4.

Pressure drop
phase kinetics
calculations

153

Pressure Drop in Reactors

4.4 Pressure Drop in Reactors

In liquid-phase reactions, the concentration of reactants is insignificantly
affected by even relatively large changes in the total pressure. Consequently,
we can totally ignore the effect of pressure drop on the rate of reaction when
liquid-phase chemical reactors. However, in gas-phase reactions, the
concentration of the reacting species is proportional to the total pressure and
consequently, proper accounting for the effects of pressure drop on the reaction
system can, in many instances, be a key factor in the success or failure of the
reactor operation.
4.4.1 Pressure Drop and the Rate Law

We now focus our attention on accounting for the pressure drop in the
rate law. For an ideal gas, the concentration of reacting species i is
gas-phase
reactions pressure
drop may be very
important

(3-46)

For isothermal operation

18)
We now must determine the ratio
as a function of volume V or the catato account for pressure drop. We then can combine the
lyst
tration, rate law, and design equation. However, whenever accounting for the
effects of pressure drop, the differential form
the mole balance (design
equation) must be used.
for example, the second-order
reaction

When

one

differential forms
of the
design equations

is being carried out in a packed-bed reactor, the differential form of the mole
balance equation in terms of catalyst weight is

-The

gram moles
gram catalyst min

law is

From stoichiometry for gas-phase reactions,

(2-17)

154

isothermal Reactor Design

Chap. 4

and the rate law can be written as

(4-20)
Note from Equation (4-20) that the larger the pressure drop
the smaller P)
from frictional losses, the
the reaction rate!
with the mole balance (2-17) and assuming
Combining Equation
gives
isothermal operation (T =

Dividing by

yields

For isothermal operation (T =

conversion and pressure:
Equation
is needed.

the right-hand side is a function of only

P)

(4-21)

We now need to relate the pressure drop to the catalyst weight in order to
determine the conversion as a function of catalyst weight.
4.4.2 Flow Through a Packed Bed

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

used most to calculate
through a packed bed of catalyst particles. The
pressure drop in a packed porous bed is the Ergun
Ergun equation

R. B. Bird, W.E. Stewart,and E.N. Lightfoot,

Wiley,
p. 200.

Phenomena (NewYork:

4.4

Pressure Drop in Reactors

where

P = pressure,
= porosity =

155

volume of void
total bed volume

volume of
total bed volume
g, = 32.174 lb,

4.17 X

factor)

lb,

(recall that for the metric system

= 1.0)

= diameter of particle in the bed, ft

= viscosity of gas passing through the bed,

= length down the packed bed of pipe, ft

= superficial velocity = volumetric flow

cross-sectional

area of pipe,
p = gas density,
=

= superficial mass velocity,

s) or

h)

-In calculating the pressure drop using the Ergun equation, the only
parameter that varies with pressure on the right-hand side of Equation (4-22)
is the gas density, p. We are now going to calculate the pressure drop through
the bed.
Because the reactor is operated at steady state, the mass flow rate at any
point down the reactor,
is equal to the entering mass flow rate,
equation of continuity),
=m
=

Recalling Equation

Equations

we have

and (4-23) gives

56

Isothermal Reactor Design

Chap. 4

Simplifying yields

(4-24)
I

where

(4-25)

For tubular packed-bed reactors we are more interested in catalyst weight

rather than the distance down the reactor. The catalyst weight up to a distance of down the reactor is

(1

weight of

volume of

catalyst

solids

density of

(4-26)

bulk density of the

where A, is the cross-sectional area.
(mass
of catalyst per volume of reactor bed), is just the product of the solid density,
, the fraction of solids, - :

Using the relationship between and

[Equation

we can change

our variables to express the Ergun equation in terms of catalyst weight:

Use this form for
multiple reactions
and membrane
reactors

(4-27)
Further simplification yields

(4-28)

where

(4-29)

157

Pressure Drop in Reactors

Equation
will be the one we use when multiple reactions are
occurring or when there is pressure drop in a membrane reactor. However, for
single reactions in packed-bed reactors it is more convenient to express the
Ergun equation in terms of the conversion X . Recalling Equation (3-42) for

+
and

F,,

(3-42)

development leading to Equation

-=
where, as before,

Equation (4-28) can now be written as

Differential form
equation
for the pressure
drop in packed
beds

- _- - _ ( 1 + EX)

of

2 T o P I P,

(4-30)

We note that when is negative the pressure drop

will be less
higher pressure) than that for E = When E is positive, the pressure drop AP
will
greater than when E = 0.
For isothermal operation, Equation (4-30) is only a function of conversion
pressure:

Recalling Equation
Two coupled
equations to be
solved numerically

(4-21)

we see that we have two coupled first-order differential equations, (4-31) and
that
be solved simultaneously. A variety of software packages and
numerical integration schemes are
for this purpose.

