Chemical Reaction Engineering g g

Lecture 5

The Scope
The Aim of the Course:
To learn how to describe a system where a (bio)chemical reaction takes place (further called reactor)

Reactors

Pharmacokinetics

Chemical plant for ethylene glycol

Microelectronic fabrication

The general mole balance equation

For any component j:

Mass balance:
Rate of flow IN Rate of flow OUT + Generation=Accumulation

Fj 0 Fj + G j =

dN j dt
volume

Gi = ri V
moles/time moles/(timevolume)

Chemical Reaction Engineering

Lecture plan ( p (Lectures 5-10) )
Lecture 5: Mole balance and design equations for batch and continuous mode reactors. Lecture 6: Rate laws in the reactor design Lecture 7: Isothermal reactor design Lecture 8: Bioreactors. Comsol modelling of reactions and reactors. H-cell with chemical H cell reaction. Lecture 9. Non-isothermal reactors. Comsol Non isothermal modelling: flow through porous bed and stirred batch reactor. Lectures 10-11. Diffusion and Reactions. Comsol modelling of biochips: reaction on the surface.

Rates of chemical reactions

A + 2 B 3C + D
Instantaneous rate of consumption of a reactant:

d [ R] / dt
Instantaneous rate of formation of a product:

d [ P ] / dt
From stoichiometry

d [ D] 1 d [C ] d [ A] 1 d [ B] = = = dt 3 dt dt 2 dt
Rate of the reaction:

1 dni d v= = i dt dt

! In the case of heterogeneous reaction the rate will b d fi d per unit area of catalyst as mol/m2s ill be defined it f t l t l/ ! In the case of continuous flow reactor change of concentration is not equal to the reaction rate

Rates of chemical reactions

A + 2 B 3C + D
Usually we interested in the concentration of one particular reagent, say A ti l t A. The reaction rate in terms of reagent A is the number of moles of A reacting per unit time, per unit volume (molm-3s-1)

rA = d [ A] / dt
However this definition is inconvenient in the case of a reactor and can be misleading as the concentration of A is varying with time and position inside the reactor:

Rates of chemical reactions

S we should rather say th t So, h ld th that: Rate of chemical reaction is an algebraic function involving g g concentration, temperature, pressure and type of catalyst at a point in the system

A product
e g 1st order reaction e.g.

rA = kC A
2nd order reaction

rA = kC A 2

The general mole balance equation

For any component j:

Mass balance:
Rate of flow IN Rate of flow OUT + Generation=Accumulation

Fj 0 Fj + G j =

dN j dt
volume

Gi = ri V
moles/time moles/(timevolume)

The general mole balance equation

Generally, the rate of reaction varies from point to point in the reactor:

Gi = ri dV

The general mole balance equation:

Fj 0 Fj + ri dV =

dN j dt

From here, design equation for different types of the reactors can be developed

Types of Chemical Reactors

Depending on loading/unloading of the reactor

Batch

Semi-Batch

Continuos Flow

CSTR (Continuous-Stirred Tank Reactor) Tubular reactor

Packed-bed reactor

Batch reactors

for small scale operation; small-scale testing new processes manufacturing expensive products processes difficult to convert to continuous operation p

Batch reactors
Fj 0 Fj + ri dV =
0
V

dN j dt

r dV =
i

dN j dt

assuming perfect mixing, reaction rate the same through the volume

dN j dt d

= rjV

integrating the equation we can get Nj vs t mole-time trajectory

Batch reactors

Pfaudlers Batch reactor

Continuous Flow Reactors

CSTR (Continuous-Stirred Tank Reactor)
In

Out

Pfaudlers CSTR reactor

Continuous Flow Reactors

CSTR (Continuous-Stirred Tank Reactor)
Fj 0 Fj + ri dV =
V

dN j dt

Fj 0 Fj

=0, operation in a steady mode

assuming perfect mixing, so gp g, Reaction rate is the same through the volume Conditions of exit stream are the same as in the reactor

Fj 0 Fj = rjV

V=

Fj 0 Fj

rj

or

v0C A0 vC A V= rA

Design equation of CSTR

Continuous Flow Reactors

Tubular reactor

usually operates in steady state primarly used f gas reactions i l d for ti easy to maintain, no moving parts produce highest yield temperature could be difficult to control, hot spots might occur

Continuous Flow Reactors

Tubular reactor
Reaction continuously progresses along the length of the reactor so the reactor, concentration and consequently the reaction rate varies in axial direaction in the model of Plug Flow Reactor (PFR) the velocity is considered uniform and there are no variation of concentration (and reaction rate) in the radial ( ) direction If it cannot be neglected we have a model of Laminar Flow Reactor.

