Lecture 4 - Batch and Semi-Batch Reactors

EQ1021 Chemical Reaction Engineering
Lecture 4. Isothermal Batch (BR) and Semi-Batch (SBR) Reactors

1 Design Equations
2 Batch Reactor
3 Semi-Batch Reactor
1
Lecture 4. Isothermal Batch (BR) and Semi-Batch Reactors (SBR)
1 Design Equations
2 Batch Reactor
2.1 Calculating the Reactor Volume
2.2 Maximizing Production
2.3 Maximizing Benefit (or Profit)
2.4 Minimizing the Cost
3 Semi-Batch Reactor
3.1 Reactor Type A
3.1.1 Solving in X
3.1.2 Instantaneous Reaction
3.2 Reactor Type B
3.2.1 Case of QV0≠QV; V≠ct ; cj0=ct, QV0=ct, QV=ct
3.2.2 Case of Qv0=Qv=ct ; V=ct ; cj0=ct.
3.3 Design problems
2
Batch Reactors
BATCH
• Batch reactors are perhaps the simplest reactors used in chemical processes.
• When using batch reactors, reactants are first placed inside the reactor and then allowed to react over
time. Batch reactors are closed systems that operate under unsteady state conditions.
• Operation
 The reactants are placed into the reactor (tC: charging time) and then allowed to react (tR: reaction
time), and products form inside the reactor. The products and unreacted reactants are then
removed (tD: discharging time), the reactor is optionally cleaned (t0: cleaning time) and the
process is repeated. The total time of operation is
tT = tC + tR + tD + t0
• Batch reactors contain ports for injecting reactants and removing products, and can be outfitted with a
heat exchanger or a stirring system. While batch reactors are generally of constant volume, some are
designed to maintain a constant pressure by varying the reactor volume.
• (See ENCYCLOPEDIA OF CHEMICAL ENGINEERING EQUIPMENT- Michigan University for the rest of characteristics)
http://encyclopedia.che.engin.umich.edu/Pages/Reactors/Reactors.html 3
Semi-Batch Reactors
• Semi-batch reactors occupy a middle ground between batch and continuous reactors. They are open
systems like CSTRs and run on an unsteady-state basis like batch reactors. They usually consist of a
single stirred tank, similar to a batch reactor.
• The operation is similar to that of a batch reactor and it consist of a charging time, a reaction time, and
discharging an cleaning times, so also:
tT = tC + tR + tD + t0
(See ENCYCLOPEDIA OF CHEMICAL ENGINEERING EQUIPMENT- Michigan University for the rest of
characteristics)
4
Lecture 4. Isothermal Batch (BR) and Semibatch Reactors (SBR)
The main objectives of this lecture are:
 Applying the principles of stoichiometry and kinetics to the simulation and design of
isothermal Batch and Semi-Batch Reactors.
 Obtaining the integrated mole balances that will relate reaction time and concentration
and/or conversion in Batch and Semi-Batch Reactors.
 Learning how to calculate the time of reaction needed to obtain a certain extent of reaction in
Batch and Semi-Batch reactors.
 Aplying economic and production criteria to optimize the operation of batch (and semi-batch)
reactors.
 Calculating the reactor volume necessary to obtain a certain production.
5
1. Design Equation
Mole Balance in a System Volume
For well-mixed
systems
Gj = Rj·V
6
1. Design Equation
Algorithm: Solving the Batch and Semi-Batch Reactors
For well-mixed
systems
Gj = Rj·V
7
1. Design Equation
Algorithm: Solving the Batch and Semi-Batch Reactors
1. Design equation (Mole Balance):

For example:
B
dN A
= R A [ c A , cB ]·V
dN A dt
Batch = R A·V Semi-
dt dNB
Batch = FB 0 + RB [c A , cB ]·V
A+B A dt
initially charged V = V0 + QV 0 · t
2. Rate law: For example, R A = ν A k c Ac B For a constant-volume

reactor
c A = c A0 ( 1 − X )
3. Stoichiometry: If 2A + B → Products  A ≡ key component
 X
c
 B = c B0 − c A0
solving in X
2
dX  X
3. Combining (for Batch Reactor, for example): c A0 = 2 kc A0 ( 1 − X )c A0  θ B − 
dt  2
4. Solving: integrate analytically, graphically or numerically (ODE solvers) 8

1. Design Equation
Algorithm: Solving the Batch and Semi-Batch Reactors (cont.)
Example 1. Reaction system in a BR: A+B →C r = kc AcB2
We would need at least one mole balance (it’s a single reaction system):
Integrate to obtain variation of concentration

= − kc AcB2 = − kc A (cB 0 − ( c A0 − c A ) )
dc A 2
dt with reaction time , with initial conditions t=0,

cA=cA0, cB=cB0
For a constant-volume
reactor
Example 2. Reaction system in a BR: A+B →C r1 = k1c AcB2

A+ A →D r2 = k 2 c A2
We would need at least two mole balances (two-reaction system):

dc A
= − k1c AcB2 − 2 k1c A2
dt solve simultaneously by Runge-Kutta 4th order
dcB with initial conditions,
= − k1c AcB
2
t=0, cA=cA0, cB=cB0
dt
9
2. Batch Reactor (BR)
Mole Balance
dN j
Fj − Fj 0 + = Gj Gj = Rj V
dt
no inlet or uniformity of dN j
outlet of properties in = R j ·V
materials the volume dt
composition reaction time tR is the natural performance

changes with time measure for a batch reactor
• Special Case 1. Constant Density Batch Systems. This includes most liquid reactions and also those gas
reactions run at constant temperature and volume
( ) = V dc

dN j d V ⋅cj dc j Cj
dc j
=
j
= R j Eq. 4-1 tR = − Eq. 4-2
dt dt dt dt Cj0 − Rj
(constant V )
• Here cj and X are related as follows:
νj ν j dX

