Lecture 6


Conceptual Reactor Design
Multi-phase
Reactors
Lecture
6
Non-isothermal reactors

Lecture
6
Conceptual Reactor Design
Multi-phase Reactors
Non-isothermal
reactors
Conceptual
Reactor
Design

Reactor Phase
Operation in the liquid phase is usually preferred
e.g. single reaction system : FEED

PRODUCT

r = k CFEED
a

< Higher concentrations of CFEED

- Rapid reaction rate - reduce reactor volumes

Gas-phase system is preferred

< When high mass transfer rates are required
< When reactor temperature is above the critical temperature of the chemical
species

The choice of reactor phase is not available for multiphase systems

Gas-liquid and Liquid-liquid Reactors

Two phase reactions
< Feed material is inherently in different phases at the inlet conditions.
< Two-phase behaviour is needed to remove an unwanted component from one of
the phases or imporve the selectivity.
< It is necessary that the phases be intimately mixed.
- Provide effective mass transfer of the reactants between the phases

Overall rate of reaction must take account of :

< The mass tansfer resistance
< The resistance of the chemical reactions

Reactor design for temperature control should consider simultaneously

< mixing
< mass transfer
< reaction

Two-film theory
Effect of mass transfer

Gas

Liquid

Gas
Film

< The rate of transfer of A through gas film:

rAG = k AG ( p A p AI )

Interface

Liquid
Film

PA

< The rate of transfer of A through liquid film:

rAL = k AL (CAI CA )

< Henrys law

(assume equilibrium conditions at the interface)

p AI = H ACAI

PAI
CAI
CA
PAI = HACAI

- Henrys law constant must be determined experimentally

where

rG, rL
kAG, kAL
pA, pAI
CA, CAI
HA

: rate of transfer in the gas and liquid film (mol m -2s-1)

: mass transfer coefficient in the gas and liquid film
: partial pressure in the gas phase and at the interface (Pa)
: concentration in the bulk of liquid phase and at the interface (mol m -3)
: Henrys Law constant (Pa m 3 mol-1)

 Effect of mass transfer (continued)

< Assume steady state (rAG= rAL= rA)

rA =

1
1
k AG

H
+ A
k AL

(p

H ACA ) = K AGL ( p A H ACA ) Where

Overall mass
transfer coefficient

1
K AGL

1
k AG

HA
k AL

Gas film Liquid film

resistance resistance

< Low solubility gases (HA is large) - kAG >> kAL/ HA : the mass transfer is liquid-film controlled
< High solubility gases (HA is small) - kAG << kAL/ HA : the mass transfer is gas-film controlled
< The capacity of dissolution
- The capacity of a gas to dissolve in a liquid is determined by the solubility of the gas.
- The capacity of a liquid to dissolve a gas is increased if it reacts with a species in the liquid.

Mass transfer can influence the selectivity.

e.g. Parallel reactions with r1 > r2
FEED 6 PRODUCT

a1
r1 = k1CFEED

2
FEED 6 BYPRODUCT r2 = k 2CFEED

< The selectivity is enhanced by the

mass transfer : The dissolving gas
species will tend to react in the liquid
film and not reach the bulk liquid.

 Effect of chemical reaction

< High reaction rate
- Reduce the liquid film resistance
- Effective increase in the overall mass tansfer coefficient
- The capacity of the liquid is increased.

< Low reaction rate

- When compared with pure physical absorption, the dissolving gas reacts and does not build up
in the bulk liquid to the same extent as pure physical absorption.
- The driving force for mass transfer is greater than that for physical absorption alone.
- Small effect on the overall mass transfer coefficient

Effect of temperature
< As temperature increases:
-

Rate of reaction increases

Solubility of the gas in the liquid decreases
Rates of mass transfer increase
Volatility of the liquid phase increases, decreasing the partial pressure of the dissolving gas

< The relative magnitude of mass tranfer enhancement and its consecutive effects depend on the
reaction system.

Contacting Patterns for Gas-liquid Reactors (I)

(B) Co-current packed bed
(A) Counter-current packed bed or
plate column
< Packing material or distillation trays
can be used to create interfacial area

G
L
L

< Poorer performance than the counter-current

type
< Effective when the flow of gas is much larger
than the flow of liquid - trickle-bed ractor
< Another method for co-current contact : feed
both phases to a pipe containing an in-line mixer
G
G

L
L

G
G

L
L
G

L
G+L

Contacting Patterns for Gas-liquid Reactors (II)

(C) Spray column

(D) Bubble column

< Induce a high gas-film mass transfer

coefficient and a low liquid-film mass
transfer coefficient
< Spray column is necessary when
- The liquid contains solids or solids are
formed in the reaction.
- The reaction has a tendency to foul a
packed bed.

