Department of Chemical and Biomolecular Engineering
CN2105 Reaction Engineering
Unit 4:
Reactor Design for Single
Reactions
Prof Ning Yan, 2024/2025 Sem 1
2
Recap
Mole balance equation: 𝑖𝑛 out
Design equations:
1 𝑑𝑁 𝑁 𝑑𝑥 𝑑𝑥
𝑟 = =− 𝑡=𝑁
𝑉 𝑑𝑡 𝑉 𝑑𝑡 −𝑟 𝑉
𝐹 𝑥 𝑐 𝑥
𝑉= 𝜏=
−𝑟 −𝑟
𝑑𝐹 𝑑𝑥 𝑑𝑥 𝑑𝑥
𝑟 = = −𝐹 𝑉=𝐹 𝜏=𝑐
𝑑𝑉 𝑑𝑉 −𝑟 −𝑟
3
Warm-up exercise
Is the reaction positive order, negative order or 0th order?
A→B
From the figure, t or We also know, when t or
4
Learning Objectives (Unit 4)
• Design of ideal reactors for single reactions
• Reactor selection
• Reactor sequencing
• Recycle reactors and autocatalytic reactions
5
Design of Ideal Batch Reactor
• Design equation (differential form):
• where A is the limiting reactant and V is the reaction volume, which may not be
equal to the reactor volume.
• Design equation for time of reaction:
• The integral is equal to the area under the curve (AUC) of the plot of
against xA.
• Under constant temperature and pressure, V = V0(1 + εAxA)
6
Design of Ideal Batch Reactor
1−𝑥
nth order reactions (n > 1) 𝑐 = 𝑐
1+𝜀 𝑥
εA > 0
𝑟 = −𝑘𝑐
εA = 0
At the same 𝑥 ,
𝜀 𝑐 𝑟
εA < 0
xA 𝑉
• For first order reactions, the curve is independent of εA.
7
Design of Ideal Batch Reactor
• If the batch reactor operates under constant temperature and pressure:
• The above equation calculates the initial reaction volume.
• If εA ≠ 0, the reaction volume varies during the reaction according to the function
V = V0(1 + εAxA).
• If the design parameter is the reactor volume, it must be equal to or larger
than the reaction volume at all time:
• For εA < 0, Vr = V0
• For εA > 0, Vr = V0(1 + εAxA)
8
Design of Ideal Batch Reactor
For batch reactor of constant density (V = V0)
• Design equation:
• Since cA = cA0(1 − xA) and dcA = −cA0dxA:
9
Design of Ideal CSTR
• Design equations:
• The value of is equal to the area of the shaded rectangle in the plot
of against xA:
Exit
xA
10
Design of Ideal CSTR
For CSTR of constant density (v = v0)
• Design equations:
• The value of is equal to the area of the shaded rectangle in the
plot of against cA:
Exit Inlet
cA cA0
11
Design of Ideal PFR
• Design equations:
• The integral is equal to the AUC of the plot of against xA:
xA
12
Design of Ideal PFR
For PFR of constant density (v = v0)
• Design equations:
• The integral is equal to the AUC of the plot of against cA:
cA cA0
13
Reactor Selection
• The choice between batch and flow reactors usually depends on the
requirements of the product and process.
• The choice of the flow reactor (CSTR or PFR) almost always depends on which
one can conduct the reaction with the smallest reactor volume.
For positive order reactions
• VCSTR = FA0 × area of rectangle
• VPFR = FA0 × AUC
• VCSTR > VPFR
xA
14
Reactor Selection
For negative order reactions
• VCSTR = FA0 × area of rectangle
• VPFR = FA0 × AUC
• VCSTR < VPFR
xA
For zeroth order reactions
• VCSTR = VPFR
How about the one on the right?
xA
15
Quiz 1
1. If εA is negative, does the reaction volume in a piston-type constant pressure
batch reactor increase or decrease as the reaction progresses?
2. If εA is positive, does the reaction volume in a flow reactor increase or
decrease as the reaction progresses?
3. For a half order reaction, should a CSTR or PFR be chosen to keep the
reactor size smaller?