X
c j = c j0 − − ck 0 = νj r ck 0 dX
ck 0 X tR = Eq. 4-3
νk ν k dt 0 − νk r [ X ] 10
Mole Balance
• Special Case 2. Batch Systems

of Gases of Changing Density (varying ρ, T, P)
dN j
variable V = Rj V Eq. 4-4
dt
variation of volume with conversion:

composition
P T
V = V0 0 ( 1 + εk X ) changes with time
P T0
variation of concentration (cj) with conversion:
νj
c j0 − c X
ν k k0

X
dX
c j [X ] = t R = ck 0
− ν k r [X ] 0
P0 T P T
(1 + ε k X ) substituting cj[X] in the 0
( 1 + εk X )
P T0 rate equation, r P T0
and integrating
Eq. 4-5
For an isothermal
reactor T/T0=1 11
Mole Balance
• Graphical representation of the performance equations for batch reactors (constant or variable
volume).

X
ck 0 dX
tR =
0 − νk r

Cj0
dc j
tR =
Eq. 4-5 Cj − Rj
Eq. 4-3
-( Eq. 4-2
in variable volume
systems, the mole balance
is integrated with respect 12
to X
Design Problems
reaction time tR is the natural performance

measure for a batch reactor
1. Calculating Reactor Volume for a given production
2. Calculating Reaction Time for:

- Maximum Production: This criterion is not strictly economic, it seeks only the highest
production in transient periods of demand higher than normal.
- Maximum Benefit
- Maximum Benefit per Unit Time. It is probably the best criteria, as it takes into
account the rate of benefit generation.
- Minimum Unit Cost. It is a conservative approach when it is not possible to assign a specific
value to the process effluent.
13
Design Problems
2.1 Calculating Reaction Volume, VR

 Select initial concentrations of reactants and temperature.
 Select production, Pℓ (kmol of main product Aℓ to be obtained per unit time):
 m3 of reactant treated 
 mol A l produced     concentrat ion of A l 
   per unit time of   
 per unit time  =    in the reactor 
   reactor cycle   3 
 mol A l /s     mol Al /m 
 m 3 /s 
Pl = QV ⋅ cl Eq. 4-9
 Usually maximum production or maximum production per unit time is selected.

 Fix the final Aℓ concentration (conversion) and calculate reaction time, tR (integration of material
balance) and QV necessary (Eq. 4-9).
 Take into account the batch cycle characteristic times:
 tC: time necessary for charging reactants in the reactor
 tD: time necessary to discharge reactor after reaction tT = t 0 + t C + t D + t R
 t0: time to clean the reactor and prepare it for a new cycle
 Calculate VR: VR = QV ⋅ tT 14
2.1 Calculating Reaction Volume VR and Reaction Time, tR.
2.1.1 Single-Reaction Systems. Constant density.
a) First-Order Irreversible Reaction: A1 → Products
c t
dc1  1 dc1 
R
c10 c 1 = c10 e − k t R Eq. 4-10
= R1 = − kc1 − = k  dt ln = k tR
dt c10 c1 0 c1
c10 − c1
Substituting by X: X = X = 1 − e − k t R Eq. 4-11
c10
tR/c10
1 X
− R1
X
 dX tR
=
0 − R1 [X ] c10
 Variation of
conversion with
reaction time, tR
tR 15
0 X 0
b) Second-Order Irreversible Reaction:
A1 → Products
1 1
t − = kt Eq. 4-12
dc1
c1
 dc1  c1 c10
r = k c12 = −  c 2 = −k 

dt
dt c10 1 0 1 X
= kt Eq. 4-13
c10 1 − X
A1 + A2 → Products
−
dc1 dc
= − 2 = k c1 c2 −
d
(c10 (1 − X )) = c10 dX = k (c10 (1 − X )) (c20 − c10 X )
dt dt dt dt
X
 dX 1  c − c10 X 
k tR =  k tR = ln  20  Eq. 4-14
0 (1 − X ) (c20 − c10 X ) c20 − c10  c20 (1 − X ) 
16
c) nth-Order Irreversible Reaction:

A1 → Products
1  1 1 
k tR =  n −1 − n −1  Eq. 4-15
c

tR n −1  c1 c10 
dc1  1 dc1
= ν 1 r = − k c1n  cn = − k  dt
dt c10 1 
0 1  1 
k tR =  ( 1 − X ) n −1 − 1  Eq. 4-16
(n − 1) c10n −1  
-ν1A1—ν2A2 → Products
Reactants in stoichiometric dc1
= ν 1k (ν 2 ν 1 ) 2 c1 1 2
β ( β +β )
proportions c2= (ν2/ν1)c1 Eq. 4-17
dt
dc1 β β
= ν 1 r = ν 1 k c1 1 c2 2
dt
Reactants in non β2
β  ν 
= ν1 k c1 1  c20 − 2 (c10 − c1 )
stoichiometric dc1 Eq. 4-18
proportions dt  ν1 
17
= k c1 − k ' c2 = k c10 (1 − X ) − k ' (c20 + c10 X )

dc1
d) First-Order Reversible Reaction: A1 ↔ A2 r =−
dt
We are going to refer the composition to that of equilibrium
r=0 : kc10 (1-Xe) = k’(c20+c10Xe)
Reagrouping terms we get: kc10 - k’c20 = (k + k’) c10Xe Eq. 4-19

substituting
64 4744 8
From the reaction rate: r = k c10 (1 − X ) − k ' (c20 + c10 X ) = k c10 − k ' c20 − (k + k ' ) c10 X
r = (k + k' ) c10 (X e − X )
In the Mole Balance:
= − (k + k' ) c10 (X e − X )
dc1 dX
= −c10
dt dt Eq. 4-20
dX 1 Xe 1 c − c1e
= ( k + k' )( X e − X ) tR = ln = ln 10
dt k + k' X e − X k + k' c1 − c1e 18
e) General Homogeneous Reaction:
 ν j AJ = 0 r =k Πc βj
j − k' Πc γj
j
j
Material balance to the BR:
dc j
dt
=ν j ⋅r − ck 0
ν j dX
ν k dt
= ν j k

