1. PETE 310 Lectures # 6 & # 7 Phase Behavior – Pure Substances (Lecture # 5) Two Component Mixtures Three & Multicomponent Mixtures

2. Learning Objectives After completing this chapter you will be able to:  Understand pure component phase behavior as a function of pressure, temperature, and molecular size.  Understand the behavior of binary and multicomponent mixtures  Behavior understood through proper interpretation of phase diagrams

3. Phase Diagrams  Types of phase diagrams for a single component (pure substance)  (PT)  (PV) or (P  )  (TV) or (T 

4. Phase Diagrams Single Component Phase Diagram

5. Phase Diagrams Vapor Pressure Curve Pressure Temperature Vapor Liquid Critical Point  l  v P c T c

6. Hydrocarbon Families Physical Properties One point in the Vapor Pressure Curve

7. Pressure vs Specific Volume Pure Substance TcTc 2-phase T Specific Volume (ft 3 / lbm) Pressure ( psia ) V v V L CP

8.  Tabulated critical properties (McCain) Pure Component Properties

9. Heat Effects Accompanying Phase Changes of Pure Substances Heat Effects Accompanying Phase Changes of Pure Substances Lv = T  V dP v dT With  V = V Mg -V Ml Btu/lb-mol Clapeyron equation

10. Heat Effects Accompanying Phase Changes of Pure Substances Heat Effects Accompanying Phase Changes of Pure Substances Lv = T  V dP v dT = Approximate relation (Clausius - Clapeyron Equation) dP v dT RT 2 P v Lv

11. Example of Heat Effects Accompanying Phase Changes  Steam flooding Problem: Calculate how many BTU/day (just from the latent heat of steam) are provided to a reservoir by injecting 6000 bbl/day of steam at 80% quality and at a T=462 o F Calculate how many BTU/day (just from the latent heat of steam) are provided to a reservoir by injecting 6000 bbl/day of steam at 80% quality and at a T=462 o F

12. COX - Vapor Pressure Charts (normal paraffins) Pressure Temperature heavier Non-linear scale Log scale

13. Determination of Fluid Properties Temperature of Test Constant V t1 V t2 V t3 = V b V t5 V t4 liquid gas Hg P 1 >> P s P 2 > P s P 3 = P s P 4 = P s P 5 =P s 12345 Ps =saturation pressure

14. Vapor Pressure Determination Pressure P S Volume V L T2T2T2T2 T1T1T1T1

15. Binary Mixtures  Relationships to analyze: P, T, molar or specific volume or (molar or mass density) - as for a pure component – +  COMPOSITION – Molar Composition

16. Hydrocarbon Composition  The hydrocarbon composition may be expressed on a weight basis or on a molar basis (most common)  Recall

17. Hydrocarbon Composition  By convention liquid compositions (mole fractions) are indicated with an x and gas compositions with a y.

18. Our Systems of Concern Gas system Oil system open

19. A separator z i (T 1,P 1 ) x i (T 1,P 2 ) y i (T 1,P 2 ) P 1 > P 2 T 1,P 2

20. with In general Mathematical Relationships

21. Key Concepts  Fraction of vapor (fv)  Mole fractions in vapor (or gas) phase  yi  Mole fractions in liquid (or oil) phase  xi  Overall mole fractions (zi)  combining gas & liquid

22. Phase Diagrams for Binary Mixtures  Types of phase diagrams for a two- component mixture Most common  (PT) zi at a fixed composition  (Pzi) T at a fixed T  (Tzi  P  at a fixed P  (PV) zi or (P  ) zi

23. Pressure vs Temperature Diagram (PT) zi CB CT CP Bubble Curve Dew Curve Pressure Temperature Liquid Gas 2 Phases Zi = fixed

24. Pressure Composition Diagrams - Binary Systems

25. Temperature vs. Composition Diagrams – Binary Systems Temperature Pressure Bubble Curve Dew Curve 2-phases x 1, y 1 PaPa PaPa CP 1 CP 2 T1sT1s T2sT2s T2sT2s T1sT1s 0 1

26. Gas-Liquid Relations z 1 =overall mole fraction of [1],y 1 =vapor mole fraction of [1],x 1 =liquid mole fraction of [1]

27. Supercritical Conditions Binary Mixture

28. Quantitative Phase Equilibrium Exercise

30. Ternary Diagrams: Review

31. Pressure Effect C3C3 C3C3 nC 5 C3C3 C1C1 Gas p=14.7 psia C1C1 nC 5 Gas 2-phase Liquid p=380 psia C3C3 nC 5 C1C1 C3C3 Gas 2-phase Liquid p=500 psia C1C1 Gas 2-phase Liquid nC 5 p=1500 psia 2-phase Liquid C1C1 nC 5 Gas p=2000 psia C1C1 nC 5 C3C3 Liquid p=2350 psia

32. Dilution Lines Ternary Diagrams: Review

33. Quantitative Representation of Phase Equilibria - Tie (or equilibrium) lines  Tie lines join equilibrium conditions of the gas and liquid at a given pressure and temperature.  Dew point curve gives the gas composition.  Bubble point curve gives the liquid composition.

34. Ternary Diagrams: Review Quantitative Representation of Phase Equilibria - Tie (or equilibrium) lines  All mixtures whose overall composition (z i ) is along a tie line have the SAME equilibrium gas (y i ) and liquid composition (x i ), but the relative amounts on a molar basis of gas and liquid (f v and f l ) change linearly (0 – vapor at B.P., 1 – liquid at B.P.).

35. Illustration of Phase Envelope and Tie Lines

36. Uses of Ternary Diagrams Representation of Multi-Component Phase Behavior with a Pseudoternary Diagram  Ternary diagrams may approximate phase behavior of multi-component mixtures by grouping them into 3 pseudocomponents  heavy (C 7 + )  intermediate (C 2 -C 6 )  light (C 1, CO 2, N 2 - C 1, CO 2 -C 2,...)

37. Uses of Ternary Diagrams Miscible Recovery Processes Solvent1 oil Solvent2

38. Exercise Find overall composition of mixture made with 100 moles oil "O" + 10 moles of mixture "A". __________________________________________________________________________________________________________________________________

39. Practice Ternary Diagrams Pressure Effect T=180F P=14.7 psia Pressure Effect O T=180F P=200 psia C1-C3-C10 Pressure Effect O T=180F P=400 psia Pressure Effect O T=180F P=600 psia Pressure Effect O

40. Practice Ternary Diagrams Pressure Effect T=180F P=1000 psia Pressure Effect O T=180F P=1500 psia Pressure Effect O T=180F P=2000 psia O T=180F P=3000 psia O T=180F P=4000 psia O

41. Practice Ternary Diagrams Temperature Effect T=100F P=2000 psia Temperature Effect O T=150F P=2000 psia Temperature Effect O T=200F P=2000 psia Temperature Effect O T=300F P=2000 psia Temperature Effect O

42. Practice Ternary Diagrams Temperature Effect T=350F P=2000 psia Temperature Effect O T=400F P=2000 psia Temperature Effect O T=450F P=2000 psia Temperature Effect O

43. Pressure-Temperature Diagram for Multicomponent Systems

44. Changes During Production and Injection Temperature t 1 Pressure t 3 t 2 Gas Injection Production t t 3 2 Gas Injection Production

45. Homework  See Syllabus please