16
Recap
Positive order reaction (A → products)
−𝑟 −𝑟
𝑥 𝑐
1 1
−𝑟 −𝑟
𝑥 𝑐
17
Recap
Negative order reaction (A → products) 0th order reaction (A → products)
−𝑟 −𝑟
−𝑟 or
𝑥 𝑐
1 𝑐 𝑜𝑟 𝑥
1
−𝑟 −𝑟
𝑥 𝑐
18
Recap
Positive order reaction
Design equations:
1 1
𝐹 ,𝑣 𝐹 ,𝑥 −𝑟 −𝑟
1
𝑉/𝐹 = ×𝑥
𝐹 𝑥 −𝑟
𝑉=
−𝑟 1 0.5 0.9 𝑥 0.25𝑐 0.5𝑐 𝑐 𝑐
𝜏/𝑐 = ×𝑥
−𝑟 Negative order reaction
1 1
𝑐 −𝑐
Constant density: 𝑥 = −𝑟 −𝑟
𝑐
1
𝜏= × (𝑐 −𝑐 )
−𝑟
0.5 0.9 𝑥 0.25𝑐 0.5𝑐 𝑐 𝑐
19
Recap
Positive order reaction
Design equations:
1 1
−𝑟 −𝑟
𝐹 ,𝑣 𝐹 ,𝑥
1
𝑉=𝐹 × 𝑑𝑥
−𝑟
𝑑𝑥
𝑉=𝐹
−𝑟 0.5 0.9 𝑥 0.25𝑐 0.5𝑐 𝑐 𝑐
1
𝜏/𝑐 = × 𝑑𝑥 Negative order reaction
−𝑟
1 1
𝑐 −𝑐 −𝑑𝑐 −𝑟 −𝑟
Constant density: 𝑥 = 𝑑𝑥 =
𝑐 𝑐
−𝑑𝑐 𝑑𝑐
𝜏= =
−𝑟 −𝑟
0.5 0.9 𝑥 0.25𝑐 0.5𝑐 𝑐 𝑐
20
Recap
Positive order reaction
1
−𝑟
0.5 0.9 𝑥
xA
Negative order reaction
1 1
−𝑟 −𝑟
0 V1 0.5 V2 0.9
0.5
𝑉 /𝐹 =
−𝑟
(0.9 − 0.5)
𝑉 /𝐹 =
−𝑟
0.5 0.9 𝑥
21
Conversion in Sequence of Reactors
• When the calculated design volume for a single reactor is too large to be
practical, the same reaction may instead be conducted in a combination of
reactors of the same or different types, arranged in series, parallel or a mixture
of both.
• When reactors are connected in series, it is mathematically more convenient to
define the conversion after any reactor with respect to the feed to the first
reactor (instead of the feed to that particular reactor, i.e. “conversion per
pass”).
• This definition is useful only if there are no side streams and the feed enters
only through the first reactor of the series.
22
Conversion in Sequence of Reactors
• Consider two CSTRs in series:
FA0 FA1 FA2
xA0 = 0 V1 xA1 V2 xA2
• Mole balance around V2:
• Combining the above equations gives:
𝐹 (𝑥 − 0)
𝑉=
• More generally: −𝑟
( )
23
Conversion in Sequence of Reactors
Example: Design equations for 3 PFRs in series
V1 V2 V3
FA0 = FA1 = FA2 = FA3 =
100 mol s−1 50 mol s−1 30 mol s−1 10 mol s−1
• Conversions based on feed to first reactor:
, ,
• Design equations (recommended):
. . .
, .
, .
• Design equations based on conversions per pass (not recommended):
. . .