Πc j
βj
j [X ] − k ' Π
j
c j j [X ]
γ


X
ck 0 dX
tR = Eq. 4-21
− νk 0 k Πc
j
βj
j [X ] − k' Π
j
c j [X ]
γj
Many times, there won’t be an analytical solution to Eq. 4-21. So a numerical

integration by Romberg or Simpson methods is compulsory
19
e) General Homogeneous Reaction. Special Case: Analytical Solution for Second-Order.
dc1
A1 + A2 ↔ A3 + A4 − = kc1c2 − k' c3 c4 with the initial conditions: c10=c20 , c30=c40=0
dt
Solving in X:
dX  2 2 X 
2
1. We have to substitute ALL composition variables in function of X: c10 = k c10 ( 1 − X ) − c10
2

dt  Kc 
1
2. Substitute α=
KC
X X
1  dX 1  dX
3. Separate variables and integrate t=  = 
kc10 0 ( 1 − X )2 − ( αX )2 kc10 0 [1 − X ( α + 1 )][1 + X ( α − 1 )]
a2 - b2 = (a-b) (a+b)
4. Decompose in partial fractions:
1  α +1 α −1  1
=  + 
[1 − X (α + 1)][1 + X (α − 1)] 1 − X ( α + 1 ) 1 + X ( α − 1 )  2 α
20
Analytical Solution for Second-Order Reaction.
5. And integrate:
X
1   α +1 α −1  1 1 + X ( α − 1 ) Eq. 4-22
t=  +  dX = ln
2 α kc10 
0  [1 − X (α + 1 )] [1 + X (α − 1)] 2 αkc10 1 − X ( α + 1 )
6. This type of solution (conveniently modified) can be applied ONLY if the following conditions are met:
- a second order reversible kinetics
- reactants in stoichiometric proportions
- no products in the initial charge to the reactor
- a constant-density system
21
f) Autocatalytic Reaction: A1 → A2 r = kc1c2
= kc10 (1 − X ) (θ2 + X )
dc1 In terms of X dX
Mole Balance to A1: = − k c1 c2
dt dt
X X
r at temperature T Xe (1 in irreversible reactions.)
b
until it begins to slow down
and then stops...
1 − θ2
2
and accelerates...
reaction starts slowly...
1 − θ2 X − ln θ2 t
2 k c10 (1 + θ2 )
22
f) Autocatalytic Reaction: A1 → A2 r = kc1c2 (cont.)
= kc10 (1 − X ) (θ2 + X )
dX
dt
 θ X 
 − ln −  + ln 2 +
1 1 X
Integrating:  θ   = k c10 t
1 + θ2   1  
  2 
c10 (1 + θ2 )
c1 = c10 (1 − X ) =
X =
[
θ2 e k c10 [1 + θ2 ]t − 1] 1 + θ2 e k c10 [1+ θ2 ]t
1 + θ2 e k c10 [1 + θ2 ]t c10 (1 + θ2 )
c2 = c20 + c10 X =
Eq. 4-23 e − k c10 [1 + θ2 ]t
1+
θ2
1 − θ2
X =
The maximum rate for this reaction is obtained when: 2
Eq. 4-24
− ln θ2
t=
k c10 (1 + θ2 ) 23
2.1.2 Multiple-Reaction Systems. Constant density.
a) Parallel, Irreversible, First-Order Reactions in a constant density system

(Analytical solution)
A1 →A2 r1 = k1 c1 (i=1)
A1 → A3 r2 = k2 c1 (i=2)
Let’s write the mole balance for the three chemical species (as V=constant, we can use cj):
dc1
= R1 = − r1 − r2 = − k1c1 − k 2 c1 = −(k1 + k 2 )c1 Eq. 4-25
dt
dc2
= r1 = k1c1 Eq. 4-26
dt
dc3
= r2 = k 2 c1 Eq. 4-27
dt
Integrating Eq 4-28: c1 = c10 e − (k1 + k2 ) t

c2 t
Substituting c1 in Eq 4-26 and integrating: c2 =
 
dc2 = k1 c10 e − (k1 + k2 ) t dt =
k1c10
k1 + k 2
{
1 − e − ( k1 + k 2 ) t }
c20 =0 0
Eq. 4-29
25
a) Parallel, Irreversible, First-Order Reactions (cont.)
Analogously, we obtain for c3:

c3 t
c3 =
 
dc3 = k 2 c10 e − (k1 + k2 ) t dt =
k 2 c10
k1 + k 2
{
1 − e − ( k1 + k 2 ) t } Eq. 4-30
c30 =0 0
The relationship between c2 and c3 is constant during all the operation: c 2 k1

=
c3 k 2
and the limit in concentration for a very long time is: k1 c10 k 2 c10
c2 ∞ = and c3 ∞ =
k1 + k 2 k1 + k 2
cj/ck0
1
c1/c10
c3/c10
In this case, k2 > k1
c2/c10
0 26
tR
b) Consecutive, Irreversible, First-Order Reactions: A1 → A2 → A3 (Analytical solution)
This is a two-reaction system: A1 → A2 r1 = k1 c1 (i=1)

