Mass Transfer 1B: Absorption

Mr L.B Moyo
langa.moyo@nust.ac.zw
OFFICE SD1
Consultation : Friday -1000-1200
Objectives
• Understand the Two-film theory & its assumptions, mass transfer
equations and coefficients
• Understand equilibrium solubility curve and discuss resistance to
mass transfer in gas-phase and iquid-phase
• Understand concept of overall mass transfer coefficients
• Analyse gas solubilities using the equilibrium curve
• Understand Henry's Law and its application and limitation
Introduction
• We now move to analysis of gas absorption. Gas absorption essentially
involved the transfer of materials from the gas phase to the liquid phase.
it is "defined" as the operation in which a gas mixture is contacted with a
liquid for the purpose of preferentially dissolving one or more
components of the gas mixture and to provide a solution of them in the
liquid.
• The gaseous component is said to be absorbed by the liquid. The
transferred component is known as the solute.
• In the simplest case, gas absorption involves as least 3 components. As an
illustration, consider an ammonia-air-water system. The gas contains
ammonia-air mixture. Ammonia is the solute and it is very soluble in water
while air is not. Hence, by means of contacting the gas mixture with water,
ammonia will dissolves preferentially in water, and a solution of ammonia
in water (ammonium hydroxide) is obtained.
• Gas absorption processes are widely used in the industry. It can be
used for removing contaminants or impurities from a gas stream.
One of the most common examples of gas absorption and stripping is
the amine absorption and regeneration unit whereby toxic H2S gas
from a fuel gas mixture is removed by liquid amine (DEA, MEA or
glycol) as will be discussed later.
• Other example include the absorption of CO2 using hot potassium
carbonate, or using the solvent Selexol® .
• Yet in other applications, it can be used for gas dehydration when an
insoluble gas is dried by contact with a dehydrating liquid. An
example is in the drying of chlorine using 98 wt% sulfuric acid.
• In air pollution control, the various oxides of nitrogen can be
removed by absorption with water, sulfuric acid, and organic
solutions. Gaseous ammonia can be removed by absorption with
water.
Equilibrium solubility curve
• The gas absorption process involves the re-distribution of solute
between the gas phase and the liquid phase when the 2 phases come
into close contact and achieves equilibrium condition.
• The relationship between solute concentration in the gas phase and
in the liquid phase at constant temperature and pressure is known as
the equilibrium distribution curve, as shown in the Figure below. The
presence of the solute in the liquid represent the its gas solubility at
the prevailing temperature and pressure.
Equilibrium curve
• The equilibrium solubility curve for gas absorption as seen here is not the same as the
equilibrium curve for distillation. Some of the important differences to observe.
• in distillation, we have seen that the equilibrium curve simply shows the equilibrium
relationship between 2 components: the more volatile and the less volatile. In gas
absorption, as noted at the beginning, in the simplest case, there will be 3 components
(e.g. NH3 , air and water).
• the equilibrium solubility curve is plotted for a particular constant temperature. Any
point on the same curve represent gas solubility at the same temperature. For the
equilibrium curve in distillation, the points represent vapour-liquid equilibrium at
different temperatures.
• there is no 45o diagonal for solubility curves, i.e. the solubility curve can lie anywhere in
the x-y plot (or p-y plot, etc). On the other hand, the equilibrium curve for distillation
normally lies above the 45o diagonal line (except, of course, for azeotropic mixtures).
• the equilibrium solubility curve is not usually plotted over the entire concentration range
from 0.0 to 1.0 mole fractions (as in customary done for design of continuous distillation
column using McCabe-Thiele Method). This is because generally most gases are soluble
in a liquid only over a narrow concentration range
Film concept in mass transfer
• As previously noted, gas absorption operation involves mass transfer from the gas
phase to the liquid phase. That means the gas molecules must diffuse from the
main body of the gas phase to the gas-liquid interface, then cross this interface
into the liquid side, and finally diffuses from the interface into the main body of
the liquid.
• In the gas phase, 3 flow regimes can be visualized
• Fully developed turbulent region where most of the mass transfer
takes place by eddy diffusion
• · A transition zone with some turbulence
• A laminar film with molecular diffusion
• Such phenomena are difficult to analyze. Instead, we will use a
simplified TWO-FILM THEORY as a basis for analysis as well as
development of various correlations of mass transfer phenomena.
Two film theory
• Once again consider the interface between the gas phase and the
liquid phase, now simplified as shown in the Figure below
• This interface can represent any point in the gas absorption
equipment where the gas contacts the liquid. See the Figure below
(right) that shows a counter-current gas absorption column. We will
study the diffusion of solute A from the gas phase into the liquid
phase, for example NH3 that is diffusing from an gaseous air-NH3
mixture into liquid phase water.
Assumptions of two-film theory:

