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Bubble column reactors

Topics Covered
• Bubble column fundamentals
• The general rate expression
• Design Equation
• Axial dispersion model
• Designing factors
• Mixing and RTD
• Practical Examples, Advantages
and Disadvantages
Heterogenous Fluid-fluid reactions

• Reasons for the use of Fluid-fluid reactions :

1. the product of reaction may be a desired


material.

2. to take place to facilitate the removal of an


unwanted component from a fluid.
Heterogenous Fluid-fluid reactions
Factors determining how to approach:

1. The Overall Rate Expression. Since materials in the


two separate phases must contact each other before
reaction can occur, both the mass transfer and the
chemical rates will enter the overall rate expression.

2. Equilibrium Solubility. solubility of the reacting


components will limit their movement from phase to
phase and it will determine whether the reaction takes
place in one or both phases.

3. The Contacting Scheme. semibatch and countercurrent


contacting schemes predominate but batch contacter are
also used
Type Of fluid-fluid Reactor
Contacting patterns for g/L contactors.
Bubble column reactors
Introduction
• Why bubble column reactors?

-Broad range of potential applications in the chemical,


petrochemical and biochemical industries.

• What is bubble column reactors?

-Bubble columns are devices in which gas, in the form of


bubbles, comes in contact with liquid.

-The purpose may be simply to mix the liquid phase.

-Substances are transferred from one phase to the other


Bubble column reactors
Bubble column reactors
-Simple vertical cylindrical vessels with intense contact
betweenn the two phases.

-The gas phase is dispersed into the liquid phase using


specific gas distributorss at the bottom of the column.

-The net liquid flow may be co-current or counter-current to


the gas flow direction or may be zero.

-Spargers, like porous plates, generate uniform size bubbles


and distribute the gas uniformly at the bottom of the liquid pool.
Type of Bubble Columns

A).Simple bubble column; B) Cascade bubble column with


sieve trays; C) Packed bubble column; D) Multishaft bubble
column; E) Bubble column with static mixers
Contacting Patterns
Gas-Liquid Mixing

A) Bubble column; B) Downflow bubble column; C) Jet loop reactor


Practical examples of reactions taking
place in bubble column reactor:

• oxidation reactions (e.g. oxidation of cyclohexane to adipic acid,


partial oxidation of ethylenee to acetaldehyde, oxidation of n-
parrafins to sec-alcohols)
• hydrogenation reactions (e.g. saturation of fatty acids,
hydrogenation of glucose to sorbitol)
• chlorination reactions (production of aliphatic and aromatic
chlorinated compounds)
• hydrotreating and conversion of petroleum residues
• Fermentation (production of ethanol and mammalian cells)
• biological waste water treatment
• oxidesulfurization of coal
• oxichlorination of ethylene to dichlorethane
• Fischer-Tropsch synthesis
• methanol synthesis
• polymerisation of olefins
Advantages offered by bubble column
reactor:

• efficient contact between the phases, the gas and the liquid,
and eventually the third phase,, the solid catalyst
• high liquid hold up, recommended for reactions taking place in
the liquid phase (as the case of bubble columns)
• reasonable inter-phase mass transfer rates at low energy
input
• limitation of pressure drop
• easy temperature control
• little maintenance due to the simple construction
• lack of moving parts
• high adaptability for a specific process
• no serious erosion and plugging problems due to the catalyst
• low costs of construction and operation
Disadvantages of bubble column reactor:

• considerable degree of backmixing in both the


liquid and the gas phase
• short gas phase residence time
• higher pressure drop with respect to packed
columns
• rapid decreasing of interfacial area above values
of the aspect ratio greater than, say 12, due to the
increased rate of coalescence
• Scale up is still poorly understood
Gas Distributions
• The gas is dispersed to create small bubbles and
distribute them uniformly over the cross section of
the equipment to maximize the intensity of mass
transfer.

• The formation of fine bubbles is especially desirable


in coalescence-hindered systems and in the
homogeneous flow regime.

• In principle, however, significant mass transfer can


be obtained at the gas distributor through a high
local energy-dissipation density.
Static Gas Spargers
Dynamic Gas Spargers
Flow Regimes
Fluid Dynamics
• Rising gas bubbles entrain liquid in their
wakes.