A2 → A3 r2 = k2 c2 (i=2)
dc1 integrate
− = k1c1 c1 = c10 ⋅ e −
Mole balance to A1: k1 t
dt
c1 is not constant
Mole balance to A2: dc2 dc2 − k1t
= k1c1 − k 2 c2 (depends on time)
= k1c10 e − k 2 c2
dt Let’s substitute c1 by dt
its value!!
We have to integrate a first-order Ordinary Differential Equation (ODE):
dc 2 y = c2 , x = t, P = k 2 ,Q = k1·c10·e -k1 t
+ k 2 c 2 = k1c10 e − 1 dy
k t
+ P y = Q( x )
dt dx
−  − −
 k 2 dt    k2 dt  −
 k 2 dt

 Pdx  Pdx  Pdx
      
y =e ⋅ e Qdx + I e c2 = e ⋅  e k1 c10 e − k1t dt + I e
 27
 
b) Consecutive, Irreversible, First-Order Reactions: A1 → A2 → A3 (cont.)
−
 k 2 dt    k2 dt  −
 k 2 dt
   dt 
c2 = e ⋅  e k1 c10 e − k1t
 + Ie

 
c2 = e − k 2 t ⋅ 

(e k2 t
k1 c10 e − k1t ) dt + I e − k2 t
c2 = k1 c10 e − k2 t ⋅ 

(e (
− k1 − k 2 )t
) dt + I e −k2 t
k1 c10 ( )
c2 = e − k 2 t ⋅ e − k1 − k 2 t + I e − k 2 t
− (k1 − k 2 ) 1444442444443
e − k1 t
To calculate the integral constant, I, we need an initial value.
t =0  e − k1 t = e − k 2 t = 1 
  k1 c10 k1 c10
  c20 = +I I = c20 +
− (k1 − k 2 ) k1 − k 2
c2 = c20 28
k1 c10  k c  −k2 t
c2 = e − 1 +  c20 + 1 10  e
k t
− (k1 − k 2 )  k1 − k 2 
1442443
I
− k2 t k1c10 − k1t − k2 t
c2 = c20 e + (e −e ) Eq. 4-31
k 2 − k1
Mole balance to A3:

c2 is not constant
dc 3
= k 2 c2
(depends on time) dc 3  −k t kc −k t −k t 
= k 2  c20 e 2 + 1 10 ( e 1 − e 2 )
dt dt  k 2 − k1 
Substitute c2 by its value!!
t
  k 2 k1c10 − k1t k 2 k1c10 − k2 t 
c
Integrate: 
3
−k2t
 dc 3 =   2 20
k c e + e − e  dt
c30 0  k 2 − k 1 k 2 − k 1 
c 3 = c 30 + c20 ( 1 − e
− k2 t
)+
c10
k 2 − k1
[k ( 1 − e
2
− k1t
) − k1 ( 1 − e
− k2 t
) ] Eq. 4-32
29
• The values of k1 and k2 govern the location and

maximum concentration of R.
Eq. 4-10 • This may be found by differentiating

Eq. 4-31 and setting dc2ldt = 0. If c20=0:
Eq. 4-32 ≡c3 1 ln (k 2 / k1 )

t max = = Eq. 4-33
k log mean k 2 − k1
• The maximum concentration of R is found by

Eq. 4-34 Eq. 4-31 ≡c2 combining Eqs. 4-31 and 4-33 to give
≡c1 k2
c2 ,max  k1  k 2 − k1
=   Eq. 4-34
Eq. 4-33 c10  k2 
30
Class Exercise
• What if we have a more complex system? Is there a theoretical solution?

k1 k2
A1 A2 A3
k3
A4
32
c) More Complex Reaction Systems (constant density)

 Conversion SHOULD NOT be used
 Identify all the species participating and write their reaction rate:
 For each species Aj, remember that:
R
R j =  ν ij ri Rate law in function of
i =1 concentrations, for reaction i
Stoichiometric coefficient of
species Aj in reaction i
 Write as many mole balances as species participate in the different rate laws (can be less than the
total number of species and more than the total number of reactions).
[ ]
R
dc1
=  ν i 1 ri c j
dt i =1
[ ]
dc2 R Integrate the multiple differential
=  ν i 2 ri c j equation system by numerical methods:
dt i =1 Runge-Kutta 4th order
…..
33
2.1.2 Multiple-Reaction Systems. ANY Complex Reaction System.
d) ANY Complex Reaction System (constant or variable density, parallel or complex reactions)
• Variable nj (Nj/Nk0) is recomended:
dN j R
= V ν ij ⋅ ri ( j = 1,2 ,..., S )
dt i =1
dn j V R
dt
=
Nk 0
ν
i =1
ij ⋅ ri [ n1 , n2 ,...nS ] ( j = 1,2 ,..., S ) Eq. 4-36
dn 1 V R 
• This equation can be applied to the S
dt
= 
N k 0 i =1
ν i 1 ⋅ r i [ n 1 , n 2 ,..., n S ] 
components of the chemical system 
to obtain a set of S differential equations dn 2 V R 
with t as independent variable and the S dt
=  ν
N k 0 i =1 i 2 i
⋅ r [ n 1 , n 2 ,..., n S ] 

nj as dependent variables:
M 

dn S V R

dt
=  ν
N k 0 i = 1 iS i
⋅ r [ n 1 , n 2 ,..., n S ]  34

2.1.2 Multiple-Reaction Systems. ANY Complex Reaction System.
• This set of ODEs (Ordinary Differential Equations) can be simulaneously integrated

by Runge-Kutta 4th order.
• If the key component is A1, the following table is obtained:
t n1 n2 ... ... nS
0 1 θ2 ... ... θS
t1 - - -
t2 - - -
. . . .
• If the batch reactor has a variable volume, the reaction system volume should be expressed as:
nt 0 =  θ j
nt P0 T 
V = V0
j
where 
nt 0 P T0  nt =  n j
 j
35
Class Exercise
• Pose the set of ODEs necessary to solve the reaction system:

