Chemical Reaction Engineering

LECTURE 10: REACTOR NETWORK (CSTR)

ChE 125: Chemical Reaction Engineering I

2nd Semester AY 2017 - 2018
Performance Curves
CSTR
 CSTR vs. PFR
−‫ݎ‬஺ = ݇‫ܥ‬஺௡ ‫ > ݊ ݁ݎ݄݁ݓ‬0

CSTR PFR

1/(-rA)

XA, in XA, out

XA
What are you going to do to increase
production capacity, or to obtain
higher conversion levels?
REACTOR NETWORKS
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ ࡯ࡻࡺࡲࡵࡳࢁࡾ࡭ࢀࡵࡻࡺ

C0 C1 C2 Ci-1 Ci CN-1
X0 X1 X2 Xi-1 Xi XN-1

CN
… … XN

V 1, τ 1 V 2, τ 2 Vi, τi VN, τN

For the ith CSTR,

C A0Vi C A0 ( X Ai − X Ai −1 )
τi = =
FA0 − rA
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ ࡯ࡻࡺࡲࡵࡳࢁࡾ࡭ࢀࡵࡻࡺ

What if you increase the

number of CSTR units in series?
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

Consider ߝ = 0 (i.e. constant density) system,

C A0Vi C A0 ( X Ai − X Ai −1 )
τi = =
FA0 − rA

C A(i −1) − C Ai
τ=
−rAi
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

For 1st – order reactions,

C A0Vi C A0 ( X Ai − X Ai −1 )
τi = =
FA0 − rA

஼ಲ ೔షభ ି ஼ಲ೔ ஼ಲ ೔షభ ି ஼ಲ೔

௜ ି௥ಲ೔ ௞೔ ஼ಲ೔
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

Solving for CAi,

஺ ௜ିଵ
஺௜
௜ ௜

For the first reactor,
For the second reactor,

‫ܥ‬஺଴ ‫ܥ‬஺ଵ
‫ܥ‬஺ଵ = ‫ܥ‬஺ଶ =
1 + ݇ଵ ߬ଵ 1 + ݇ଶ ߬ଶ
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

For the nth reactor,

‫ܥ‬஺ ேିଵ
‫ܥ‬஺ே =
1 + ݇ே ߬ே

‫ܥ‬஺଴
‫ܥ‬஺ே =
1 + ݇ଵ ߬ଵ 1 + ݇ଶ ߬ଶ … 1 + ݇ே ߬ே
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

If the cascade is isothermal (same k) and the

CSTRs have the same volume (i.e. same ߬)

஺଴
஺ே ே
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

For 2nd – order reactions,

C A0Vi C A0 ( X Ai − X Ai −1 )
τi = =
FA0 − rA

஼ಲ ೔షభ ି ஼ಲ೔ ஼ಲ ೔షభ ି ஼ಲ೔

௜ ି௥ಲ೔ మ
௞೔ ஼ಲ೔
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

Solving for CAi,

−1 + 1 − 4(݇௜ ߬௜ )(−‫ܥ‬஺ ௜ିଵ )
‫ܥ‬஺௜ =
2݇௜ ߬௜

Note: We have discarded the negative root because

reactant concentrations cannot be negative
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

C1
C0 C2

F1
F0 F2

C3

V1, τ1 V2, τ2 V3, τ3 F3

What if the CSTRs have different sizes?

 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

C1
C0 C2

F1
F0 F2

C3

V1, τ1 V2, τ2 V3, τ3 F3

Two possible problems:

• What is the final effluent composition given a network of reactors?
• What combination of ideal CSTRs is best suited to achieve a
specified conversion?
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

C1
C0 C2

F1
F0 F2

C3

V1, τ1 V2, τ2 V3, τ3 F3

Two ways to determine volumes

• If the intermediate conditions (C or X) are given, solve directly
• Determine minimum total volume by optimization.
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

Which of the two configurations would give the

best system for a given exit conversion?
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

OPTIMIZATION:
To minimize the total volume required for 2 CSTR in
series, derive the VTOT expression with respect to X1
and equate to zero.

݀ ܸ௧௢௧
=0
݀ܺଵ

Then solve for X1 and the corresponding V1 and V2

using the CSTR design equation.
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡭ࡸࡳࡱ࡮ࡾ࡭ࡵ࡯ ࡹࡱࢀࡴࡻࡰ

OPTIMIZATION:
To minimize the total volume required for 3 CSTR
in series, solve for:

d (Vtot ) d (Vtot )
=0 =0
dX 1 X2
dX 2 X1
(holding X2 constant) (holding X1 constant)

Then solve X1 and X2 simultaneously. Calculate the

corresponding V1, V2 and V3 using the CSTR design equation.
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡳࡾ࡭ࡼࡴࡵ࡯࡭ࡸ ࡹࡱࢀࡴࡻࡰ

Which of the two configurations would give the

best system for a given exit conversion?

τ1 X1 τ2 X 2 − X1
= =
C0 −r1 C0 −r2
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡳࡾ࡭ࡼࡴࡵ࡯࡭ࡸ ࡹࡱࢀࡴࡻࡰ

We need to minimize the total reactor volume. How?

 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡳࡾ࡭ࡼࡴࡵ࡯࡭ࡸ ࡹࡱࢀࡴࡻࡰ

OPTIMIZATION:
Area is maximized when M
is at the point where the
slope of the curve equals
the slope of the diagonal NL
of the rectangle.

Depending on the shape of

the curve, there may be
more than one or there
may be no “best” point.
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡳࡾ࡭ࡼࡴࡵ࡯࡭ࡸ ