In principle various methods could be used for the removal of carbon dioxide.

but absorption
in liquids is generally the most economic type of process.
For economic reasons the absorbent must have a large capacity for carbon dioxide, be
capable of regeneration by driving off carbon dioxide, and have a high specific absorption
rate. Liquids used for the absorption of carbon dioxide may merely dissolve the gas
physically or may contain a solute which reacts with dissolved gas. The specific rate of
absorption into physical solvents is in general much less than that into chemical
absorbents.

The main advantages of carbonate solutions for CO 2 removal are the

high chemical solubility of CO 2 in the carbonate/bicarbonate system
and low solvent cost.
The major difficulty is a relatively slow reaction in the liquid phase
causing low mass transfer rates and therefore requiring a large contact
surface. In order to increase process efficiency, rate promoting
additives are commonly used.
An evaluation of the effect of some of the promoters frequently
mentioned in the literature: diethanolamine (DEA), 2-aminoethoxyethanol (AMET), triethanolamine (TEA), triethylamine (TREA) and
methyl-diethanolamine (MDEA).

Gas-liquid mass transfer

A numerical model of a gas-liquid contactor typically consists of two main
parts: the micro model, describing the mass transfer between the gas and the
liquid phase and the macro model describing the mixing pattern within the
individual gas and liquid phases. Frequently applied micro models include:
1. The stagnant film model (Whitman, 1923).
2. The Higbie penetration model (Higbie, 1935).
3. The Danckwerts surface renewal model (Danckwerts, 1951).
4. The film penetration model (Dobbins, 1956 and Toor & Marchello, 1958).

The stagnant film model assumes the presence of a stagnant liquid

film, while the penetration model and the surface renewal model
approach the gas-liquid mass transfer using dynamic absorption in
small liquid elements at the contact surface. In this project the Higbie
penetration model is selected because:
I.

Higbie penetration model is physically more realistic than the

stagnant film model.

II.

The stagnant film model is not a dynamic model and thus less
suited for modelling dynamic processes.

III.

The Higbie penetration model was favoured to the Danckwerts

surface renewal model because the Higbie penetration model is
easier to implement.

The rate or absorption will be determined partly by the hydrodynamnic conditions (flow-rate,
geometry or packing or plate, physical properties of liquid, etc.) and partly by the physicochemical propertics of the system (solubility of carbon dioxide in the absorbent, diffusivity of
dissolved carbon dioxide and of reactants in solution, kinetics of reactions occurring in
solution, etc.). The hydrodynamic factors can, it is believed, be adequately described by two

quantities: kL (the liquid-film coefficient for absorption without reaction) and a (the
interfacial area which is effective in gas-absorption). The value of each of these can be
determined under any given set of hydrodynamic conditions.
If there is resistance to transfer on the gas side of the interface this must also be evaluated and
allowed for in the usual way.

There is a considerable amount of information in the literature regarding volumetric liquidfilm coefficients (kLa) ror the physical absorption of carbon dioxide, oxygen, etc. In various
types and sizes of packing.

The various theories or models which have bcen proposed for the gas-absorption process,
particularly the film model and various surface-renewal models, can be used to predict the
ratios of the rates of absorption with and without various

In gas-liquid jet reactors with two-phase nozzles such as an ejector, both gas and liquid
phases are concentrically introduced and the kinetic energy of the liquid jet is utilized to
disperse gas into fine bubbles. Therefore, larger gas-liquid interfacial areas and higher mass
transfer rates can be obtained than in other types of reactors.
Recently, jet reactors are increasingly used in various industries, such as absorber of
sparingly soluble gases, in waste water treatment and as fermentors in the production of
single-cell protein from biomass.
INTRODUCTION (report atay)
The Ejector Venturi Scrubber Is a wet type of contactor, which utilizes a liquid aedia to
absorb objectionable gases and particulates from a flue gas discharge stream.
Using a mechanical pump to impart a high velocity to the liquid, which accelerates the slower
moving (relatively) gas stream. The liquid is disrupted into droplets as it passes through an
atomizing nozzle. The gas is drawn through the system by transfer or momentum from the
liquid. This type is ca1led an ejector venturi scrubber. The two types of venturi scrubber

have entirely different energy consumption, atomization, and scrubbing efficiency

characteristics. This study focuses on ejector type.
The ejector uses the high velocity energy of the liquid jet stream to (1) breakup and distribute
the liquid stream into a multitude of small drops, and (2) to pump the gas through the
scrubbing system and connecting ductwork. This is a highly efficient way of atomizing the
1iquid and a less efficient way of pumping gas.