A1 → A2 r1 = k1 c1 (i=1)
A2 → A3 r2 = k2 c2 (i=2)
in function of molar ratios (nj) if neither A2 nor A3 were initially present in the reactor.
Solution:
Key component: A1
dn1 V n
=− k1· N10 1 = − k1· n1
dt N10 123V
c1
 
dn2 V  n1 n2 
= k N − k 2 N10  = k1· n1 − k 2 · n2
dt N10  1 11023 V 123 
V

 c1 c2 
dn3
= k 2 n2
dt
36
Class Exercise
• Pose the set of ODEs necessary to solve the reaction system:

A1 → A2 r1 = k1 c12 (i = 1)
A2 → A3 r2 = k 2 c22 (i = 2)
in function of molar ratios (nj) if neither A2 nor A3 were initially present in the reactor.
Solution:
2
dn1 V  n  N
=− k1· N10 1  = − k1· 10 n12
dt N10 142V43  {V
c1 c if V 10
is constant
nt P0 T
= 10 (k1·n12 − k 2 ·n22 )
dn2 N where V = V0
dt V nt 0 P T0
dn3 N
= 10 k 2 n22
dt V
37
•Let’s consider a generic reaction

-ν1A1 - ν2 A2 ↔ ν3A3+ νℓAℓ
where Aℓ is the desired product.

Production is defined as Pℓ , kmol of desired product obtained per
unit time. N V ·c
Pl = l = R l Eq. 4-37
tT tT
VR: volume of reactants processed per batch cycle.
tT : total time of the batch, tT=tC+tR+tD+t0
Main product QV: volume of reactants processed per unit time of the cycle.
concentration
VR
increases with time QV =
tT
cℓ : concentration of desired product in the reactor, at the
end of the reaction time
Constant- density system

νl Eq. 4-38
cl = cl0 + ck 0 X
V ⋅c − νk ν l VR ν l Nk 0
Pl = R l Pl = ck 0 ⋅X = ⋅X 38
tT If cl 0 = 0
− ν k tT − ν k tT
• Determining the Maximum Production:
Variation of
Variation of production with
conversion with Pl batch time, tT
X
batch time, tT
ν l Nk 0
Xm Pl = ⋅X
− ν k tT
X
Pl ∝
tT
0 tTm tT 0 tT
• For maximum production,  dX

 tT −X


dPl dPl  ν l   dt =0
=0 =   Nk 0 T
dtT dtT  − ν k   t 2 
 T 
 
Eq. 4-39
• Then:
 dX   dX  X
tTm   − X m = 0   = m Maximum Pℓ is given by a
 dtT m  dtT  m tTm tangent to the curve
X=f(tT)
39
• Chemical processes are intended for an economic benefit
• The conditions of maximum economic profit (or benefit), Bm, do not correspond to that of maximum
production.
• Two types of parametres can be maximized:

• Maximum net benefit: Bm
• Maximum benefit per unit time: (B/tT) m
• And two types of batch time calculated:

• tT1: cycle that determines the maximum benefit
• tT2: cycle that determines the maximum benefit per unit time
Let’s define Benefit!

40
• Benefit is given by:
 €  Product value Reactants price Fixed costs Operational costs

B = − − −
 batch  14€4/4batch € / batch
44444244444444
€ / batch
3 14444444
€ / batch
4244444444 3
Increase in value of the reacting mixture, W Reactor system costs, C T
 w · (N )
S
 € 
• So, B = j j - N j 0 − CT Eq. 4-40
 batch  j =1
• where wj represents the price of every chemical species Aj in the reactor and CT, the total cost of a batch.
• Fixed costs, A[V]: reactor depreciation. Fraction of the reactor (or plant) price that has to be gained per
unit time to be able to buy a new one at the end of its use.
• Operational costs: costs due to charging, reaction, discharging and improductive time.
41
• Let’s consider that there are several reactions taking place simultaneously in the batch reactor, but
only one gives the desired product (most valuable).
• For a system with several parallel reactions, and no change in volume:
ν ij
(c )
R
− c j 0 = ck 0  Xi
− ν ik
j
i =1
S R
ν ij R  S ν ij 
• So, W = V  w c j k0
− ν ik
X i = ck 0 V
123   w j

 Xi
− ν ik 
j =1 i =1
Nk 0
i =1  j =1
1442443
∆ wi
where ∆wi is the net increase in worth undergone by the reactor content due to every reaction i taking
place in the BR.
S
νj
• In case of a single reaction: W = ck 0 V ∆ w X where ∆w = 
j =1 −ν k
wj
42
• Fixed costs, A[V]: reactor depreciation. Fraction of the reactor (or plant) price that has to be gained per
unit time to be able to buy a new one at the end of its use.
• Operational costs:
• CC·tC: charging cost, due to the time used in preparing and charging the reactor.
• CR·tR: reacting cost, due to the time of reaction.
• CD·tD: discharging cost.
• C0·t0: cost due to the improductive time of the reactor, reactor downtime.
• Depreciation (in €/h) is included in each one of the operational costs.
The total cost of a batch, CT is: CT = C0 · t 0 + CC · tC + CD · t D + CR · t R

