Session 2 - Useful Equations

Training - 1

Vapor-liquid equilibria fundamental equations

n

The K-values are defined as:

i
and
n

i i

Training - 2

i =1

i =1

Vapor-liquid equilibria fundamental equations

K-Value Ki = yi / xi i = 1, .., n Component material balance li = fi / (1 + Ki L/V) i = 1, .., n li = mols component i in liquid fi = mols component i in feed L = total mols liquid V = total mols vapor

Training - 3

Phase equilibria in ideal mixtures

Ideal mixtures - Raoults law K i = P i* / P Molecules are of same
n n n

Size Shape Molecular type

Training - 4

Basic phase equilibria relations

n

K-values can be calculated via the equation of state approach

yi f li Ki = = v xi fi

or the activity coefficient approach

l v l sat sat sat i g ifi Pi exp P - Pi RT yi Ki = = fiv P xi

Training - 5

Although most LTD technologies use the equation of state (EOS) approach we will focus on the activity coefficient approach because it more readily demonstrates the effect of non-idealities

Training - 6

K-values - rigorous equation

g i i Fi,Pi * Fi,P

L i

Training - 7

Ki P P* T ViL xi yi gi Fi,P Fi,Pi *

Vapor-liquid equilibrium constant Pressure Vapor pressure Absolute temperature Liquid molar volume of component i Liquid mole fraction of component i Vapor mole fraction of component i Liquid phase activity coefficient of component i Fugacity coefficient of mixture at system pressure Pure component fugacity coefficient at its vapor pressure

Training - 8

K-values
Non-ideal mixtures Ki = Pi* Ei gi / P Ei = non-ideal gas corrections gi = activity coefficient Application: very low to moderate pressures
n n
Training - 9

Ei is close to unity for low pressures Ei becomes a significant correction at moderate pressures

VLE - effect of pressure

Very low P Low P Moderate P High P Very high P Vacuum 1 - 3 atm. 3 - 17 atm. 17- 70 atm. >70 atm.

Training - 10

K-values
Calculation of non-ideal gas corrections

Pi* and ViL are properties of the pure compound Fi,Pi * and Fi,P are calculated u sin g an equation of state :
Redlich-Kwong (RK) Soave-Redlich-Kwong (SRK) Peng-Robinson (PR)
Training - 11

Activity coefficient
gi accounts for differences in
n n n

molecular type molecular size molecular shape Regular NRTL Wilson Uniquac van Laar Margules Unifac

gi models:
n n n n n n n

Training - 12

Activity coefficient
n n

Only Unifac is predictive (based on group contributions) Parameters for all other methods must be determined from experimental vapor-liquid equilibria data

Training - 13

Group contribution estimation methods

CH3 CH3 - CH2 - C = OH CH3 T - Amyl Alcohol Method 1 -CH3 -CH2-C-OH
Training - 14

Method 2 3 1 1 1 C H -CH2H in OH Sec-Tert 4 9 1 1 1

Activity coefficient
Margules:

g1 = [A12 + 2(A 21 - A12 )x1]x 2 2

A12 and A21 are adjustable parameters

Training - 15

Activity coefficient
Interaction parameters required for every pair of compounds in the mixture.

Training - 16

Activity coefficient
In LTD we use Regular NRTL Unifac hydrocarbon systems non-ideal systems non-ideal systems fill in missing interaction parameters

Uniquac -

Training - 17

ACTIVITY COEFFICIENTS 1 ETHYLBENZENE 2 ETHYLCYCLOHEXANE P = 1 ATM.

Training - 18

Training - 19

Activity coefficient
n

Activity coefficient of a component rises to its highest value when the component is most dilute
n n

Infinite dilution If infinite dilution activity coefficient is 2.0 then that component has volatility that is twice what its vapor pressure would indicate.

is unity when the composition approaches 100%

Training - 20

Activity coefficient
Non-ideality has an effect on column design
n n n n

More difficult to keep heavy key component out of overhead product Easier to strip light key component out of bottoms product Will change feed tray location Overall effect on column depends on factors such as product specifications, etc.

Training - 21

Training - 22

Training - 23

Azeotropes
n

A result of non-idealities which boosts the volatility of one component to match the other component (binary mixture). If a third component is added it will have an effect on the activity coefficients thus changing the volatilities. Two components which form an azeotrope do not necessarily stick together in a multi-component mixture.

