Previous Lecture

Design structure for isothermal reactors

(algorithm)

Design of CSTRs
Todays Lecture
Example

Design of PFRs

Pressure drop in reactors

Example 4-2 Close to 12.2 billion metric tons of ethylene glycol (EG)
were produced in 2000, which ranked it the twenty-sixth most
produced chemical in the US that year on a total pound basis.
About one-half of the ethylene glycol is used for antifreeze while
the other half is used in the manufacture of polyesters. In the
polyester category, 88% was used for fibers and 12% for the
manufacture of bottles and films. The 2004 selling price for
ethylene glycol was $0.28 per pound. It is desired to produce 200
million pounds per year of EG. The reactor is to be operated
isothermally. A 1 lb mol/ft3 solution of ethylene oxide (EO) in water
is fed to the reactor together with an equal volumetric solution of
water containing 0.9 wt% of the catalyst H2SO4. The specific
reaction rate constant is 0.311 min-1, as determined in Example 4-1.

A B catalyst
C
The specified ethylene glycol (EG) production rate:
 (a) If 80% conversion is to be achieved, determine the necessary
CSTR volume.
CSTR Design A B catalyst
C
equation :

Rate law
Stoichiometry

Combination:
(b) If two 800-gal reactors were arranged in parallel, what is the
corresponding conversion?
CSTR Design equation

Rate law

Stoichiometry

Combination:

By trial and error, the conversion exiting each of the CSTRs in

parallel is 81%.
(c) If two 800-gal reactor were arranged in series, what is the
corresponding conversion?

The two equal-sized CSTRs in series will give a higher conversion

than two CSTRs in parallel of the same size when the reaction order
is greater than zero.
 Design Equations for Isothermal Reactors
REACTOR DIFFERENETIAL ALGEBRAIC INTEGRAL
FORM FORM FORM

X
dX
BATCH
N AO
dX
(rA )V t N AO
dt 0
rAV

FAO ( X )
V
CSTR (rA )

dX X
dX
PFR FAO (rA ) V FAO
dV
0
rA

X
dX dX
PBR FAO (rA' ) W FAO '
dW 0
rA
 PFR
Gas-phase reactions are carried out primarily in
tubular reactors where the flow is generally
turbulent.
Assuming no dispersion and there are no radial
gradients in either temperature, velocity, or
concentration.
Should be aware of the change of the volume.

The majority of gas-phase reactions are catalyzed by passing the reactant

through a packed bed of catalyst particles.
 PFR, 2nd order rxn, liquid phase, isothermal
No pressure drop X dX
mole balance F dX r V FA0
A0 A No heat exchange
0 rA
dV
rate laws rA kCA2
Stoichiometry C A C A0 (1 X )
FA0 X dX v0C A0 X
combination V kC2
A0
0
2
1 X kCA0 1 X
2

kCA0 Da2
or X
1 kCA0 1 Da2

Damkhler number for 2nd-order reaction

 PFR, 2nd order rxn, gas phase, isothermal

No pressure drop dX
dX V FA0
X

mole balance FA0 dV rA No heat exchange 0 rA

rate laws
rA kCA2
FA FA FA0 (1 X ) (1 X )
Stoichiometry C A C A0
v v0 (1 X ) v0 (1 X ) (1 X )

combination V FA0
X 1 X
2
dX See (A-7)
kCA0 1 X
0 2 2

v0
1 X
2
V 2 (1 ) ln(1 X ) X
2

kCA0 1 X
Example 4-3 Ethylene ranks fourth in the Unite States in total pounds of
chemicals produced each year, and it is the number one organic chemical
produced each year. Over 50 billion pounds were produced in 2000, and it
sold for $0.27 per pound. Sixty-five percent of the ethylene produced is
used in the manufacture of fabricated plastics, 20% for ethylene oxide, 16%
for ethylene dichloride and ethylene glycol, 5% for fibers, and 5% for
solvents.
Determine the plug-flow reactor volume necessary to produce 300 million
pounds of ethylene a year from cracking a feed stream of pure ethane. The
reaction is irreversible and follows an elementary rate law. We want to
achieve 80% conversion of ethane, operating the reactor isothermally at
1100 K at a pressure of 6 atm. k 0.072 s 1 @ 1000 K
C2 H 6 C2 H 4 H 2 A BC The activation energy is 82 kcal/g
mol.
The molar flow rate of ethylene (B):
PFR design equation

Rate law
(elementary)

Stoichiometry

Combination:
(b) It was decided to use a bank of 2-in. schedule 80 pipes in parallel that are 40 ft
in length. For pipe schedule 80, the cross-section are, Ac, is 0.0205 ft2. The number
of pipes necessary is
Pressure drop in reactors
In gas-phase reactions, the concentration of the
reacting species is proportional to the total
pressure and proper accounting for the effects
of pressure drop on the reaction system can be
a key factor in the success or failure of the
reactor operation (e.g. PBR).
When accounting for the effects of pressure
drop, the differential form of the mole balance
must be used.
 PBR, 2nd order rxn, gas phase, isothermal

dX
mole balance FA0 rA '
dW
rate laws
rA ' kCA2
Stoichiometry C A0 ( j v j X ) P T0 C A0 (1 X ) P T0
Cj CA
1 X P0 T 1 X P0 T
2
P
2
dX C A0 (1 X )
combination
FA0 k
dW 1 X P0
2
dX kCA0 1 X P
2
dX
or
f ( X , P)
dW v0 1 X P0 dW
What is the relationship between X and P? If PBR: Ergun equation
 Solid Catalyzed Reactions

Reaction rates are usually expressed in terms of mass of

catalyst loading.

