# Qualitative Phase Behavior and Vapor Liquid Equilibrium Core

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1 2/22/2017 Qualitative Phase Behavior and Qualitative Phase Behavior Introduction There are three different phases: solid, liquid, and gas (vapor) Energy must be added to melt a solid to form liquid If enough additional energy is added, the liquid can be vaporized We must know the phase or phases that exist at given conditions of pressure, volume and temperature to ascertain the corresponding energy level Separate substances into two classifications: Pure substances or single component systems Mixtures of substances or multi-component systems 1

2 2/22/2017 Learning Objectives By By the the end end of of this this lesson, lesson, you you will will be be able able to: to: Describe pure component phase behavior Describe multicomponent phase behavior and phase envelopes Define critical point, cricondentherm, cricondenbar, dense phase, retrograde condensation Summarize the effect of C6+ characterization on the shape of the phase envelope Recognize the effect of various non-hydrocarbon components on the shape of the phase envelope List examples of fundamental applications of phase envelopes in facilities design and operations P-T Diagram for a Single Component System Critical Point Tc & Pc 2

3 2/22/2017 Vapor Pressure - Gas Cooling Using Propane Propane = vapor Vapor Pressure - Gas Cooling Using Propane Propane = liquid 3

4 2/22/2017 Vapor Pressure - Gas Cooling Using Propane Saturated liquid/vapor Saturated vapor Saturated liquid Vapor Pressure - Gas Cooling Using Propane P cond = 1.70 MPa P chiller = 0.23 MPa Let s now find the condensation pressure at known temperatures P cond =? P chiller =? T chiller = -23 C T cond = 50 C 4

5 2/22/2017 Vapor Pressure - Gas Cooling Using Propane T chiller = -10 F T cond = 122 F P chiller =? P cond =? P cond = 243 psia P chiller = 35 psia 5

6 Phase Behavior of C2 nc7 System Liquid C 2 H 6 + n-c 7 H 16 Binary System Phase Envelope True critical point locus Pseudo critical point locus Vapor T Bubble = 117 C T Dew = 245 C 6 1

7 T-P-x Diagram for C 2 -nc 7 System Pressure Multi-Component Phase Behavior P 92, Fig 4.5 Liquid E Cricondenbar N B B Critical Point C D D A A M Cricondentherm E Temperature 7 2

8 Multi-Component Phase Behavior P 92, Fig 4.5 Pc Critical Point C E Cricondenbar N D B A B A Pressure Pressure Liquid Tc Temperature Multi-Component Phase Behavior P 92, Fig 4.5 Liquid Isobaric Retrograde Region E Cricondenbar N B B Critical Point C D D D E A M Cricondentherm A Vapor Isothermal Retrograde Region M Cricondentherm E Vapor Temperature 8 3

9 Effect of C 6 + Characterization on Phase Envelope for Non-Associated Gas Characterization based on TBP analysis of C 6 + Effect of CO 2 on a Rich Natural Gas Phase Behavior Hydrocarbons are frequently produced with nonhydrocarbon impurities Water Carbon dioxide Hydrogen sulfide Nitrogen C 7 C 9 C

10 Effect of CO 2 on a Rich Natural Gas Phase Behavior Effect of H 2 S on a Rich Natural Gas Phase Behavior 10 2

11 Effect of N 2 on a Rich Natural Gas Phase Behavior Summary of Components Effect on Phase Envelope The impact Heavy components of light and such heavy as components C6+ have great on impact the shape on the of dew phase point envelope curve can be summarized: Since heavy components have low vapor pressure, they have no significant effect on the bubblepoint curve Light components have significant effect on the bubblepoint curve due to their high vapor pressure 11 3

12 Pump Suction Pressure Conditions A B Pump inlet Pressure, kpa Pressure Operating Pressure C Inside pump at impeller eye -150 Required Operating Temperature kpa psia C F A B -100 B A C Liquid In storage tank Temperature Temperature, F -50 B 0 T = -40 C(-40 F) Cricondentherm Temperature Of Processed Gas = -3 C[26.6 F] A 50 Vapor Hydrocarbon Dewpoint Specification (-3 C[26.6 F]) 100 Cricondentherm Temperature Of Processed Gas = -25 C[-13 F] Pressure, psia Temperature, C 12 1

