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

Heinzle)

1 The Semi-Batch Reactor

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.

Motivations for Using Semi-Batch Reactors

1. Control of concentration of reactants to improve the selectivity of a reaction. 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.

1.1

Basic Balances for a Semi-Batch Reactor

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 Figure 1. The semi-batch reactor.

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)

Total Material Balance

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

Rate of accumulation Mass flow 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

Component Balance Equation

All important components require a component balance. For a given reactant A
Rate of flow Rate of production Rate of accumulation of A = of A in + of A by reaction

dn A = NA0 + rAV dt where NA0 is the molar feeding rate of A per unit time. 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.

Energy Balance Equation

Whenever changes in temperature are to be calculated, an energy balance is needed. With the assumption of constant cp and constant , as derived in the Chapter Basic Concepts, the balance becomes
cp V

dT = 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)

1.2

Case A.

Semi-Batch Reactor

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 and the enthalpy balance equation is V cp dT = 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.

1-3

Case B. Parallel Reaction in an Adiabatic Semi-Continuous Reactor with 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)

T 0, F 0, cP0 , 0, CB0

rQ

V, T, nA, n B , nC , nD
Figure 2. Adiabatic semi-batch reactor.

Two reactions are assumed to occur in parallel A + B > C A + 2 B > D The total energy balance from the Chapter Basic Concepts is given by

dT (n i c pi ) dt i =1

= F0

T0

i =1

Ci0

cpi dT + V

rij

ij j =1

( H j)
The reaction

In this case the number of components, S=4 and the number of reactions, R=2. enthalpies at standard temperature, TSt, are then H1St = HFC HFA HFB H2St = HFD HFA 2 HFB All heats of formation, HFi, are at standard temperature. Assuming that the temperature dependencies for the specific heats are given by cpi = ai + bi T then hi = hiSt +
T

TSt

c pi dT =

hiSt + ai (T TSt) +

bi 2 2 (T TSt ) 2

and the reaction enthalpies, H1 and H2, at temperature T are H1 = H1St + (aC aA aB) (T TSt) + H2 = H2St + (aC aA 2 aB) (T TSt) + bC bA bB 2 2 (T TSt ) 2
b C b A 2b B 2 2 (T TSt ) 2

Semi-batch Reactor and Safety (Technische Chemie I, Prof. E. Heinzle) With stoichiometric coefficients, A1 = 1 and A2 = 1, the total heat of reaction is then rQ =

rij ij

j =1

(H j ) = rA1 H1 + rA2 H2

The total heat capacity in the accumulation term is 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 F0

T0

Ci0

i =1

cpi dT
T

= F0 CB0 a B (T0 T ) +

bB 2 T0 T 2 2

Substitution into the energy balance then gives

dT = dt

b 2 F0 C B0 a B (T0 T ) + B T0 T2 2 V cp

) + V rQ