C) Hydrate forming temperature © G-G (Gas Gravity, Air =1) © P (bar a) operating pressure th = 7.483 x Log (P) + 16.55 x Log (G-G) — 0.931 x Log(P) x Log(G-G) - 9.072 Remark: In the above formula, Log is napierian logarithm ! This correlation tends to overestimate hydrate forming temperatures when exceeding 20 deg.C(Plot present in the 1998 edition of the GPSA Engineering data book after having disappeared for years) L. To im mepaion of 7 gay i i Hydrate-Forrring Curvel Gas Water Dew Curve (The mest common case) Initial Saturation Conditions: 69 ber a and 489 degCPressure Hydrate-Forming Curve/Water Dew Curve (Some specific and rare cases) Water Dew curve. lydrate-Forming cur ‘Temperature resume, at8Effect of Diethylene glycol on conditions for hydrate formation i636 3 ao 80 i) 70 Temperature, dea F a HYDRATE-FORMING INHIBITORS METHANOL (MeOH/ Molecular Weight : 32.04) Generally 100 % pure MeOH MONOETHYLENE GLYCOL (MEG/ Molecular Weight : 62.07) ‘Aqueous Solution using MEG concentrations between 60 and 80 Wt.% DIETHYLENE GLYCOL (DEG/ Molecular Weight : 106.12) Aqueous Solution using MEG concentrations between 60 and 80 Wt.%‘Some Physical Properties of Methanol and Glycols Methanol | Monoethylene | Diethylene ‘Methanol and Glycols used for Hydrate Inhibition Giyeot Giyeo! ‘Moon MEG DEG Formula (Hs OH caH6 02 (CaH10 08 ‘Molecular Weight e204 62.10 106.10 Boling Point at 760 mm Ho eae as 1973 2088 ‘Vapor Pressure af 25 deg.C mm Hg 720 01 001 Density at 25 deg. gina 790 110 1113 Density at 60 deg.¢ kgina 1085 1088 Freezing Point eg 78 133) EX Viscosity at 25 deg. oP 052 1650 28.20 Viscosity at 60 deg. oP. 4.88 699 ‘Spoctic Heat at 25 dog. kealikg K 0.60 058) 085) {Latent Heat of Vaporization at 70 mm Hg koala 202 129 Flash Point eae 120 1158 1238 Notes 1. These properties are laboratory rect on pure compounds bu sheut nc be couse with commerce spetisatons 2. heals cecompase at ampersture below ther aresphore tong pole Approunal decampastion temperate ae Moaoethylene Glycol (MEG) 165 degC (329 dex.F) Diethslene Glycol DEG) 164.4 degC (328 des.) { SLUG OF METHANOL FOR PIPELINE “DRYING” ‘Methanol Film in Pipe Scrapers Methanol Slug Slug of Methanol (m3) Pipeline inside Diameter (m) Thickness of Methanol film left on pipe inner wall (m) Pipeline length (m) Methanol initial concentration of methanol slug (weight %) Methanol final concentration of methanol slug (weight %) aQrase ga Q=IxDxExL/Log(Ci/Cf) (0.6 mm 30 wt. % 29.6 x Log (Xyo)_ (Napierian Logarithm) (Av-129.6) * At (deg.F) Hydrate Point Lowering * Xoo Mole Fraction of Water in Aqueous Solution EXAMPLE: Required At = 35 deg.F Xqoo = © 09-1208) = 0.763 Methanol concentration expressed as wt.%, (W): W = 100 x (1 ~ 0.763) x 32.04 = 35.6 0.763 x (18.02 — 32.04) + 32.04 Where 18.02 Molecular weight of water; 32.04 Molecular weight of Methanol 51 METHANOL: RATIO OF VAPOR TO LIQUID COMPOSITION VERSUS PRESSURE otaest Gas Temperature (So.0) 4417 44 7210 128 156 toa sot + * + 5 10 16 20 pa 2 s 0 6 0 8 © KG of MeQH/(MSm gas x Wt %e MeOH inliquid phase)‘Solubility of Methanol in pure Liquid Hydrocarbons iquid hydrocarbon (Weight %) \ 40 30 20 10 0 10 20 30 40 50 60 Temperature (degC) Solubility of Methanol in Liquid Paraffinic Hydrocarbons versus Temperature at various Methanol Concentrations Weight % MeOH = mole % MeOH x 32.04 x 100 mole % MeOH x 32.04 + mole % Hydrocarbons x MW hydrocarbonsZz = e PER. cuYcot soLuol SOLUBILITY OF GLYCOLS IN HYDROCARBONS 2000 rt |e Ld DEe-[s0% BENZENE (Si Lg Tt [1 \ F Tes-conDENsaTEW) t = See. coMDENSArE()—| EG HEPTANELSY [somoce from Benzene, SO%ES [FO™ BENZENE Sone Tbox Means —— Cc (row tennexane | i 10010 TEMPERATURE, *F.GAS DEHYDRATION NATURAL GAS DEHYDRATION PROCESSES m PHYSICAL ABSORPTION (TRIETHYLENE GLYCOL SOLUTION) m PHYSICAL ADSORPTION (MOLECULAR SIEVES) m REFRIGERATION (When HC LIQUID Extraction is also required) 8WATER DEW CURVE OF WATER SATURATED NATURAL GAS HAVING THE COMMON WATER CONTENT VALUE OF 7 LB/MMSCF (112.1 mg/Sm3) FOR PP. Pressure (bar a) BBsSsIss 170 160 3 298 7654 3 2 1 ° 1 RANSPORTATION 23456789 ‘Temperature (deg.C)GAS DEHYDRATION BY PHYSICAL ABSORPTION Triethylene Glycol (TEG) Solutions (Lean Solutions) * TEG SOLUTION at 98.7 Wt.% TEG 20 to 42 | Solution/kg of absorbed Water 2.4 to 5 US Gallon Solution/LB of absorbed Water Maximum Water Dew Point Depression : 37 deg.C (67 deg.F) @ REGENERATION at Atmospheric Pressure REGENERATION at a Temperature of 204 deg.C * TEG SOLUTION > 99 Wt.