13 Effect of Pressure on Dewpoint Control Processing Temperatures Effect of Pressure on Dewpoint Control Processing Temperatures Cooling Cooling of a Gas in Facility Piping Cold Separator B Sales Gas A B A 13 2

14 Process Flow Diagram for an Amine System Inlet Sweet Gas To Dehydration Lean Amine Pressure Sour Gas Inlet Filter Coalescer A LC Amine Contactor Distance = L B High Pressure Pipeline Phase Envelope Operation in the dense phase region To Amine Level Control Valve LC Rich Amine To Closed Drain Gas Processing to lower dew point L J K I Temperature 14 3

15 Learning Objectives You are now able to: Describe pure component phase behavior Describe multicomponent phase behavior and phase envelopes Define critical point, cricondentherm, cricondenbar, dense phase, retrograde condensation Summarize the effect of C6+ characterization on the shape of the phase envelope Recognize the effect of various non-hydrocarbon components on the shape of the phase envelope List examples of fundamental applications of phase envelopes in facilities design and operations 15 4

16 Learning Objectives Qualitative Phase Behavior and Vapor Liquid Equilibrium By the end end of of this this lesson, lesson, you will you be will able be to: able to: Explain the concept of equilibrium vaporization ratio, K List the common methods of estimating K values Describe flash, bubble point and dew point calculations and list examples of their application Describe the effect of composition on bubble point, dew point, and flash calculations for a hydrocarbon mixture Describe stabilization of hydrocarbon liquids using stage separation Summarize the differences between Reid Vapor Pressure (RVP) and True Vapor Pressure (TVP) 16 1

17 Quantitative Vapor-Liquid-Equilibrium Calculations For the following feed to the separator what are vapor rate (V), liquid rate (L), compositions of the vapor and liquid streams (y i and x i )? Feed Property Value z C2 mol % 90 z nc7 mol % 10 F, kmol/h or lbmol/hr 100 T, C [ F] 75 [167] P, kpa [psia] 5000 [725] Quantify Phase Behavior Pressure, kpa Temperature, F Vapor Property Value y C2 mol %? y nc7 mol %? V, kmol/h or lbmol/hr? Liquid Property Value x C2 mol %? x nc7 mol %? L, kmol/h or lbmol/hr? DP, 100% Vapor 1200 BP, 0% F Temperature, C Pressure, psia 17 2

18 Pressure, kpa Quantify Phase Behavior Temperature, F DP, 100% % Vapor BP, 0% V= F= L= Temperature, C Quantitative Vapor-Liquid-Equilibrium Calculations For the following feed to the separator what are vapor rate (V), liquid rate (L), compositions of the vapor and liquid streams (yi and xi,)? Feed Property Value z C2 mol % 90 z nc7 mol % 10 F, kmol/h or lbmol/hr 100 T, C [ F] 75 [167] P, kpa [psia] 5000 [725] Vapor Properties Value y C2 mol % 97.6 y nc7 mol % 2.4 V, kmol/h or lbmol/hr 75 Liquid Properties Value x C2 mol % 67.2 x nc7 mol % 32.8 L, kmol/h or lbmol/hr 25 Pressure, psia

19 Pressure, kpa Quantitative Vapor-Liquid-Equilibrium Calculations Temperature, F DP=270 F 1300 DP, 100% Vapor BP=113 F % % % BP DP % At Bubble Point 700 L = % 600 V = 0 BP, 0% At Dew Point 400 L = V = DP=132 C 0 0 BP=45 C Temperature, C Quantitative Vapor-Liquid-Equilibrium Calculations Temperature, F UDP 8000 BP 1200 DP=7650 kpa DP=1110 psia 1100 BP=7210 kpa BP=1045 psia LDP DP=3283 kpa DP= psia Temperature, C Pressure, kpa Pressure, psia Pressure, psia 19 4