• As a rule, this upward flow of liquid is


much greater than the net liquid flow rate.

• Because of continuity, regions therefore


exist in which the liquid is predominantly
moving downward.
Fluid Dynamics

Radial distribution of liquid velocity in a bubble column


Cell Structure in BCs
Concentration profile
• There is a concentration
drop around the spherical
bubble because it is
migrating outward,

• At the planar gas-liquid


interface there should be a
discontinuity in CA at the
interface due to the
solubility of species A and a
consequent equilibrium
distribution between
phases.
Bubble Size
Sauter diameter dbS
(mean bubble diameter, calculated from the volume to
surface ratio)
0.6 0.25
2    0.5  G 
d bs  0.4    G  
eM   L   L 
This formula is based on Kolmogorov's theory of isotropic
turbulence.
For low-viscosity liquids, the maximum bubble diameter
is given by
Bubble Size Distribution (BSD)
• Narrow BSD
– For bubble columns with relatively low gas
volume fraction.
– In homogeneous regime.
• Wide BSD
– As gas velocity and therefore, gas volume
fraction increases, a heterogeneous or churn-
turbulent regime sets in.
Bubble Rise Velocity
Dispersion of the Liquid Phase
Dispersion of the Gas Phase
Gas Holdup
• Gas holdup is one of the most important
operating parameters because it not only
governs phase fraction and gas-phase
residence time but is also crucial for mass
transfer between liquid and gas.

• Gas holdup depends chiefly on gas flow rate,


but also to a great extent on the gas – liquid
system involved.
Gas Holdup
• Gas holdup is defined as the volume of the gas phase
divided by the total volume of the dispersion:
VG
G 
VG  VL
• The relationship between gas holdup and gas velocity
is generally described by the proportionality:

 G ~ U Gn
• In the homogeneous flow regime, n is close to unity.
When large bubbles are present, the exponent
decreases, i.e., the gas holdup increases less than
proportionally to the gas flow rate.
Gas Holdup

• The relation of Akita and Yoshida is suitable for estimating


the gas holdup and is based on the investigation of
numerous systems
Interphase Forces
• Drag force
-Resultant slip velocity between two phases.

• Virtual mass force


-Arising from the inertia effect.

• Basset force
-Due to the development of a boundary layer around a
bubble.

• Transversal lift force


-Created by gradients in relative velocity across the bubble
diameter, may also act on the bubble.
Specific Interfacial Area
• The area of the gas – liquid interface is one of the most important
process parameters. Especially at high reaction rates (e.g., when a
bubble column is employed as an absorber), the interfacial area
becomes a crucial factor in equipment sizing. Like gas holdup,
interfacial area depends on the geometry, operating conditions, and
gas – liquid system. Gas holdup and interfacial area per unit volume
are related as:
Specific Interfacial Area
• The specific interfacial areas attainable in various gas – liquid
reactors can be compared on the basis of power input P per unit
volume. Experimental values can be described by the relation. The
exponent m is between 0.4 and 1
Interface behaviour for the liquid-
phase reaction
• Case A: Instantaneous reaction with low C,

• Case B: Instantaneous reaction with high CB

• Case C: Fast reaction in liquid film, with low CB

• Case D: Fast reaction in liquid film, with high C,

• Case E and F: Intermediate rate


with reaction in the film and in
the main body of the liquid

• Case G: Slow reaction in main


body but with film resistance

• Case H: Slow reaction, no mass


transfer resistance
Conti…
Volumetric Mass-Transfer
Coefficient
• The mass-transfer coefficient
and the gas rate are again
proportional to one another:
where n can be between 0.7 and
0.92
Volumetric Mass-Transfer
Coefficient
• According to experimental results, the col umn diameter above
about 15 cm has no effect on mass-transfer coefficient. Some
correlations nonetheless include reactor diameter. Akita and
Joshida state that the value of the column diameter used for
calculation should not be increased beyond 0.6m. Based on this
premise, their correlation for kL a is
The General Rate Equation
• Assumptions:

- gaseous A is soluble in the liquid but that B does not


enter the gas.