% TEG © REGENERATION UNDER VACUUM © USE OF STRIPPING GAS © Processes by licensors (DRIZO, COLDFINGER) Maximum Water Dew Point Depression : >56 deg.C (> 100 deg.F) Note: (US gale) x 8,245 = (cg) ‘Gas Dehydration by Physical Absorption using TEG (basic plan) Simplitieg Process Flow Diagram + ov cas SAE souscesc Mecoow Rime” seon0s 0g Poe gg, OE aol vania] [Ta tne aaa =} +S, cam s sss 409.0 Se owen | son ses veedGar 2210-01 i og i eee =o oe THT] SF Don | tne | po | pectmeater | | Le [Jase wont Sie Greets! 81Boiling Temperature (dog F) Boiling Points of Aqueous Comercial Grade TriethyeneGiycol ‘Solutions at 760 nmHg Pressure 0 1 2 9 % 9 % 97 98 "99 100 |WL% TEG inthe Lean Solution Standard TEG Unit (skid or package)Natural Gas TEG Dehydration Unit TEG UNIT FOR GAS DEHYDRATION at 70 bar a Maximum performances (no stripping gas) Inlet Water Inlet Water Content Outlet Water Outlet Water Content Dew Point | Ib/MMSCF] mole% | Dew Point | ibiMMSCF] mole% Deg.C Deg.C (ppm V) 4 ~~—«| «687 0.14 7 | 63 [0.013 30 39.9 oes [9 37 (78) 200 23 0.048 “19 18 (38) 85 ySchematic seetion through a bubble-cap tray tower i q { { 67 i Various Types of Packing AS &S Se spined ing at na Gas : (Le SZ i Coat OF ] Vv we i “are cy i> & S ° S a zB g 3 3 2 a 6 @ 2 2 € S x wi ‘TRAYS OR PACKING REQUIRED FOR GLYCOL DEHYDRATORS 4 5 6 SOLUTION CIRCULATION RATE (GAL.SOLUTIONLB H20)Equilibrium Weter Dewpoint versus Gas Terrperature at various TEG concentrations (classical TEGUrit) Actual Water Dew point is § to 10 deg.C above Equilibrium 8 8 8 é Gas Equilibrium Water Dewpoint (deg.c) a & 8B ‘TEES Absorber Temperature (deg.C) Feed gas flow rate through Absorber for different Absorber inside diameters (inch) Base: Feed Gas temperature = 100 dag.F/Feed Gas Gravity = 0.7 200 190 96 ines tee 108 ines 170 160 150 140 130 120 110 100 388883ses 10 20 30 40 50 60 70 80 90 100 110 120 130 140 Absorber operating presssure (bar a) nTypical Temperature profile in Direct-Fired TEG Reboiler Fire Tube 42 deg c 927 deg. 593 deg. ¢ — 760 deg. 1427 deg.c ; mee! 213.deg.c! 221 deg.c 218 dog 10083 deg. HOW TO IMPROVE THE TEG CONCENTRATION OF THE LEAN SOLUTION Pop. = EOP v1 20 Vapor to THRO = i i Condenser oo Rich Solution TV :H20 Vapor Pressure at T op. 21 H20 Y1 20 (17.06 bar a at 204 deg.C) Z2TEG Y2TEG P op. : Reboiler Operating Pressure T op. : Reboiler Operating Temperature Reboiler Theoretical Tray (204 deg.C or 400 deg.F) T OP. Regeneration of X1H20 P op. TEG solution x2 TEG Lean Solution . Decrease P. op (Vacuum operation) To decrease X1 H20 . Decrease Y1 H20 (Stripping Gas Injection)Stripping Gas system in TEG Dehydration Unit ‘String Gos rection inthe rebar ‘Stripping Gas injection ina dedicated Stpping Colum i i] { 5 NS-0 tipping Gas njcton nthe at reboter Na>0 inten of Supping cota between eboter and accuser Etfect of Stripping Gas on TEG Concentration ooo coe oor floss = ona | | Al atmospheric pressure | (seater, naiimim ggg | TEG concenraion owsler tact aooelp O87 We TERS rece 855 pola : oo2 To equlsum stages shove i sos Tease i ‘= Numborf aul soo Sagopa FES oboe 1 2 3 4 5 6 i Stipping Gas, SCF/GAL. TEG mYStripping Stil with external Reflux Lean solution o Circulation Pumps ‘Stripping Gas Retin rum ettux Pump fen Sotto tom Fah Oram // Water absorbed irom gasSimplified Process Flow Diagrams of Enhanced TEG Regeneration Systems COLDFINGER® ESTIMATED PERFORMANCES OF TEG REGENERATION PROCESSH TEG Concentration | Water Dew Point Depression (wt. %) Possible (deg.C) VACUUM 99.2 0 99.9 55 to 80 STRIPPING GAS | _ 99.2 0 99.98 55 to 80 | pRIZo@ > 99.99 100 to 120 COLDFINGER® 99.96 up to 80DEGRADATION AND CONTAMINATION OF TEG SOLUTIONS vosanz sors aE “conneisonternn an TOO HIGH TEMPERATURE | WITH INERT GAS See a cormunpy| tment or pare snr ae ones on = INSTALLATION ON THE RICH “| — ae SSS, ‘stunner sina Tecitine | __eeoccommmaran}-—conadoon | iASSRUESRG sacred romain, —srrevon | foie «sone rouse tesovesevess aes teasaaar vouung |e otesser INTHE ABSORBER _EOe —_— "ENTRAINMENT a TEG Dehydration Unit: Filtration & Charcoal Filter locations Pye —& ie rem ‘Chacnd Fite location Puificaionc’theLenSdiuin ‘Mechanical fiter (sold fiter to remove particles down wo S micrometers (y). The solid content in the TEG solution ‘Should be maintained below 0.01 % Carbon filter: recommended retention times 15/20 minutes caFIELD MEASUREMENTS TO ENSURE A “GOOD” LEAN TEG SOLUTION pH 7-15 HYDROCARBON CONTENT < 0.3 weight % IRON CONTENT < 15 mg/l WATER CONTENT < 1.5 weight % SUSPENDED SOLIDS < 200 mg/l FOAMINDG TENDENCY Resolved in 5 seconds