Ejector also have been widely used in industry for purposes other than scrubbing (see Table
1.1). They are known by various names., which are usually associated with the application.
Among such names are injector, ejector, eductor and water jet heat exchanger. The steam
injector, for example, is a jet pump designed to supply feed water to a steam boi1er, the
driving fluid being a proportion of the steam generated by the boi1er. The water jet ejector, on
the other hand, is designed to draw leakage air and other non-condensable gases from the
exhaust of a steam turbine p1ant. The water jet heat exchanger is essentia1ly the same as a
steam jet injector, the name signifying that the pump supp1ies heat to the feed water.

MECHANISM BY WHICH A LIQUID JET, INJECTED THROUGH A NOZZLE

INTO A CHAMBER OF GAS,BREAKS UP INTO DROPLETS
Jet breakup is a complex process which is dependent upon the physical properties of both the
liquid and gas phases, the velocities and temperatures of the fluids and the nozsle geometry.
Raman (1983) measured the absorption efficienciey of 6-10% CO2 in NaOH and sodium
carbonate-bicarbonate buffer solutions. Experiments were carried out in a high energy venturi
scrubber, where the gas flow was introducted by a blower and the liquid was introduced
through two spray nozz1es. His experimental results showed that higher throat velocities and
GAS ABSORPTION THEORY
The first theory of gas absorption was proposed in 1923 by Whitman. His two film concept
relates the overall transfer coefficient to the individual film transfer coefficients. The
re1ations are :

where kg and kl, are the overall gas side and liquid side transfer coefficients. kg and kl are the
respective individunl f.lm coefficients, and H is the Henrys Law constant for the solute.
For the case where the solute gas is very solub1e In the liquid phase, small changes of solute
in the gas phase will produce large solute concentration changes in the 1iquid phase. In that
case., the gas phase resistance dominates.Conversely, when the solute gas is relatively
insoluble in the liquid phase, the liquid phase is the major resistance kl kl
Gas Side Mass Transfer Coefficient

Ear1y investigators noted a similar dependence of mass, heat and momentum transfer upon
eddy activity. The existing empirical correlation for heat, mass and momentum transfer were
manipulated by Chilton and Colburn to obtain analogies between these processes in terms

of quantities designated as j-factors. The j-factor for mass transfer is defined as

and that for heat transfer, is

Liquid side mass transfer coefficient

In order to evaluate the liquid film coefficient. k1, the cases of physical absorption and
absorption with chemical reaction are considered be1ow.
Physical absorption
Higbie (1935) proposed the Penetration Theory which accounts for the transient diffusion
of solute from the gas to the liquid phase. By solving the partial differential equation, he
obtained the following
Equation for the mass flux at a point on the liquid surface which ie exposed to a solute gas:

From the definition of mass transfer coefficient

Higbie assumed that the time of exposure te, was the same for all the liquid elements brought
up to the surface from the bulk liquid. The exposure time, te can be estimated from the
hydrodynamic conditions within the system.
The Dankcwerts (1951) surface renewal model assumes that the chance of an element of
surface being replaced with fresh liquid is independent of its time of exposure. Fresh fluid
elements remain in contact with the surface for variable times, t. The fractiona1 rate of
renewal, s, of the area exposed to penetration is assumed to remain constant and the surface
age distribution function is.

This represents the porbability that any element area will be exposed for time, t, before being
replaced with fresh fluid. The average absorption rate is

Ansorption with chemical reaction

An excellent review of the theory of absorption with chemica1 reaction has been presented by
Danckwerts and sharrna (1966). Absorption with chemical reaction is commonly encountered
in processes for the removal or recovery of acid gases. These processes include the removal
of CO2 and H2S in natural gas distribution. the manufacture of CO2 and sodium carbonate,
and the manufacture of sodium sulfite for use in the paper and pulp industry. The absorbent is
usually selected to maximize the amount of gas which will dissolve in the solvent, and to
minimize the cost of regeneration of the solvent.

According to Astarita (1966) absorption with chemical reaction can be thought of as

occurring in the following stepwise fashion:

i) Diffusion of gaseous reactants from the bulk of the gas to the gas liquid interface.
ii) Diffusion of gaseous reactants from the interface to the bulk of the 1iquid phase.
iii) Chemical reaction within the liquid phase.
iv) Diffusion toward the liquid surfece of reactants initially present in the bu1k liquid phase:
and diffusion of reaction products away from the liquid surface.

If step (i) is rate controlling, the overall rate is not influenced by chemical reaction and the
process may be regarded as a simple mass transfer phenomenon.
van Krevelen and Hoftijzer (1968) have claasified chemical absorption processes into four
groups according to the rate of chemica1 reaction.

a) Very fast irreversible reactions (e.g. ammonia absorption In sulfuric acid) have so smal1 a
chemical resistance that the rate is determined practically by the mass transfer in the gas
phase.

b) Fast reversible reactions (e.g. absorption of hydrogen sulfide in alkaline liquors) where the
rate of absorption is determined by mass transfer in the gas phase, and by mass transfer of
the reactants and reaction products in the 1iquid phase.

c) Moderate speed reactions (e.g. absorption of CO2 in alkaline solutions), in which the rate
of absorption is determined by mass transfer of the reactants in the 1iquid phase.

d) For very slow reactions, rate of absorption is determined by diffusion of the reactants in
the liquid phase and by the rate of reaction in the 1iquid phase.

