CHEE 321: Chemical Reaction Engineering 2. Isothermal Reactor Design Single Reaction in Batch, CSTR, PFR 2b.

Solving Problems using Stoichiometric Tables

(Fogler Ch 3.5-3.6, Ch 4.1-4.4)

Design Equations for Isothermal Reactors

IDEAL REACTOR DIFFERENTIAL FORM ALGEBRAIC FORM INTEGRAL FORM

BATCH

N A0

dX A = ( rA )V dt

t = N A0

XA

dX rAV

CSTR

FA0 ( X A ) V= ( rA )

PFR

dX A = (rA ) FA0 dV
dX A = ( rA' ) FA0 dW

V = FA0

XA

dX rA

PBR

W = FA0

XA

dX rA'

Factors influencing rate of reaction (rj)

(-rA) = k [f(CA, CB, ..)]
Factors affecting rate coefficient (k)
temperature catalyst type (if present in system) pressure

k = A exp(-Ea/RT) A, Ea are constant

Generally negligible

Factors affecting concentration

conversion (number of moles) volume

Ci =

Ni Fi = V v

The total number of moles in the reactor can change due to stoichiometry What about volume (or volumetric flow) of the reaction mixture? The answer depends upon whether it is a gas or liquid system, and also upon the reactor type (constant or variable volume).

Effect of pressure and temperature on liquid phase concentration

Let us say that we have Ni moles of a chemical species in a total liquid volume of V. Accordingly, the concentration of species i is:
Ci = Ni V

But We usually assume liquid is an incompressible fluid: density does not change significantly with temperature and pressure, therefore, the volume of a fixed mass of liquid does not change significantly either.
Conclusion: Concentration of a species in liquid-phase can be considered to vary negligibly with changes in pressure and temperature.

Effect of pressure and temperature on gas phase concentrations

Concentration, by definition, is moles of species per unit volume.
Ni Ci = V

The idea here is to find out if and how concentration may vary with pressure and temperature.

Equation of State for a Real Gas

PV = z NT RT

z=1 for ideal gas

Total concentration (and thus concentration of each species) in gas phase is a function of both pressure and temperature.

NT P = V z RT

FT P = for a gas-phase flow system v z RT

How do we calculate total number of moles (or molar flowrate)?

For a single reaction, change in moles is directly related to reaction stoichiometry and conversion. First identify the limiting reactant. This is used to: Set up reaction stoichiometry Define reaction conversion Construct stoichiometric table (next slides)
XA =

Limiting reactant A:
A+ B C+ D
a a a b c d

mols of species-A reacted mols of species-A fed F FA = A0 FA0 N A0 N A for batch = N A0

Stoichiometric Table for Batch Reactors

Reaction stoichiometry and conversion control how NT changes in the system
Species
A B C D I (inert) Total

A+ B C+ D
a a a

Initial Amount (mol)

NA0 NB 0 NC0
ND 0

Change (mol)
( NA0 X A ) b ( NA0 X A ) a c ( NA0 X A ) a d ( NA0 X A ) a
0

Remaining (mol)
NA = ( NA0 NA0 X A ) b NB = ( NB0 NA0 X A ) a c NC = ( NC0 + NA0 X A ) a d ND = ( ND0 + NA0 X A ) a NI = NI 0
NT = NT 0 + NA0 X A

NI 0
NT 0

= increase in the total number of

moles per mole of A reacted

d c b = + 1 a a a

Fogler 3.5

Calculating Concentration for Batch Reactors

A. Constant volume reactors
Case I: Liquid Phase-Reaction e.g. polymerization reaction Case II: Gas Phase-Reaction with =0 (no change in total number of moles) e.g. water gas shift reaction: CO + H2O CO2 + H2 methane oxidation : CH4 + 2O2 CO2 + 2H2O Case III: Gas Phase-Reaction with 0 (V=const) e.g. ammonia synthesis: propane oxidation (combustion): N2 + 3H2 2 NH3 C3H8 + 5O2 3CO2 + 4H2O [ <0] [ >0]

B. Variable volume reactors (not very common!)

Calculating Concentration for Batch Reactors

Constant Volume Batch Reactors Cases I & II (Continued)
Recall, our goal is to calculate volume for the different batch reactor operations. We can get the number of moles of any species (Ni) as a function of conversion from stoichiometry and material balances.

Ci =

Ni V

Case I: Liquid Phase-Reaction: incompressible fluid means V=V0

[volume of liquid in the reactor could be < reactor volume]

Case II: Constant Volume Reactor Gas Phase-Reaction with =0

[gas occupies the total volume of the reactor]

No change in total moles and no change in reactor volume (V = V0) If isothermal, also no change in P (ideal gas) N P

RT

Calculating Concentration for Batch Reactors

Constant Volume Batch Reactors Case III (Continued)
Case III: Constant Volume Reactor Gas Phase-Reaction with 0

V = V0

[gas occupies the total volume of the reactor]

However, total number of moles in the system changes. Therefore, the pressure and/or temperature in such systems vary with conversion. (Variation of pressure can be used to monitor the progress of a reaction). Pressure at any conversion X can be expressed according to the following relationship derived from the ideal gas law:
( N + N A0 X A ) T N T P = T = T0 P0 NT 0T0 NT 0 T0

Calculating Concentration for Batch Reactors

Variable Volume Batch Reactor Case IV (Continued)
Case IV: Variable Volume Reactor with Gas Phase-Reaction (0)

V V0
The pressure in such systems may be constant or vary with conversion. At any given conversion, X, the reactor volume is related to initial reactor volume (V0) and other operating parameters (P0, T0, P, and T). Additional information must be supplied!