, ,
24
CSTRs in Series
FA0 FA1 FA2 FA(N−1) FAN
xA0 = 0 V1 xA1 V2 xA2 xA(N−1) VN xAN
( )
• Summing up:
• The volume of a single CSTR required to conduct the same reaction:
25
CSTRs in Series
• Substitute into the previous equation:
• For positive order reactions, −rAn > −rAN (n = 1, 2, …, N − 1):
• For negative order reactions, −rAn < −rAN (n = 1, 2, …, N − 1):
• For zeroth order reactions, −rAn = −rAN (n = 1, 2, …, N − 1):
26
Equal Size Constant Density CSTRs in Series
FA0, v0 FA1, v1 FA(N−1), vN−1 FAN, vN
xA0, cA0 V1, τ1 xA1, cA1 V2, τ2 xA(N−1), cA(N−1) VN, τN xAN, cAN
( )
• Since the system is constant density, v0 = v1 = v2 = … = vN:
( ) ( ) ( )
• For first order kinetics, rAn = −kcAn:
( )
27
Equal Size Constant Density CSTRs in Series
• Apply the above equation to each reactor and let τ1 = τ2 = … = τN = τ:
( ) ( )
• Rearranging gives:
• Multiply by N to obtain overall space time:
28
Equal Size Constant Density CSTRs in Series
• As N → ∞:
→
• This is the space time of a PFR.
• Therefore:
29
Equal Size Constant Density CSTRs in Series
30
Different Size Constant Density CSTRs in Series
FA0, v0 FA1, v1 FA(N−1), vN−1 FAN, vN
xA0, cA0 V1, τ1 xA1, cA1 V2, τ2 xA(N−1), cA(N−1) VN, τN xAN, cAN
( )
( )
Self-study
31
Different Size Constant Density CSTRs in Series
• Graphical solutions of:
, , …,
( )
Self-study
32
Different Size Constant Density CSTRs in Series
• Given the number of reactors (N), feed composition (cA0), product composition
(cAN) and rate law:
• Number of equations = N (mole balance around each reactor)
• Number of unknowns = 2N − 1 (τ1, τ2, …, τN, cA1, cA2, …, cA(N−1))
• There can be multiple solutions for the space times and intermediate
concentrations (equivalently, reactor volumes and intermediate conversions).
• The optimal solution is the one that gives the smallest total reactor volume.
Refer to Levenspiel pg 132-133 for details.
Self-study
33
Rules of Thumb for CSTRs in Series
• There may exist an optimal arrangement where the total reactor volume is
minimised (for a given conversion) or the conversion is maximised (for a given
total volume). Depending on the shape of the rate-concentration curve, there
may be more than one, exactly one or no optimal arrangement.
• For nth order reactions (n > 0), there is always one optimal arrangement:
• For n > 1, the small reactors should be placed before larger ones.
• For n = 1, the reactors should have equal sizes.
• For n < 1, the large reactors should be placed before smaller ones.
• The advantage of a minimum-size system over an equal-size system is usually
quite small and the overall economic considerations almost always favour the
equal-size system.
34
CSTRs in Parallel
FA0 α1FA0 xA1 xAf
xA0 = 0 V1
α2FA0 xA2
=
FA0 FA
xA0 = 0 xA
V2
V
αNFA0 xAN
VN
xA1 = xA2 = …. = xAN = xA V = V1 +V2 +…+ VN
35
CSTRs in Parallel
• Consider the case where xA1 = xA2 = … = xAN = xAf (all τ’s are equal):
• Summing up:
• The volume of a single CSTR required to conduct the same reaction:
• Substitute into the previous equation:
• This relation applies for CSTRs in parallel as long as the conversion is the
same for all reactors.
36
Quiz 2
1. For a second order reaction, should a single CSTR or a series of multiple
CSTRs be chosen?
2. For a negative order reaction, is a PFR operationally equivalent to an infinite
series of infinitesimally small CSTRs?
37
PFRs in Series
FA0 FA1 FA2 FA(N−1) FAN
V1 V2 VN
xA0 = 0 xA1 xA2 xA(N−1) xAN
( )
• Summing up:
38
PFRs in Series
• The volume of a single PFR required to conduct the same reaction:
• Substitute into the previous equation:
• This relation always applies to PFRs in series.
39
PFRs in Parallel
FA0 α1FA0 xA1 xAf
V1
xA0 = 0
α2FA0 xA2
V2
αNFA0 xAN
VN
• where α1 + α2 + … + αN = 1.
