ChE 400 - Reactive Process Engineering

ChE

Multiple Reactions

L11L11-1

We have largely considered single reactions

so far in this class
How many industrially important processes
involve a single reaction?
The job of a chemical engineer is therefore
to design

ChE 400 - Reactive Process Engineering

ChE

Multiple Reactions

L11L11-2

We need to develop tools that will allow us to

quantify how well (or how poorly) we are
doing at producing a desired product
There are three concepts that we need to
develop for multiple reactions:
Conversion (similar to single reactions)
Xj =

Selectivity
Sj =

Yield

Yj =

ChE 400 - Reactive Process Engineering

ChE

Multiple Reactions

L11L11-3

So far, we have exclusively looked at simple system with only one reaction occuring.
However, many reaction systems of practical relevance involve many reactions
occuring at the same time, either in parallel or in series (i.e. sequentially).
Lets look at steam cracking of ethane (~ 80 bio. to/a world production!):
C2H6 -> C2H4 + H2

(I) ethene (ethylene) formation

C2H6 -> C2H2 + 2 H2

(II) acetylene formation

C2H4 -> C2H2 + H2

(III) acetylene formation from ethylene

C2H6 + H2 -> 2 CH4

(IV) methane formation

3 C2H6 -> C6H6 + 6 H2

(V) benzene formation

C2H6 -> 2 C(s) + 3 H2

(VI) coke formation

C2H2 -> 2 C(s)

(s) + H2

(VII) coke formation (explosion!)

C(s)
(s) + H2O -> CO + H2

(VIII) coke gasification

We distinguish between parallel reactions and series reactions.

ChE 400 - Reactive Process Engineering

ChE

Conversion, Selectivity, Yield

L11L11-4

Simple example:

A -> B; A -> C
(caveat :

Conversion: X j =

Selectivity:

or:

SB =

SB =

Yield:

YB = XA . SB

Production rate:

FB = YB FA0

note the formulation

with mol numbers, not
concentrations! -> Why?!)

preferred form !

(remark :
you must
be sure that you
know all products!)

(and similar for C)

Typically,
Typically, selectivity
selectivity is
is the
the crucial
crucial quantity!
quantity!

Why?

ChE 400 - Reactive Process Engineering

ChE

Selectivity: Complications

L11L11-5

Selectivity:

SB =

N B N B ,0

A
N A N A,0

Definition ambiguous if product formed from more than one reactant!

Example: Andrussov process (HCN synthesis)
(1)
(2)
(3)
Conversions of methane and ammonia can be very different. Extent to which
reaction proceeds via (2) or (3) rather than (1) will be different. Hence:
SHCN,CH4 SHCN,NH3

Selectivity
Selectivity needs
needs aa reference
reference point!
point!

ChE 400 - Reactive Process Engineering

ChE

Si: even more problems

L11L11-6

Selectivity:

SB =

What if I dont know the reaction equations (hence no i!) ?

(Often the case for very complex reactant mixtures, networks of many parallel and
series reactions!)
(Simplified) Example:

Methane Coupling
2 CH4 + 1/2 O2 <=> C2H6 + H2O
CH4 + 2 O2 => CO2 + 2 H2O

(1)
(2)

Assume equal amounts of methane react along (1) & (2):

1 mol CH4 -> 0.25 mol C2H6 + 0.5 mol CO2.
If we did not know the reaction equations
we might be tempted to calculate: SC= = nC= / (nC= + nCO2) = 0.25 / 0.75 = 1/3.
But we reacted equal amounts of CH4 along both pathways: shouldnt SC= = 0.5 ?!

atom selectivity:

S j ,i =

ChE 400 - Reactive Process Engineering

ChE

Selectivity: one last slide

dN B A

dN A B

Also called instantaneous selectivity in batch reactors

S B =

or local selectivity in (plug) flow reactors:

S B =

And for once we can also use concentrations!

S B =
( Why ?? )

L11L11-7

S B =

differential selectivity:

dN B A

=
dN A B

Example reaction:
A -> B -> C

Lets look at a reactant, which can form a desired product D, and an

undesired side-product U in parallel reactions.
A

Total Cost

Reactor Cost

Separations Cost
0

L11L11-8

Two problems:
repair of low S generally not possible
undesired side-product usually needs to be separated

Cost ($$$)

ChE 400 - Reactive Process Engineering

ChE

Selectivity: Parallel Reactions

0.1

0.2

0.3

0.4

0.5

Conversion (X)

0.6

0.7

ChE 400 - Reactive Process Engineering

ChE

Parallel Reactions: Selectivity II

L11L11-9

rD = kD CAd = k0,D exp{-ED/RT} CAd

rU = kU CAu = k0,U exp{-EU/RT} CAu

Differential
Selectivity: S = D rD / (D rD + U rU)

(S)-1 = 1 + U rU/D rD

(S)-1 ~ D/U rU/rD = DU k0U/k0D exp{-(EU-ED)/RT} CA(u-d)

(d-u)
S ~ exp{-(ED-EU)/RT} CA(d-

(I) d > u

S increases with

PFR (BR) > CSTR

no dilution
high pressure

(II) d < u

S increases with

CSTR
or PFR w/high recycle
dilution
low pressure

(III) ED < EU

S decreases with

(IV) ED > EU

S increases with

ChE 400 - Reactive Process Engineering

ChE

Differential and Total S

L11L11-10

k1

Parallel reactions,
different rctn orders

(Reactor) Selectivity:

SD =

k2

r1 = k1 CAd
r2 = k2 CAu

Local selectivity: SD= (or equivalently with Fj!)