20 Equilibrium in Practice Equilibrium is a very important concept in VLE calculations At equilibrium: The pressure of the liquid and vapor phase are the same The temperature of the liquid and vapor phase are the same The composition of the phases does not change with time It takes time to achieve equilibrium Calculations are performed assuming equilibrium with adjustments for how closely the process actually approaches equilibrium Equilibrium in Practice Equilibrium is a very important concept in VLE calculations In absorption and fractionation calculations, no true equilibrium exists At equilibrium: The assumption The pressure of equilibrium the liquid and must vapor be phase corrected are the by same an efficiency factor The temperature of the liquid and vapor phase are the same The composition of the phases does not change with time The concept of equilibrium in a two-phase system does not This does not mean that molecules are not crossing the phase mean that the system is static boundary. Molecules are moving from the vapor to the liquid and Molecules from the liquid still continuously to the vapor transfer but the net between movement phasesof these No molecules net change is zero. in composition occurs It takes time to achieve equilibrium Calculations are performed assuming equilibrium with adjustments for how closely the process actually approaches equilibrium 20 1

21 Basis for VLE Calculations At equilibrium: Vapor phase pressure = Liquid phase pressure Vapor phase temperature = Liquid phase temperature Vapor phase energy = Liquid phase energy Component fugacity in vapor phase = component fugacity in liquid phase Raoult s Law P T If we assume the vapor phase is an ideal gas Vapor Partial Pressure P = system pressure; = vapor phase mol fraction If we assume the liquid phase is an ideal solution Then at equilibrium, This is called Raoult s Law and it can be used to estimate K-values for systems where the ideal gas and ideal liquid assumptions are valid. yi K i x i PVi P Vapor Liquid Liquid Partial Pressure = vapor pressure at system temperature, = liquid phase mol fraction 21 2

22 Equilibrium Vaporization Ratio 10 K-Value Chart for C 3 in Natural Gas Mixture at 0 C 10 K-Value Chart for C 3 in an NGL Mixture at 0 C K-values from EOS K-Value 1 K-values from Raoult s Law Vapor pressure of C 3 at 0 C = 474 kpa or 69 psia Pressure, kpa Equilibrium Vaporization Ratio K-Value K-values are a function of: Temperature Pressure Liquid composition Vapor composition 1 K-values from Raoult s Law K-values from EOS Pressure, kpa 22 3

23 Methods for Estimating K Values As discussed on the previous slide, correlations based on an Equation of State are the most common method of estimating K-values These are included in process simulation software packages For demonstrating how equilibrium calculations are performed we will be using the K-value charts in Appendix 5A of the Chapter 5 in the Campbell GC&P Text, Vol. 1 The C3 K-value charts are shown to the right. Propane Propane Temperature C Temperature F Pressure, MPa Pressure, psia 23 4

24 Flash Calculation (P 115) Overall material balance F L V Eq 5.15a Component material balance zf i xl i yv i Eq5.15b At equilibrium y K x x y /K i i i Liquid and Vapor Phase Mole Fraction for F = 1 zi zi xi & yi Eq 5.16a L VK ( L/ K ) V i Sum of mole fractions must be equal to 1 zi zi x i 1 & yi 1 Eq 5.16b L VK ( L/ K ) V BP, DP and Flash Calculations Sum of mole fractions = 1 For bubblepoint, L = F = 1, V = 0 zi yi 1 ( L/ K ) V For dewpoint, V = F = 1, L = 0 zi xi 1 L VK i zi zi x i 1 & yi 1 L VK ( L/ K ) V i i i y z K 1 Eq 5.13 i Flash Calculation ( 0 < V and L < 1) N N N zi( Ki 1) yi xi 0.0 Eq 5.17 V( K 1) 1 i 1 i 1 i 1 i i i i i i i i i P T Known: P, T, F, z i Unknown? L, V, x i, y i x z / K 1 Eq 5.14 i i i Please PAUSE the video as needed. 24 1