COLOR Clear yellow or slightly amber Ditterence in water contents between the lean solution and the rich solution is generally between 2 and 6 weight %. TEG LOSSES FROM SOME EXISTING TEG GAS DEHYDRATION UNITS (expressed as liter of TEG per 108 m3 of gas at standard conditions) HANDIL (T0TAL INDONESIE) 5 to 10 /MSm3 BU HASA (Gasco) 9 V/MSm3 ABK (TOTAL ABK) 8 /MSm3 “This survey was carried out end 1980's or beginning ofthe 1990's Note: TEG losses are generally between 13 and 40 VMSm3 of gasjamp de gaz de NORTH FIELD Le developement du champ de a é ‘yan ay 26 Be gs 26 B az 26 S a One dry two-phase pipe Ge ay — Be = x z is One wet multi-phase pipe 3) BE ZoPHYSICAL ADSORPTION THE ADSORPTION OPERATION EXPLOITS THE ABILITY OF CERTAIN SOLIDS PREFERENTIALLY TO CONCENTRATE SPECIFIC SUBSTANCES FROM GASES (WATER, ACID GASES) ONTO THEIR SURFACES. IT IS A REVERSIBLE PHENOMENON RESULT OF INTERMOLECULAR FORCES OF ATTRACTION BETWEEN MOLECULES OF THE SOLID AND THE SUBSTANCE ADSORBED. WATER CONDENSES UPON THE SURFACE OF THE SOLID EVEN THOUGH ITS PRESSURE MAY BE LOWER THAN ITS VAPOR PRESSURE. SUCH A CONDENSATION WILL BE ACCOMPANIED BY AN EVOLUTION OF HEAT {about 1000 kcal/kg of adsorbed water). MAIN ADSORPTION SOLIDS e CHARCOAL e@ ALUMINA e SILICA GEL e MOLECULAR SIEVES (natural or synthetic ZEOLITE) MOLECULAR SIEVES Gas Dehydration : 3A Type DRY GAS FINAL WATER CONTENT: DOWN TO 1 ppm Vol.MOLECULAR SIEVE STRUCTURE ACTIVE PART OF MOLECULAR SIEVE INCLUDES A SILICOALUMINATE STRUCTURE (ZEOLITE). IT IS A CRISTALINE STRUCTURE. THIS IS THE MAJOR ADVANTAGE AGAINST THE OTHER TYPES OF ADSORBENT WHICH HAVE AN AMORPHOUS STRUCTURE. ZEOLITE IS NATURAL OR SYNTHETIC. A BINDER (ALUMINA GENERALLY) IS USED TO FIX THE STRUCTURE. CRISTALINE STRUCTURE GIVES WAY TO PASSAGES OF DIAMETER 11.5 ANGSTROM. METALLIC IONS ARE ADDED TO ADJUST THE DIAMETER THE DIAMETER OF THE PORES TO ADSORB THE REQUIRED MOLECULES. » POTASSIUM (K) FOR 3 A TYPE (Used for Gas Dehydration) = SODIUM (Na) FOR 4A TYPE * CALCIUM (Ca) FOR SA TYPE than 3 years Infact a number of (adsorption ADSORBENT Regeneration) cycles Ten INTERNAL ARRANGEMENT OF AN ADSORBER a‘Gas Dehydration by Physical Adsorplion with Molecular Sioves / | | 4 ttt Pune Regeneration Gas "Fe OO ‘Simplified Process Flow Diagram ec Congest Recydle Gas Vee Po tee : Fier q ~_Mocdr Sve une epost Coin Phase | a1 REGENERATION GAS FLOW RATE (REGENERATION AT SAME PRESSURE AS ADSORPTION) we " | 6 o | ee feo 33" 28 1 ge ° ze os ° i 20 2 we 20 40 “ 2” i FEED GAS TEMPERATURE (405.0) ' { a4[LB Sieve MMSFD Feed Gas x Adscrpton Ojie hau) versus Feed Gas Wier Cote 2 = Insite pours of sews LB o SiovettMSCFD x Adsorption eye hours) Fac Gon ier Cater LMSC) ‘Molecular Sieve lifetime is not more then 3 years. In fact, a number of (Adsorption + Regeneration) cycles 99 PART 2ACID GASES Main Properties ‘Component Molecular ‘Catical Critical “Atmospheric ‘Atmospheric ‘Weight Presse ‘Temperature Boiling Point | Freezing Point (ara) (ee0) (eg.c) dee) 1s 34.082, wo T0902 “603 “855 co #0) 738 a "aS “566 8 FeSmae (nartirt} ‘000610008 (orem | osreoois (oo>0 9m) ‘agi Oe (0502002) cerry (20a Rem)C02 Freezing Temperature (1 |S IN AMBIANT AIR (including Air COZ concentration of 350 ppm V) = 1000 ppm Vv con work continuously 1 5000 ppm V_ Persone! con be repeatedly exposed for 8 houra a day end 5 days a week 15000 ppm V_ Shert time exposure 9 (C02 FREEZING CURVES (Gas is rmainly Methane) 600 Tabara Gas 278bar a Gas 60 | anabara Gas Sf | 139 bara Gas 104bar a GasSWEETENING PROCESSES DEPEND ON THE TYPE OF CONTAMINANT TO BE REMOVED * DEEP CO2 and/or H28S REMOVAL * H2S SELECTIVE REMOVAL * CO2 BULK REMOVAL GAS SWEETENING PROCESSES * CHEMICAL ABSORPTION * PHYSICAL ABSORPTION * PHYSICO-CHEMICAL ABSORPTION * PHYSICAL ADSORPTION * CRYOGENIC FRACTIONATION (CO2 Removal only) * MEMBRANES / PERMEATION (CO2 Bulk Removal) * DIRECT CONVERSION OF H2S INTO SULPHUR 100101 SOLVENT USED: ALKANOLAMINES IN AQUEOUS SOLUTIONS ‘Sweet Gas Lean Amine Solution ABSORBER or CONTACTOR Rich Amine Solution CHEMICAL ABSORPTION PROCESS PRINCIPLE 102Basic Principle of a Chemical Absorption for Gas Sweetening Os a ee ‘ABSORBEUR (Absorber) en ‘ORZACIDE HS +002 fies Gas) aC aC €¢ = (Regenerator) REGENERATEUR et) ALKANOLAMINES FOR CHEMICAL ABSORPTION * MONOETHANOLAMINE (MEA) Primary Amine 15 to 20 wt. % MEA Public Domain CO2/H2S Removal * DIGLYCOLAMINE (DGA®) 2-2Aminoethoxyethanol Primary Amine more than 50 wt. % DGA Patented process for several years (FLUOR) Non selective CO2/H2S Removal Non select * DIISOPROPANOLAMINE (DIPA) Secondary Amine Around 45 Wt. % MDEA Patented process (ADIP from SHELL) Selective H2S Removal * METHYLDIETHANOLAMINE (MDEA) Tertiary Amine Around 45 Wt. % Patented processes Selective H2S Removal * DIETHANOLAMINE (DEA) Secondary Amine 25 to 35 wt. % DEA Public Domain Non selective CO2/H2S RemovalChemical Formulas of Amines 108 PRIMARY AMINE MONOETHENOLAMINE (MEA) DIGLYCOLAMINE @ (DGA) 4 H | | N-CH2-CH2-OH WoH2-cH2-0-cH2-CH2-OH H H SECONDARY AMINE DIETHANOLAMINE (DEA) DIISOPROPANOLAMINE (DIPA) (CH2-CH2-OH-N-CH2-CH2-OH CH CHOWN CH CHLOH H CHS oH CHS TERTIARY AMINE i METHYLDIETHANOLAMINE (MDEA) i (CH2-CH2-OH-N-CH2-CH2-OH i i CHS i 05 q PHYSICAL PROPERTIES OF ALKANOLAMINES - AMINE MEA GA, DEA ira MDEA Te primary Primary | secondary | secondary | —_tentary ‘Moteular Weight 61.08 105.14 vos [13319 1947 2 Amos. Boing Poin age m Pa aie, | ar Frezng oie ac ws | es | 20 0 no Critical Pressure ba 59.9 at 327 377 388 Cita! Temperature ‘ec 5800 018 2 sa 019 Density at 20dez.C hyn 1018 1057 ws 8 1085 Specific Heatat156degC | Wika. K | 256 2390 2511 2886 2am, BemslGnscisn 55 | vinx | 0256 [eawarouec | 0220 ougais Vapor Pressreat20deg0 | amt Ey H 001 oor Heat of vaporization at 760 ours mmHg ape kak 825 509 ‘oun vicotiy cr | atiamage | aaissaze | 2/5 101 20dsnC Senin wasn eopacsnn [omnes [oeawn | armn | Smpieal® : Hew orneacion — [ aTULS [ag 250 0 750 sm i Hew orteason aminenias | PTUL® | 650 om ” 30 “0 i 3 qAlkanolamine General Process Flow Diagram 107 MEA Sweetening Process Flow Diagram[BAB NGL CENTRE /GAS TREATING /DGA FLUOR ECONAMINE PROCESS (Original Design) ms < ty "s ? 3 a “t_ yl aig , 5 Y r + 8 109 FLUOR ECONAMINE PROCESS BAB PLANT (GASCO/On-Shore ABU DHABI) DESIGN FIGURES Summer | Winter Feed Gas Flow Rate MMSCFO 114 109 > Feed Gas coz mole % 331 3.36 H2s mole % 117 1.19 ‘Treated Gas coz ppm V 50 H2s ppm V 16 110MDEA PROCESS LICENSORS © BASF aMDEA02 or aMDEA03 Aqueous solution: generally 50 wt.% aMQEA © DOW CHEMICAL s&s GAS SPEC Process (Cs 3 38tent) Aqueous solution: generally 50 wL@ Solvent © UOP ed AMINE GUARD BROCESS (UCARSOL Solvent) Aqueous solution: generadfy 50 wt.% Solvent ©® TOTAL (now no More licenser) Activated MDEA Aqueous solution: generally 50 wt.% Solvent 1 UOP Amine Guard Process (UCARSOL Solvent) 112TOTALFINAELF ACTWATED MOEA PROCESS Se iets SSR SaPat SRL colic tabi en Tae Ga eet eat, SES ier ae Bea a Bakar wg 113 Mechanical Filter (main filter) Objective: Removal of the solids from the amine solution to absorber to prevent corrosion and foaming. «Target: lean amine solid content < 100 ppm Wt. Characteristics: Generally leaf-type precoat filter *Filtration mesh: 10 » maximum. Inlet flow rate: 10 to 20 (for large units) % of the solution circulation rate. *Velocity: 1 to 2 gal/minute per ft2 of surface area Pressure drop: 1 b maximum. Alternative: Back washable sock filter. Cartridge filter (frequent replacement of the cartridges). Particulate content ‘micron | Below or equals to 10| 50 Equals to or above 100 ‘Amine solution color clear grey black 4APPROXIMATE OPERATING GUIDELINES FOR AMINE GAS TREATING PROCESSES Amine MEA | DGA® | DEA | MDEA Strength weight % | 15-20 50-70 25-35 30-50 Rich Solution Loading mole/mole | 0.35-0.40 | 0.33-0.45 | 0.40-0.50 | 0.46-0.50 Lean Solution Loading mole/mole 0.12 0.10 0.08 0.01 ‘Acid Gas Pickup mole/mole | 0.23-0.28 | 0.25-0.35 | 0.32-0.42 | 0.45-0.49 Reboiler temperature degC 107-122 | 122-127 | 110-122 | 118-124 Advantages/Disadvantages of Chemical Absorption Processes ADVANTAGES DISADVANTAGES Not strongly affected by Acid Gas partial pressure - Low absorption of hydrocarbons from Feed Gas - Basic Process in the Public Domain Reasonable cost of solvents + Large Industrial references « Exothermie Chemical Reaction which requires large ‘quantity of energy forthe Regeneration of the solution «Foaming tendency when the solution is slightly polluted (hydrocarbons, solid particles) «Solution degraded by oxygen (must be kept away from air contact) = Need constant water make-up (boiler feed water quality) «Treated Gas high water content + Solvent storage area to be heated 6 115PHYSICAL ABSORPTION PHYSICAL ABSORPTION PHYSICAL SOLVENTS AND ASSOCIATED PROCESSES WATER WASH : Not Recommended (heavy corrosion) SELEXOL Process : UOP licensor (originated by NORTON) Based on the use of Dimethyl Ether of Potente (DMPE) ¢ IFPEXOL 2: IFP licensor (but with |FPEXO: Py Based on the use of Methanol r e FLUOR SOLVENT: No more ay; FLUOR is no more procesesthe sor. Based on the use of pidpMlene Carbonate © MORPHYSORB: New development (end 1990's) from Krupp Uhde (use of Morpholine) « PURISOL/RECTISOL: Lurgi’s Processes based on the use of Methanol "7 118IFPEXOL | IFPEX 2: Gas Swostoning Process! Simplified Flow Diagram 19 MORPHYSORB " (KRUPP UHDE) 120EXAMPLE OF SULPHUR SPECIFICATIONS PURITY 99.8 wt.