Multiphase Chemical

Reactor Engineering
Quak Foo Lee
Ph.D. Candidate
Chemical and Biological
Engineering
The University of British Columbia
 Different Types of
Reactor

Fluidized Bed Reactor Fixed Bed Reactor

Slurry Bubble Column Reactor Trickle Column Reactor

Batch Reactor
 Fixed Bed Rector

Fixed Bed Reactor that converts sulfur in diesel fuel to H2S

Fluidized Bed Reactor

Fluidized Bed Reactor using H2SO4 as a catalyst to bond butanes

and iso-butanes to make high octane gas
Batch Reactor

Stirring Apparatus
 Straight Through
Transport Reactor

Riser
Settling
Hopper

Standpipe

The reactor is 3.5 m in diameter and 38 m tall.

Sasol/Sastech PT Limited
Slurry Phase Distillate
Reactor
Packed Bed Reactor
CSTR
Hand holes for charging
reactor

Connection for heating

or cooling jacket

Agitator
 Plug Flow Model
CA,out
H
t=
Vρ

C A ,in ≅ C A ,out
 Particle surrounding by
fluid of essential constant
CA,in concentration, CA,m

Gas + solids
Batch Mix Flow: Charge
Reactor
 Residence time
distribution

 Particle stays in the

reactor for certain
length of time
Countercurrent Flow

 If solids are moving plug

flow and we have constant
flowC Acomposition 
 Residence time of solids:
H
t=
Vρ

 Heat Effects !!
Heat Effects on Reactions
of Single Particles
 Normally (developed) dealing with exothermic and endothermic
reaction.
 If reaction occurs at a rate such that the heat absorbed (endothermic)
or generated (for exothermic) can’t be transferred rapidly enough,
then non-isothermal effects become important:
The particle T ≠ the fluid T
 For exothermic reaction, Tp will increase and the rate of reaction will
increase above that expected for the isothermal case.
 Two conditions:
 i) Film ∆T (external ∆T) Tf (bulk fluid) ≠ Tp (particle)
 ii) Intraparticle ∆T (internal ∆T) Tr=Rp ≠ Tr=∞
 Non-Reacting

1. Small particles  highly conductive

particles

2. Small particles  volumetric

reaction
 1)Small Particles:
Highly Conductive
Particles
 Particle initially at uniform T
Tp = Tp
 At t = 0, we drop it into our
furnace

Fluid at Tf
 Energy Balance
dH
Qconvection + Qradiation = m
dt
Heat in by convection and radiation = change in enthalpy of particle

d ( C pT p )
[
4πR hcv (T f − T p ) + σ ∈m T − T
2
( w
4 4
p )] = m dt
Where,
Area of sphere = 4πR2
Hcv = convection coefficient
σ = Stefan-Boltzman constant
Єm = emissivity of the particle (wall has Є = 1)
 Energy Balance

hr = σ ∈m
(T w
4
− Tp4 )
(T F − Tp )

m p C p dTp
( hcv + hr ) ⋅ (TF − Tp ) =
Aρ dt

Can solve this equation to get Tp =f(t)

 Find hcv
 Have film: ∆H Tf ≠ Tp
 Use mass transfer analogy to get hcv

hcv d p 1 1
= Nu = 2 + 0.6 Re p Pr 2 3

kf

Vd p Cpµ µ
Re p = ; Pr = ;ν =
ν kf ρ
 2. Small Particles:
Volumetric Reaction
 Small such that no
internal gradients

Heat generated by reaction = Heat transferred to surrounding

V p ( − rAv ) ⋅ ( − ∆H r ) = hA p (T p − T f )
Steady State:

Volume of
particle Rate of Exothermic Rxn:
( − ∆H r ) ⋅ ( − rAv )  R 
reaction -∆Hr = (+)
(T p − Tf )= ⋅
  -rAv = (+)
h 3
 3. Large Particles:
Possible Internal Particle
Gradients
 We have to solve the conduction equation
 Non reacting particle: the conduction equation for sphere:

1 ∂  2 ∂T  ∂T
 r ke  = ρC p ,s
r ∂r 
2
∂r  ∂t
Surface :

( )
dT Ke = effective thermoconductivity
ke = h T f − Tp within the particle
dr r=R
r=R
∂T/∂r = 0 at steady state

Heat transferred into particle

Heat conducted into
Note: accommodate radiation in the
particle at r =Rp
definition of h if that is the case
 Boundary Conditions
∂T
=0
Symmetry condition ∂r r =0

Initial condition t = 0;Tp = Tp ,0 ;T ( r ) = Tp

Internal gradient Tr = 0 ≠ Tr = R0
Tr r =0
≠ Tr r = R0

External gradient T f ≠ Tr r =R
 Reacting Systems
 General equation for volumetric
reactions
(Reaction in porous particles)

 Recall continuity equation:

continuity for A
 Solve (1), (2), (3)
Together
Continuity for A
∂ C A 1 ∂  2 ∂C A 

