Flash SS - 12

Technische Universitt Mnchen
3 Flash Calculation and Phase Diagrams Task of flash calculations and definitions Boiling and condensation points of mixtures Phase diagrams of binary mixtures Ideal mixtures Real mixtures Azeotropic mixtures Isothermal and adiabatic flash Algorithm of Rachford and Rice Newtons method Graphical solutions Iteration schemes
Flash Calculation and Phase Diagrams Thermal Separation Processes SS 12 1
Task of flash calculation
T ?? Feed
zi : mean mole fraction over both phases
Flash-Drum
Basis for calculation Conservation of the components i = 1,2K Conservation of energy (first law) Gas-Liquid-Equilibrium Questions How do the components i = 1,2K distribute over the gas and liquid phase? Temperature T
Flash Calculation and Phase Diagrams Thermal Separation Processes SS 12
The two phases are in equilibrium! No special labeling of equilibrium conditions!
Equilibrium values and separation factors

Gas-Liquid-Equilibrium with extended Raoults law
Definition equilibrium values
with extended Raoults law ideal liquid (Raoults law)
dependent on xi
dependent on p and T only j boils higher than i
Definition separation factors ideal mixtures

Flash Calculation and Phase Diagrams
Thermal Separation Processes SS 12
Boiling temperature and pressure of a liquid mixture

Closing condition gas phase
Boiling condition
xi given i(xi) T given psi(T) p can be calculated

(if pressure dependence of i can be neglected)
Iteration required?
p given psi(T) iteration required
Iteration scheme for ideal mixtures

See exercise
Condensation temperature and pressure of a gaseous mixture

Closing condition liquid phase
Condensation condition
yi given i(xi) cannot be calculated T given psi(T) iteration required i(xi) ?

See exercise
Iteration required?
p given psi(T) iteration required
Iteration scheme for ideal mixtures

Boiling and condensation lines of binary mixtures (1)

Gas-Liquid-Equilibrium with extended Raoults law Lower boiling 1
Higher boiling 2
Explicit expression using the separation factor

Often used for a constant separation factor 12
Boiling line
Gas phase as ideal gas
Law of Dalton
Boiling and condensation lines of binary mixtures (2)

Lower boiling 1
Higher boiling 2
Boiling line Condensation line
Ideal mixtures Boiling line Condensation line linear non-linear
Boiling line in (p,x,y)-Diagram of an ideal binary mixture
Benzene
Higher boiling 2 Lighter boiling 1
Saturation vapor pressure of the pure components psi(T) (Wagner equation, Antoine equation,)
Diagram valid only for a one temperature T

8
(p,x,y)-Diagram of an ideal binary mixture
1 subcooled liquid 2 saturated (boiling) liquid 3 first gas bubble 4 wet steam 5 saturated (boiling) liquid 6 saturated gas Liquid
gas and liquid
7 completely evaporated
8 last liquid droplet 9 superheated gas Lowering of the pressure p at constant temperature T
Benzene
(T,x,y)-Diagram of an ideal binary mixture

Gibbs phase rule 1 subcooled liquid 2 saturated (boiling) liquid 3 first gas bubble 4 wet steam 5 saturated (boiling) liquid 6 saturated gas
gas and liquid
7 completely evaporated
8 last liquid droplet 9 superheated gas
Liquid
Benzene
More realistic in Thermal Separation Processes
Increasing of the temperature T at constant pressure p

Thermal Separation Processes SS 12 10
Lever rules in the (T,x,y)-Diagram
Balance of total mole amount
Mole balance of component 1 (benzene)
Lever rules
Benzene
11
(x,y)-Diagram for binary mixtures

Boiling line: state of the liquid Condensation line: state of the gas
often entitled as McCabe-Thiele-Diagram Diagram also possible for T = const, for Thermal Separation Processes the diagram for p = const required
Benzene
Information about temperature T gets lost
Equilibrium line y1=y1(x1)
Benzene Flash Calculation and Phase Diagrams Thermal Separation Processes SS 12 12
(x,y)-Diagram for constant separation factors
Valid only for few mixtures
Benzene
easy separation task: wide boiling difficult separation task: tight boiling
13
Real binary mixtures with deviations from Raoults Law

positive deviation negative deviation
Raoults law
Henrys law
Water
Water Flash Calculation and Phase Diagrams
14
Real binary mixtures

positive deviation from Raoults law Smaller interactions between the two components Both components in the liquid are more active in the mixture as in the pure liquid; they behave as if they would be present with a higher mole fraction x1 respectively x2 Activity coefficients > 1 Higher actual partial pressures in the gas phase p1 and p2 as corresponding to the mole fractions x1 respectively x2 Higher boiling pressure p = p1 + p2 Lower boiling temperature T
pos. deviation
neg. deviation
negative deviation from Raoults law Higher interactions between the two components Both components are in the liquid less active in the mixture as in the pure liquid; they behave as if they would be present with a lower mole fraction x1 respectively x2 Activity coefficients < 1 Lower actual partial pressures in the gas phase p1 and p2 as corresponding to the mole fractions x1 respectively x2 Lower boiling pressure p = p1 + p2 Higher boiling temperature T
15
Azeotropic binary mixtures