1444 424444 3
C'
If only the reaction time is variable, we can divide the total cost in a constant term C’ and a variable term
CR·tR.
CT = C' +CR · t R Eq. 4-41
43
 € 
The benefit equation is: B  = W − CT = (ck 0 V ∆ w X ) − (C' + CR t R ) Eq. 4-42
 batch 
2.3.1 Variation of benefit (B) with batch time (tT)
dW
= d (W − CT ) =
dB dCT
−
dtT dtT dtT dtT
But tT has a constant component (t’) and a variable component, tR:
for constant t’ dt T dt' dt R

t T = t 0 + tC + t D + t R = + =1 dt T = dt R
14243 dt R dt R dt R
t' { {
0 1
dB dW dCT dW d (C' + CR t R ) dW
= − = − = − CR
dtT dtT dtT dt R dt R dt R
44
2.3 Maximizing Benefit (or Profit). 2.3.1 Variation of Benefit (B) with Batch Time (tT).
R
dW dX i
• Multiple Reactions:
dt R
= ck 0 V
123 i =1
∆wi
dt R
Nk 0
dW dX
• Single Reaction: = ck 0 V ∆ w
dt R 14243 dt R
cons tan t
So, for a single reaction, dW/dtR is analogous to dX/dtR:
dW
X W dt R
dW
Variation of dt R Increase of net worth
conversion with
with reaction time, tR
reaction time, tR
t'
0 tR 0 tT = t' + t R
45
2.3 Maximizing Benefit (or Profit). 2.3.1 Variation of Benefit (B) with Batch Time (tT).
Single Reaction: dX
dB
= ck 0 V ∆ w − CR
dtT dt R
Benefit has a peak:

• dX/dtR: diminishes with tR,
dX CR dB
so there is a reaction time for which: = =0
dt R ck 0 V ∆ w dtT
B
-CR
maximum
Benefit
tR
C0·t0 tT = t' + t R
CC·tC
W
CD·tD
t0 tC tD
CR
46
2.3 Maximizing Benefit (or Profit). 2.3.2 Cuantitative determination of benefit (B)
Single Reaction: B = ck 0 V ∆ w X − C' − CR t R
We know:
• All the costs
• All the fixed times X

dX
• Reaction kinetics t R = ck 0 Eq. 4-3
− ν k ⋅ r [X ,T ]
0
Let’s give values to X:

B Bm
X tR B tT=t’+ tR
0 0 -C’ t'
tRm
X1 tR1 B1 tT1
tT = t' + tR
… … … …
X<Xe tR B tT t0 tC tD
47
2.3 Maximizing Benefit (or Profit). 2.3.3 Calculating batch time for maximum benefit.
• Graphical method
Represent the curve B-tT. Read Bmax and total batch time tT1 values.
• Analytical Method
The maximum benefit and the time needed to reach it, tT1, can be calculated without graphing
B = f [tT].
Assume a single-reaction system. When the batch time is equal to tT1 (time for which the maximum
benefit is achieved), then dB / dtT = 0. From Eq.
dB dX
= Nk 0 ⋅ ∆w ⋅ − CR = 0
dtT dtT
dX − ν k ⋅ r [X ,T ] dX
and from the mole balance to the batch reactor: = =
dt R ck 0 dtT
Combining both equations:

a) V is known
− ν k r [X m ,T ]
Eq. 4-43 CR = Nk 0 ∆w = −ν k r [X m ,T ] V ∆w
ck 0 b) V is unknown 48
2.3 Maximizing Benefit (or Profit). 2.3.3 Calculating batch time for maximum benefit.
− ν k r [X m ,T ]
CR = Nk 0 ∆w = −ν k r [X m ,T ] V ∆w Eq. 4-43
ck 0
a) V is known
We also know the kinetic parameters, - νk, ∆w and CR. Equation 4-43 can be solved directly to determine the
conversion for maximum benefit (Xm).
Integrating Eq. 4-3 to an upper limit of Xm , allows to calculate tR1 and tT1 = t '+ tR1
b) V is unknown
Choose a value for QV, volume of reactants processed per unit time.
Then, propose a volume value, V. As T is known, Xm can be calculated from Eq. 4-43,
tR by integrating the mole balance (Eq 4-3), the total time as tT=t`+tR and V=QV·tT
Fix V STOP
N V=V’? Y
Eq. 4-43 Xm, tT

and V
Calculate Calculate Calculate V=QV·tT for a given QV
Xm tR tT
Mole
49
Balance
2.3 Maximizing Benefit (or Profit). 2.3.4 Cycle of maximum benefit per unit time.
B  dB
• Net benefit per unit time B / tT will be maximized d   tT ⋅ −B
t
 T= dtT
when its first derivative with respect to time is zero. =0
dtT tT2
 dB  B
• Solving the equation:   =
 dtT  m tT 2
therefore (B / tT) is maximum when the slope of the curve B = f [t] is equal to B/tT2 .
B
L
This is only true at point L of the curve
of benefit vs tT.
This point is determined by the tangent to the curve tR2

B = f [tT] that can be drawn from the origin 0
(line 0L in the figure). tT2 tT = t' + tR
t0 tC tD
50
2.4 Minimizing Unit Cost.
• It is a conservative approach when it is not possible to assign a specific value

to the process effluent.
C ′T  €  C ′′ + CR ·t R  € 
 = where C ′′  = C0 · t 0 + CC · tC + CD· t D + [charge price ]
Nk 0 X  kmol  Nk 0 X  batch 
Production per batch Operational costs and Raw materials’ cost
if νj =- νk depreciation
 C ′T   C ′T 
d   d  
• The condition for minimum:  Nk 0 X  =  Nk 0 X  =0
dtT dt R
d (Nk 0 X ) Nk 0 X
= Eq. 4-43
 C ′T  dt R t ′′ + t R
CR Nk 0 X − (C ′′ + CR ·t R )Nk 0
dX
d   Pr od ,
 Nk 0 X  = dt R
=0 Nk 0 X
dt R (Nk 0 X )2
d (Nk 0 X ) Solving
= slope
dt R
Nk 0 dX C ·N ⋅ X Nk 0 X Nk 0 X
= R k0 = = t ′′
dt R (C ′′ + CR ·t R ) C ′′ + CR ·t R t ′′ + t R
0 minimum t ′′ + t R
CR
cost 51
3. Semi-Batch Reactor (SBR)
Why?
• To remove a “poisonous” product