% mini H2S CONTENT 10 ppm (wt.) max COLOR OF SOLID SULPHUR BRIGHT YELLOW Standard CLAUS PLANT (3 catalytic stages): SIMPLIFIED PROCESS FLOW DIAGRAM Aad Gas and Ae Probing wen 12S conto below 8 ntAdvantages/Disadvantages of Physical Absorption Processes ADVANTAGES DISADVANTAGES « Low Energy Requirements - Performances dependent strongly upon Acid Gas Partial Pressure + Corrosion Effects minimized « Performances dependent strongly upon Feed Gas Temperature - Low Treated Gas Water Content - Absorption of Hydrocarbons which can build up and reduce Solvent efficieney No Need For Dilution Water + Claus Plant Feedstock containing hydrocarbons (Pure Solvent required) (Produced Sulfur with black spots) « Absorption of Mereaptans -Can Need External Mechanical Refrigeration cycle - Vacuum Regeneration can be needed -High Cost of Solvents 123 SULFINOL PROCESS (SHELL LICENSOR) Mixture of two solvents * Chemical Solvent : AMINE (MDEA or DIPA) * Physical Solvent : SULFOLANE Process called SULFINOL M with MDEA Process called SULFINOL D with DIPA Combines advantages of chemical and physical absorptions but with the drawback of a physical absorption (Hydrocarbon Absorption) 14FEED GAS ADSORSER TREATED GAS K.0. ORUM ¥.0. DRUM — > FEEDGAS FLASH VESSEL PUEL Gas TREATED. Gas eS suLFNOL Flute REGENERATOR REFLUX ACCUMULATOR Hear EXCHANGER i i oe | Soon | { 5 To solvent FROM SOLVENT RECLAIMER MAKE UP TANK AND ‘SOLVENT RECLAIMER ACID GAS SHELL SULFINOL PROCESS: SIMPLIFIED PROCESS FLOW SCHEME 125 @ PHYSICAL ADSORPTIONADSORPTION PROCESS MOLECULAR SIEVES TYPE: 4A, 13) e Molecular Sieves Natural or Synthetic ZEOLITES Classified as ALUMINOSILICATES Crystalline Structure (cavities of uniform form and shape) Affinity between Polar Molecules and Zeolites Used to removed H2S and CO2 when they are present in small quantities Used to remove Mercaptans 1 cop — WET ACID GAS 1 Free Water TREATED GAS DEPRESSURISATION scpnessunisarion . ¢ cf Adsorver A. { Aosorber © pene pl crt A: Adsorption MOLECULAR SIEVE UNIT © + Heating TWO (2) BEDS SYSTEM R : Cooling Y PHYSICAL ADSORP)@ Gaseous PERMEATION (Membranes) For the bulk removal of CO2 Membrane material: Cellulose Acetate, Polyimide GASEOUS PERMEATION g 5 a4 é 88 :. - oie ae 129 190MEMBRANE TYPE « SPIRAL WOUND Membrane « HOLLOW FIBER Membrane 131 (Membrane) ES ecnongs) (DUAL CRS 3 \ - \ PERMEATE TURE “WHIGH PRESSURE Huish pressure 5 CHANNEL SPACER ESTDUAL ERS MEMBRANEICLOTH COMPOSITE WHICH PRESSURE GAS MIXTU \ \ jan S—<—<—$—$— PERMEATE CHANNEL SPACER 4 o! SPIRAL-WOUND ELEMENT CONSTRUCTION(Membrane) HOLLOW FIBER MEMBRANE ELEMENT (CYNARA) CO; RICH GAS i“ ~~ Seal Gasket F —— Epoxy coating Fea [; HL | —— auminio Tube ii Diam. 3t04em \ Holes Diam, 5 to 7 mm RESIDUE GAS Fibers Bundle Diam. 4” and 9 1/2" Length 41m CO, RICH GAS = Feep cas MAIN SUPPLIERS OF MEMBRANES -CYNARA Hollow Fiber (Cellulose Acetate) = -KVAERNER e Spiral W ound (Cellulose Acdate) Hollow Fiber (Polyimide © o -UBE INDUSTRIES * Hollow Fiber (C ellugye Acetate) -UOP Spiral W ound (Cellulose Acetate)tage Membrane System Block Diagram Feed t Stage Sales Pre-Treatment First Stage fe Membrane Vent (5 to 10 mole % C1) i 135 - i tage Membrane System Block Diagram | “To reduce permeation of Hs (Methane) Feed | First Stage Sales Pre-Treatment Vent | Second Stage Membrane First Stage | c. Membrane “ompressor Second Stage Pre-TreatmentKVAERNER Spiral Youre pom Compete dhe Spur coacn Far | [B20 L wf es, 4 | = | Potcing For r = J esov (Momibrenes: Module + |p Tams | 120degF 400 | t i oa lo of YY Moco 3 Y ie Tt cate — oo VentSome large Base Load Membrane Plants [Membrane Plant Location | Capacity Date ‘CO2in/out IKVAERNER ASAMERA (Indonesia) 310MMSCFD} 1996 31/15 mole% jUOP QADIRPUR (Pakistan) 265MMSCFD | 1993 7/2 mole % jUOP KADANWARI (Pakistan) 210MMSCFD| 1993 12/3 mole % ICYNARA | WILLIAMS FIELD SERVICE (USA) | 300 MMSCFD| 1992 11/6 mole % ‘Remark: A large plant based on the CYNARA technology is now in operation in Malaysia and another one also in Thailand (as far as we know, end 1990's) ) 140@ DIRECT CONVERTION OF H2S TO SULFUR (LIQUID REDOX PROCESSES) 141 Liquid REDOX Sulfur Recovery ‘Avi Lo-Cat IT simplified Process Flow