Analytical Solution. If E
0, or if we can neglect ( E X ) with respect i o 1
1
can obtain an analytical solution to Equation (4-30) for isothermal operation (Le., T
isothermal operation with E = 0, Equabecomes
tion

158

Isothermal Reactor Design

Isothermal with

Chap. 4

(4-32)
Rearranging gives us

---- - a
Taking

inside the derivative, we have

Integrating with P =

at W = 0 yields
2

Taking the square root of both sides gives

I

Pressure ratio
only for E 0

(4-33)

where again

Equation (4-33) can be used to substitute for the pressure in the rate law, in
which case the mole balance can be written solely as a function of conversion
and catalyst weight. The resulting equation can readily be solved either analytically or numerically.
If we wish to express the pressure in terms of reactor length we can use
Equation (4-26)to substitute for Win Equation (4-33). Then
(4-34)

Example 4-5 Calculating Pressure Drop in a Packed Bed

Calculate the pressure drop in a 60 ft length of 1

schedule 40 pipe packed
in diameter when 104.4
with catalyst pellets
of gas is passing
the bed, The temperature is constant along the length of pipe at 260C. The void
fraction is 45% and the properties of the gas are similar
of
at this temperature. The entering pressure is 10 atm.

4.4

Pressure Drop in Reactors

At the end of the reactor z

159

L and Equation (4-34) becomes

Evaluating
the pressure drop
parameters

For

-in. schedule 40 pipe, A,

0.01414

104.4

7383.3

0.01414
For air at

and

atm,

0.0673
= 0.413

From the problem statement,

= 0.0208 ft

4.17 X

lb

Substituting the values above into Equation (4-25) gives us

1 - 0.45)

7383.3

h)

0.0208 ft

0.01244
164.1

(266.9 + 12,920.8) ft
h
1
1
atm
x
144
14.7
X

atm 25.8 0.0775 m

ft3

160

Isothermal Reactor Design

0.0775

60 ft

atm
= 2.65 atm

P=
AP

= 7.35 atm

P=

Chap. 4

(E4-5.5)

(E4-5.6)

Reaction with Pressure Drop

Analytical solution: Now that we have expressed pressure as a function
of catalyst weight [Equation
we can return to the second-order isothermal reaction,

to relate conversion and catalyst weight. Recall our mole balance, rate law, and

Mole balance:

(2-17)

Rate law:

(4-19)

Stoichiometry. Gas-phase isothermal reaction with

0:

P
-

(4-35)

Using Equation (4-33) to substitute for PIP, in terms of the catalyst weight,
we obtain
Only
for

Combining:

- = -( 1 -

Separating variables:

--

Integrating with limits X = 0 when W

yields

Solving for conversion gives

[(I

0 and substituting for

161

Pressure Drop in Reactors

(4-36)

Solving for the catalyst weight, we have

Catalyst weight for

1- {I -

second-order

reaction in
with AP

We now proceed (Example 4-6) to combine pressure drop with reaction in a

packed bed for the case where we will
that E X 1 in the Ergun equation
in the rate law in order to obtain an analytical solution. Example 4-7
but
removes this assumption and solves Equations (4-21 ) and (4-3 1) numerically.
Example

The economics

Calculating X in a Reactor with Pressure Drop

7 billion pounds of ethylene oxide were produced in the United

States in 1997.The 1997 selling price was $0.58 a pound, amounting to a commercial value of $4.0 billion. Over 60% of the ethylene oxide produced is used to make
polyesethylene glycol. The major end uses of ethylene oxide are antifreeze
ter
surfactants
and solvents (5%). We want to calculate the catalyst
weight necessary to achieve 60% conversion when ethylene oxide is to be made by
the vapor-phase catalytic oxidation of ethylene with air.

