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Vapor Liquid Equilibrium : RachfordRice Equation
3. Discussion:
Distillation towers are used to separate mixtures of chemicals into two or more streams, each a relatively
pure stream of one of the chemicals. The physical process governing that separation is vapor-liquid
equilibrium.
Take a mixture of two or more chemicals in a temperature regime where both have a significant vapor
pressure. The composition of the mixture in the vapor is different from the liquid. By harnessing this
difference, you can separate two chemicals, which is the basis of distillation. To calculate this phenomenon,
there is a need to predict thermodynamic properties such as fugacity, and then perform mass and energy
balances over the system.
Phase separation is only one part of distillation process, it is the basis for the entire process. Vapor-
liquid equilibria problems are expressed as algebraic equations.
Flash distillation (sometimes called "equilibrium distillation") is a single stage separation technique. A
liquid mixture feed is pumped through a heater to raise the temperature and enthalpy of the mixture. It then
flows through a valve and the pressure is reduced, causing the liquid to partially vaporize. Once the mixture
enters a big enough volume (the "flash drum"), the liquid and vapor separate. Because the vapor and liquid
are in such close contact up until the "flash" occurs, the product liquid and vapor phases approach
equilibrium.
Simple flash separations are very common in industry, particularly petroleum refining. Even when
some other method of separation is to be used, it is not uncommon to use a "pre-flash" to reduce the load
on the separation itself.
Suppose you know the temperature, pressure, and overall composition of the inlet stream. The mole
fractions of the chemicals in the inlet are called {zi}. In the phase separator, however, the liquid and vapor
are separated. The mole fraction of the chemicals in the vapor phase are called {yi} and those in the liquid
phase are called {xi}. When the vapor and liquid are in equilibrium, you can relate the mole fractions of each
chemical in the vapor and liquid by the equation:
The members of the set {Ki} are called K-values, and they can be predicted from thermodynamics.
For now, assume that their values are known.
To derive the equation governing the phenomenon, you first sum the mole fractions of vapor and
liquid over all components.
2
Next, make a mass balance for each component over the phase separator. F is the total molar flow
rate, V is the molar flow rate of the vapor, and L is the molar flow rate of the liquid. The mole balance is then
This is called the RachfordRice equation. Notice that, if the K-values and inlet compositions {zi} are
known, this is a nonlinear equation to solve for v. Once the value of v is known, one can calculate the
value of the liquid compositions, {xi}, and vapor compositions, {yi}, using Eqs. 1 and 3. The mole balance is
then complete.
4. Resources:
Matlab
5. Procedure:
1. Suppose you have a mixture of hydrocarbons in the inlet stream. You want to find the fraction of the
stream that is vapor and the mole fraction of each chemical in the vapor and liquid streams. Table 1
shows the flow rates and K-values at 180 o F and 70 psia, using a basis of one mole per unit of
time.
TABLE 1. Mole Fractions and K-values for VaporLiquid
Mole Fraction Phase Equilibrium, K-value
Propane 0.1 6.8
n-Butane 0.3 2.2
n-Pentane 0.4 0.8
n-Octane 0.2 0.052
1
8. The following stream is at 126 psia and 178 oF. Calculate the fraction that is vapor by solving the
RachfordRice equation using MATLAB by creating a function file (filename: vpequil8.m) and
issuing fzero command in MATLAB command window. Determine the mole fraction of each
chemical in the vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by creating an m-file
(filename: yourSurname_le08_p08.m) Show the results.
Mole Fraction Phase Equilibrium, K-value
Methane 0.1 1.6
Ethane 0.2 2.65
Propane 0.7 0.762
9. A feed F is split into a vapor product V and a liquid product L in a flash tank. The feed is 50%
pentane, 30% hexane and 30% cyclohexane ( all I mole %). K pentane = 1.685 , Khexane = 0.742 and
Kcyclohexane = 0.532. Determine the fraction that is vapor by solving the Rachford-Rice equation using
MATLAB by creating a function file (filename: vpequil9.m) and issuing fzero in MATLAB command
window. Determine the mole fraction of each chemical in the vapor (Eq.1) and liquid stream (Eq. 8)
using MATLAB by creating an m-file (filename:yourSurname_le08_p09.m). Show the results.
