BASIC DESIGN EQUATIONS FOR

MULTIPHASE REACTORS
 Starting Reference
1. P. A. Ramachandran and R. V. Chaudhari, Three-Phase
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)

2
 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.

3
 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
Complex
or solid catalyst (two liquid phases)

4
Hierarchy of Multiphase Reactor Models

Model Type Implementation Insight

Empirical Straightforward Very little

Ideal Flow Patterns

Phenomenological

Volume-Averaged
Conservation Laws

Pointwise Conservation Very Difficult Significant

Laws or Impossible

5
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
- PDF’s of the various phases

Fluid micromixing
Reactor
- Bubble coalescence & breakage
- Catalyst particle agglomeration & attrition 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,…)
6
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
- PDF’s of the various phases
Reactor
Heat transfer phenomena Model
- Liquid evaporation & condensation
- Fluid-to-wall, fluid-to-internal coils, etc.

Energy dissipation
- Pressure drop
(e.g., stirrers, fluid-fluid interactions,…)

7
 Elements of the Reactor Model
Micro or Local Analysis Macro or Global Analysis

• Gas - liquid mass transfer • Flow patterns for the

• Liquid - solid mass transfer gas, liquid, and solids
• Interparticle and interphase • Hydrodynamics of the
mass transfer gas, liquid, and solids
• Intraparticle and intraphase • Macro distributions of
diffusion the gas, liquid and solid
• Intraparticle and intraphase • Heat exchange
heat transfer • Other types of transport
• Catalyst particle wetting phenomena
8
 Reactor Design Variables
Qin Qout
Feed Tin Reactor Tout Product
Cin Cout

Reactor Process Reaction Flow

=f
Performance Variables Rates Patterns

• Conversion • Flow rates • Kinetics • Macro

• Selectivity • Inlet C & T • Transport • Micro

• Activity • 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 t
Q (m3/s) Reactor System Q (m3/s)

y(t) dt Fraction of the outflow with a

E(t ) dt  
MT / Q 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

1 Plug-flow Plug-flow Fixed Trickle-Bed

Flooded-Bed

2 Backmixed Backmixed Backmixed Mechanically

agitated

3 Plug-Flow Backmixed Backmixed Bubble column

Ebullated - bed
Gas-Lift & Loop

14
Ideal Flow Patterns in Multiphase Reactors
Example: Mechanically Agitated Reactors

VR = vG + VL + VC
or
1 = G + L + C
Vr G Vr (1   G   L )
G  L 
QG QL 15
 First Absolute Moment of the
Tracer Response for Multiphase Systems
For a single mobile phase in contact with p stagnant phases:
p
V1 +  K1j Vj
j=2
1 =
Q1

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

p
V1 +  K1j Vj
j= 2
1 = p
Q1 +  K 1j Qj
j= 2

C j 
K1j =   is the partition coefficient of the tracer
C1 equil.
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
1 - XA =  e p c
Eext ( t ) dt
0
Hp(kc) = pdf for the stagnant phase 
=  e- (k W W / Q1) t Eext ( t ) dt
0 17
 Illustrations of Ideal-Mixing Models
for Multiphase Reactors
Stirred tank
Trickle - Bed
Bubble Column  

  Flooded - Bed

 
 
 


z z
 

 


 









G L G L
• Plug-flow of gas • Plug-flow of gas
• Backmixed liquid & catalyst • Plug-flow of liquid
• Batch catalyst • Fixed-bed of catalyst
18
• Catalyst is fully wetted • Catalyst is fully wetted
Intrinsic Reaction Rates
Reaction Scheme: A (g) + vB (l)  C (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
z 5. Isothermal operation
6. Liquid is nonvolatile
7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
G L

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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 by (Input by Gas- - (Loss by Liquid- =0 (1)
+
convection) Liquid Transport) solid Transport)

Ql Al z  Ql Al z  dz
 k a
l B  A*
 Al Ar dz- ks a p  Al  As Ar dz= 0 (2)

Dividing by Ar.dz and taking limit dz  

(3)

(4)

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Gas Limiting and Plug flow of liquid

22
Gas Limiting and Plug flow of liquid
Solving the Model Equations

23
 Concept of Reactor Efficiency
Rate of rxn in the Entire Reactor with Transport Effects
R 
Maximum Possible Rate

24
 Conversion of Reactant B
(in terms of Reactor Efficiency)

25
 Gas Limiting and Backmixed Liquid
Stirred Tank Key Assumptions
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
z
 

 


5. Isothermal operation
 




6. Liquid is nonvolatile





7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
G L

26
 Gas Limiting and Backmixed Liquid
Concentration or Axial Height

Relative distance from catalyst particle

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

-Concentration of liquid reactant in the liquid bulk is constant [≠f(z)] [=Bl,0]
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 (Rate of rxn of B at (Note: No transport to gas
= since B is non-volatile)
flow) the catalyst surface)

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Gas Limiting and Backmixed Liquid
Solving the Model Equations

29
 Flow Patterns Concepts
for Multiphase Systems
A B
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, D - Cocurrent or E
C D
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)
Basis: Plug flow with superimposed
“diffusional” transport in the
direction of flow
C  2C C
 Dax u R
t z 2
dz
C C
@z=0 u0C0  uC  Dax @z=L 0
z z
z uL L
Let η Peax  τ
L Dax u
C 1  2C C
τ    τR
t Peax η 2
dη
1 C C
C0  C  @  = 1 0
@  = 0 Peax η η 32