BASIC DESIGN EQUATIONS

FOR MULTIPHASE
REACTORS

Starting Reference
1. P. A. Ramachandran and R. V. Chaudhari, ThreePhase Catalytic Reactors, Gordon and Breach
Publishers, New York, (1983).
2. Nigam, K.D.P. and Schumpe, A., Three-phase
sparged reactors, Topics in chemical engineering, 8,
11-112, 679-739, (1996)
3. Trambouze, P., H. Van Landeghem, J.-P. Wauquier,
Chemical Reactors: Design, Engineering, Operation,
Technip, (2004)

Objectives
1. Review microkinetic and macrokinetic processes that
occur in soluble and solid-catalyzed systems.
2. Review ideal flow patterns for homogeneous systems
as a precursor for application to multiphase systems.
3. Derive basic reactor performance equations using ideal
flow patterns for the various phases.
4. Introduce non-ideal fluid mixing models.
5. Illustrate concepts through use of case studies.

Types of Multiphase Reactions

Reaction Type

Degree of Difficulty

Gas-liquid without catalyst

Straightforward

Gas-liquid with soluble catalyst

Gas-liquid with solid catalyst
Gas-liquid-liquid with soluble
or solid catalyst

Gas-liquid-liquid with soluble

or solid catalyst (two liquid phases) Complex
4

Hierarchy of Multiphase Reactor Models

Model Type
Empirical

Implementation

Insight

Straightforward

Very little

Ideal Flow Patterns

Phenomenological
Volume-Averaged
Conservation Laws
Pointwise Conservation Very Difficult
or Impossible
Laws

Significant

Macrokinetic Processes in Slurry Reactors

Hydrodynamics of the multi-phase dispersion
- Fluid holdups & holdup distribution
- Fluid and particle specific interfacial areas
- Bubble size & catalyst size distributions
Fluid macromixing
- PDFs of the various phases
Fluid micromixing
- Bubble coalescence & breakage
- Catalyst particle agglomeration & attrition

Reactor
Model

Heat transfer phenomena

- Liquid evaporation & condensation
- Fluid-to-wall, fluid-to-internal coils, etc.
Energy dissipation
- Power input from variouis sources
(e.g., stirrers, fluid-fluid interactions,)

Macrokinetic Processes in Fixed-Bed Reactors

Hydrodynamics of the multi-phase flows
- Flow regimes & pressure drop
- Fluid holdups & holdup distribution
- Fluid-fluid & fluid-particle specific interfacial areas
- Fluid distribution
Fluid macromixing
- PDFs of the various phases

Reactor
Model

Heat transfer phenomena

- Liquid evaporation & condensation
- Fluid-to-wall, fluid-to-internal coils, etc.
Energy dissipation
- Pressure drop
(e.g., stirrers, fluid-fluid interactions,)
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Elements of the Reactor Model

Micro or Local Analysis
Gas - liquid mass transfer

Macro or Global Analysis

Liquid - solid mass transfer

Flow patterns for the

gas, liquid, and solids

Interparticle and interphase

mass transfer

Hydrodynamics of the
gas, liquid, and solids

Intraparticle and intraphase

diffusion

Macro distributions of
the gas, liquid and solid

Intraparticle and intraphase

heat transfer

Heat exchange

Catalyst particle wetting

Other types of transport

phenomena
8

Reactor Design Variables

Feed

Qin
Tin
Cin

Qout
Tout Product
Cout

Reactor

Reactor
=f
Performance

Process
Variables

Rates

Conversion

Flow rates

Kinetics

Selectivity Inlet C & T

Activity

Reaction

Flow

Patterns
Macro

Transport Micro

Heat exchange
9

Ideal Flow Patterns

for Single-Phase Systems

Q (m3/s)

Q (m3/s)
a. Plug-Flow
Q (m3/s)

Q (m3/s)

b. Backmixed Flow
10

Impulse Tracer Response

x(t)

MT t

y(t)
t
Q (m3/s)

t
Q (m3/s)

y(t) dt
E(t ) dt

MT / Q

Reactor System

Fraction of the outflow with a

residence time between t and t + dt

E(t) is the P.D.F. of the residence time distribution

Tracer mass balance requirement:

MT Q y(t) dt
o

11

Fluid-Phase Mixing: Single Phase, Plug Flow

Q
(m3/s)

12

Fluid-Phase Mixing: Single Phase, Backmixed

Q
(m3/s)

Mi = Mass of tracer injected (kmol)

13

Idealized Mixing Models for

Multiphase Reactors
Model Gas-Phase

Liquid Phase

Solid-Phase

Reactor Type

Plug-flow

Fixed

Trickle-Bed
Flooded-Bed

Plug-flow

Backmixed Backmixed

Backmixed

Mechanically
agitated

Plug-Flow

Backmixed

Bubble column
Ebullated - bed
Gas-Lift & Loop

Backmixed

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Ideal Flow Patterns in Multiphase Reactors

Example: Mechanically Agitated Reactors
(t-g)
EG(t)

(t)
QG

XL(t)
QL
0

XG(t)

or

t
QL

1 = G + L + C
Vr G
QG

-t/
e

EL(t)

QG

VR = vG + VL + VC
G

(t)

Vr (1 G L )
QL

15

First Absolute Moment of the

Tracer Response for Multiphase Systems
For a single mobile phase in contact with p stagnant phases:
V1 +
1 =

K1j Vj

j=2

Q1

For p mobile phases in contact with p - 1 mobile phases:

V1 +
1 =

K1j

C j
=

C1 equil.