+
C

A +fB

Ethylene and oxygenare fed in stoichiometricproportions to a packed-bed reacat a prestor operated isothermally at 260C. Ethylene is fed at a rate of 0.30
sure of 10 atm. It is proposed to use 10 banks of 1 -in.-diameter schedule 40
packed with catalyst with 100 tubes per bank. Consequently,the molar flow rate to
The properties of the reacting fluid are be
each tube is to be 3
considered identical to those of air at this temperature and pressure. The density of
the -in.-catalystparticles is 120
and the bed void fraction is 0.45.The rate law is
=

lb

cat. h

with3
k = 0.0141
Chem., 45, 234 (1953).

lb mol
at 260C
atm . cat.. h

162

isothermal Reactor Design

Chap. 4

Solution

mole balance:

1.

(E4-6.1)
2. Rate law:
=

(E4-6.2)

113 213

1/3

The algorithm

3. Stoichiometry. Gas-phase, isothermal

+
(E4-6.4)

(E4-6.5)
We
evaluatethe
combine stepeither
1) Analytically
2) Graphically
3) Numerically,or
4) Using software

Combining the rate law and concentrations:

(E4-6.7)
For stoichiometric feed,

(E4-6.8)

=
where k
5. Developing the design equation. For a packed-bed reactor, the relationship
1 is
between and W when

is valid
E

=0

(4-33)

PO

or

(E4-6.9)

Combining Equations

and (E4-6.

we have

4.4

163

Pressure Drop in Reactors

Separating variables to form the integrals yields

Integrating gives us

we obtain

Solving for

(E4-6.11)
divide feed rates by 1000):

6. Parameter evaluation per tube

Ethylene:

=3X

Oxygen:

1.5 X

lb

= 0.54

1.5 X

lb

lb

1.08 lb

lb

0.79 mol
I

inerts

= 5.64 X

= 2.03

Summing:

3.65

1)

atm
= 0.0141

k' =

1 - [1

3 atm

lb mol
0.63 = 0.0266 cat

-0.15)
a

For 60% conversion, Equation (E4-6.11) becomes

1 (1 -

(E4-6.12)

In order to calculate
Evaluating the
drop
parameters

we need the superficial mass velocity, G. The mass flow rates of each entering
species are:

Isothermal Reactor Design

164

mol
X 28 h
mol
0.54

mol

mol X 28
h
lb mol

Chap.

30.24

- 17.28

56.84

The total mass flow rate is

104.4 h

This is essentially the same superficial mass velocity, temperature, and pressure as in Example 4-5. Consequently, we can use the value of
calculated
in Example 4-5.
atm
0.0775 (0.01414

0.0166
_cat

Substituting into Equation (E4-6.12) yields

lb mol
cat
45.4 lb of catalyst per tube
or 45,400 lb of catalyst total
This catalyst weight corresponds to a pressure drop of approximately 5 atm.
If we had neglected pressure drop, the result would have been
1
k

Neglecting
pressure drop
results in poor
design (here 53%
vs. 60%

0.0266
=

35.3

1
1 - 0.6
of catalyst per tube (neglectingpressure drop)

and we would have had insufficient catalyst to achieve the desired

Substitutingthis catalyst weight
35,300 total) into Equation (E4-6.10)
gives a conversion of only 53%.

4.4

Pressure Drop in Reactors

Example 4-

Pressure Drop with Reaction-Numerical

Rework Example
for the case where volume change is nor
Ergun equation and the two coupled differential equations
conversion and
are solved
I

Solution
Rather than rederive everything starting
the
etry, and pressure drop equations, we will use th
4-6 Combining
(E4
and

Next. we

.3)

Program examples
POLYMATH,
MatLab can be
loaded from the
CD-ROM (see
the Introduction)

For the reaction conditions

in Example 4-6, we
the
0, and y
1.0 and the parameter values
W 0,
cat,
-0.15, k'
0.0266
1.08
E
cat, and
large number of ordinary differential equation solver software
are extremely user friendly have become available. We shall
ODE solvers)
use POLYMATH4 to solve the examples in the
text. However, the CD-ROM
as all the MATLAB and
contains an example that uses ASPEN, as
MATH solution programs to the example
With POLYMATH
simply
enters Equations (E4-7.3) and (E4-7.4) and the corresponding parameter value into
the computer (Table
with the
they
(rather, boundary) conditions
are solved and displayed as shown Figure E4-7.1,
the Ergun equation in Example
We note that neglecting E X
-0.09) to obtain an
solution resulted in less than a 10% error.
Developed by Professor M. Cutlip of the University of Connecticut. and Professor M.
Corporation,
Shacham of Ben Gurion University. Available from the
Box 7939, Austin, TX 78713.