Hence we calculate ND: N D =

SD

For V = const.

FB
1
=
=
FA0 FAe
FA0 FAe

SD =

C A0

1
C Ae

FAe

dFA

FA 0

C Ae

dC A

CA 0

total
totalSS==integral
integralaverage
averageof
oflocal
localSS

ChE 400 - Reactive Process Engineering

ChE

PFR vs CSTR

L11L11-11

SD =

C A0

1
C Ae

C Ae

dC A

CA0

SD=

SD

dd<<uu

dd>>uu

SD

CAe

CA0

CA

CAe

CA0

CA

If rctn order of desired reaction > rctn order of side reaction,

PFR better, otherwise CSTR better

Why?

ChE 400 - Reactive Process Engineering

ChE

Parallel Reaction Networks

L11L11-12

More interesting case:

Network of many parallel reactions,

SD
1

some with higher r.o., some with

lower r.o. than desired reaction

CAe

CA0

Optimum yield for CSTR first,

followed by PFR
(Exact shape of S-CA curve, and hence also precise sizing of
reactors is dependent on specific network!)

CA

ChE 400 - Reactive Process Engineering

ChE

Conversion in Multireaction Systems

L11L11-13

Lets again consider the simple parallel reaction system:

A -> B,

r1= k1 CA

A -> C,

r2= k2 CA

How can we express the concentrations CA, CB, CC in terms of XA?

We cant at least not directly! We have to distinguish between XA,1 and XA,2!
While we still can define a XA = (NA0 NA)/NA0 , we have to distinguish between the
different pathways to do our book-keeping (i.e. mass balances) for B and C:
B:

CB= CA0 XA,1

C:

CC= CA0 XA,2

A:

CA=
but also:
CA=

Everything else remains unchanged we now simply have one more quantity to keep
track of, i.e. the different Xji!

ChE 400 - Reactive Process Engineering

ChE

Series Reactions: Selectivity

L11L11-14

A -> B -> C
Very common: partial vs total oxidation reactions
(Almost) all oxidation reactions follow a sequence of successively deeper oxidation.
Example: Ethane oxidation
C2H6 + O2 -> C2H4 + H2O (oxidative dehydrogenation)
C2H4 + O2 -> 2 CO + 2 H2 (syngas formation)
CO + H2 + O2 -> CO2 + H2O
(combustion)

Lets assume a PFR for A -> B -> C, with 1st order kinetics:
rA =

, rB =

Plugging this into the PFR design equation, we get:

C A ( ) =
CC ( ) =

CB ( ) =

Check the derivation in the

textbook (p. 160ff)!
You should be able to derive
this yourself.

So, what does this look like?

ChE 400 - Reactive Process Engineering

ChE

Series Reactions: CSTR

L11L11-15

What about the same series reaction in a CSTR?

(Same procedure: rate laws into design equation, substitute CB0 and CC0 by expressions
in terms of CA0)

CA =

C A0

CB =

C A0 k1

CC =

C A0 k1k2 2

So, what does this look like?

How is it different from a PFR?
For
Forseries
seriesreactions,
reactions,there
thereisisalways
alwaysan
anoptimum
optimumresidence
residencetime
time
to
toachieve
achieveaamaximum
maximumyield
yieldtowards
towardsthe
theintermediate
intermediateproduct
product
For
Forpositive
positiveorder
orderkinetics,
kinetics,the
theoptimum
optimumyield
yieldininthe
thePFR
PFRisis
always
alwaysgreater
greaterthan
thanthat
thatininaaCSTR
CSTR
How can we rationalize this?

How about the BR?

L11L11-16

PFR vs CST R: Series Reaction

PFR vs CST R: Series Reaction

Maximum in CB
-> optimum in
residence time!
time
How can I calculate
the optimum?
Look for dCB/d = 0!
Do it for the PFR!

0.8
0.8

conc.[a.u.]
[a.u.]
conc.

ChE 400 - Reactive Process Engineering

ChE

Series Rctns - Maximum Yield

A - PFR
A - PFR
B - PFR
B - PFR
C - PFR
C - PFR
A - CSTR
A - CSTR
B - CSTR
B - CSTR
C - CSTR
C - CSTR

0.6
0.6

0.4
0.4

0.2
0.2

time
time[a.u.]
[a.u.]

PFR:

CSTR:

(log mean
rate constant)-1

(geometric mean
rate constant)-1

What if C and not B is the desired product?

10
10

ChE 400 - Reactive Process Engineering

ChE

Example:

L11L11-17

We wish to produce a product B from a reactant A in a PFR with V = 4 l/min

and CA0 = 2 mol/l. However, another reaction is also occurring, forming
an undesired product C. (Both reactions are irreversible, 1st order, with
kB= 0.5 min-1 and kC = 0.1 min-1).
(a)

Assuming a series reaction A -> B -> C, calculate the maximum achievable yield of
B, as well as the necessary reactor volume.

(b) Assuming parallel reactions A -> B and A -> C, calculate the reactor volume
necessary to achieve the same conversion of A as in (a).
What is the yield of B in this case?
Procedure:
(a) Calculate opt, from there CB(opt) and CA(opt). From these you obtain SB,max and
XA,max.
(b) Calculate (XA=0.865), from there: V = 13.36 l.l With from the equation for CB
in a PFR/series reactions

Check
-2 and
-3, incl.
Check it
it in
in LDS,
LDS, examples
examples 44-2
and 44-3,
incl. the
the CSTR
CSTR case!
case!