CHEMICAL REACTION ENGINEERING

Process design of industrial chemical reactors

Building blocks:
The stoichiometric equation
D C B A + +
In the chemical reaction process the integrity of the atomic species should be preserved.
In what follows, A is considered as the limiting reactant.
The stoichiometric equation expresses the overall reaction process; the effective reaction
mechanism is often made of different elementary steps.

The conversion of the limiting reactant
continuous-flow reactors
0
0
A
A A
A
F
F F
fed A of moles
reacted A of moles
X

= =
batch reactors
0
0
A
A A
A
N
N N
A of moles initial
reacted A of moles
X

= =

The stoichiometric table

Species Initially Change Remaining
A N
A0
-(N
A0
X
A
) N
A
= N
A0
- (N
A0
X
A
)
B N
B0 -(N
A0
X
A
) N
B
= N
B0
- (N
A0
X
A
)
C N
C0 (N
A0
X
A
) N
C
= N
C0
+ (N
A0
X
A
)
D N
C0 (N
A0
X
A
) N
D
= N
D0
+ (N
A0
X
A
)
I N
I0
- N
I
= N
I0
N
T0
N
T
= N
T0
+ ( + - - 1) N
A0
X
A

The thermodynamic equilibrium
This state is obtained when the system Gibbs free energy (G = H TS) reaches its minimum
value at a given operating temperature [(G
prod.
G
react.
)
T
= 0]
0 = = +
T A B C D
G G G G G
A A A
a T R G G ln
0
+ =
0 ln ln
0 0
= + = + K T R G
a a
a a
T R G
T
A B
C D
T



where K is the so called equilibrium constant, the value of which can be obtained when the
molar free energies for pure compounds are known at the system temperature.
Usually, G
0
values are tabulated at 298K; to obtain then K as a function of temperature, the
following equation is utilized
2
0
ln
T R
H
T d
K d
T
P

a
A
is the activity of component A, i.e. the ratio of the fugacity value for A at system conditions,
and the corresponding one at a properly chosen reference condition, a
A
= f
A
/f
A0
.
For the ideal gaseous systems, f
A
= y
A
P, and the standard state is f
A0
= 1 atm., so that

P K P
y y
y y
K
y
A B
C D
= =
+ 1

(P is in atm., and is the algebraic sum of products and reactants stoichiometric coefficients).
This relation shows the influence of pressure on the equilibrium composition.
For the ideal liquid systems, a
A
x
A
.
For the heterogeneous systems involving solid phases, these are assumed to exist in the pure
state; as a result, the respective activities are equal to unity.
When the molar fractions are expressed as functions of X
A
, the knowledge of K allows to
determine the system equilibrium composition.
[Example 5, Chem. Eng. Handbook, p. 4-83].
When several reactions occur, the composition of the equilibrium mixture depends on the
simultaneous equilibria of all possible reactions; it is possible, however, to determine a
pseudo-equilibrium yield by limiting calculations to the relatively fast reactions and to the
relatively abundant chemical species.
[Example 3, Chem. Eng Handbook, p. 4-66].
Different procedures have been proposed to solve the set of simultaneous equilibrium and
balance equations; the most general scheme is to find the set of N
i
s which minimizes the
system Gibbs free energy at given values of T and P
i i i i i syst
y N T R N P T R G N G ln ln
0
+ + =
(an ideal gaseous system is assumed) with the additional requirement that the total number of
atomic weights of each kth element matches the initial system constitution
k k i i i
B a N =
The solution to this problem is through the method of Lagranges multipliers (see Dr Jand
lecture for the application to biomass gasification).