166

Reactor Design

Chap. 4

POLYMATH SCREEN SHOWING EQUATIONS TYPED

IN AND READY TO BE SOLVED.

TABLE

Equations

Initial Values
1
0

15
0266

Scale:

a,

w f = 60

0.000

ooo
U

Figure E4-7.1 Reaction rate profile down the PBR.

However, larger errors will result if large values of E X are neglected! By taking into
E = -0.15) in the pressure
account the change in the volumetric flow rate
drop term, we see that 44.0 lb of catalyst is required per tube as opposed to 45.4lb
when E was neglected in the analytical solution, Equation (E4-7.4).Why was less
The
that
catalyst required when was not neglected in Equation
the numerical solution accounts for the fact that the pressure drop will be less
because E is negative.

4.4

167

Pressure Drop in Reactors

It is also interesting to learn what happens to the volumetric flow rate along the
length of the reactor. Recalling Equation
=

Volumetric flow
rate increases
with increasing
pressure drop

----

(3-44)

let f be the ratio of the volumetric flow rate, to the entering volumetric flow
rate,
at any point down the reactor. For isothermal operation Equation (3-44)
becomes

E4-7.2 shows X, y
y =
and f down the length of the reactor. We
see that both the conversion and the volumetric flow increase along the length of the
reactor while the pressure decreases. For gas-phase reactions with orders greater
than zero, this decrease in pressure will cause the reaction rate to be less than in the
case of no pressure drop.
4.000

3.200

2.400

1.600

0.800

0.000
W

Figure
of added

conversion

Output in graphical

from POLYMATH

We note from Figure

that the catalyst weight necessary to raise
the conversion the last 1% from 65% to 66% (3.5 lb) is 8.5 times more than
that (0.41 lb) required to raise the conversion 1% at the reactor's entrance.
Also, during the last 5% increase in conversion, the pressure decreases from
3.8 atm to 2.3 atm.

168

Isothermal Reactor Design

Chap. 4

4.4.3 Spherical Packed-Bed Reactors

When small catalyst pellets are required, the pressure drop can be significant. In
4-6 we saw that significant design flaws can result if pressure
drop is
or if steps are not taken to minimize pressure drop. One type
of reactor that minimizes pressure drop and is also inexpensive to build is the
spherical reactor, shown in Figure 4-8. In this reactor, called an ultraformer,
dehydrogenation reactions such as
aromatic t

paraffin
are carried out.

Figure 4-8
Products.) This reactor

petroleum naphtha.

Reactor. (Courtesy of Amoco Petroleum

S I X used by Amoco for reforming

one in a series of
by K. R

Sr.

Another advantage of spherical reactors

that they are the most economical shape for high pressures. As a first approximation we will assume that
the fluid moves down through the reactor in plug
Consequently, because

4.4

169

Pressure Drop in Reactors

of the increase in cross-sectional area, A,, as the fluid enters the sphere, the
will decrease. From the Ergun equation
superficial velocity, G =
[Equation

we
that by decreasing G, the pressure drop
he reduced significantly,
resulting in higher conversions.
Because the cross-sectional area of the reactor is small near the inlet and
outlet, the presence of catalyst there would cause substantial pressure drop;
thereby reducing the efficiency of the spherical reactor. To solve this problem,
(Figscreens to hold the catalyst are placed near the reactor entrance and
ures 4-9 and 4-10). Were is the location of the screen from the center of the
Feed

Products
Figure 4-9
of a

Schematic drawing
reactor.

axis

the inside

Figure 4-10 Coordinate system and

variables used with a spherical reactor. The

initial and final integration values are slhown
as

and

reactor. We can use elementary geometry and integral calculus to derive the
following expressions for cross-sectional area and catalyst weight as a function
of the variables defined in Figure 4-10:
A,
Spherical reactor
catalyst weight

By using these formulas and the standard pressure drop algorithm, one can
a variety of spherical reactor prablems. Note that Equations
and

170

Isothermal Reactor Design

Chap. 4

(4-39) make use of L and not L'. Thus, one does not need to adjust these formulas to treat spherical reactors that have different amounts of empty space at
L L ' ) . Only the upper limit of integration needs
the entrance and exit
to be changed, = L + .
Example 4-8 Dehydrogenation Reactions in a Spherical Reactor

Reforming reactors are used to increase the octane number of petroleum. In a

reforming process 20,000 barrels of petroleum are to be processed per day. The corand 440 molls, respectively. In the
responding mass and molar feed rates are 44
reformer, dehydrogenationreactions such as
paraffin

olefin

occur. The reaction is first-orderin paraffin.Assumethat pure paraffin enters the reacand a corresponding concentration of 0.32
tor at a pressure of 2000
Comparethe
and conversion when this reaction is carried out in a tubular packed bed 2.4 in diameter and 25 m in length with that of a sphericalpacked
bed 6 m in diameter. The catalyst weight is the same in each reactor, 173,870 kg.
k'

Additional information:
= 0.032
= 0.4

= 0.02

.
= L' = 27

= 2.6

Solution

We begin by performing mole balance over the cylindrical core of thickness Az

shown in Figure

Figure E4-8.1 Spherical reactor.

Pressure Drop in

4.4

Following
the

171

Reactors

I . Mole balance:

algorithm

In - out generation = 0
Dividing by

and taking the limit as

0 yields

In terms of conversion
(E4-8.1)

(E4-8.2)

(E4-8.3)

x (1 + 1 -

(E4-8.4)

where
P

that
( y with a subscript) represents the mole fraction and y alone represents
the pressure ratio,
The variation in the dimensionless pressure, y, is given by incorporating the
variable y in Equation (4-24):

The equations in
boxes are the key
equations used
in the ODE solver

The units of

for this problem are

(E4-8.7)

program

(E4-8.8)

For a

reactor

(E4-8.10)

172

Isothermal Reactor Design

Parameter
Recall that

Chap.

= 1 for metric units.

- 0.4)

(E4-8.11)
X

0.02

+ (25,630

0.01
I

The last term in, brackets converts

Recalling other params) to
L = 27 dm, R = 30 dm, and
eters, m 44
= 2.6
Table E4-8.1 shows the POLYMATH input used to solve the above equations.
The MATLAB program is given as a living example problem on the CD-ROM.
POLYMATH PROGRAM

TABLE

Initial Values

Equations

.02
rhoca

1-phi)
10.01
5-phi)

= 0,

54

For the spherical reactor, the conversion and the pressure at the exit are
A comparison
between reactors

0.81

= 1980

If similar calculations are performed for the tubular packed-bed reactor (PBR), one
finds that for the same catalyst weight the conversion and pressure at the exit are

= 0.71

308

Figure E4-8.2 shows how conversion, and

pressure, vary with
catalyst weight in each reactor. Here and represent the tubular reactor and

Pressure Drop

4.4

173

Reactors

IKEY:

0.800
y2

0.400

n. 200

oao
1.200

0.

Figure

Pressure and conversion for:

1.600

tubular PBR; 2, spherical PBR.

and
represent the
reactor In addition to the higher
spherical reactor has the economic benefit of reducing the
at the exit
sion cost because of higher

the
and compres-

Because
pressure drop in the spherical reactor is very small, one
could increase the reactant flow rate significantly and still maintain adequate
pressure at the exit. In fact, Amoco uses a reactor with similar specifications to
process 60,000 barrels of petroleum naphtha per day.

Pressure Drop in Pipes

Wormally, the pressure drop for gases flowing through pipes without
packing can be neglected. For flow in pipes, the pressure drop along the length
of the pipe is given by
du

where D

(4-40)

pipe diameter, cm
= average velocity of gas,

= Fanning friction factor

4

G=

The friction factor is a function of the Reynolds number and pipe roughness.
The mass velocity G is constant along the length of the pipe. Replacing with
and combining with Equation
for the case of constant T and
Equation (4-40) becomes