-solubility of gasous phase obeys Henery’s Law

-reaction may occur in the liquid film , in the bulk liquid


or in both

-Whitman’s two fim theary applicable


The General Rate Equation
• The overall rate expression for the reaction will
have to account for the mass transfer resistance
(to bring reactants together) and the resistance
of the chemical reactions step.

• Considers the following second-order reaction


Conti…
Hence the overall rate expression is:

Where
The Rate Equation for Straight
Mass Transfer (Absorption)
• No chemical reaction takes place
• Also known as Physical Absorption
• Here we have two resistances in series, of the gas
film and of the liquid film.

• The final rate


equation is as follows:
Design Equation For Bubble Column
Reactor
• We assume that the rate is fast enough so that no unreacted
A enters the main body of the liquid. This assumes that the
Hatta modulus is not very much smaller than unity.

• Here we must make two accountings, a differential balance for


the loss of A from the gas because G is in plug flow, and an
overall balance for B because L is in mixed flow.

• Focusing on rising gas, we have

..(i)
Where moles A/mole inert in the gas
Conti…

• For the liquid as a whole and for the gas as a


whole, a balance about the whole reactor gives

..(ii)
Conti…

• Integrating Eq.(i) along the path of the bubble and


also using Eq.(ii) gives
Axial Dispersion in Bubble Column
Reactor
• Most realistic model is that of dispersed plug-flow in both
phases but this is also the most complicated model.

• simple axial dispersion is reasonably well in practice.

• Because the residence time of the liquid phase in the


column is usually much longer than that of the gas, hence
liquid phase will be well-mixed even when the gas phase is not.

• In our case reaction is very fast and occurs wholly within the
liquid film surrounding the bubbles and concentration in the bulk
of the liquid of the species A is zero, and the mixing pattern in
the liquid has therefore no influence on the rate of transfer.
Axial Dispersion in Bubble Column
Reactor: Model Development
• Assumptions:

- The fluid velocity and the concentrations of any dissolved


species are assumed to be uniform at any cross-section of
the pipe,
-Mixing or ‘dispersion’ in the direction of flow (i.e. in the
axial r-direction) is taken into account
- fluid have a constant density so that the mean velocity u is
constant.
Conti…
• The axial mixing is described by exactly the same way as
in molecular diffusion.

where DL is the dispersion


coeficient in the longitudinal
direction.

• Fluid near the centre of


the pipe travels more quickly
than that near the wall, the
overall result being mixing in
the axial direction.
Conti…

• Axial dispersion is caused primarily by


differences in velocity at different radial positions
rather than by turbulent eddy.

• system is not in a steady state with respect to


the tracer distribution, the concentration will vary
with both z the position in the pipe and, at any
fixed position, with time.

• Consider a material balance between z and (z +


dz), in a time interval dt unit area of cross-
section.
Conti…
Conti…
• For very fast steady state gas-liquid reaction,
the reactant A is transferred & thus removed
from the gas phase at a rate which is
proportional to the concentration of A in
the gas, i.e. as in a homogeneous first-
order reaction.
so we have

• Reaction vessel is considered to be ‘closed’,


i.e. reaction is assumed to be confined to the
reaction vessel itself
Conti…
• Boundary conditions:
- rate of transfer is made up of two contributions, the
convective flow & diffusion-like dispersive flow
1. Across the plane at the inlet to the reactor, these two
fluxes must be equal which gives
Conti…
• 2. Now consider the outlet pipe from the reactor

• fluid leaving the reactor must have the same


concentration of reactant as the fluid just inside
the outlet plane, which yields

• To solve the differential on substituting


in the diff eq.() we get
Conti…
Conti…
Axial Dispersion in Bubble Column
Reactor

• For bubble column two-phase gas-liquid system,

Where Gas hold-up=fraction of the tube cross-


sectional area occupied by the gas, i.e. the region
in which gas dispersion occurs.

• Empirical equation for the gas-phase dispersion


coefficient is:
Conti…
• Empirical equation for the gas-phase dispersion
coefficient is:

• For two-phase bubble column for steady-state


conditions

• reactant A at the exit & inlet of the column

where
Conti…
• The rate of transfer per unit volume of
dispersion is thus:

• From Henry law,


• From the ideal gas law the gas-phase
concentration

By using above eq. we have


Factors to be considered for the
Design Of Bubble Column Reactor

• (a) Contacting pattern. Bubble tanks approximate


plug G/mixed L.