Coupled through the

ε = 2  r De  − rAv (1)
∂t r ∂r  ∂r 

reaction rate
Energy balance
∂T 1 ∂  2 ∂T 
ρ C p (1 − ε ) = 2  r ke  + rAv ( − ∆ H r ) (2)
∂t r ∂r  ∂r 
k r C AmCSn = ( − rAv )
k r ( T ) C C = ( − rAv )
m n (3)
A S
 In Steady State
 Showed that for steady conditions:

dT dC A
− ke = De ( − ∆H r )
dr dr
Integrate at r = 0, r = R

For sphere
De
( Tr =0 − TS ) = ( C A,s − C A,r =0 ) ⋅ ( − ∆H r )
ke
TS = Tr r=R
 Some Notes
 If we know CA,s (surface concentration) and CA,r=0 (CA
within pellet at r = 0), we can calculate temperature
gradient, previous equation tell us either we need or
don’t need to worry about T gradient within particle.

 Where isothermal (approach) approximation can be

used and where internal T gradients must be
considered.

 Volumetric reaction for porous particles, heat is

generated in a volume.
 Shrinking Core: Non-
Isothermal
 Heat generated at reaction front, not throughout the volume
1 ∂  2 ∂T  ∂T
 r ke  = ρC p ,s Tc

r ∂r 
2
∂r  ∂t Ts

 In Steady State, rc

k e ∂  2 ∂T  r Tf
r =0
r ∂r  ∂r 
2
R

 Solve

T − Tc
=
( 1
rc − 1r ); dT Tc − Ts
= 1 1 2
Tc − Ts ( 1
R − r1c ) dr ( )
R − rc r
T Conditions

Tc = T r = r
c

Ts = T r = R
T = T r =r
Boundary Condition 1: r
= rc
Heat is generated = Heat conducted out through product layer
Area

dT
akr CS ,0C A ,c ( − ∆H r ) = − ke
dr r = rc

− akr CS ,0C A ,c ( − ∆H r )  1 1 
TC − TS = ⋅  − 
ke  R rc 
Boundary Condition 2: r
=R
Heat arriving by conduction = Heat removed for
from within particle convection

= h(TS − T f )
dT
− ke
dr r=R

 ke  1 
TS − T f = − ( TC − TS )   
(
 hR  R R1 − r1c ) 

Can be obtained
Bi-1
from B.C. 1
 Solution
 Combine equations and eliminate TS to get Tc-Tf

TC − T f
= akr CS ,0C A ,c ( − ∆H r ) ⋅ rc2
1  1 − 1  + 1
ke  rc R  hR 2
 Recall from Isothermal
SC Model
 De 
 2
C A ,c  akr CS ,0 rc 
=
C A, f  De  1  1 1
1 +  −  1 − 

 ak C r  r
 r s ,0 c  c  Bim  R

Substitute CA,c into (Tc –Tf) equation

 Tc - Tf

TC − T f C A, f ( − ∆ H r )
=
11 1 1 1 1 1 1 1
 −  + 2  −  + +
ke  rc R  hR De  rc R  akr CS ,0 rc k m R 2
2

Conduction Convection Diffusion in Reaction Mass

Product Layer Transfer
 Can Heat Transfer Control
the Rate in Endo- and
Exothermal Rxn?
 Consider CA,c ≈ CA,f ; initially rapid reaction

a) Endothermic
with poor heat transfer, heat will be consumed in reaction, and if
can’t transfer heat in, TC will drop
 reaction rate ↓ markedly and rate of reaction become the slow
step occurring at a rate dictated by the flow of heat.

b) Exothermic
initial rapid reaction and with poor Q, TC will increased, then rate
of reaction ↑ and eventually reach point where gaseous reactant
can’t be transferred fast enough (external mass transfer or
diffusion). Hence rate is limited.
Fixed Bed
Reactor
 Fixed Bed Reactor
 Solids take part in reaction  unsteady state or semi-batch mode
 Over some time, solids either replaced or regenerated

CA,out
Regeneration
Breakthrough
curve

CA,out /CA,in
1 2

CA,in t
 Isothermal Reaction:
Plug Flow Reactor
 Plug flow of fluid – no radial
gradients, and no axial dispersion

 Constant density with position

 Superficial velocity remains constant

Plug Flow Model

z + dz CA,f + dCA,f

z CA,f

U0 =
(
Vgas m 2 / s )
U0 (m/s) superficial velocity
( )
Axs m 2
 Mass Balance
Input – Output – Reaction = Accumulation

[
U 0C A , f − U 0 ( C A , f + dC A , f ) ] ∂
− [ ( − rAv ) ⋅ dz ] = (ε ⋅ ∂C A , f ⋅ ∂z )
∂t
Divide by ∂z and take the limits as ∂z  0

∂C A , f ∂C A , f
ε +U0 + rAv = 0
∂t ∂z

ε is void fraction in bed

 Void fraction
For first order reaction, fluid only:

 mol  1 dN A
rAv  3  = = kv (1 − ε ) C A , f
''

 m reactor⋅ s  Vr dt
For steady state:
Volume of reactor
∂C A , f
→0
∂t
Therefore,
dC A , f
U0 + k v'' (1 − ε ) C A , f = 0
dz
Conversion as a function
of Height
Integrating with CA,f = CA,f,in at z = 0