25 Bubble Point Example Calculate the bubble point temperature of the following mixture at 2000 kpa [290 psia] Feed Composition Assume T=5 C Assume T = 30 C The bubble point temperature is approximately 15 C Assume T =15 C Component zi ki (yi)/(ki) ki (yi)/(ki) ki (yi)/(ki) Methane Ethane Propane n-butane Note that methane and ethane contribute more to the bubble point than propane and butane Dew Point Example Calculate the dew point temperature of the following mixture at 2000 kpa [290 psia] Feed Composition Assume T=70 C Assume T = 60 C Assume T =67 C Component zi ki (xi)/(ki) ki (xi)/(ki) ki (xi)/(ki) Methane Ethane Propane n-butane The dew point temperature is approximately 67 C Note that propane and butane contribute more to the dew point than methane and ethane 25 2

26 Flash Calculation Example Perform a flash calculation for the following mixture at 2000 kpa [290 psia] and 40 C [104 F]. Feed Composition K value at 30 C and 2000 kpa Assume L=0.8 V=0.2 Assume L=0.7 V=0.3 Assume L=0.77 V=0.23 Component zi Ki xi=zi/(l+vki) xi=zi/(l+vki) xi=zi/(l+vki) yi=(ki)(xi) Methane Ethane Propane n-butane The liquid fraction (L) is about 23% of the feed (F) and the vapor fraction (V) is about 77% of the feed (F) The liquid phase composition is highlighted in yellow and the vapor phase composition is highlighted in light brown. Note that methane and ethane concentrate in the vapor phase and propane and butane concentrate in the liquid phase 26 3

27 Stabilization of Hydrocarbon Liquids For crude oil, condensate and C5+ NGL mixtures the vapor pressure specification, with few exceptions, is near or below one atmosphere at a specified temperature. The purpose of a near atmospheric vapor pressure specification is to facilitate the storage and transportation of the product due to pressure and emission limitations on storage tanks, rail cars, road tankers and marine tankers. How is it done? Stage separation with heat input as required Distillation column Stage separation Stabilizer column Debutanizer column Stabilization of Hydrocarbon Liquids The liquid leaving the last point in the process where it is separated from the vapor stream is at its bubble point Separation conditions fix the vapor pressure of the liquid at some specified temperature (ex: 100 F [37.8 C]) Stage separation Stabilizer column Debutanizer column 27 1

28 Stabilization of Hydrocarbon Liquids If stage separation is used the temperature and pressure of the final separation stage will determine if the vapor pressure of the product If a crude oil or condensate stabilizer is used, the vapor pressure of the product will be determined by the stabilizer column bottom conditions If the product is a C5+ NGL mixture, the vapor pressure will be determined by the debutanizer bottom conditions Stage separation Stabilizer column Debutanizer column Two-Stage (or Three-Stage) Separation Flash stabilization is the most common method of stabilizing crude oil. Condensate can be stabilized this way as well but stabilizer columns are more commonly used in condensate systems. V 1 V 2 If gas is flashed off of the stock tank it is considered a separation stage V 3 F 1 F 2 F 3 Stock Tank L 1 L 2 L

29 Two-Stage (or Three-Stage) Separation Increasing the number of intermediate separation stages increases total liquid production, system complexity, and capital cost. In some systems, one of the separation vessels may also be the vessel where crude oil is dehydrated. The first-stage pressure is fixed by inflow performance and/or export gas pressure. F 1 It is seldom greater than 13.8 Mpa (2000 psia) V 1 L 1 Two-Stage (or Three-Stage) Separation F 2 Pressure at the last stage will be at, or near, atmospheric pressure and is fixed by temperature and vapor pressure specification. V 2 L 2 V 3 If crude oil meets vapor F 3 pressure specification upstream Stock of stock tank, it is Tank not a stage Intermediate stage pressures can be adjusted to yield maximum liquid recovery at stock tank conditions and/or minimize compression power. L 3 V 1 V 2 V 3 F 1 F 2 If crude oil meets vapor F 3 pressure specification upstream Stock of stock tank, it is Tank not a stage L 1 L 2 L