• (b) kg and kl. For liquid droplets in gas kg is high, k, is low.


For gas bubbles rising in liquid kg is low, k, is high.

• (c) Flow rates. more flexible in that they work well in a wider
range of Fl/Fg values.

• (d) If the resistance is in the gas film dominates stay away


from bubble contactors.
Conti…
• (e) Solubility.For gases of low solubility in the liquid, thus
high H value liquid film controls

• (f) Reaction lowers the resistance of the liquid film,


so

-For absorption of highly soluble gases, chemical reaction is


not helpful.

-For absorption of slightly soluble gases, chemical reaction


is helpful and does speed up the rate.

• (g) Kinetic Constant of the Reaction. The kinetics of the


reaction need to be known or measured which may be
affected by temperature.
Mixing in bubble phases and
Residence time distribution
• If an isolated bubble rises in the reactor, then the
flow pattern in this phase is clearly unmixed, and
this phase should be described as a PFTR.

• Possible flow patterns:


1. In simplest case ,an isolated bubble which rises a
clearly unmixed situation.
Conti…

2. 2. If bubbles flow upward, but continuously break up and


coalesce, the residence time distribution of the species in this
pase is narrow or roughly that of a PFTR,

3. If the bubble is in a continuous phase which is being stirred,


then in the limit of very rapid stirring, the residence time
distribution will be same as in CSTR.

• 4. However with stirring and coalescence and breakup, both


effects tend to mix the contents of the bubbles or drops
CFD Modeling of Bubble Columns

• Eulerian-Lagrangian approach
-To simulate trajectories of individual
bubbles (bubble-scale phenomena)

• Eulerian-Eulerian approach
-To simulate the behavior of gas-liquid
dispersions with high gas volume fractions
(e.g. to simulate millions of bubbles over a
long period of time)
High Aspect-Ratio Bubble Columns
• Bubble column with a low aspect ratio or a single- impeller
agitated tank behaves essentially as a well-mixed reactor

• A much more desirable situation is the gas to be in a state of


plug flow.

• To approximate to plug flow, the logical development is to


use a bubble column which is tall in relation to its diameter.

• if the same volume of liquid is contained in a tall, smaller


diameter column, there are two advantages:

1. probability that the gas (and possibly the liquid) will be


more nearly in a state of plug flow.
Conti…
Conti…
2.Assuming that gas is supplied at the same
volumetric flowrate:

-superficial gas velocity through the column will


be increased.
-specific interfacial area and the gas hold-up also
increase with superficial gas velocity
-which increase in the rate of reaction per unit
volume of dispersion.

One disadvantage of a tall column is the cost of


compressing the gas to overcome the additional
hydrostatic head.
Heat Transfer
• the following relation for the heat transfer coefficient α
can be derived
Bubble Column Modeling
Mass transport Fluid
mixing properties

Reaction
Fluid Dynamics

Enhancement
Phase distribution
transfer
resistance Limitation
Mass transfer
Gas hold-up Heat transfer
Interfacial area
Bubble driving force
recirculation mixing

Fluid
Turbulence
Bubble breakage properties
shear stress
And coalescence
terminal
velocity
residence time
References
• Coulson & Richardson's CHEMICAL ENGINEERING VOLUME 3 THIRD
EDITION “Chemical & Biochemical Reactors & Process Control” , J.
F. RICHARDSON ,Department of Chemical Engineering,University of
Wales Swansea and D. G. PEACOCK ,The School of Pharmacy,London

• “Chemical Reaction Engineering” Third Edition,Octave


Levenspiel;Department of Chemical Engineering,Oregon State
University

• “THE ENGINEERING OF CHEMIlCAL REACTIONS”,LANNY D.


SCHMIDT,University of Minnesota

• “Scaling up bubble column reactors” ,M.I. Urseanu ,Vant Hoff


Institute for Molecular Sciences (HIMS)

• “Bubble Coulmn”,Quak Foo Lee ,Department of Chemical and Biological


Engineering,The University of British Columbia