Continuous Flow Reactors

PFR (plug flow reactor) useful approximation of a tubular reactor

Fj 0 Fj + ri dV =

dN j dt

For every slice of volume:

No accumulation 0

Fj 0 Fj + ri V = 0

ri =

Fj|V Fj|V +V V

ri =

dFj dV

From here, a volume required to produce given molar flow rate of product can be determined

Continuos Flow Reactors

Design equation for PFR
rj =

dFj

dV =

dFj rj

dV

V =

Fj

dFj rj

Fj 0

Fj 0

dFj rj

Fj

If we know a profile of molar flow rate vs. Volume we can calculate the required volume to produce given molar flow rate at the outlet

Continuous Flow Reactors

Packed-Bed reactor here the reaction takes place on the surface of catalyst
reaction rate defined per unit area (or mass) of catalyst

rA = mol A reacted/s g catalyst l t d/ t l t

Continuous Flow Reactors

W catalyst weight coordinate

as in the PFR case, we can calculate design equation now in , g q terms of catalyst weight coordinate

FAW FAW +W + ri W = 0 | |

ri =

FAW FAW +W | | W

dFA rA = dW

Reactors Mole Balance: Summary

Sizing of reactors
Here well find how to find the size of a reactor is relation between the reaction rate and conversion factor is known

Conversion in the reactors

aA + bB cC + dD
if we are interested in species A we can define the reactant A as the basis of calculation

b c d A + B C + D a a a
conversion:
Moles of A reacted XA = Moles of A fed

maximum conversion for reversible reactions is the equilibrium conversion Xe.

Batch reactor design equations

[ Moles of A reacted ] = [ N A0 ] X A [ Moles of A in reactor, N A ] = [ N A0 ] [ N A0 ] X A
dN A = (rA )V dt dN A dX = N A0 dt dt

N A0

dX = (rA )V dt d

Design equation for Batch Reactor

the equation can be integrated to find the time necessary to achieve required conversion hi i d i the longer reactants spend in the chamber the higher is the degree of conversion

Design equations for flow reactors

[ Moles of A fed ] [ Moles of A reacted ] [ FA0 ][ X ] = [ time] [ Moles of A fed ] [ Moles of A fed ] [ FA0 ][ X ] = [ time]
Molar flow rate fed to the system Molar flow rate of the consumption of A in the system Molar flow rate of A leaving the system F X = F
A0

[ FA0 ] [

[ A]

molar flow rate is concentration * volume rate

[ FA ] = [ FA0 ] (1 X ) = C A0v0

Design equations for flow reactors

CSTR:

[ FA ] = [ FA0 ] (1 X )
FA0 FA FA0 X V= = rA rA
Because the reactor is perfectly mixed, the exit composition is mixed identical to the composition inside the reactor

Design equations for flow reactors

Tubular Flow Reactor (PFR):

dFA rA = dV

[ FA ] = [ FA0 ] (1 X )
dX V = FA0 rA 0
X

FA0 dX rA = dV

to integrate we need to know rA depends on the concentration (and therefore on conversion)

Design equations for flow reactors

Packed-Bed Reactor: similar derivation, but W instead of V

dFA rA = dW

[ FA ] = [ FA0 ] (1 X )
dX W = FA0 0 rA
X

= FA0 dX rA dW

from this equation we can find weight of catalyst W required to achieve the conversion X

Levenspiel plot
reactor volume required is always reciprocal in rA and proportional to X X.
PFR:

dX V = FA0 rA 0

CSTR:

FA0 X V= rA

Levenspiel plot:

Example (2.2, p.48)

Reaction AB described by the data below and the species A enter the reactor at a molar flow rate of 0.4 mol/s:

Calculate the volume necessary for 80% conversion

Example (2.2, p.48)

Solution:
Based on the table the Levenspiel plot can be constructed

The design equation for the CSTR:

FA0 V= X ( rA1 )exit

mol m3 s V = 0.4 20 0.8 = 6.4m3 s mol

Example (2.3, p.50)

Calculate based on the same data the volume of PFR:
Again, we construct the Levenspiel plot

The design equation for the PFR:

V =

0.8

FA0 dX = 2.165m3 rA1

Reactors in series
CSTR in series

1st reactor t
FA0 FA1 + rA1V1 = 0 FA1 = FA0 FA0 X 1

2nd reactor
FA1 FA 2 + rA 2V2 = 0 FA 2 = FA0 FA0 X 2

1 V1 = FA0 X1 rA1 1 V2 = FA0 ( X1 X 2 ) rA 2

Mean residence time (Space Time)

mean residence time defined as:

V = v0

Reactor design equations: Summary

Problems
Class p ob e P2-7b (p ) C ass problem: b (p.74) Home problems:
P2 5b P2-5b P2-6a Hippopotamus stomack
http://www.engin.umich.edu/~cre/web_mod/hippo/index.htm