VLE Flash Calculations for Non-Ideal Systems

We introduced flash calculations for ideal systems (Raoults Law) previously. With our revised models of chemical potential, we are now able to handle non-ideal systems quite accurately. The basic P,T-flash problem: Given: P,T, z1,z2,, zn Find: V,L, x1, x2,xn, y1, y2,, yn

Feed z1 z2 z3=1-z1-z2 Tf, Pf

P,T

Vapour y1 y2 y3=1-y1-y2 Liquid x1 x2 x3=1-x1-x2

1

Use a flash calculation whenever the overall composition of the system is known, but the composition of each phase is not.
CHEE 311 Flash Calculations Handout for non-ideal mixtures

VLE Flash Calculations from a Phase Diagram

To the right is the Txy diagram for the highly non-ideal system of Ethanol(1)Toluene(2) at P=1 atm. 1. Given a feed stream containing 25% ethanol, between what temperatures do we have two phases?

2. At 90C, what are the compositions of the liquid and vapour streams?

3. Under these conditions, what fraction of the system exists as a vapour?

CHEE 311

Flash Calculations Handout for non-ideal mixtures

VLE Flash Equation

When a phase diagram is not at hand, a flash calculation using a model for the phase behaviour is required. Whenever confronted with a flash problem, apply one of the general flash equations:
z iK i =1 1 + V ( K 1 ) i i

(10.17)

or
zi =1 1 + V ( K 1 ) i i

(14.16)

This is the most versatile approach to solving flash problems In all but simple P,T flashes for binary systems, the general flash equation will produce the quickest answer.
CHEE 311 Flash Calculations Handout for non-ideal mixtures 3

Partition Coefficient, Ki
The partition coefficient, Ki = yi / xi, is used to simplify the general flash equation. It reflects the tendency of a component to vapourize. Those components with a large partition coefficient (Ki >1) concentrate in the vapour, while those with Ki <1 concentrate in the liquid phase. The partition coefficient in a VLE system is provided by our phase equilibrium expression (derived from equivalence of chemical potential). Recall,

y i iP = x i iPisat
Therefore,

iv Vil (P Pisat ) where, i = sat exp RT i

y i iPisat Ki = = xi iP

Note that for a non-ideal system, Ki is a function of P,T and the compositions of both the liquid and vapour phase.

CHEE 311

Flash Calculations Handout for non-ideal mixtures

Solving Non-Ideal Flash Problems

The Classic P,T-flash problems involves: Given: P,T, z1,z2,, zn Find: V,L, x1, x2,xn, y1, y2,, yn For a three component system, the VLE flash equation is:
z3 z1 z2 + + =1 1 + V(K 1 1) 1 + V(K 2 1) 1 + V(K 3 1)

14.16

Or, substituting for the partition coefficients:

z3 z2 z1 + + =1 sat sat sat P P P 1 + V( 1 1 1) 1 + V( 2 2 1) 1 + V( 3 3 1) 1P 2P 3P

The general solution involves: Find the vapour phase fraction (V0) that satisfies 14.16. Substitute V into:

xi =
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zi and solve for yi using: yi = K i xi 1 + V(K i 1)

Flash Calculations Handout for non-ideal mixtures 5

Solving Non-Ideal Flash Problems

The non-ideal flash equation requires knowledge of the vapour and liquid compositions to evaluate i and i, respectively. These are the unknowns that we are attempting to calculate Therefore, flash calculations always require iteration. Suppose you are given P,T, z1, z2, z3 and you are asked to find V, and the phase compositions. 1. Calculate the DEWP and BUBLP of the feed at the given temperature to ensure that two phases exist. 2. Use Raoults law to simplify the flash problem to the degree that it can (easily?) be solved. This involves setting i = 1 and i =1 for all components Calculate Pisat for each component at the given T Solve for V using the flash equation, 14.16 Solve for xi, and yi These are ESTIMATES that serve only to get us started!
CHEE 311 Flash Calculations Handout for non-ideal mixtures 6

Solving Non-Ideal Flash Problems

3. Using the latest estimate of xi and yi, along with the P,T given, calculate: i for each component using an activity coefficient model i for each component using an equation of state for the vapour. Calculate Ki = iPisat / iP for each component 4. Using the revised partition coefficients, calculate V through a trial and error procedure on the general flash calculation.
zi =1 1 + V ( K 1 ) i i

5. Recalculate xi,and yi for each component.

xi =

zi 1 + V(K i 1)

yi = K ixi

6. Repeat steps 3 through 5 until the solution converges.

CHEE 311 Flash Calculations Handout for non-ideal mixtures 7

Non-Ideal VLE Calculations

The Pxy diagram to the right is for the non-ideal system of chloroform-dioxane. Note the P-x1 line represents a saturated liquid, and is commonly referred to as the bubble-line. BUBL LINE

PBUBL

x i iPisat = i i

P-y1 represents a saturated vapour, and is referred to as the dew line (the point where a liquid phase is incipient).

