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Semi Batch Reactor

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Heinzle) 1

The semi-batch reactor is probably the most frequent type of reactor in the chemical industry,

particularly in the fine chemical branch, in organic chemistry laboratories and in biotechnological

processes.

2. Addition of reactants in small increments to control the composition distribution of the

product (e.g polymerization).

3. Control heat production of reaction (exothermic reactions).

4. Avoid toxicity of substrates for producing organisms or isolated enzymes.

5. Removal of product to increase conversion and selectivity.

6. Avoid accumulation of reactants prone to thermal decomposition.

7. Simulate continuous production especially for small scale.

In a surprising contrast, the semi-batch reactor is the least covered in the chemical and biochemical

industry. The major reason for this discrepancy is the difficulty in getting analytical solutions of the

differential equations describing such a type of reactor. Additionally, in semi-batch reactors everything

is usually varying, concentrations, temperature and volume. The methodology we are using in this

course, however, provides a straight forward approach to the solution of this problem. Starting from

basic material and energy balancing, a solution of the governing differential equations is easily

obtained by numeric integration, e.g. using BerkeleyMadonna. Such tools also allow straight forward

optimization of feeding profiles.

A semi-batch reactor with one feed stream and heat transfer to a cooling jacket is shown in Fig. 1.

CA0 , F 0, nAF0, T 0

CA

V

T

Q

Tj

A semi-batch reactor with typically varying volume always requires an explicit total material balance

besides balances for components of interest and an energy balance. The balance region is usually the

whole reactor.

Semi-batch Reactor and Safety (Technische Chemie I, Prof. E. Heinzle) 2

A total material balance is necessary, owing to the feed input to the reactor, where

of mass in the reactor = rate in

d( V)

= F0 0

dt

Here, 0, is the feed density.

The density in the reactor, , may be a function of the concentration and temperature conditions

within the reactor. The assumption of constant density conditions is usually valid, particularly for

liquid phase reactions giving

dV

= F

dt

For a given reactant A

accumulation of A = of A in + of A by reaction

dn A

= NA0 + rAV

dt

In terms of concentration, this becomes

d(V C A )

= F0 CA0 + rA V

dt

where F is the volumetric feed rate and CA0 is the feed concentration. Note that both the volumetric

flow and the feed concentration can vary with time, depending on the particular reactor feeding

strategy.

needed. With the assumption of constant cp and constant , as derived in the Chapter Basic Concepts,

the balance becomes

dT

cp V = F0 cp (T0 T) + rQ V + Q

dt

Note that the available heat transfer area may also change as a function of time, and may therefore also

form an additional variable in the solution. Note also that although constant and cp have been

assumed here, this is not a restrictive condition and that equations showing the variations of these

properties are easily included in any simulation model as is shown in Case B below.

Semi-batch Reactor and Safety (Technische Chemie I, Prof. E. Heinzle) 3

A semi-batch reactor is used to convert reactant, A, to product, B, by the reaction A 2B. The

reaction is carried out adiabatically. The reaction kinetics are as before

rA = k CA2

and the stoichiometry gives

rB = 2 rA = + 2 k CA2

The balances, for the two components, A, and B, with flow of A, into the reactor, are now

d(V C A )

= F CA0 + rA V

dt

d(V C B )

= rB V

dt

dT

V cp = F cp (T0 T) + k CA02 (1 XA)2 (HA)V

dt

since, for adiabatic operation, the rate of heat input into the system, Q, is zero.

With initial conditions for the initial molar quantities of A and B, (V CA, V CB), the initial

temperature, T, and the initial volume of the contents, V, specified, the resulting system of equations

can be solved to obtain the time varying quantities, V(t), VCA(t), VCB(t), T(t) and hence also

concentrations, CA, and CB, as functions of time. Examples of semi-batch operations are given in the

simulation examples HMT, SEMIPAR, SEMISEQ, SELCONT, RUN and SEMIEX.

Large Temperature Changes

Let us assume an adiabatic, semi-continuous reactor with negligible input of mechanical energy (Fig.

2).

Semi-batch Reactor and Safety (Technische Chemie I, Prof. E. Heinzle) 4

T 0, F 0, cP0 , 0, CB0

rQ

V, T, nA, n B , nC , nD

A + B > C

A + 2 B > D

The total energy balance from the Chapter Basic Concepts is given by

S S T0 R rij

(n i c pi )

dT

dt

= F0 Ci0 cpi dT + V ij

( H j)

i=1 i=1 T j=1

In this case the number of components, S=4 and the number of reactions, R=2. The reaction

enthalpies at standard temperature, TSt, are then

Assuming that the temperature dependencies for the specific heats are given by

cpi = ai + bi T

then

T

bi 2

c pi dT =

2

hi = hiSt + hiSt + ai (T TSt) + (T TSt )

2

TSt

bC bA bB 2

H1 = H1St + (aC aA aB) (T TSt) + (T TSt2 )

2

b C b A 2b B 2 2

H2 = H2St + (aC aA 2 aB) (T TSt) + (T TSt )

2

Semi-batch Reactor and Safety (Technische Chemie I, Prof. E. Heinzle) 5

R rij

rQ = ij

(H j ) = rA1 H1 + rA2 H2

j=1

S

V cp = (n i c pi ) = nA(aA+bAT)+nB(aB+bBT)+nC(aC+bCT)+nD(aD+bDT)

i =1

With only component B in the feed, the flow term in the energy balance becomes

( )

S T0

bB 2

F0 Ci0 cpi dT = F0 CB0 a B (T0 T ) + T0 T 2

i=1 T 2

dT

b

(

F0 C B0 a B (T0 T ) + B T02 T 2

2

) + V rQ

=

dt V cp

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