C A, f  kv'' (1 − ε ) 
X A = 1− = 1 − exp − z 
C A , f ,in  U0 

Note 1: Same equation as for catalytic reactor with 1st order reaction
Note 2: Can be used in pseudo-homogeneous reaction
 Balance on Solid
 aA (fluid) + S (solid)  Products
 Input – Output – Reaction = Accumulation
 Over increment of dz: input = 0, output =0

∂C s
( − rsv ) ⋅ ∆z = (1 − ε ) ⋅ ∆z
∂t

Volume fraction of solid =

mol
m3 of solid
m3 of solid · s
m of reactor volume
3
Balance on Solid

∂C s
(1 − ε ) + rsv = 0
∂t

 ( − rav ) = a ⋅ ( − rsv )

∂C s rAv
+ =0
∂t a ( 1 − ε )
 Solve These Equations

= 0 (In quasi steady state, we ignore the

accumulation of A in gas)

∂C A , f ∂C A , f a (1 − ε ) ∂Cs
∂C A , f
ε +U0 + rAv = 0 − =0
∂t ∂z
Av
∂z U0 ∂t
er
tut

∂C 'A , f
ti

∂Cs'
bs

+ =0
Su

∂z ∂t
∂C s rAv
+ =0 C 'A , f = f ( z ,t )
∂t a (1 − ε )
Cs' = f ( z ,t )
a) Shrinking Core Model
b) Uniform reaction in porous particle, zero order
in fluid
c) Uniform reaction, 1st order in fluid and in solid
d) Park et al., “An Unsteady State Analysis of
Packed Bed Reactors for Gas-Solid Reactions”,
J. Chem. Eng. Of Japan, 17(3):269-274 (1984)
e) Evans et al., “Application of a Porous Pellet
Model to Fixed, Moving and Fluid Bed Gas-
Solid Reactors”, Ind. Eng. Chem. Proc. Des.
13(2):146-155 (1974)
 a) In Shrinking Core
Model
rAv = ak v (1 − ε )C A ,c C S ,o
Recall that De For SCM
C A ,c akv CS ,o rc2 3
=  rc 
C A, f 
1 +
De  1 

1 1 Cs = Cs ,o  
 ak C r  r − 1 − Bi  R  R
 r S ,o c  c  m 

∂ r R 3
Solid Phase
rc2 c + kv C A ,c rc = 0 Solve
CA,f = f(z)
∂t 3 rc = f(z,t)
Liquid Phase ∂C A , f
U0 + akv (1 − ε ) Cs ,oC A ,c = 0
∂z
 Conversion vs Time

t=0 t>0

z
Overall Conversion of
Solid

L 3
 rc 
∫  R  dz 1 L

3 ∫ c
1− X s = 0
L
= 3
r dz
LR 0
∫ dz
0
 Height Vs time
(Graphical)
Unreacted
z/L bed depth

Reaction
All CA has zone
been
reacted

Completely
reacted

t/τ
Particles at bed
entrance are
completed reacted
b) Uniform Reaction in Porous
Particle
and Zero Order in Fluid
CS
dX S 1− X S =
= k (1 − X S ) where C0
dt 1
− dX S = dCS
C S ,0

U0 ∂C A , f
⋅ + kCS = 0
a(1 − ε ) ∂z
∂C S
+ kCS = 0
∂t
c) Uniform Reaction and 1st
order in Fluid and in solid

rAv = akv (1 − ε ) C ACS

rAv = akv (1 − ε )η CS

∂C A , f
U0 + akv (1 − ε )η C A ,s CS = 0
∂z
∂C A ,s
+ akv (1 − ε )η C A ,s CS = 0
∂t
 Non-Isothermal Packed
Bed Reactor
 For mass continuity  did balance on
fluid and on solid
 For energy balance, we do balance
on each phase
Non-Isothermal Packed
Bed Reactor
 Assumptions:
1) Adiabatic reaction – no heat lost through shell to
surroundings (no radial temperature gradients) q
=0
2) Biλ is small – uniform T within particle (an
exothermic reaction Tp > Tg)
3) Plug flow of gas and use Tref =0 for enthalpy
calculations
4) Assume an average density can be used (ρg =
constant)
 Modeling

q =0

Tf + dTf z + dz
Tf z

Tf,0

U0  kg 
G 2  = U0ρg
m s 
Moving Bed Reactor
Solids in
Vs
Gas out

∆z

U0

Gas in

Solids out
 Moving Bed Reactor
(MBR)
 Steady state reactor where solids moving at
near their packed bed voidage
 Counter or co-current operation
 Solid usually move downward (vertical shaft
reactor or furnace)
 Voidage is near that of a packed bed
 Slightly above random loose-packed
voidage
 Solids move mainly in a plug floe, but region
near wall have a velocity distribution
 Advantages of MBR
 True counter-current flow
 Uniform residence time (essentially plug flow)
 Reasonable ∆P
 Throughput variable
 Generally larger particle dp > 2-3 mm
 Difficulties coping with wide size distribution of
particles (fines tend to block up the void
spaces)