Training - 24

Azeotropes
A very specific result of the more general phenomena: Compounds do not necessarily end up where their vapor pressures say they will end up

Training - 25

Ammonia in C2 fractionator
Vapor Pressure psia 390 220 30 Ideal Relative Volatility 1.77 1.0 0.14

NBP Ethylene Ethane NH3 -154.7 -127.5 -28.0

NH3 in small amounts will distribute between ethylene and ethane

n
Training - 26

Reason: activity coefficient of NH3 (dilute) is in the order of 7.5

Relative volatility of 1,3 Butadiene to n-Butane

Training - 27

Comparison of relative volatilities of C4 hydrocarbons to 1-3 Butadiene with and without an 80-mol % acetonitrile 20-mol% water solvent No Solvent 1,3 Butadiene cis-2-Butadiene Isobutylene 1-Butene n-Butane Isobutane 1.00 0.72 0.90 0.90 0.86 0.93 Solvent 1.00 1.35 1.83 1.96 2.84 3.63

Training - 28

Azeotropes
n n

A solvent can be added specifically to break the azeotrope. Extractive distillation

Training - 29

Extractive distillation

Training - 30

Liquid-Liquid Equilibrium
n n

In cases considered above the components are miscible Highly non-ideal mixtures can lead to immiscibility a second liquid phase separates itself from the first. Oil and water do not mix!

Additional phase relationships are needed

Training - 31

Training - 32

Water/hydrocarbon
Three phase equilibria
n n n

The point of three phase equilibrium is sometimes called an azeotrope. The proper term is heterogeneous azeotrope. Temperature is a minimum. Composition of phases are not equal.

Training - 33

Liquid-liquid equilibrium
L-L equilibrium fundamental equation

L1x L1 = L2 x L2 i i i i
applies to any two liquid phases in equilibrium, L-L or V-L-L

Training - 34

Water - hydrocarbon systems

n

Non-ideality is high enough so that

n n

Hydrocarbon phase contains very little water Water phase contains very little hydrocarbon

Training - 35

Water - hydrocarbon systems

L1 L1 gi i

L2 L2 gi i

For a water/hydrocarbon mixture we can assume L1 = water phase

L1 xw L1 gw

=1 =1

L2 = hydrocarbon phase
L2 xw
Training - 36

* xw

X*W =

mole fraction solubility of water in the hydrocarbon phase when full L-L equilibrium is attained

SDB I/9.4-9.1

Training - 37

Training - 39

V-L-L equilibrium - water/hydrocarbon

Therefore for the hydrocarbon phase in equilibrium with the vapor

L2 * gw w L2 w

=
o w * w

Training - 41

V-L-L equilibrium - water/hydrocarbon

and for the water phase in equilibrium with the vapor

L1 w

o w

Training - 42

V-L-L equilibrium - Water/Hydrocarbon

n

Water K-values can be calculated with simplified relationships outlined above.

n

SDB I

9.4-5 through 9.4-9

n n

Avoids using an activity coefficient method Of course, an activity coefficient method can be used.
n n

This is the most general approach Highly non-ideal systems other than water-hydrocarbon

Training - 43

Two Liquid Phases

n

Rigorous VLLE

Water decant option

L1 L2
Training - 44

L W

Rigorous VLLE Calculations

Vapor VLE K-values VLE K-values

Liquid 1

LLE K-values

Liquid 2

Must enable two-liquid phase calculations.

Training - 45

Water Decant Option

Vapor VLE K-values Water Vapor Pressure

Liquid

Water Solubility

Pure Water

WATER DECANT = ON
Training - 46

V-L-L equilibrium - Water/Hydrocarbon

Decant feature in PRO/II
n n

Special water calculations for water/hydrocarbon mixtures. Possible only for a hydrocarbon K-value type, e.g., SRK, CS, BK10, etc.

WATER DECANT = OFF

Water K-value calculated by chosen K-value method.

Training - 47

V-L-L equilibrium - Water/Hydrocarbon

WATER
n n n

DECANT = ON, SOLUBILITY = SIMSCI

DECANT=ON is a modification of the chosen K-value method K-value method must be a hydrocarbon method A hybrid method - separate methodology for water and hydrocarbons

Training - 48

V-L-L equilibrium - Water/Hydrocarbon

WATER DECANT = ON, SOLUBILITY = SIMSCI
n

Water K-Value in hydrocarbon phase calculated from solubilities.

n

Solubilities from choice of methods.

n n n n

Water K-Value in water phase calculated from vapor pressure. Hydrocarbon K-values from chosen K-value method Logic in flash and column to detect second liquid phase. Also is an option to calculate water properties from steam tables.

Training - 49

Azeotropes
n

A solvent that forms a heterogeneous azeotrope with one of the components of a homogeneous azeotrope can be added specifically to break the azeotrope. Example: Add benzene to recover pure ethanol from an aqueous mixture.

Training - 50

Training - 51

Azeotropic system for the production of absolute ethanol using benzene

Training - 52