< Induce a low gas-film mass transfer coefficient

and a high liquid-film mass transfer coefficient
< Ineffective for a reaction with a high viscosity
liquid
< Advantage over a packed bed
- The liquid hold-up per unit reactor volume is higher.
- The liquid contains a dispersed solid.
- A packed bed will become clogged.

G
G

Mixed-flow
behaviour

Plug-flow
behaviour

Mixed-flow
behaviour

G
G

Plug-flow
behaviour

G
G

L
L

Contacting Patterns for Gas-liquid Reactors (III)

(E) Agitated tanks
< The gas is sparged through the liquid
< Low driving force
< When the liquid is viscous, a sparged agitated vessel allows good contact
between the gas and the liquid.
G

L
G
L
L
G

Counter-current packed beds offer the largest mass transfer driving force and
agitated tanks the lowest

Liquid-liquid Reactors
Liquid-liquid reactions
< Much of the discussion for gas-liquid reactions also applies to liquid-liquid reactions.
< The reaction may occur in one phase or both phases simultaneously

Mass transfer between two immisible liquids

<
<
<
<

Two liquid-film resistances exist

One liquid must be dispersed in the other
In most cases the liquid with the smaller liquid flowrate will be dispersed in the other
Overall mass transfer coefficient depends on the physical properties of the liquids and the
interfacial area.
< Interfacial area is governed by the size of the liquid droplets and the volume fraction of the
dispersed phase.

Dispersion of liquid
< External power input is required through an agitator or from pumping
< The degree of dispersion depends on
- Power input
- Interfacial tension between the liquids and physical properties

< Too effective dispersion might lead to the formation of an emulsion.

Contacting Patterns for Liquid-liquid Reactors (I)

Counter-current packed bed or
plate column

Multi-stage agitated
contactor
< A large number of stages
< Low back mixing

LL
LL HL

In-line static mixer

< Suitable for reactions with
short residence time
< Dispersion is promoted by
repeatedly changing the
direction of flow locally

LL
LL HL

LL HL

HL

LL

HL

LL

HL

HL

LL

LL

LL HL

LL HL
HL

LL HL
HL

Plug-flow for both heavy and light phases

Contacting Patterns for Liquid-liquid Reactors (II)

Spray column with light
liquid dispersed

Spray column with heavy

liquid dispersed

LL
LL HL

LL
LL HL

HL

Agitated tank with settler

LL HL

HL

LL

HL
HL
LL
LL

LL

LL HL

LL HL

LL HL
HL

HL

< Multi-stage agitated tank and settler

Spray columns generally

give a lower driving force

- counter-current flow arrangement

- cross-flow arrangement :
- useful if the reaction is limited
by chemical equilibrium

 Suitable for gas-solid non-catalytic reactions

Example :

CaCO3

CaO

CO2

heat

< Air and fuel fluidize the solid particles and produce the high temperature
necessary for the reaction.

Kilns
Reactions involving free-flowing solid, paste, and slurry
materials can be carried out in kilns.
< Rotary kiln : rotation of cylinder shell
Example :

CaF2

calcium flouride

H2SO4
sulfuric acid

< Static kiln : rotation of mechanical rake

2HF

CaSO4

hydrogen flouride calcium sulfate

Reactor Configuration
from Optimisation of a Superstructure
So far, we have reviewed at length the factors influencing
the choice of reactor configuration and conditions
based on the development of the CONCEPTUAL ISSUES.

Another approach : Optimisation of Superstructure

Superstructure
< Includes all the structural features that might be candidates for the final design
< Contains redundunt features that need to be removed

A combined structual and parameter optimisation carries out the

evolution of the superstructure to the final design.

Optimisation of Isothermal Reactors

A simple superstructure for a
homogenous reaction
< Consider two options of using either a plugflow or mixed-flow reactor

Feed

Product

Multi-phase reactors by introducing

superstructure for each phase
< Consider a plug-flow or mixed-flow reactor in
each phases and mass transfer between the
phases.

Product 1

Feed 1

PHASE 1

Mass Transfer
PHASE 2

Optimise for maximum yield,

maximum selectivity,
minimum cost, etc

Feed 2

However, only conventional designs will result

Product 2

Novel Reactor Arrangements

Complex mixing patterns might lead to novel reactor arrangements or designs.
Gas

Gas feed
Gas product
Liquid

Liquid
Liquid
feed

Gas
Liquid

Open up the possibilities of further design options in the superstructure.

- we might obtain much better overall performance of the reactor.

Mathematical Methods for

Superstructure Optimisation
A simple superstructure with plug-flow, semi-plug flow and mixed-flow options.

Complex arrangements
cannot be obtained.