(rA' ) in mol/timemass of catalyst

The design equations can be derived in a manner similar to

those for homogeneous reactors - by using mass (w) instead
of volume (V).

Examples of solid catalyzed reactions:

Steam Methane Reforming (SMR) for HYDROGEN production
Conversion of NOx and CO in automobile catalytic converter
Styrene production
General Mole Balance for Packed Bed Reactors

FAO FA

Input - Output + Gen = Accumulation

FA w FA w w (rA' ) w 0

FA w FA w w FA w FA w w
(r )
'

w
A

w w+w
dFA
(rA' )
dw
X X Mass of catalyst = w
dX dX
FAO (rA ) w FA0
'

dw X 0
( r '
A)
Pressure Drop in Packed Bed Reactors
Flow of fluids through packed beds is accompanied by
substantial pressure drop across the bed.

From reaction perspective, do we need to account for

pressure drop in packed bed reactors ?

The answer depends on the type of reaction

For liquid-phase reactions, small changes in pressure does not affect

concentration and consequently does not affect the reaction rates.

However, for gas-phase reactions, the concentrations are a function

of pressure. Reduction in pressure implies reduction in
concentration and, consequently, a reduction in reaction rates.
Relationship between concentration and
pressure
Fi
Recall, Ci (ri) = k(T) f(Concentration)
v

Case I: Liquid phase reactions

Concentration does not depend on
v = vO =constant pressure. No need to calculate
pressure to solve for conversion
Case II: Gas phase reactions

Po T
v vo (1 X )( ) Inlet Conditions
P To
F FAO (1 X )
CA A
v vo (1 X )( Po / P)(T / TO )
Relationship between concentration and
pressure

Case II: Gas phase reactions (cont.)

FA FAO (1 X )
CA
v vo (1 X )( Po / P)(T / TO )

For isothermal reactor

(1 X ) P
C A C AO (P/PO) may vary along the reactor length
(1 X ) Po

(ri) = k(T) f(Concentration) (ri ) f ( P, T , X )

Pressure Drop in an Isothermal PBR
Ultimately, we want to write two coupled differential equations that
describes how the two variables - conversion (X) and pressure (P) -
change with reactor length or mass of catalyst packed

Variation of conversion with catalyst weight

dX (rA' ) From GMBE
f1 ( P, X )
dW FA0

Variation of pressure with catalyst weight

dP
f 2 ( P, X ) ??
dW

Next, we will review equation describing pressure drop in

packed beds
 Pressure Drop in Packed Bed Reactors
ERGUN equation for pressure drop in a packed bed:
P g c s D p 3 150(1 )
1.75
z uo 1 s ( D p uo / )
2

Laminar Turbulent
Position (NRE < 1) (NRE > 1000)

P Pressure drop ( N / m 2 or Pa ) density (kg/m 3 )

D p Particle diameter (m) uo superficial velocity (m/s)
s sphericity D p uo
N RE
porosity

dP G 1 150(1 ) Differential equation

3 1.75 G for pressure drop in bed
dz g c D p Dp of spherical packing
 Pressure Drop in Packed Bed Reactors
dP G 1 150(1 )
3 1.75 G
dz g c D p Dp

In the above equation, some of the parameters are:

characteristic of the packing [porosity (, particle (Dp)] Fixed for a given packed bed

characteristic of fluid property [viscosity (), density ()] Varies with operating condition
characteristic of operating parameters [mass velocity (G)] and reaction mixture

The packing characteristics are usually considered to be invariant

with respect to reactor length.

This leaves us with the following parameters to be evaluated as a

function of reactor length
the fluid properties: viscosity () and density ()
the operating parameter G
Evaluating terms in Ergun equation
dP G 1 150(1 )
3 1.75 G
dz g c D p Dp

Superficial Mass velocity (G)

G is the mass flow rate per unit area (kg/m2-s).

Here, u and u0 are velocities (in m/s)

G o u o u NOT to be confused with volumetric flow
rate (v)

For a reactor with a constant cross-section, G is constant.

Thus, if G is known at inlet it need not be evaluated at any other reactor
position z
Evaluating terms in Ergun equation
dP G 1 150(1 )
( 3 )[ 1.75 G]
dz gc Dp Dp

Viscosity ()
Viscosity of gases are weak function of pressure. We can
assume the gas mixture viscosity to be independent of
pressure.

The viscosity of gases depend on the mixture composition. In a

reactor, mixture composition will change, the gas mixture
viscosity will also change.
Density ()
Density of gases depend on pressure.
There are two ways of handling the pressure term:
(i) in terms of inlet density, P/Po, T/To
(ii) in terms of local P, T and composition
 Ergun equation
Pressure drop in a porous bed: Dominant for turbulent flow

dP G 1 150(1 )
3 1.75G
dz g c D p Dp
Dominant for laminar flow
constant mass flow rate

v 0v0 P0 T FT v0 P T0 FT 0
v v0 0 0
P T0 FT 0 v P0 T FT

dP G 1 150(1 ) 1 P0 T FT
3 1.75G
dz g c D p Dp 0 P T0 FT 0
 Ergun equation (cont.)
dP G 1 150(1 ) 1 P0 T FT
3 1.75G
dz g c D p Dp 0 P T0 FT 0
Pressure drop in terms of Catalyst weight:

W 1 AC z c
G 1 150(1 )
0 3 1.75G
0 g c D p Dp
2 0

AC C (1 ) P0

dP T P0 FT dP T P0
(1 X )
dW 2 T0 P / P0 FT 0 FT FT 0 FA0X dW 2 T0 P / P0