• Make room in the reactor (extract a product when it’s a reaction with volume expansion)
• To increase Selectivity:
A + B →
kD
D R D = k D c Ac B k D cB
SD / U =
A + A → UkU
RU = kU c 2
A kU c A
slow addition of A
(If a reactant has a negative order effect on rate on the
desired product, add it in small quantities)
B
• To shift equilibrium, strip off product
• To control temperature, especially in exothermic reactions
• Disadvantages: same as the Batch Reactor

• Advantages: good temperature control and the capability of minimizing unwanted side reactions through
the maintenance of a low concentration of one of the reactants.
53
We’re going to study two types of reactors
• 3.1 Reactor type A: there’s only an input of reactants and no output. One of the reactants is initially
charged to the reactor.
 3.1.1 General case
 3.1.2 Instantaneous reaction slow addition of A
• 3.2 Reactor type B: There are feed and exit streams (with flowrates Qv0 and Qv, respectively):
 3.2.1 Case of QV0≠QV; V≠ct ; cj0=ct, QV0=ct, QV=ct.
 3.2.2 Case of Qv0=Qv=ct ; V=ct ; cj0=ct (CSTR start-up)
Fj0, QV0 Fj, QV

FA0 c’B0 FA
c ′j 0
FB0 c’A0 FB
55
3.1 Reactor type A
dN j
0 − Fj 0 + = Rj V
dt
FB0, cj0=cte
QV0 QV =0 → V = V0+QV0 t
It is advisable to work with the extensive variables Nj and
calculate rate in function of Nj and V
Mole balance to component A
Composition and
c’A0
volume
dN A dc A dV
changes with time =V + cA = RA V
A initially charged to the
dt dt dt
{
QV 0
reactor
B added in the feed dc A QV 0
Eq. 4-44 = RA − c A solve simultaneously
dt V0 + QV 0 t
by Runge-Kutta
4th order
Mole balance to component B
Q (c − cB )
Initial conditions
dNB dcB dV dcB
= FB 0 + RB V V + cB = FB 0 + RB V = RB + V 0 B 0 t =0
dt dt dt
{ dt V0 + QV 0 t c A = c ′A0 ; cB = cB′ 0
QV 0
Eq. 4-45 56
3.1 Reactor type A. Solving in X.
Let’s choose A as key component:
= R A [X ] V [t ]
dN A dX
FB0, = −N A′ 0 Eq. 4-46
dt dt
QV0
N A′ 0 (1 − X )
cA =
V0 + QV 0 t
ν substitute in Eq. 4-46
c’A0 Composition and FB 0 t − B N A′ 0 X
νA
volume cB =
changes with time V0 + QV 0 t
A initially charged to the

reactor
B added in the feed
dX − R A [X ] (V0 + QV 0 t ) solve this single equation by Runge-

Eq. 4-47 =
dt N A′ 0 Kutta 4th order
57
3.1 Reactor type A. 3.1.2 Instantaneous Reaction.
νAA + νBB → D
If A and B react so fast that the reaction can be considered instantaneous, the
reaction rate depends on B molar flow:
FB0,
QV0 −ν A
RA V ≡ ν A ⋅ r ⋅ V = FB 0
νB
c’A0 Indeed, applying the mole balance to component B, considering that it reacts
and disappears as soon as it enters the reactor (instantly reacts with A), yields:
dNB − FB0
Qv 0 cB0 + ν B r V = RB =
123 { dt V
FB0 RB
0
B disappears and cannot
accumulate
Eq. 4-48
Mole balance to component A:
νA
N A′ 0 − FB0 t
νA νB
dN A integrating N A = N A′ 0 − FB0 t cA =
=F
{A0 + ν A ⋅ r ⋅ V νB V0 + QV 0 t
dt 0 58
3.1 Reactor type B.
dN j
Fj − Fj 0 + = Rj V
dt
cj0=cte
QV ≠ QV0 → dV/dt = (QV0-QV) → V =V0 +(QV0-QV)t
Fj0, QV0 Fj, QV dNj/dt = V dcj/dt +cj dV/dt
FA0 FA
FB0 FB 3.2.1 Case of QV0≠QV; V≠ct ; cj0=ct, QV0=ct, QV=ct.
c’A0
initial concentration
dc j dV
inside: c ′j 0 V + cj = Fj 0 − Fj + R j V
dt dt
{
All reactants initially charged with a QV 0 −QV
concentration
that can differ from that of the feed
dc j
V + c j (QV 0 − QV ) = c j 0QV 0 − c j QV + R j V
There is an inlet and an oulet with the dt
same or different flowrates
dc j
=
(
QV 0 c j 0 − c j ) + Rj Eq. 4-49
V=V0+(QV0-QV)t dt V0 + (QV 0 − QV )t 59
3.2 Reactor type B. 3.2.1 Case of QV0≠QV; V≠ct ; cj0=ct, QV0=ct, QV=ct.
dc j
=
(
QV 0 c j 0 − c j ) + Rj Eq. 4-49
dt V0 + (QV 0 − QV )t
Fj0, QV0 Fj, QV cj variation with t can be calculated by integration of the S