Minimum azeotrop Higher positive deviation from Raoults law (much lower interaction) Larger activity coefficients > 1 Maximum of the boiling pressure p = p1 + p2 Minimum of the boiling temperature T At minimum of boiling point it holds x1 = y1 K1 = K2 = 1 At azeoptropic point boiling and condensation line touch, no separation effect at all
Minimum azeotrop Maximum azeotrop
Conditions for Azeotrop
Maximum azeotrop Higher negative deviation from Raoults law (much higher interaction) Smaller activity coefficients < 1 Minumum of the boiling pressure p = p1 + p2 Maximum of the boiling temperature T At maximum of boiling point it holds x1 = y1 K1 = K2 = 1 At azeoptropic point boiling and condensation line touch, no separation effect at all Flash Calculation and Phase Diagrams Thermal Separation Processes SS 12 16
Isothermal-isobaric flash
Given Mole fractions feed and flash conditions Mole amount feed Wanted Mole fractions gas and liquid Mole amount gas and liquid Equations Closing conditions Gas-Liquid-Equilibrium
Mole balances for components

Isothermal-isobaric flash: method of Rachford-Rice
Definition gas fraction
Closing condition Mole balances for components i = 1,2,K
Implicit relation for gas fraction
18
Iteration scheme for ideal mixtures with Newtons method
wanted solution Newtons method

better estimation
tangent
estimation
19
Iteration scheme with the Newton-Raphson-Method (numerical derivative)
NewtonRaphsonMethod
Approximation with finite differences
Excel-Sheet
20
Iteration scheme for real mixtures
Newtons method
more complex since the equilibrium values Ki of the components i = 1,2,K usually depend on the mole fractions xi of the components i = 1,2,K
21
Graphical solution for binary mixture in a (T,x,y)-Diagram
Benzene
22
Graphical illustration of the solution for binary mixtures in a (x,y)-Diagram

Mole balances for components i = 1,2 Operating line, balance line
Slope
Equilibrium line
Point on the diagonal
Balance must be fulfilled Equilibrium state
Balance line
Intersection of balance line and equilibrium line give state of the wet steam mixture x1: saturated liquid y1: saturated gas
23
Special cases for binary mixtures in a (x,y)-Diagram

Mole balances for components i = 1,2 Operating line, balance line
Equilibrium line
Slope Point on the diagonal
Special cases
NG = 0
NL = 0
24
Analytical solution for constant separation factors

Operating line, balance line Analytical relation for the equilibrium line Equalizing results in a quadratic equation for x1 Solution
25
Adiabatic flash
Energy balance
Kaloric equation of state required Given State and mole amount of feed Flash pressure Wanted Mole fractions Gas and liquid Mole amount gas and liquid Equation Closing conditions Gas-Liquid-Equilibrium
Mole balances
Iteration scheme for adiabatic flash for ideal mixtures

Kaloric equation of state required
Newtons method
adiabatic flash with real mixture more complex Process simulators (AspenPlus, Unisim, Pro II, Chemcad,)

Flash SS - 12

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Flash SS - 12

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Technische Universitt Mnchen

Technische Universitt Mnchen

Task of flash calculation

The two phases are in equilibrium! No special labeling of equilibrium conditions!

Technische Universitt Mnchen

Equilibrium values and separation factors

Definition equilibrium values

with extended Raoults law ideal liquid (Raoults law)

Definition separation factors ideal mixtures

Thermal Separation Processes SS 12

Technische Universitt Mnchen

Boiling temperature and pressure of a liquid mixture

Closing condition gas phase

xi given i(xi) T given psi(T) p can be calculated

p given psi(T) iteration required

Iteration scheme for ideal mixtures

Thermal Separation Processes SS 12

Technische Universitt Mnchen

Condensation temperature and pressure of a gaseous mixture

Closing condition liquid phase

yi given i(xi) cannot be calculated T given psi(T) iteration required i(xi) ?

p given psi(T) iteration required

Iteration scheme for ideal mixtures

Thermal Separation Processes SS 12

Technische Universitt Mnchen

Boiling and condensation lines of binary mixtures (1)

Explicit expression using the separation factor

Gas phase as ideal gas

Technische Universitt Mnchen

Boiling and condensation lines of binary mixtures (2)

Boiling line Condensation line

Ideal mixtures Boiling line Condensation line linear non-linear

Flash Calculation and Phase Diagrams

Thermal Separation Processes SS 12

Technische Universitt Mnchen

Boiling line in (p,x,y)-Diagram of an ideal binary mixture

Diagram valid only for a one temperature T

Thermal Separation Processes SS 12

Technische Universitt Mnchen

(p,x,y)-Diagram of an ideal binary mixture

Technische Universitt Mnchen

(T,x,y)-Diagram of an ideal binary mixture

Increasing of the temperature T at constant pressure p

Technische Universitt Mnchen

Lever rules in the (T,x,y)-Diagram

Balance of total mole amount

Mole balance of component 1 (benzene)

Flash Calculation and Phase Diagrams

Thermal Separation Processes SS 12

Technische Universitt Mnchen

(x,y)-Diagram for binary mixtures

Information about temperature T gets lost

Equilibrium line y1=y1(x1)

Benzene Flash Calculation and Phase Diagrams Thermal Separation Processes SS 12 12

Technische Universitt Mnchen

(x,y)-Diagram for constant separation factors

Valid only for few mixtures

Flash Calculation and Phase Diagrams

Thermal Separation Processes SS 12

Technische Universitt Mnchen

Real binary mixtures with deviations from Raoults Law

Water Flash Calculation and Phase Diagrams

Thermal Separation Processes SS 12