Q1 +

K1j Vj

j= 2
p

K 1j Qj

j= 2

is the partition coefficient of the tracer

between phase 1 and j
16

Relating the PDF to Reactor

Performance
For any system where the covariance of sojourn times is zero
(i.e., when the tracer leaves and re-enters the flowing stream at
the same spatial position), the PDF of sojourn times in the reaction
environment can be obtained from the exit-age PDF for a
non-adsorbing tracer that remains confined to the flowing phase
external to other phases present in the system.
For a first-order process:

- H (k ) t
p
c

1 - XA = e
Hp(kc) = pdf for the stagnant phase

= e
0

Eext ( t ) dt

- (k W W / Q1 ) t

Eext ( t ) dt
17

Illustrations of Ideal-Mixing Models

for Multiphase Reactors
Stirred tank

Trickle - Bed

Bubble Column

Flooded - Bed

Plug-flow of gas
Backmixed liquid & catalyst
Batch catalyst
Catalyst is fully wetted

Plug-flow of gas
Plug-flow of liquid
Fixed-bed of catalyst
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Catalyst is fully wetted

Intrinsic Reaction Rates

Reaction Scheme: A (g) + vB (l)
(l)

19

Gas Limiting and Plug-Flow of Liquid

Key Assumptions
1. Gaseous reactant is limiting
2. First-order reaction wrt dissolved gas
3. Constant gas-phase concentration

4. Plug-flow of liquid
5. Isothermal operation
6. Liquid is nonvolatile
7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients

L
20

Concentration or Axial Height

Gas Limiting and Plug flow of liquid

Constant gas phase
concentration valid for pure
gas at high flow rate

Relative distance from catalyst particle

(Net input
(Input by Gas- - (Loss by Liquid- = 0
+
by
Liquid
solid Transport)
convection)
Transport)

Ql Al z Ql Al

(1)

k
a
A
Al Ar dz- k s a p Al As Ar dz= 0
l B
z dz

(2)

Dividing by Ar.dz and taking limit dz

(3)
(4)

21

Gas Limiting and Plug flow of liquid

22

Gas Limiting and Plug flow of liquid

Solving the Model Equations

23

Concept of Reactor Efficiency

R Rate of rxn in the Entire Reactor with Transport Effects
Maximum Possible Rate

24

Conversion of Reactant B
(in terms of Reactor Efficiency)

25

Gas Limiting and Backmixed Liquid

Key Assumptions

Stirred Tank
Bubble Column

1. Gaseous reactant is limiting

2. First-order reaction wrt dissolved gas

3. Constant gas-phase concentration

4. Liquid and catalyst are backmixed

5. Isothermal operation

6. Liquid is nonvolatile
7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients

26

Concentration or Axial Height

Gas Limiting and Backmixed Liquid

Relative distance from catalyst particle

oncentration of dissolved gas in the liquid bulk is constant [f(z)] [=Al,0

oncentration of liquid reactant in the liquid bulk is constant [f(z)] [=B

A in liquid bulk: Analysis is similar to the previous case

27

Gas Limiting and Backmixed Liquid

A at the catalyst surface:

For Reactant B:
(Net input
=
by flow)

(Rate of rxn of B
at the catalyst
surface)

(Note: No transport to
gas since B is nonvolatile)

28

Gas Limiting and Backmixed Liquid

Solving the Model Equations

29

Flow Patterns Concepts

for Multiphase Systems
A

A - Single phase flow of gas or

liquid with exchange between the
mobile phase and stagnant phase.
Fixed beds, Trickle-beds, packed
bubble columns
B - Single phase flow of gas or
liquid with exchange between a
partially backmixed stagnant phase.
Semi-batch slurries, fluidized-beds,
ebullated beds

30

Flow Patterns Concepts

for Multiphase Systems
C

C, D - Cocurrent or
E
countercurrent two-phase
flow with exchange between
the phases and stagnant
phase.
Trickle-beds, packed or
empty bubble columns
E - Exchange between two
flowing phases, one of
which has strong internal
recirculation.
Empty bubble columns and
fluidized beds

31

Axial Dispersion Model (Single Phase)

C
2C
C
Dax
u
R
2
t
z
dz
@z=0

Let

u0C0 uC Dax

uL
Peax
Dax

C
z

Basis: Plug flow with

superimposed diffusional
transport in the direction of
flow

@z=L

C
0
z

@ = 1

C
0

C
1 2C C

R
2
t
Peax
d
@ = 0

1 C
C0 C
Peax

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