NT P0 T Z V = V0 ( ) ( ) NT 0 P T0 Z 0

For ideal gas

N T P0 T ( ) V = V0 N T 0 P T0

NT = NT 0 + N A 0 X A

Stoichiometric Table for Flow Reactors

Reaction :
Species
A B C D I (inert) Total

A+ B C+ D
a a a

Define i = Fi 0 / FA0
(Limiting reagent A)

Feed Flow Rate (mol/s)

FA0 FB 0 = B FA0

Change within Reactor (mol/s)

( FA0 X A ) b ( FA0 X A ) a c ( FA0 X A ) a d ( FA0 X A ) a
-

Effluent Rate from Reactor (mol/s)

FA = FA0 (1 X A ) b FB = FA0 ( B X A ) a c FC = FA0 (C + X A ) a d FD = FA0 ( D + X A ) a FI = FI 0
FT = FT 0 + FA0 X A

FC 0 = C FA0
FD 0 = D FA0 FI 0 = I FA0 FT 0 = FA0 (1 + B + C + D + I )

FA0 X A

Note the similarity between flow and batch reactor stoichiometric tables

d c b + 1 a a a

Fogler 3.6

Calculating Concentration for Flow Reactors

Concentration in Flow Reactors :
Ci = Fi v

From stoichiometry and mole balances, we have Fi = f(XA) What value of v (flowrate) should we use? Liquid phase reactions (incompressible) Gas phase reactions (ideal gas)
v = v0 (

v = v0
FT P0 T )( ) FT 0 P T0

FT = FT 0 + FA0 X A
For isothermal and isobaric reactors with no change in number of moles (i.e. =0) v = v0 If 0, flowrate at reactor outlet is usually different than inlet flowrate (i.e, v v0)

General Algorithm for Solving Isothermal Reactor Problems

1. 2.

General Mole Balance Equation (GMBE) Rate Laws

Write down rate law in terms of limiting reactant

3.

Stoichiometry
relate concentration to volume and number of moles (for batch reactors) or to volumetric flow rate and molar flow rate (for flow reactor) Relate volume or volumetric flow rate to conversion, pressure and temperature

4.

Combine and Solve

Substitute rate law and stoichiometry in to the GMBE

See Fogler Figure 4.1

General Algorithm (Fogler, Figure 4-2)

Isothermal Reactor Design (Single Reaction)

Constant volume (or volumetric flow) systems
Generally easier to set up and solve Liquid-phase or gas phase systems with no change in moles

Example 1: Batch Reactor Example 2: Week 3 Tutorial

Systems with changing volume (or volumetric flow)

Gas phase systems with change in moles due to reaction

Example 3: Gas-Phase reaction in a PFR Example 4: Gas-Phase reaction in a CSTR

Example 1
Constant volume batch reactor with reaction A B and 2nd order reaction GMBE: Rate Law: Stoichiometry: Combine:
dN A = rAV ; N A = N A0 at t = 0 dt
2 rA = kC A

C A = C A0 (1 X A )
N A = C AV ; dN A dC A dX =V = VC A0 A dt dt dt

2 2 2 rA = kC A = kC A 0 (1 X A )

dX A = kC A0 (1 X A ) 2 dt

Integrate and Solve:

t=

1 XA kC A0 1 X A

Example 1 (contd): constant volume batch reactor

For 2nd order reaction order reaction
t= 1 XA kC A0 1 X A

For a

1st

1 1 t = ln k 1 X A

(see Fogler Ex. 4.1)

Time to reach 90% conversion can vary from hours to less than a second, depending on the magnitude of k (or kCA0 ) [See Table 4.2 in Fogler] 1st order: if k=10-4 s-1, 6.4 h to reach 90% conversion 2nd order: if kCA0=10-4 L/(mol-s), 25 h to reach 90% conversion Practical issues with batch reactors: - Table 4.3 in Fogler - Can you think of others?

Example 3 (PFR, variable flow)

Estimate the volume of a plug-flow reactor (in m3) required for production of ethylene from ethane (C2H6 C2H4 + H2) based on the following data and assumptions: a. The feed is pure ethane at 1 kg s-1, 1000K and 2 bar (abs). b. The reaction is first-order and irreversible at low conversion, with k = 0.254 s-1 at 1000 K. c. The reactor is operated isothermally and isobarically. d. Conversion of ethane is 20% at the outlet.

(Similar to Fogler Ex. 4.3)

Effect of changing NT: Examine Fogler Fig 4.7 and 4.8

Example 4 (CSTR, variable flow)

It is being considered that the following gas-phase reaction be carried out in a CSTR: A + 2B 4C The reactor will be operated isobarically and isothermally. The rate law for the reaction is given as: (-rA)=k CACB where, k = 8 L/mol-min at the operating temperature. The total feed volumetric flow rate to the reactor at operating temperature and pressure is 10 L/min. The feed consists of A, B and an inert (I). The feed molar flow rates are FA0= FB0= 1 mol/min and FI0=2 mol/min. Calculate the volume of reactor required to achieve 80% conversion of the limiting reactant.

Isothermal Reactor Design (Single Reaction)

A warning
In perhaps no area of engineering is mere formula plugging more hazardous; the number of physical conditions that can arise appear infinite, and the chances of a simple formula being sufficient for the adequate design of a real reactor are vanishingly small.
From Fogler, Ch 4 intro