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

Heinzle)

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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.

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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.

is the feed density. Note also that although constant ρ and cp have been assumed here. Prof. as derived in the Chapter Basic Concepts. Energy Balance Equation Whenever changes in temperature are to be calculated. . ρ. owing to the feed input to the reactor. 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. particularly for liquid phase reactions giving dV = F dt Component Balance Equation All important components require a component balance. depending on the particular reactor feeding strategy. The density in the reactor. 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. ρ0. where ⎛ Rate of accumulation⎞ ⎛ Mass flow⎞ ⎜ of mass in the reactor⎟ = ⎜ rate in ⎟ ⎝ ⎠ ⎝ ⎠ d( ρ V) = F0 ρ0 dt Here. and may therefore also form an additional variable in the solution. E. Heinzle) 2 Total Material Balance A total material balance is necessary. Note that both the volumetric flow and the feed concentration can vary with time. With the assumption of constant cp and constant ρ. the balance becomes ρ cp V dT = F0 ρ cp (T0 – T) + rQ V + Q dt Note that the available heat transfer area may also change as a function of time. an energy balance is needed. may be a function of the concentration and temperature conditions within the reactor.Semi-batch Reactor and Safety (Technische Chemie I. The assumption of constant density conditions is usually valid.

specified. V(t). the rate of heat input into the system. SEMISEQ. as functions of time. 2).2 Case A. Parallel Reaction in an Adiabatic Semi-Continuous Reactor with Large Temperature Changes Let us assume an adiabatic. 1-3 Case B. Q. The reaction is carried out adiabatically. With initial conditions for the initial molar quantities of A and B. V. A. the resulting system of equations can be solved to obtain the time varying quantities. with flow of A. into the reactor. the initial temperature. B. Semi-Batch Reactor A semi-batch reactor is used to convert reactant. V CB). and CB. Heinzle) 3 1. SEMIPAR. is zero. 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 ρ cp dT = F ρ cp (T0 – T) + k CA02 (1 – XA)2 (–ΔHA)V dt since. SELCONT. VCB(t). for the two components. Examples of semi-batch operations are given in the simulation examples HMT. VCA(t). (V CA. and B. T(t) and hence also concentrations. T. . semi-continuous reactor with negligible input of mechanical energy (Fig. E. The reaction kinetics are as before rA = – k CA2 and the stoichiometry gives rB = – 2 rA = + 2 k CA2 The balances. CA. by the reaction A → 2B.Semi-batch Reactor and Safety (Technische Chemie I. for adiabatic operation. to product. and the initial volume of the contents. Prof. RUN and SEMIEX. A.

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. S=4 and the number of reactions. Adiabatic semi-batch reactor. are then ΔH1St = ΔHFC – ΔHFA – ΔHFB ΔH2St = ΔHFD – ΔHFA – 2 ΔHFB All heats of formation. ρ 0. nD Figure 2. Prof. Heinzle) T 0. ΔH1 and ΔH2. F 0. nA. CB0 4 rQ V. at temperature T are ΔH1 = ΔH1St + (aC – aA –aB) (T – TSt) + ΔH2 = ΔH2St + (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 . enthalpies at standard temperature. TSt. cP0 . ΔHFi. 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 S = F0 ∑ S T0 i =1 Ci0 ∫ cpi dT + V ∑ R rij T νij j =1 (− ΔH j) The reaction In this case the number of components.Semi-batch Reactor and Safety (Technische Chemie I. R=2. are at standard temperature. T. E. nC . n B .

E. Prof.Semi-batch Reactor and Safety (Technische Chemie I. Heinzle) With stoichiometric coefficients. the total heat of reaction is then rQ = 5 ∑ R rij νij j =1 (−ΔH j ) = rA1 ΔH1 + rA2 ΔH2 The total heat capacity in the accumulation term is V ρ cp = ∑ (n i c pi ) = nA(aA+bAT)+nB(aB+bBT)+nC(aC+bCT)+nD(aD+bDT) i =1 S With only component B in the feed. the flow term in the energy balance becomes F0 ∑ S 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 ρ cp ( )⎤⎥⎦ + V rQ . νA1 = –1 and νA2 = –1.

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