Nuang (1976) analyzed mass transfer into and out of droplets both experimentally and
theoretically. He stated that there are four stages of mass transfer in the life of each drop.

a) mass transfer to 1iquid jet

b) mass transfer during drop breakup
c) mass transfer during drop free fall
d) mass transfer during drop coalescence

Need For CO2 removal

As the main contributor to the greenhouse effect, the recovery and effective utilization of CO2
has received increasing attention. The absorption technique is most commonly employed for
the removal of CO2 emitted from industrial waste gas.
However, due to the very low solubility of CO2, the liquid-side mass transfer usually becomes
the dominant factor. Thus, it is essential to increase the mass transfer rate of CO2 absorption
into absorbents.
The interfacial area and mass transfer coefficient are the important parameters for the design
of gas liquid contacting equipment and have been extensively studied for various
configurations . It has been generally recognized that the dominant parameter affecting the
interfacial area and mass transfer coefficients in gas liquid systems is the specific energy
input to the system.
Liquid side mass transfer coefficient

Et Specific total energy input J/m3

Hold up

Mass Transfer Theories

1.Two Film Theory (Whitmaun,1923)
2.Penetration Theory (Higbie, 1935)
3.Surface Renewal Theory (Dankwerts,1951)
4.Film-Penetration Theory (Toor and Marchello, 1958)

1.Two Film Theory (Whitmaun,1923)

It states that diffusion is a steady state process and the resistance to mass transfer lies in two
films on both sides of the interface.
It is described by Fick's first law,
In the film theory, the mass transfer coefficient kL is directly proportional to the
diffusion coefficient
k L=

D AB and inversely proportional to the film thickness :

D AB

NA =

D AB

dC A
dy

2.Penetration Theory (Higbie, 1935)

It states that diffusion is unsteady state process and the molecules of the solute are in constant
random motion, where clusters of these molecules arrive at the interface, remaining there for
a fixed period of time, and some of them penetrate while the rest mixes back into the bulk of
the phase. The process is described by Fick's second law with the boundary conditions:
2

C A
CA
=D AB
2
t
y

3.Surface Renewal Theory (Dankwerts,1951)

This is similar to the Penetration theory except that molecules arriving at the interface
remain, there, for different random periods of time. Furthermore in order to apply this we
need to know the rate of renewal of the surface , which is a very difficult task and may, only
be achieved experimentally.
Mass transfer rates across the interface between two phases (e.g., gas and liquid) will be
enhanced by surface renewal process. Suppose that the surface contains elements of the
surface and a random distribution of ages would exist for each element.
N A =Ci

D AB
4t

This variation has been developed by Vetrocoke in Italy. Use of various additives like amino
acids, arsenic trioxide, and selenium and tellurium oxides in hot potassium carbonate
absorbent solution which increase CO2 absorption rate, and decrease the steam required for
stripping CO2 from the solution.
The Vetrocoke processes have also employed air stripping for removing CO2 from additive
containing hot potassium carbonate solutions in cases in which CO2 is not recovered as a pure
gas.

Absorption of CO 2

The absorption of CO2 into lean potassium threonate solutions can be described by the
following equation (Danckwerts, 1970).

where

N CO

is the molar flow of CO2 crossing the liquid surface with interfacial area A, kL

is the physical mass transfer coefficient,

PCO is the CO2 partial pressure and

2

H CO2 is

the Henry constant of CO2 in solution. The enhancement factor, E, is the ratio between the
amount of gas absorbed in the reactive liquid and the amount that would be absorbed if no
reaction took place. The enhancement factor is a function of the Hatta number, Ha, and the
infinite enhancement factor,

The dimensionless Hatta number is defined as

Carbon dioxide absorption kinetics in potassium threonate

A.F. Portugal, F.D. Magalhes, A. Mendes

Mass Transfer
The absorption of CO2 into lean potassium threonate solutions can be described by the
following equation

where NCO2 is the molar flow of CO2 crossing the liquid surface
with interfacial area A, kL is the physical mass transfer coefficient,
PCO2 is the CO2 partial pressure and HCO2 is the Henry constant of
CO2 in solution.

Absorption: Fundamentals & Applications

By R. Zarzycki, A. Chacuk

Mass Transfer and Absorbers: International Series of

Monographs in Chemical ...
By T. Hobler