40
PFRs in Parallel
• Consider the case where xA1 = xA2 = … = xAN = xAf (all τ’s are equal):
• Summing up:
• Comparing with the earlier expression for Vsingle PFR:
• This relation applies for PFRs in parallel as long as the conversion is the same
for all reactors.
41
Rules of Thumb for CSTRs and PFRs
• For nth order reactions (n > 0), the reactors should be arranged in series:
• For n > 1, the reactant concentration should be kept as high as possible, i.e.
arrange in the order PFR(s) – small CSTR(s) – large CSTR(s).
• For n < 1, the reactant concentration should be kept as low as possible, i.e.
arrange in the order large CSTR(s) – small CSTR(s) – PFR(s).
• For rate-concentration curves with a turning point, there are no simple rules. A
close examination of the curve is a good way to determine the best
arrangement.
42
Recycle Reactor
FA0 FA
V
xA0 = 0 xA
RFA
where R is the recycle ratio.
• The recycle reactor is a PFR with controlled back-mixing. Therefore, it may be
viewed as a hybrid of PFR and CSTR.
• The design equation is (details in Appendix):
43
Recycle Reactor
• Two limiting cases exist:
1. As R → 0, , i.e. a PFR
2. As R → ∞, A1 → 0, A1 + A2 → A2, , i.e. a CSTR
• R determines the balance between “plug flow” (i.e. PFR) and “mixed flow” (i.e.
CSTR) properties.
44
Quiz 3
1. For a negative order reaction, is the total volume required for a series of
PFRs equal to the volume required for a single PFR?
2. For a first order reaction, is the volume required for a recycle reactor larger or
smaller than that for a PFR?
45
Autocatalytic Reactions
• Consider autocatalytic reaction:
• A→R k0 (uncatalysed)
• A+R→R+R k (catalysed)
Assume k >> k0, reaction only occurs in the presence of both A and R.
Assume first order kinetics for both A and R
rA = −kcAcR = −kcA0(1 − xA)cA0xA = −kcA02(1 − xA)xA
The curve exhibits a minimum point (maximum rate), suggesting a
mix of “positive order” and “negative order” behaviours.
The reactor of choice depends on xA:
If xA is to the left of the minimum point, a CSTR should be used.
If xA is to the right of the minimum point, a recycle PFR with the
optimal recycle ratio or a sequence of reactors consisting of a
leading CSTR should be used.
46
Autocatalytic Reactions
Using a sequence of reactors consisting of a leading CSTR
CSTR CSTR
• For the arrangement on the right, the completion of the reaction depends
almost entirely on separation after reaction, i.e. the separator should recycle all
the unreacted reactant to the CSTR.
47
Autocatalytic Reactions
Using a recycle PFR with the optimal recycle ratio
Derivation provided in appendix
• Left hand sum is the AUC between and xA, while right hand sum is the area
of rectangle with length and width :
𝑅𝑥
xA
𝑅+1
48
Appendix: Design Equation for Recycle Reactor
FA0 1
FA1 FA2 2 FA
V
xA0 = 0 xA1 xA xA
RFA, xA
• Mole balance around blue system boundary:
• Mole balance around point (1):
• Mole balance around point (2):
49
Appendix: Design Equation for Recycle Reactor
FA1 FA2
V
xA1 xA
• From earlier:
• The PFR can hence be treated as having an initial flow rate of (R + 1)FA0, inlet
conversion of and outlet conversion of xA:
50
Appendix: Recycle Reactor
• The integral can be approximately represented by rectangle A1:
𝑅𝑥
xA
𝑅+1
51
Appendix: Autocatalytic Reactions
Using a recycle PFR with the optimal recycle ratio
• Design equation:
• To determine the optimal R value such that V is minimum, differentiate with
respect to R using the Leibniz rule and equate the derivative to zero:
• where is −rA evaluated at xA = .
Since =𝑥 − :
𝑑𝑥 1 𝑅𝑥
= 𝑥 −
−𝑟 −𝑟 𝑅+1