A more complex superstructure of reactor components allows series, parallel,

series-parrallel and parralled-series arrangements of plug-flow, semi plug-flow
and mixed-flow options.
< Three compartments open up different arrangements of mixing patterns.
FEED

A greater number of compartments - A greater number of possibilities

Mathematical Methods for Superstructure

Optimisation
Superstructure for two phase reactions with three reactor compartments in
each phase
< The complexity should not increase unnecessarily by adding combinations of mixing patterns
and mass transfer between phases that can never be possible in a practical reactor.
< Mass transfer is only allowed with the corresponding shadow compartment.

FEED

PHASE 1

Mass

Transfer

FEED

PHASE 2

Straightfoward to extend the superstructure to include multiple feeds and products

Mathematical Methods for Superstructure Optimisation

Optimisation of superstructure for reactor design
< Highly non-linear equations: reaction kinetics, mass transfer and any hydrodynamic models
< A combined structural and parameter optimisation
< Resulting in a MINLP problem
Can be solved by methods based on mathematical programming
< e.g. branch and bound algorithms
< Such problems can be non-convex, so depending on the starting point, the algorithm can get trapped
in the neighbourhood of a local extremum
< Global optimisation methods exist, but are computationally intesive
Stochastic optimisation (simulated annealing) has proved to be a relatively simple and reliable method.
< Stochastic optimisation reduces the chances of being trapped near a local optimum , therefore
solutions close to the global optimum can be obtained.

Simulation
simulate a specific structure

Pertubation Moves
New features of design

Evaluation
Objectve function / Constraints

Simulated annealing
Accept / Reject

There are usually a number of competitive solutions that are

close to the global optimum.

Case Study: Synthesis of "-Chlorocarboxylic Acids

Cl2 + C4A MC4A + HCl
2Cl2 + C4A DC4A + 2HCl
MC4A - "-monochlorobutanoic acid, DC4A - ","-dichlorobutanoic acid

r1 = y (k 1 + k 2 )CLMC A + k 1k 2 CLDC A + k 2 CL C A
1
2

1
2

1
2

] (1+ k C )
3

L Cl2

r2 = k 3r1CL Cl

k1 = e

( 5.22 3120 T )

y = 0.037

k2 = e

( 0.00176 1880 T )

k 3 = 0.00136

Catalyst molar fraction

Salmi T, Paatero E, Fagerstolt K, Chem. Eng. Sci., 48(1993), pp.735-751.

Problem Data
Feed and Reaction Conditions
P = 10 bar
! Liquid feed: 13.3 kmoles of C A
4
! Gas feed: 100 kmoles of Cl
2
! Temperature bounds: 100 OC # T # 500 OC
!

Phase equilibria and mass transfer

!

HCl2 = HHCl = 211.76 bar

a = 254.6 m2/m3 ,

DCl2 = 6.66*10-9 m2/sec,

gg = 0.5,

*L = 10-4 m

DHCl = 8.45*10-9 m2/sec

Film model for mass transfer

Salmi T, Paatero E, and Fagerstolt K, Chem. Eng. Sci., 48(1993), pp.735-751
Romanainen and Salmi T, Chem. Eng. Sci., 47(1992), pp.2493-2498

Conventional Designs

Counter current
packed bed

Mechanically
agitated vessel

Bubble column

Yield = 69.5%

Yield = 74.4%

Yield = 72.8%

Results
Reactor designs

Network model

Gas product
Liquid product

Gas Feed
Gas Product

Liquid

Gas

Liquid Feed
Liquid Product

Liquid feed
Gas feed

Yield = 96.9%
Vol = 9.93m3
Liquid Gas Liquid Gas
product feed product product

Results and Comparison

Yield

New design

Volume (m3)

69.5 %

16.1

74.4 %

12.0

72.8. %

12.2

96.9 %

9.9

Non-isothermal Reactors
Non-isothermal operation brings additional complexity to the superstructure
approach.
< Temperature profiles used to identify the optimum temperature profile for reactors.

(a) Isothermal.

(b) Monotonic increasing

(concave/convex).

(e) Asymptotic/exponential.

(c) Monotonic increasing

(concave/convex).

(f) Single peak maximum.

(d) Asymptotic/exponential.

(g) Single peak maximum.

 Representation of temperature profiles

T (L) = a0 + a1L + a2 L2
Where

T = reactor temperature at point L

L = dimensionless reactor length (0<L<1)
ai = adjustable constants when optimising the temperature profile

Optimisation of temperature profile

< The objective function is maximised or minimised by varying the shape of
the temperature profile.
< Assume that heat can be added or removed wherever required at whatever
rate required so that the optimal temperature profile can be achieved.
< Optimum profile provides an ultimate target to aim for in the final design.
But it may not be achieved exactly due to practical issues.
- Sub-optimal performance

 Superstructure allows heat to be transferred indirectly or directly

through intermediate feed injection.
Optimisation of superstructure can be carried out reliably using
simulated annealing.

Cooling

Heating