Introduction to multicomponent

distillation

Prepared by
Bikash Kumar Mahato
Assistant Professor
IOE, Pulchowk Campus
 Introduction
• In multicomponent distillation, as in the distillation of binary mixtures, the
calculation of equilibrium stages uses mass and enthalpy balances and vapor-liquid
equilibria.
• A mass balance can be written for each component for the column but there is only
one enthalpy balance for the column. The phase equilibria are much more complex
than for binary systems, because of the several components and because the
equilibria depend on temperature, which changes from stage to stage.
• In binary systems the temperature and equilibria also change from stage to stage, but
except with azeotropes, the more volatile component is more volatile than the other
component throughout the column.
• In multicomponent mixtures one component may be more volatile than the average
in one part of the column and less volatile than the average in another part, which
leads to complex concentration profiles.
• In practice the field is dominated by the use of digital computers because of the
mass of numbers needed to quantify the operating and engineering variables and the
many iterations required to obtain convergence of the solutions to the equations.
 Multicomponent phase equilibria.
• The vapor-liquid equilibria for a mixture are described by distribution coefficients or K factors(also known as
equilibrium vaporization ratio), where K for each component is the ratio of mole fractions in the vapor and
liquid phases at equilibrium.
𝑦𝑖
𝐾𝑖 =
𝑥𝑖
• If Raoult's law and Dalton's law hold, values of Ki can be calculated from the vapor pressure and the total
pressure of the system:
𝑃𝑖 = 𝑥𝑖𝑝𝑖𝑣
𝑦𝑖 = 𝑝𝑖/𝑝
Using above equation we get,
𝑥𝑖𝑝𝑖𝑣 𝑝𝑖𝑣
𝐾𝑖 = =
𝑝𝑥𝑖 𝑝
• The K factors are strongly temperature dependent because of the change in vapor pressure. Distillation
calculations, including the bubble and dew point calculations, can be done using the K-values, if available.
• The DePriester chart or nomographs shown in next slide may be conveniently used to obtain K-values for
lower hydrocarbons at different temperatures and pressures. The ratio of K factors is the same as the relative
volatility of the components.
𝑦𝑖/𝑦𝑟 𝑦𝑖 /𝑥𝑖 𝐾𝑖 𝑝𝑖𝑣 𝑝𝑖𝑣
α𝑖𝑟 = = = = (α𝑖𝑟 = only if raoult’s is applicable)
𝑥𝑖/𝑥𝑟 𝑦𝑟 /𝑥𝑟 𝐾𝑟 𝑝 𝑟𝑣 𝑝 𝑟𝑣
Conti.
 Conti.
• The computation of the bubble point, the dew point and equilibrium in a multicomponent
mixture involves an iterative approach. We describe here a technique using the equilibrium
vaporization ratio, K.
• Bubble point calculation method.
• In an n-component mixture, let us select the rth component as the "reference
component. The relative volatility of the ith component with respect to the rth is given
as K,

• In a bubble point calculation problem, the liquid composition is known and the total
pressure is given. We start with an assumed temperature and calculate the vapour
pressures or K-values of all the components.
• Then we can calculate the values of yi= Kixi(=xiPiv/P if the solution is ideal). At the
bubble point, the sum of the yi’s should be unity, i.e,
 Conti.

• The boiling point of the reference substance may be taken as the initial guess. The values
of Ki (i = 1, 2,.... ..... n) and αir are calculated at this temperature and put in previous
equation to get a revised value of Kr.
• We use this revised value of Kr to determine the second approximation to the bubble point.
Computation is repeated till previous eq. is satisfied to the desired degree of accuracy.
• Dew point calculation:
• For the calculation of the dew point of a vapour of known composition, i.e. known yi’s, we may
start with an assumed value of the dew point, and obtain the vapour pressures (or K-values) of
all the components at this temperature.
• Since the total pressure is given, we can calculate the mole fractions of the components in the
liquid phase, xi=yi/Ki, (=yiPi/Piv, if the solution is ideal).
• If the assumed temperature is the correct dew point, the sum of xi must be unity. The following
equations may be used for an efficient iterative computation.
 Conti.

• One of the components is selected as the reference component and the boiling
point of the reference component is taken as the initial guess of the dew point
of the vapour mixture.
• The vapour pressures and the values of α𝑖𝑟 of all the components are
calculated at this assumed temperature and substituted in previous Eq.
• A revised value of Kr and the corresponding temperature are then obtained.
This is the second approximation to the dew point. The computation is
repeated till the desired accuracy is achieved.
 Problem
• Calculate the bubble point of an ideal solution containing 20 mole% n-
pentane(1) and 40 mole% each of n-hexane(2) and n-heptane(3) at 1.5
bar total pressure. Use Antoin equation to calculate vapour pressures
of the components.
Component A B C
n- pentane 15.8365 2477.07 233.21
n- hexane 15.9155 2738.42 226.2

n- heptane 15.877 2911.32 226.65

• Calculate the dew point of a vapour containing 15 mol% n-butane(1),

Component A B C
n- butane 15.6815 2154.9 238.74
n- pantane 15.8365 2477.07 233.21
Cyclo-hexane 15.7794 2778 223.14
n- hexane 15.9155 2738.42 226.2
n- heptane 15.877 2911.32 226.65
 Multicomponent flash distillation
• We shall now analyze flash vaporization of an n-component mixture. For simplicity, we
assume that vapour-liquid equilibrium of the multicomponent mixture can be
quantitatively described by K-values.
• The material balance equations for the component i are given below (the notations are
the same as in the previous section; an additional subscript i is used to denote the ith
component).

• Eliminating F from above eq. we get,

• Putting xWi=yDi/Ki and simplifying we get,

• If we define a vaporization ratio (it is the ratio of the moles of liquid to the moles of
vapour produced on phase separation) as f=W/D, we may write

• If the temperatures of the flash drum and the feed composition are known, Ki’s can be
calculated from the vapour pressure equations and above Eq. can be solved by using any
suitable numerical technique to calculate f, i.e. the fraction of liquid vaporized on
flashing.
 Conti.
• It is rather simple to determine if a mixture would at all flash into two
phases. We may specify the following conditions in this regard.

• If the above two conditions are satisfied, the mixture would separate into two
phases under the given conditions.
 Problem
• We have a mixture of 25 mol% n-hexane(1), 40 mol% n-heptane(2) and 35
mol% n-octane(3) at 400 K and 2 bar total pressure. Will the mixture separate
into two phases? If so, calculate the compositions of the liquid and the vapour
products. Assume the solution to be ideal.

Component A B C
n- ocatne 15.9635 3128.75 209.85
n- hexane 15.9155 2738.42 226.2
n- heptane 15.877 2911.32 226.65