CAPE3320/5311M

Reaction Engineering

Heterogeneous reaction

Dr. Xiaojun Lai

• Introduction of heterogeneous reaction

• Resistance forces
• Modelling of heterogeneous reaction
• Packed bed catalyst rector
• Gas-liquid reaction systems
1
What is heterogeneous reaction? 
Homogeneous reaction

Heterogeneous reaction
2
What is the Catalyst? A substance that affects the rate of a reaction but emerges
from the process unchanged.
What does catalyst do in reaction?
If chemical reaction only on catalyst surface

Resistance steps in heterogeneous reaction

• Mass transfer from bulk to surface

Example. Dilute A diffuses through a stagnant liquid film onto a plane surface
consisting of B, reacts there to produce R which diffuses back into the mainstream
(Figure 10.4). Develop the overall rate expression for the L/S reaction
 Mass transfer

coefficient ?

• Mass transfer from bulk to surface

• Surface chemical reaction

Mass transfer from bulk to surface=Surface chemical reaction

This result shows that l/k, and l/k" are additive resistances.
 
If k<< k" Mass transfer is controlling step.
If k<< k" Chemical reaction is controlling step.

8
Definition of reaction rate in heterogeneous reaction

• Mass of catalyst
• Volume of catalyst
• Surface of catalyst
Examle for Sa: 10 grams of catalyst may cover as much surface area as a football field

For nth order reaction: For a first order reaction:

Heterogeneous reaction mechanism in detail

Bulk scale

Pore scale
Pore scale Single particle Bulk of particles
Nanoscale Microscale Macroscale
Pore scale

Single cylindrical pore of length L

First-order reaction

Objective: Finding change of reactant concentration in pore scale

14
 Boundary
condition

After solution of
Differential Equation

𝑘
where
√
 
Thiele Modulus: mL = L
pore) 𝐷
(1st order in single
Single catalyst particle

Spherical porous particle radius R

Objective: Finding Change of reactant concentration
in a porous particle

FA(in) at r = WAr Area = WAr 4 r2r W: Mass flux of reactant A,

(mol/m2.s)
FA(out) at r = WAr Area = WAr 4 r2r+r
rm : mean radius between r and r+Δr
ρC: Density of the particle
-rA = -r A V = -r A (4 rm2) r
CA : number of reactant A moles
= -rA (4 r ) r
m
2

16
 Mass balance becomes:
WAr 4 r2r - WAr 4 r2r+r - rA (4 rm2) r = 0

After dividing by (-4π) and taking the limit as Δr→0, Δr = dr,

we obtain the following differential equation:

ODE

Boundary condition

17
 Thiele modulus

By dimensionless previous ODE

M  T= 𝑘
Comparing to
√
 
MT= L
𝐷
for 1st order in single pore)

(nth order in particle)

If Thiele modulus <<1 : Chemical reaction is controlling step

If 1<< Thiele modulus : Mass transfer is controlling step
  MT
Packed bed reactor (PBR)

Multiphase catalytic packed-bed reactors

 Plug flow reactor (PFR)
• Also called a tubular reactor
• Reactants are consumed as they flow
down the length of the reactor
• Reaction rate is based on the volume
of reactor, V
Packed bed reactor (PBR)
• Cylindrical shell, vertically oriented
• Often gravity-driven flow
• Heterogeneous reaction: fixed bed of
catalyst inside
• Reaction occurs on the surface of the
catalyst pellets
• Reaction rate is based on the mass of the
solid catalyst, W, not reactor volume V
Packed bed reactor (PBR)
For a fluid-solid heterogeneous system, the rate of reaction of a substance A is defined as
gmol A reacted
r  '
A
sec g catalyst
The mass of solid is used because the amount of the catalyst is what is important to the –r’ A
W

FA0 FA
W W  W

FA (W ) F A(W  W )
rA' W
FA (W )  FA (W  W )  rA' W  0

FA dFA
W  FA 0  rA'
Design equation for PBR:

Conversion
Weight of catalyst (lb)

X
dX
W  FA 0 
0
 r ' A
Molar flow of A (t=0)

Rate of reaction
(lbmol A)/[(h)*(lb of catalyst)]
 Equilibrium and Thermodynamics
for a reversible reaction, e.g. from thermodynamics

  K = exp (- )  =
  AR

At equilibrium, CAe = k2CRe

When is constant:
K= = =
= ()
XAe =

Equilibrium conversion XAe is a function of temperature

 Exothermic
Example :

 A  R 298 = -14130 J/mol; 298 = -75300 J/mol; pA = CpR = constant

Find relationship XAe vs T in the temperature range 0 – 100 C

  K298 = exp (- ) = exp (- =

  = ()  = 300 exp( ())

(where = 298 K),

  XAe =
Calculation: Equilibrium Conversion as a function of Temperature

T (oC) T (K)
5 278 4851 1.000
15 288 2671 1.000
25 298 861 0.999

85 358 1.841 0.648

95 368 0.925 0.481
Plot: Equilibrium Conversion as a function of Temperature (exothermic)
1.200

1.000

0.800

0.600
XAe

0.400

0.200

0.000
0 20 40 60 80 100 120 140 160

Temperature (celsius)
  In the case of endothermic reaction, e.g. 298 = 75300 J/mol

Limit is in opposite direction

1.200

1.000

0.800

0.600

0.400

0.200

0.000
-60 -50 -40 -30 -20 -10 0 10 20 30
   Rate of reversible reaction

-rA=k1CA – k2CR; (CA0 = 1 mol/L)

rate constant k1(298)= 0.942 min-1; Activation energy E1 = 48900 J/mol

= ()  = ())

 =

So : -rA=k1CA – k2CR = ()) CA0 (1-XA) ()) CA0 XA

Rate of reaction is a function of T and X A   = 300 exp( ())

Adiabatic Reactor ( assuming Cp is a constant during the reaction)
  XA =

XA -rA 1/-rA
0 0.03 33.33
0.08 0.05 20.00
0.2 0.1 10.00
0.35 0.2 5.00
0.46 0.3 3.33
0.64 0.3 3.33
0.67 0.2 5.00
0.69 0.1 10.00
0.7 0.05 20.00
  XA =
 Cooling

Combined Adiabatic Reactor