Diagram ‘at pee ‘Spent sluon wi ferrous ons (resus en seuien)POLISHING TREATMENT (H2S Removal) Non regenerative DRY BEDS *Conversion of H2S into S via chemical reaction between a metal oxide (example: ZnO) and H2S Process applied to small H2S quantities 20 to 40 kg/day Sulfur production GUIDELINES FOR THE SELECTION OF ACID GAS PROCESSES BASED ON SULFUR PRODUCTIONS It is often said (with the care to be taken about such statements) that : e Up to 40 kg/day Sulfur: Non regenerative Dry Beds e Up to 20-30 t/day Sulfur: Liquid Redox Processes * For 10 and more t/day Sulfur: Amine+ClausH2S SCAVENGERS For small produced gas H2S concentrations (traces) Liquid-based Processes * Injection in the Feed Gas Stream Amine, Triazine-based products (not recovered) ¢ Process applied to very small H2S quantities in the produced Gas Injection rate: 0.2 to 0.6 liter/ppm (Vol.) H2S.MMSCF of Gas HYDROCARBON LIQUID EXTRACTION FROMCONTENTS « HYDROCARBON LIQUID EXTRACTION TECHNICS ¢ FRACTIONATION ¢ STORAGES LOADING WHY HYDROCARBON LIQUID EXTRACTION FROM NATURAL GAS ? e@ TO RECOVER GASOLINE (C5+) e TO EXTRACT NGL (NATURAL GAS LIQUID) FOR LPG MANUFACTURE, e TO SATISFY A SALES GAS HYDROCARBON DEW POINT @ TO MEET SALES GAS REQUIRED HEATING VALUE e TO AVOID TWO-PHASE FLOW PATTERN IN A GAS TRANSPORTATION LINE 143BG SALES GAS SPECIFICATIONS SPECIFICATIONS UNITS VALUES GROSS CALORIFIC VALUE kJ/m3 (1)_| between 38000 and 40500 WOBBE INDEX kJ/m3 (1) | between 47300 and 52200 H2S CONTENT ppmvol. |<3.3 TOTAL SULPHUR ppm vol. (2) |< 35 ‘OXYGEN CONTENT mole % |<0.1 ‘CO2 CONTENT mole% |<2 WATER DEW POINT. <-17 deg.C at 41 bar g HYDROCARBON DEW POINT <-2deg.C at any pressure < 69 bar g (1) m3 at Standard Conditions ( 60 deg.F and 14.7 psia) (2) expressed as H2S 49 Compositional Analysis FRIGG GAS (WellFluid) HYDROCARBON DEW CURVE mole | N2_ | 0.4000 co2 | 04122 C1 (95.6796 2 | 33970 3 | 0.0289 ic4 | 0.0050 nc | 0.0050 ics 000s | rcs | 0.0010 C6 | 0,0009 crs | 0.0039 ce | 00022 | cos | 0.0098 cis} oon | cu+| 00139 | 12+ | 0.0098 14s | 0101 16+ | 0.0047 18+ | 0.0028 €20+ | 0.0013 n ” * 100 110 Temperature (deg.0) Vapor zone (Uiquide Vapor) zoneHC LIQUIDS FROM GAS: DEFINITION OF TERMS (1) Feed Gas Flow Rate at Normal Conditions : 1 atm a and 0 deg.C (2) NGL trom Cold Separator (no stabitization) (9) NGL from Stabitzation (C1/C2 removal) (4) Orginal Design Figures (Summer case) COMPONENTS ‘Abbreviation C1/C2|C3|C4/C5+ DEFINITION British /French LIQUEFIED NATURAL GAS (1) | LNG /GNL —— | NATURAL GAS LIQUID NGL /LGN j—-—} LIQUEFIED PETROLEUM GAS| LPG /GPL +—>| NATURAL GASOLINE. or CONDENSATE i (1) not included inthis presenta merit dedicated chapter) i st 3 i ip re waves [Sa ; Plant | __Plant__| Phase t = | Location ‘OATAR, ‘ABU DHABI | ABU DHABI | ALGERIA i custome | ovsione | oFrsHose | onsione | Feedoasiato | nnam (7 37700 “27692 367500 | 638554 = | nciraw tm 170 59 56 2 : nol @ ow o @ t mole 3% mole % mole % mole % : ‘cozmes eae a g er 105s 018 009 E |ce rae 2238 oes 292 3 |o sr aot os | sts 2 Ne “n aoe vs | ate & | nce 087 1073 23.20 21.05 3 |cs 220 538 ax 469 2 | ns 2.95 542 9.65 397 q con 240 932 822 615 2 [rou 10000 700.00 100.00 100.00, i Moicuar Weight 3160 su78 3690 01 é 132(GASOLINE + NGL) EXTRACTION FROM NATURAL GAS. LPG MANUFACTURE Block Flow Diagram ee LEAN GAS REMOVAL aawans | RAW GASOLINE NGL FRACTIONATION To Storage Lec ca. 5] asouine STABILIZATION STABILIZED GASOLINE To Storage HYDROCARBON LIQUID EXTRACTION TECHNICS Gas Cooling and Chilling for the Condensation of Hydrocarbons a ISENTHALPIC EXPANSION (JOULE-THOMPSON VALVE) m= EXTERNAL MECHANICAL REFRIGERATION m ISENTROPIC (POLYTROPIC) EXPANSION = PHYSICAL ABSORPTION (Refrigerated Oil Absorption) Each of the above processes can be combinedProssure 2 * ° ® ® “ggpes8 Thermodynamic Paths for Hydrocarbon Liquid extraction Temperature T@ ISENTHALPIC EXPANSION JOULE-THOMSON (J-T) VALVE i 17 4 y JOULE-THOMSON EFFECT (Isenthalpic Expansion) FOR HYDROCARBON LIQUID EXTRACTION uTValve Residue Gas Low Tamporature Sopaator }) Lato er Hydrocarbon Liquid (raw Gasoline) (Lean Satsion) (eh Souton)Pressure Pe ISENTHALPIC EXPANSION OF NATURAL GAS Gas/Gas Exchanger Effect v2 12 1) Temperature 159 LTS process with gas/gas heat exchanger 180PHASE DIAGRAM PATHS FOR NGL RECOVERY WITH Joule ~ Thomson EXPANSION (J.7. VALVE) PRESSURE ‘bar(a) 150 | ose envtoe a maura gu am rary spat ]B Phase envelope of cold separator gae meeting sales (gas specication / AT /aP =043°C/bar . =e [PN r= len gas | Loan gas cK | | 2s \ 90. fe \ \ eee “TI | 38 | | ae | lL, jo S| 2 _T rewwenarune -o “HC Liquid mole around 9. 0 700 ISENTHALPIC EXPANSION OF NATURAL GAS - GAS COOLING - RULE OF THUMB : 0.4/0.5 deg.C/bar AP - SHOULD THE GAS BE WET (presence of water vapor) HYDRATE INHIBITION SHALL BE REQUIRED TO AVOID HYDRATE-FORMING Lean Gas mole % : around 90.LTS Process based on J-T valve Advantages Disadvantages - Simple Process - Not sensible to gas flow rate variations - Easy to operate and maintain - Low investment costs - Gas Dehydration Process - Low Hydrocarbon Liquid Recovery Liquid recovery affected by upstream pressure variations - Requires high upstream pressure - Residue Gas available at low pressure @ EXTERNAL MECHANICAL REFRIGERATIONFeed Gas External Cooling for NGL Extraction External Mechanical Fetrigeration Pressure 185 LTS process based on the use of an external mechanical refrigeration cycle ‘ae econ Vi . Low Tear Spar Es | ten innoiny Residue Gas nen lMelnne— HydocarbonLgud (NOL) teense (hen sar) 166 [sed nrememns nn ens 8LTS process based on the use of an external mechanical refrigeration cycle (Feed Gas circuit and mechanical refrigeration cycle) tte ‘trae ser en spay PX Hr ii (an NAL) gen Fetigeaton Fu (M) canponsser Coser w o w Freezing Points of aqueous glycol solutions Monoethyiene glycol + += Diethyere glycol ° ° g § 3 8 © 10 20 30 40 50 60 70 80 90 100 Glycol per cent by weight 187 168‘Comparison between pure Refrigeration Fluids etngerant twaeosar | Dew Tonpertiats.0:3bara eae cost Wore 0 wor stb FREON TART 1709 39 wes edu FREON 212 (6) v9 coos ne neu FREON 22.20 (6) ace “04 aa ‘mea ‘AMON. vr0w = a tow Eman (9 so. cas: 12799 tow eT ENE (69) sansa soa @ bee smo won| wor | ABS oe PROPYLENE 116) 2008 a7 sae tow sone we | awaQ ow vs (1) reper ar rom Ganja and eig 3 (2) 000 nat xt Ay) Cececnanrusinannie (4 Component no peso nati gases (2) 0. rss a3. 784eg i (Fem Pot eNom 169 i Propane Vapor Pressure Curve . Critical Point 45 40 _ 36 @ 5 30 5 2 25 g 5 20 a g 15 = 10 | ; 0 Sat ss 50 -40 -30 -20 10 0 10 20 30 40 50 60 70 80 90 100 Temperature (deg.C) 170ii Tithe PP Pere a4 E, i i m3 External Mechanical Refrigeration Cycle (Single-Stage)Refrigeration Fluid Pressure/Enthalpy Diagram Single-stage refrigeration cycle: Thermodynamic path “ at i i i i i i wu mez Eathal me Tame Aa 173 CYCLE THERMODYNAMIC BALANCE Eneray In CHILLER Aart > COMPRESSOR kw Energy Out DESUPERHEATER Aa2 » CONDENSER az KW + Aat Aa2 Aas Note: AQ@2 and AQ are positive vaues (niet enthalpies = outlet enthalpies) AQ1 and KW are positive valves. (outlet enthalpies - inlet enthalpies) 1%Single-Stage Propane Cycle eon gee SS atatoee A owe 0a TS taba i “" j QRoemeve rroncwrmsonten enmaeier mnt i F i sy j Mechanical Refrigeration Cycle with vapor Economizer mginoe| q cman i i g i Clemnoemnaanca ———— ] [ my iRefrigeration Fluid Pressure/Enthalpy Diagram Retrigeration cycle with economizer: Thermodynamic path @Q ls cnier (vaporizer) aa Wer Wks Enthalpy TWiiwe wee 7 PROPANEGYCLEWITHECONOMZER conoensen ad | bees q at) scomaniioR] ‘Sage este « q goss 32cm ‘pop =a2701 xii = 072 Cipro aoe 178LTS Process based on External Refrigeration ‘Advantages Disadvantages . Well suited to LPG recoveries (especially butane) - Independent from Feed Gas pressure variations « Use of well known pure refrigeration fluids - Can be installed downstream of of any other process without problem - Gas Dehydration Process Not suited to LPG high yield recovery = Not suited to C2 recovery Not suited to high pressure Feed Gas (above 80 bar) - High energy required - Make-up facilities required - Expensive process Mixed Fluid Refrigeration Cycle aporized mixed tid @ salve 0 pecwaon) ra Ta ‘Saluatag taut trad 1 NGL 2034 Pomer = 2044208 a &IFPEXOL Thtegrated Funetions Process ExXtracts All with MethanOL, | IFP licensor of IFPEX 1 (Gas dehydration and NGL extraction) and IFPEX 2 (Gas Sweetening) all with Methanol TREATED GAS | DEHYDRATION WEETENING (IFPEX 2) + NGL EXTRACTION (IFPEX 1)ISENTROPIC EXPANSION POLYTROPIC EXPANSION Pressure ISENTROPIC (POLYTROPIC) EXPANSION OF NATURAL GAS Food Gas Phase Envelope Lean Gas; ‘Temperature 184eritane POLYTROPIC EXPANSION THROUGH TURBOEXPANDERTurbo-expander : Cut-away illustration‘TURBOEXPANDER PLAN of the 70/80's _ J, ale: 183 ca 2 KT KA TURBOEXPANDER PLAN of the 80'S | oto O6UEfgon cousernon couanen Tuten courntsson Tee on EXPORT. Ware tas 2254 Fd er Kafer ea hrs a 1 wrestler lor rare mrept sae | 6 | ear COLDBOX 2 Tt Vahe pumprou owes ecstion pups rt enn oncom tran stom) ‘Weng ian ‘eeUp to Date Turboexpander plan for LPG high yield recovery reg i i m4 j C02 FREEZING CURVES (Gas is mainly Methane) Gas ——— Liquid ---vee __ 200 | ora bara Gas 47h bara Gas S £9 |an8 bar a Gas i 13.9 bar a Gas 2 no eT £ Permitted Zone 0.4 bar a Gas = “750 5 = 300 ‘> 950 3 900 02 Freezing Zone S950 set 8 +” Liquid Phase TT ae ee | ° 5 10 18 20 C02 mole % in Feed 192Turbo-Expander Process . Allows to recover energy = Can be installed downstream of other process to improve NGL. recovery Up to date processes with inlet pressures around 75 bar a leads to LPG high yield recovery Advantages Disadvantages Well suited to Ethane recoveries « Highly dependent upon Feed Gas pressure - Needs an upstream Feed Gas Dehydration « Requires additional compression to restore the Feed Gas pressure - Requires additional extemal ‘eftigeration cycle for ethane recovery = Can require a large number of rotating equipment e@ LEAN OIL ABSORPTION PROCESS 193REFRIGERATED LEAN OIL ABSORPTION prvnnnaaasnana a spans nasa sannna 4 ! RECOVERY | Revection separation — ' ! ' \ ' ' . t ' i Refrigeration | ! 1 ' t ' ' ! ' ' ' ' ' ' t ' ' I 1 1 A 1 1 1 1 i 1 rent Absorber t ' Prods! to f 1 1 Pipeline wis | ' ' wo 7 | ' ! ' Residue I { Ges + ! ' 1a | { . | ‘Rich OW Demethonizer — | I : L--~----------- care ert mnie herrea niente 4 ? i 3 sea Absorbers Demethanizer sil NGL Fractionation Dehydators, Example of a Refrigerated Oil Absorption Process for LPG Extraction| @ FRACTIONATION > GASOLINE > NGL i q i ] : 'Bison i | 19 4 i Gasoline Extraction and Stabilization by a Fractionation Column with Reflux cq et) I pee F | i | eanaiaed,—|gnierey — ytecomag Sa litt | sae lt : } _ nee 3 3 : : pn ; ion i i 200GPA LPG Specifications (from GPA Standard 2140-92) Characteristics ‘Commercial | Commercial ‘Commercial Propane Propane Butane BP Mixtures HDS ‘Composition a Predominantly | Predominantly | — Predominantly not loss than 80 Propane andior | Butanes andor | Mixture Butanes | ig. Vol. % Propane Propylene Butylenes «andlor Butylenes ‘not more than 5 with Propane andor | ig. Vol. % Propylene Propylene Vapor Pressure at $7.8 deg.C 1494 KPA 9 489 KPa 0 1494 KPA. 1434 KPA G, Volatile residue: “Temperature at 95 % evaporation, 98.3 degC 22 deg.c 2.2 degc -98.3.deg.C Max. Butane & heavier 25 v0). % 25 vol % Max. Pentanes & heavier 2v0l.% 20h. % ‘Rsidval matter: - Residue on evaporation of 100 ml, max: 0.08 mi - 0.05 mit Corrosion, Copper stip, max. wet Net Nat Net “Total Sulfur 185 ppm weight | 140 ppm weight | 140 ppm weight 423 ppm weight Free water content ‘none none ‘one ‘none 202NGL Fractionation Train Conmari! Propane Commercial Butane 25 bar — LPG POLISHING TREATMENTS TO REMOVE H2S and SULFUR COMPOUNDS *HIGH CONTAMINANT CONTENT. - AMINE (Chemical Absorption) + DEHYDRATION (Physical Adsorption) Example : ADIP (NGL 1/2 at QGPC) and RUWAIS (GASCO) *LOW CONTAMINANT CONTENT - MOLECULAR SIEVES (Physical Adsorption) Generally 4A, 13X Types Example : ADGAS (two first LNG trains)@ HYDROCARBON LIQUIDS STORAGE TANKS GASOLINE STORAGE TANKS Stabilized Gasoline: Floating Roof Tank Non-stabilized Gasoline: Fixed Roof TankFLOATINF ROOF TANK Example STORAGE TANKS PRESSURIZED TANKS + PRODUCT AT AMBIANT TEMPERATURE: PRESSURE IS VAPOR PRESSURE AT THIS TEMPERATURE (for Propane, it will be around 14 bar a at 40 deg.C) + STORAGE TYPE: SHERES (up to 5000 m3 volume) REFRIGERATED TANKS + PRODUCT AT ATMOSPHERIC PRESSURE (for Propane, it will be around -42 deg.C) + STORAGE TYPE: CYLINDRICAL TANK (up to 40000 m3 and even more) 2081PO Pressurized Storage Tank : SPHERE No longer peri not maunded (Europoan Aet of 1082) 210FRENCH REGULATION FOR LPG PRESSURIZED TANKS (Based on EUROPEAN ACT of 1982) ABOVE GROUND STORAGE TANK : MAXIMUM VOLUME LIMITED TO 500 m3 MOUNDED STORAGE TANK : MAXIMUM VOLUME LIMITED TO 10000 m3The first LPG Refrigerated Tanks installed REFRIGERATED STORAGE TANK. =f, | ol i i Vapor Retin te Grewaton ine (1) Submerged Puce lca! maori he prod) FULL INTEGRITY PRE-STRESSED CONCRETE REFRIGERATED TANK FOR PROPANE ‘ one LPG at Aumospheric Boling Pont Inataton 8 i ana218 C3 and C4 products subcooled by the C3 product (Open Loop) compnesson| Hoa Propane to Storage a CHILLER 216@ LPG LOADING AND EXPORT LPG product Loading Facilities Cae© Refrigerated Tank BOIL-OFF RECOVERY 219 LPG tanks Boil-off recovery by a dedicated propane open loop (Boil off vapor amounts fo 0.10 % of the storage capacity per day) LES Condensed propane (63 from Plant 3 bore tum 4 trom Plant | J Tank UT C4 boi vap 2022