10. The exit gas from ammonia reactor is at 250 bar and contains 61.5% H 2, 20.5% N2 and 18% NH3.
The gas is cooled to 25 0 C (partly condensed), and is then separated in a flash drum into a
recycled vapor stream V and a liquid product L containing most of the ammonia. K NH3 = 0.0393,
KH2 = 60.8 and KN2 = 35.6 . Calculate the fraction that is vapor by solving the RachfordRice
equation using MATLAB by creating a function file (filename: vpequil10.m) and issuing fzero
command in MATLAB command window. Determine the mole fraction of each chemical in the
vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by creating an m-file (filename:
yourSurname_le08_p10.m) Show the results.
function y=vpequil(v)
z=[0.1 0.3 0.4 0.2]
K=[6.8 2.2 0.8 0.052]
sum1=0.;
for i=1:4
num=(K(i)-1)*z(i)
denom=1+(K(i)-1)*v
sum1=sum1+num/denom
end
y=sum1
Command Window:
>> vpequil
z=
K=
num =
0.5800
3 Command Window:
>> vpequil(0.2)
z=
num =
0.5800
denom =
2.1600
sum1 =
0.2685
num =
0.3600
denom =
1.2400
sum1 =
0.5588
num =
-0.0800
denom =
0.9600
sum1 =
0.4755
num =
-0.1896
denom =
0.8104
sum1 =
0.2415
y=
0.2415
ans =
0.2415
4 Calculator Output:
function y=vpequil(v)
z=[0.1 0.3 0.4 0.2];
K=[6.8 2.2 0.8 0.052];
sum1=0.;
for i=1:4
num=(K(i)-1)*z(i);
denom=1+(K(i)-1)*v;
sum1=sum1+num/denom;
end
y=sum1;
Command Window:
>> fzero(@vpequil,0.2)
ans =
0.4258
6 Script Window: < Cuesta_le08_p06.m >
function y=Cuesta_le08_p06(v)
z=[0.1 0.3 0.4 0.2];
K=[6.8 2.2 0.8 0.052];
v=0.4258;
sum1=0.;
for i=1:4
molfracLiquid(i)=z(i)/(1+(K(i)-1)*v)
molfracVapor(i)=molfracLiquid(i)*K(i)
end
Command Window:
>> Cuesta_le08_p06
molfracLiquid =
molfracVapor =
Command Window:
>> v=fzero(@Cuesta_le08_p07,0.2)
v=
0.7079
7 Script Window: < Cuesta_le08_p072.m >
mole fraction
function y=Cuesta_le08_p072(v)
z=[20 30 50];
K=[3.7 1.4 0.6];
v=0.7079;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end
Command Window:
>> Cuesta_le08_p072
x=
ans =
Command Window:
>> v=fzero(@Cuesta_le08_p08,0.2)
v=
0.6767
8 Script Window: < Cuesta_le08_p082.m >
mole fraction
function y=Cuesta_le08_p082(v)
z=[0.1 0.2 0.7];
K=[1.6 2.65 0.762];
v=0.6767;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end
Command Window:
>> Cuesta_le08_p082
x=
ans =
Command Window:
>> v=fzero(@Cuesta_le08_p09,0.2)
v=
0.6907
9 Script Window: < Cuesta_le08_p092.m >
mole fraction
function y=Cuesta_le08_p092(v)
z=[0.5 0.3 0.2];
K=[1.685 0.742 0.532];
v=0.6907;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end
Command Window:
>> Cuesta_le08_p092
x=
ans =
Command Window:
>> v=fzero(@Cuesta_le08_p10,0.5)
v=
0.8500
10 Script Window: < Cuesta_le08_p102.m >
mole fraction
function y=Cuesta_le08_p102(v)
z=[0.615 0.205 0.18];
K=[60.8 35.6 0.0393];
v=0.8500;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end
Command Window:
>> Cuesta_le08_p102
x=
ans =