ChE 400 - Reactive Process Engineering

Multiple Reactions

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
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ChE 400 - Reactive Process Engineering
Multiple Reactions

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
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Yj =

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ChE 400 - Reactive Process Engineering
Multiple Reactions
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.

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ChE 400 - Reactive Process Engineering
Conversion, Selectivity, Yield
Simple example: A -> B; A -> C

(caveat : note the formulation

Conversion: X j = with mol numbers, not
concentrations! -> Why?!)

Selectivity: SB =
preferred form !

(remark : you must

or: SB = be sure that you
know all products!)

Yield: YB = XA . SB

Production rate: FB = YB FA0 (and similar for C)

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Typically,
Typically, selectivity
selectivity is
is the
the crucial
crucial quantity!
quantity! Why?
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ChE 400 - Reactive Process Engineering
Selectivity: Complications
N B N B ,0 A
Selectivity: SB =
B

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
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Selectivity
Selectivity needs
needs aa reference
reference point!
point!
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ChE 400 - Reactive Process Engineering
Si: even more problems
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 (1)
CH4 + 2 O2 => CO2 + 2 H2O (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 ?!
ChE

atom selectivity:
S j ,i =
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ChE 400 - Reactive Process Engineering
Selectivity: one last slide
dN B A Example reaction:
differential selectivity: S B =
dN A B A -> B -> C

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!

dN B A
S B = =
ChE

dN A B
( Why ?? )
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 Selectivity: Parallel Reactions
Lets look at a reactant, which can form a desired product D, and an
ChE 400 - Reactive Process Engineering

undesired side-product U in parallel reactions.

Two problems:
D
A repair of low S generally not possible
U undesired side-product usually needs to be separated
Cost ($$$)

Total Cost Reactor Cost

Separations Cost
ChE

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

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Conversion (X)
 Parallel Reactions: Selectivity II
D rD = kD CAd = k0,D exp{-ED/RT} CAd
ChE 400 - Reactive Process Engineering

A
U 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)

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

(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
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(III) ED < EU S decreases with

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ChE 400 - Reactive Process Engineering
Differential and Total S
Parallel reactions, k1
A D r1 = k1 CAd
different rctn orders A
k2
U r2 = k2 CAu

(Reactor) Selectivity: SD =

Local selectivity: SD= -

Hence we calculate ND: N D = (or equivalently with Fj!)

FAe
FB 1
SD =
FA0 FAe
=
FA0 FAe S
FA 0
D dFA

. C Ae
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1
For V = const. SD =
C A0 C Ae S
CA 0
D dC A

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total
totalSS==integral
integralaverage
averageof
oflocal
localSS
 PFR vs CSTR
C Ae
1
ChE 400 - Reactive Process Engineering

SD =
C A0 C Ae S
CA0
D dC A

SD=

dd<<uu dd>>uu
SD SD
1 1

CAe CA0 CA CAe CA0 CA

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

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PFR better, otherwise CSTR better

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ChE 400 - Reactive Process Engineering
Parallel Reaction Networks
SD
More interesting case:
1
Network of many parallel reactions,
some with higher r.o., some with
lower r.o. than desired reaction

CAe CA0 CA

Optimum yield for CSTR first,

followed by PFR

(Exact shape of S-CA curve, and hence also precise sizing of

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reactors is dependent on specific network!)

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ChE 400 - Reactive Process Engineering
Conversion in Multireaction Systems
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=
ChE

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

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ChE 400 - Reactive Process Engineering
Series Reactions: Selectivity
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:

Check the derivation in the
C A ( ) = CB ( ) = textbook (p. 160ff)!
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You should be able to derive

this yourself.

CC ( ) =
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ChE 400 - Reactive Process Engineering
Series Reactions: CSTR
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)

C A0 C A0 k1 C A0 k1k2 2
CA = CB = CC =

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
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CSTR

How can we rationalize this? How about the BR?

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ChE 400 - Reactive Process Engineering
Series Rctns - Maximum Yield
PFR vs CST R: Series Reaction
PFR vs CST R: Series Reaction
Maximum in CB 1
1

-> optimum in
residence time!
0.8
time 0.8

A - PFR

[a.u.]
A - PFR

conc.[a.u.]
0.6 B - PFR
0.6 B - PFR
C - PFR
C - PFR

How can I calculate

A - CSTR
A - CSTR

conc.
B - CSTR
B - CSTR
0.4
the optimum?
C - CSTR
0.4 C - CSTR

Look for dCB/d = 0! 0.2

0.2

Do it for the PFR!

0
0
0 2 4 6 8 10
0 2 4 6 8 10
time
time[a.u.]
[a.u.]

PFR: CSTR:
ChE

(log mean (geometric mean

rate constant)-1 rate constant)-1

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ChE 400 - Reactive Process Engineering
Example:
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
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in a PFR/series reactions

L11-
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Check it
it in
in LDS,
LDS, examples
examples 44-2
-2 and
and 44-3,
-3, incl.
incl. the
the CSTR
CSTR case!
case!