DEW LINE

PDEW =
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1 y i i

iPisat
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Flash Calculations Handout for non-ideal mixtures

What is i?
As mentioned previously:

iv Vil (P Pisat ) i = sat exp RT i

and how can it be calculated? What is i - This symbol stands for the solution fugacity coefficient of component i in a non-ideal vapour mixture - Solution fugacity coefficients can be calculated as shown in Lectures 11&12
v

How abouti ? - This is a pure-species property, called the fugacity coefficient of i at saturation; i.e., at P= Psat(T) for a given T - Examples illustrating its calculation were given in Lecture 9
sat

As for the exponential term, it is called the pointing factor (see Lecture 10)

CHEE 311

Flash Calculations Handout for non-ideal mixtures

Non-Ideal BUBL P Calculations

The simplest VLE calculation of the five is the bubble-point pressure calculation. Given: T, x1, x2,, xn Calculate P, y1, y2,, yn To find P, we start with a material balance on the vapour phase:
i =n i=1

yi = 1

Our equilibrium relationship provides:

x i iPisat yi = iP x i iPi yi = 1 = iP i i x i iPisat P= i i

Flash Calculations Handout for non-ideal mixtures

(14.8)

which yields the Bubble Line equation when substituted into the material balance: sat

or

(14.10)
10

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Non-Ideal BUBL P Calculations

Non-ideal BUBL P calculations are complicated by the dependence of our coefficients on pressure and composition. Given: T, x1, x2,, xn Calculate P, y1, y2,, yn To apply the Bubble Line Equation:

requires:

x i iPisat P= i i
i = (T,P, y1, y 2 ,..., y n ) i = (T, x1, x 2 ,..., x n ) Pisat = Pisat (T )
?

Therefore, the procedure is: calculate Pisat, and i from the information provided assume i=1, calculate an approximate PBUBL use this estimate to calculate an approximate i repeat PBUBL and i calculations until solution converges.
CHEE 311 Flash Calculations Handout for non-ideal mixtures 11

Non-Ideal Dew P Calculations

The dew point pressure of a vapour is that pressure which the mixture generates an infinitesimal amount of liquid. The basic calculation is: Given: T, y1, y2,, yn Calculate P, x1, x2,, xn To solve for P, we use a material balance on the liquid phase:
i=n i=1

xi = 1

Our equilibrium relationship provides:

xi =

y i iP iPisat

(14.9)

From which the Dew Line expression needed to calculate P is generated:

P=

1 y i i sat iPi i

(14.11)
12

CHEE 311

Flash Calculations Handout for non-ideal mixtures

Non-Ideal Dew P Calculations

In trying to solve this equation, we encounter difficulties in estimating thermodynamic parameters. Given: T, y1, y2,, yn Calculate P, x1, x2,, xn

P=

1 y i i sat iPi i

i = (T,P, y1, y 2 ,..., y n ) ? i = (T, x1, x 2 ,..., x n ) Pisat = Pisat (T )

?

While the vapour pressures can be calculated, the unknown pressure is required to calculate i, and the liquid composition is needed to determine i Assume both parameters equal one as a first estimate, calculate P and xi Using these estimates, calculate i Refine the estimate of xi and estimate i ((12.10ab) Refine the estimate of P Iterate until pressure and composition converges.
CHEE 311 Flash Calculations Handout for non-ideal mixtures 13

Non-Ideal Bubble and Dew T Calculations

The Txy diagram to the right is for the non-ideal system of ethanol(1)/toluene(2) at P =1atm. Note the T-x1 line represents a saturated liquid, and is commonly referred to as the bubble-line. DEW LINE

PBUBL

x i iPisat = i i

T-y1 represents a saturated vapour, and is referred to as the dew line (the point where a liquid phase is incipient).

PDEW =
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1 y i i

BUBL LINE

iPisat
14

Flash Calculations Handout for non-ideal mixtures

Non-Ideal BUBL T Calculations

Bubble point temperature calculations are among the more complicated VLE problems: Given: P, x1, x2,, xn Calculate T, y1, y2,, yn To solve problems of this sort, we use the Bubble Line equation:

x i iPisat P= i i

14.10

The difficulty in determining non-ideal bubble temperatures is in calculating the thermodynamic properties Pisat, i, and i.

i = (T,P, y1, y 2 ,..., y n ) i = (T, x1, x 2 ,..., x n ) Pisat = Pisat (T )

Since we have no knowledge of the temperature, none of these properties can be determined before seeking an iterative solution.
CHEE 311 Flash Calculations Handout for non-ideal mixtures 15

Non-Ideal BUBL T Calculations: Procedure

1. Estimate the BUBL T Use Antoines equation to calculate the saturation temperature (Tisat) for each component at the given pressure:

ln Pi

sat

Bi Bi sat = Ai Ti = Ci T + Ci Ai ln P

Use TBUBL = xi Tisat as a starting point 2. Using this estimated temperature and xis calculate Pisat from Antoines equation Activity coefficients from an Excess Gibbs Energy Model (Margules, Wilsons, NRTL) Note that these values are approximate, as we are using a crude temperature estimate.