FA0 c ′j 0 c’B0 simultaneous equations obtained by applying the differential
FA
equation Eq. 4-49 to each one of the components
FB0 c’A0 FB
dc1 QV 0 (c10 − c1 )
= R1 +
dt V0 + (QV 0 − QV )t
dc2 QV 0 (c20 − c2 ) Integration by Runge-Kutta 4th
= R2 +
dt V0 + (QV 0 − QV )t order for the boundary
conditions
…
t=0; cj = c’j0 (j=1, 2,...S)
dcS QV 0 (cS 0 − cS )
= RS +
V0 + (QV 0 − QV )t
initial concentration
dt inside: c ′j 0
60
3.2 Reactor type B. 3.2.2 Case of QV =QV0=ct; V=ct
dc j
=
(
QV 0 c j 0 − c j ) + Rj Eq. 4-49
dt V0 + (QV 0 − QV )t
Fj 0
dc j
=
(
QV 0 c j 0 − c j )+R Eq. 4-50
Fj j
dt V0
cj variation with t can be calculated by integration of the S simultaneous

composition equations obtained by applying the differential equation Eq. 4-50
changes to each one of the components
dc1 Q (c − c1 )
= R1 + v 0 10
dt V0
dc2 Q (c − c2 ) Integration by Runge-Kutta 4th order
= R2 + V 0 20 for the boundary conditions
dt V0 t=0; cj = c’j0 (j=1, 2,...S)
…
dcS Q (c − cS )
= RS + V 0 S 0
dt V0
61
3.3 Design Problems: same as that of the Batch Reactor
reaction time tR is the natural performance

measure for a semibatch reactor
1. Calculating Reactor Volume for a Given Production
2. Calculating Reaction Time for Maximum Production

This criterion is not strictly economic, it seeks only the highest production in transient periods of
demand higher than normal.
3. Calculating Reaction Time for:

- maximum benefit
- maximum benefit per unit time. It is probably the best criteria, as it takes into
account the rate of benefit generation.
4. Calculating Reaction Time for Minimum Unit Cost.

It is a conservative approach when it is not possible to assign a specific value to the process effluent.
62

Lecture 4 - Batch and Semi-Batch Reactors

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Lecture 4 - Batch and Semi-Batch Reactors

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EQ1021 Chemical Reaction Engineering

Lecture 4. Isothermal Batch (BR) and Semi-Batch (SBR) Reactors

The main objectives of this lecture are:

1. Design equation (Mole Balance):

2. Rate law: For example, R A = ν A k c Ac B For a constant-volume

4. Solving: integrate analytically, graphically or numerically (ODE solvers) 8

Example 1. Reaction system in a BR: A+B →C r = kc AcB2

Integrate to obtain variation of concentration

dt with reaction time , with initial conditions t=0,

Example 2. Reaction system in a BR: A+B →C r1 = k1c AcB2

We would need at least two mole balances (two-reaction system):

composition reaction time tR is the natural performance

• Special Case 2. Batch Systems

variation of volume with conversion:

variation of concentration (cj) with conversion:

reaction time tR is the natural performance

1. Calculating Reactor Volume for a given production

2. Calculating Reaction Time for:

2.1 Calculating Reaction Volume, VR

 Usually maximum production or maximum production per unit time is selected.

a) First-Order Irreversible Reaction: A1 → Products

b) Second-Order Irreversible Reaction:

c) nth-Order Irreversible Reaction:

= k c1 − k ' c2 = k c10 (1 − X ) − k ' (c20 + c10 X )

We are going to refer the composition to that of equilibrium

r=0 : kc10 (1-Xe) = k’(c20+c10Xe)

Reagrouping terms we get: kc10 - k’c20 = (k + k’) c10Xe Eq. 4-19

e) General Homogeneous Reaction:

Material balance to the BR:

Many times, there won’t be an analytical solution to Eq. 4-21. So a numerical

e) General Homogeneous Reaction. Special Case: Analytical Solution for Second-Order.

Analytical Solution for Second-Order Reaction.

f) Autocatalytic Reaction: A1 → A2 r = kc1c2

reaction starts slowly...

f) Autocatalytic Reaction: A1 → A2 r = kc1c2 (cont.)

a) Parallel, Irreversible, First-Order Reactions in a constant density system

Integrating Eq 4-28: c1 = c10 e − (k1 + k2 ) t

a) Parallel, Irreversible, First-Order Reactions (cont.)

Analogously, we obtain for c3:

The relationship between c2 and c3 is constant during all the operation: c 2 k1

b) Consecutive, Irreversible, First-Order Reactions: A1 → A2 → A3 (Analytical solution)

This is a two-reaction system: A1 → A2 r1 = k1 c1 (i=1)

We have to integrate a first-order Ordinary Differential Equation (ODE):

b) Consecutive, Irreversible, First-Order Reactions: A1 → A2 → A3 (cont.)

b) Consecutive, Irreversible, First-Order Reactions: A1 → A2 → A3 (cont.)

Mole balance to A3:

b) Consecutive, Irreversible, First-Order Reactions: A1 → A2 → A3 (cont.)

• The values of k1 and k2 govern the location and

Eq. 4-10 • This may be found by differentiating

Eq. 4-32 ≡c3 1 ln (k 2 / k1 )

• The maximum concentration of R is found by

• What if we have a more complex system? Is there a theoretical solution?

c) More Complex Reaction Systems (constant density)

• This set of ODEs (Ordinary Differential Equations) can be simulaneously integrated

• Pose the set of ODEs necessary to solve the reaction system:

• Pose the set of ODEs necessary to solve the reaction system:

•Let’s consider a generic reaction

where Aℓ is the desired product.

Constant- density system

• Determining the Maximum Production:

• For maximum production,  dX

• Chemical processes are intended for an economic benefit