• · Steady-state: concentrations at any position in the tower do not

change with time.
• · Interface between the gas phase and the liquid phase is a sharp
boundary.
• · Laminar film exist at the interface on both sides of the interface
• · Equilibrium exists at the interface, thus there is negligible resistance
to mass transfer across the interface: (xi, yi) is the equilibrium
concentration.
• · No chemical reaction: rate of diffusion across the gas-phase film
must equal the rate of diffusion across the liquid-phase film
Two film theory and equilibrium curve
• In the analysis of gas absorption, we are interested in the transfer of
materials throughout the entire gas absorption equipment, not just a
single location in the equipment. Therefore the two-film theory can
be analyzed more effectively by using the equilibrium solubility curve.
• The concentrations at the interface in the gas ( yAi ) and in the liquid (
xAi ) is represented as a point M on the equilibrium solubility curve.
Point M thus has the coordinates ( yAi, xAi ). As we move along the
column along the continuous interface, we can trace out an
equilibrium curve.
• [ Remember that one of the assumptions of the two-film theory is
that equilibrium condition exists at the interface ]
• Very often, the subscript "Ai" is dropped, and the equilibrium curve is
simply a relationship between y and x; i.e. y = f(x).
• The concentrations in the bulk gas phase ( yAG ) and in the bulk liquid
phase ( xAL ) is represented as a point P above the equilibrium curve.
Point P thus has the coordinates ( xAL, yAG ). Point P is located above
the equilibrium curve.
• Notation :
yAG = composition of A in the bulk gas phase (mole fraction)
xAL = composition of A in bulk liquid phase (mole fraction)
( xAi, yAi ) = equilibrium interface compositions (mole fraction)
• Analysis of Mass Transfer Process using Two-Film Theory
• In the gas-phase, the concentration falls from yAG in the bulk gas to yAi
at the interface. Thus, there is a concentration driving force for mass
transfer from the bulk gas to the gas film to the interface.
• At the interface, the component A crossed the interface and enters
the liquid side.
• In the liquid-phase, the concentration falls from xAi at the interface to
xAL in the bulk liquid. Thus, there is a concentration driving force for
mass transfer from the interface to the liquid film to the bulk liquid.
• The mass transfer process can be represented by the line PM. See the
Figure above.
• Mass transfer can be described by a set of mass transfer equations.
Click here for more information.
•
• NOTE : The bulk concentrations yAG, xAL are not equilibrium values,
otherwise there would be no diffusion of A.
• The two-film theory and equilibrium curve can be expressed in other
ways, e.g. in terms of partial pressure (for the gas phase) and
concentration (for the liquid phase); but the analysis for them is the
same as outlined before for mole fractions ( x and y).
Mass transfer equations
• In commercial absorption equipment, both the liquid and the gas are
usually in turbulent flow and the film thickness is not easy to
determine. Therefore instead of analysis of mass transfer using Fick's
Law, it is more convenient to write the molar flux of A using mass
transfer equation of the form below:
• Molar Flux, NA = Mass Transfer Coefficient x Driving Force
• At a point A (xAL, yAG), we can write the mass transfer equations for
each of the phases:
 NA molar flux of component A, mole/(area.time)
ky mass transfer coefficients in the gas phase
concentration driving force in the gas phase (mole
( yAG - yAi )
fraction)
kx mass transfer coefficients in the liquid phase
concentration driving force in the liquid phase (mole
( xAi - xAL )
fraction)
The k-values above are also known as film mass transfer coefficients, and they are
usually determined experimentally, or by correlations. Because there are many analogies
between heat transfer and mass transfer, many correlations originally derived from heat
transfer are used for the prediction of mass transfer coefficients.
 Mass transfer coefficient
• The previous definitions for molar flux NA require the knowledge of the
interface concentrations. Since experimental sampling of the
concentrations at the interface is very difficult or virtually impossible; it is
more useful to define the mass transfer equation using overall mass
transfer coefficients KX and KY

xA* is the concentration (mole fraction) in liquid phase that is in equilibrium with yAG.
yA* is the concentration (mole fraction) in vapor phase that is in equilibrium with xAL.
• Driving force for mass transfer: ( yAG - yA* ) in the gas phase (as
indicated by line PC) and ( xA* - xAL ) in the liquid phase (line PD)
• Relationship between film and overall mass transfer coefficients:
• It can be shown that kx, ky, KX, and KY are related through the
following equations:

• where m" is the slope of line segment DM, and m' is the slope of line
segment MC as shown. If the equilibrium line is straight, then m' =
m".
• kx , ky , KX , and KY all change with positions in the tower.