30 Single Separation System ST Separator would be required to operate at vacuum conditions to meet the vapor pressure specification Single Separation System 30 C [86 F] X X Compression ratio is limited by compressor type and gas properties Maximum compressor discharge temperature is C [ F] For hydrocarbon gases with a relative density of 0.6 to 0.7 and a suction temperature of around 40 C, the compression ratio is limited to about For heavier molecular weight gases the maximum compression ratio may approach 5.0. Scrubber liquids are frequently recycled back to a lower pressure separation stage Most molecules in scrubber liquids heavier than butane stay with the crude oil ST Separator would be required to operate at vacuum conditions to meet the vapor pressure specification X X 30 C [86 F] Most molecules lighter than propane flash off and leave with the export gas Propane and butane molecules get trapped in the system and create recycle effect that increases flash gas flow through the compressors 30 4

31 Vapor Stream Compositions for 4-Stage Separation Example Phase Envelopes for 4-Stage Separation System Total mol % of C3, ic 4, and nc 4 = = 61.8 mol % Vapor Streams 31 5

32 Liquid Stream Compositions for 4-Stage Separation Example Phase Envelopes for 4-Stage Separation System Pressure, kpa Liquid Streams Temperature, C 32 6

33 Liquid Production and Compression Power vs. Number of Separation Stages Stage Separation Guidelines (Excluding Stock Tank) The optimum number of stages required for separation is a function of the inlet separator pressure and vapor pressure specification of the liquid Inlet Separator Pressure, kpa Inlet Separator Pressure, psia Number of Stages Greater than 6900 Greater than

34 Schematics of RVP and TVP Sample Cylinders Schematic of an LPG Sample Cylinder True Vapor Pressure (TVP) Schematics of RVP and TVP Sample Cylinders Reid Vapor Pressure (RVP) The RVP test is applicable for crude oils, condensates, and petroleum products such as gasoline or petrol mixtures A liquid sample is collected in the lower 20% chamber The 80% chamber is filled with air at atmospheric pressure & connected to the 20% chamber The actual vapor pressure of the product at a specified temperature TVP specifications must always be referenced to a temperature (between C [ F]) If V/L = 0, the vapor pressure is essentially equivalent to the bubble point of the mixture As V/L increases, the measured vapor pressure will Schematic decrease of an RVP Sample Cylinder Schematic of an RVP Sample Cylinder 34 1

35 Vapor Pressures vs. Temperature for Typical C 5+ NGLs Assume: RVP = 83 kpa (12 psi) at 37.8 C (100 F). What is TVP? TVP 96 kpaa 14 psia Reid Vapor Pressure vs. True Vapor Pressure for Crude Oil kpa The ST Separator operates at 52 C and 132 kpa. What is the approximate RVP of the oil leaving the separator? 125 F C kpa RVP 10 psi RVP 132 kpa 19 psia

36 Learning Objectives You are now able to: Explain the concept of equilibrium vaporization ratio, K List the common methods of estimating K values Describe flash, bubble point and dew point calculations and list examples of their application Describe the effect of composition on bubble point, dew point, and flash calculations for a hydrocarbon mixture Describe stabilization of hydrocarbon liquids using stage separation Summarize the differences between Reid Vapor Pressure (RVP) and True Vapor Pressure (TVP) PetroAcademy TM Gas Conditioning and Processing Core Hydrocarbon Components and Physical Properties Core Introduction to Production and Gas Processing Facilities Core Qualitative Phase Behavior and Water / Hydrocarbon Phase Behavior Core Thermodynamics and Application of Energy Balances Core Refrigeration, NGL Extraction and Fractionation Core Relief and Flare Systems Core Separation Core Gas Dehydration Core Fluid Flow Core Pumps and Compressors Overview Core Contaminant Removal (Dehydration and Sweetening) Core Heat Transfer Equipment Overview Core 36 3

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