CHEE 311

Flash Calculations Handout for non-ideal mixtures

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Non-Ideal BUBL T Calculations: Procedure

3. Estimate i for each component. We now have estimates of T, Pisat and i, but no knowledge of i. Assume that i=1 and calculate yis using:

x i iPisat yi = iP
Plug P, T, and the estimates of yis into your fugacity coefficient expression to estimate i.

14.8

Substitute thesei estimates into 14.9 to recalculate yi and continue this procedure until the problem converges. Step 3 provides an estimate of i that is based on the best T, Pisat, i, and xi data that is available at this stage of the calculation. If you assume that the vapour phase is a perfect gas mixture, all i =1.
CHEE 311 Flash Calculations Handout for non-ideal mixtures 17

Non-Ideal BUBL T Calculations: Procedure

4. Our goal is to find the temperature that satisfies our bubble point equation:

x i iPisat P= i i

(14.10)

Our estimates of T, Pisat, i and i, are approximate since they are based on a crude temperature estimate (T = xi Tisat) Calculate P using the Bubble Line equation (12.11) If Pcalc < Pgiven then increase T If Pcalc > Pgiven then decrease T If Pcalc = Pgiven then T = TBUBL The simplest method of finding TBUBL is a trial and error method using a spreadsheet. Follow steps 1 to 4 to find Pcalc. Change T and repeat steps 2, 3, and 4 until Pcalc = Pgiven

CHEE 311

Flash Calculations Handout for non-ideal mixtures

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Non-Ideal DEW T Calculations

The dew point temperature of a vapour is that which generates an infinitesimal amount of liquid. Given: P, y1, y2,, yn Calculate T, x1, x2,, xn To solve these problems, use the Dew Line equation:

1 P= y i i iPisat i
Once again, we havent sufficient information to calculate the required thermodynamic parameters.

14.11

i = (T,P, y1, y 2 ,..., y n ) i = (T, x1, x 2 ,..., x n ) Pisat = Pisat (T )

Without T and xis, we cannot determine i, i or Pisat.
CHEE 311 Flash Calculations Handout for non-ideal mixtures 19

Non-Ideal DEW T Calculations: Procedure

1. Estimate the DEW T Using P, calculate Tisat from Antoines equation

Ti

sat

Calculate T = yi Tisat as a starting point 2. Using this temperature estimate and yis, calculate Pisat from Antoines equation i using the virial equation of state Note that these values are approximate, as we are using a crude temperature estimate.

Bi = Ci A i ln P

CHEE 311

Flash Calculations Handout for non-ideal mixtures

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Non-Ideal DEW T Calculations: Procedure

3. Estimate i, for each component Without liquid composition data, you cannot calculate activity coefficients using excess Gibbs energy models. A. Set i=1 B. Calculate the Dew Pressure:

1 y i i sat iPi i C. Calculate xi estimates from the equilibrium relationship: P=

xi =

D. Plug P,T, and these xis into your activity coefficient model to estimate i for each component. E. Substitute these i estimates back into 12.12 and repeat B through D until the problem converges.
CHEE 311 Flash Calculations Handout for non-ideal mixtures 21

y i iP iPisat

Non-Ideal DEW T Calculations: Procedure

4. Our goal is to find the temperature that satisfies our Dew Line equation:

1 P= y i i iPisat i

(14.11)

Our estimates of T, Pisat, i and i, are based on an approximate temperature (T = xi Tisat) we know is incorrect. Calculate P using the Bubble Line equation (14.10) If Pcalc < Pgiven then increase T If Pcalc > Pgiven then decrease T If Pcalc = Pgiven then T = TDew The simplest method of finding TDew is a trial and error method using a spreadsheet. Follow steps 1 to 4 to find Pcalc. Change T and repeat steps 2, 3, and 4 until Pcalc = Pgiven
CHEE 311 Flash Calculations Handout for non-ideal mixtures 22

9.3 Modified Raoults Law

At low to moderate pressures, the vapour-liquid equilibrium equation can be simplified considerably. Consider the vapour phase coefficient, i:

iv Vil (P Pisat ) i = sat exp RT i

Taking the Poynting factor as one, this quantity is the ratio of two vapour phase properties: Fugacity coefficient of species i in the mixture at T, P Fugacity coefficient of pure species i at T, Pisat If we assume the vapour phase is a perfect gas mixture, this ratio reduces to one, and our equilibrium expression becomes,

y i i P = x i iPisat
or
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y iP = x i iPisat
Flash Calculations Handout for non-ideal mixtures 23

Modified Raoults Law

Using this approximation of the non-ideal VLE equation simplifies phase equilibrium calculations significantly. Bubble Points:

x i iPisat P= i i

P = x i iPisat
i

Setting i =1makes BUBL P calculations very straightforward. Dew Points:

1 P= y i i iPisat i

P=

1
i

yi

iPisat

CHEE 311

Flash Calculations Handout for non-ideal mixtures

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