The chemical kinetics
For homogeneous systems, the reaction rate, r
A
, is defined as the number of moles of reactant
A which disappear per unit time and volume
( ) ( ) ..... , ,
B A A
c c g T k r =
where k is the reaction rate (constant), and is proportional to the fraction of collisions
between molecules that together have the minimum energy E;
g is proportional to the number of molecular collisions per unit time and
volume;
c indicates volumetric concentrations, mol/vol.
( )
T R
E
e A T k

=
where A is the pre-exponential or frequency factor;
E is the activation energy, J/mol or cal/mol;
R is the gas constant (8.314 J/mol K = 1.987 cal/mol K).
( ) ...... ...... , ,
b
B
a
A B A
c c c c g =
where a and b (the reaction orders with respect to A and B) may be different from and ,
respectively, unless an elementary reaction is considered.
Heterogeneous reactions take place usually at the boundary between different phases, so that
the reaction rate is sometimes referred to the interfacial surface area, or to the catalyst mass,
etc., instead of the reactor volume. In addition, the global reaction rate is affected in these
cases also by mass transport of some reactants to the reaction sites.
A simple approach, to apply homogeneous kinetic concepts to thermally induced reactions in
solids (like wood or biomass), postulates a pseudo single-step overall reaction mechanism of
first order in solid conversion (which replaces concentration)
( )
W g
W
X k
t d
X d
= 1
where intra-particle and external mass transfer resistances are incorporated in the overall
kinetic expression. In addition, it is also assumed that the global reaction rate, k
g
, is
characterized by an apparent activation energy and a pre-exponential factor.
Detailed, comprehensive models for heterogeneous reaction kinetics are available.

The mole balance equation for the limiting reactant
Conservation equation for finite volumes

( ) ( ) ( ) ( )

time moles
reaction chemical by
nce disappeara of rate
time moles
system the of out
flow of rate
time moles
system the o
flow of rate
time moles
on accumulati
of rate
int


=
S V
A A
V
A
dV r dS n F dV c
t d
d

where n is the unit vector normal to dS and directed out of the system.

By means of the application of the divergence theorem

=
V
A
S
A
dV F dS n F
the conservation equation valid at a given point is obtained
A A
A
r F
t d
c d
=

The flow mixing
Perfect mixing (all variables are spatially uniform throughout the system volume)
Batch reactors
0
;
A
A A
A
A
c
r
t d
X d
r
t d
c d
= =

Continuous-flow reactors
A
A A
A A A
r
X c
Q
V
V r F F
0
0
; = = =
where is the spatial time and Q the in- and out-coming volumetric flow rate.

Plug flow (no axial dispersion only axial convective flow and variables radially uniform)
Continuous-flow tubular reactors

= = =
Ae
X
A
A
A
A
A A
A
A
r
X d
c
c
r
d
X d
r
d
c d
0
0
0
; ;



The continuous-flow reactor performance can be estimated in terms of the Damkohler
number
V
F
r
c
r
Da
A
A
A
A
0
0
0
0
= =
which is the ratio between the moles of the limiting reactant that can be converted per unit
time (at the reactor entry conditions), and the corresponding molar flow to the reactor.

The energy balance

out flow mass

by leaving
energy of rate
in flow mass
by added
energy of rate
gs surroundin
the on done
work of rate
gs surroundin
the from flow
heat of rate
system the within
on accumulati
energy of rate


Steady-state reactors (perfect mixing)
( )
A A
T
R
T
T
pi i i S i i i i i i h
X F H dT c F T T S U H F H F Q
0 0 0 0
0
0 = = +

Semi-batch reactors
( ) V r H dT c F T T S U
t d
T d
c N
A
T
R
T
T
pi i i S pi i i
=

0
0


Multiple reactions
This method is applicable when the stoichiometric equation and the reaction kinetics are
known for each reaction taking place into the system.
The molar balances
c j r r
V d
F d
r
i
j i j
j
, 1 ;
1
,
= = =

=

where c is the number of compounds in the system and r the total number of reactions. A
continuous, plug flow reactor has been considered here. For each reaction, the following
equations apply
A i
B i C i D i
r
r r r
,
, , ,
= = =


The reaction rate for each component is given as a function of temperature and volumetric
concentrations, which in turn can be expressed in terms of molar flows, pressure and
temperature. For a liquid system (constant density), c
A
= F
A
/Q. For a gaseous system
T R
P
F
F
T R
P
y c
c
j
j
A
A A

=
= =
1

The energy balance
( )

= =
=
r
i
T
j i R j i S
c
j
pj j
H r T T a U
V d
T d
c F
1
, ,
1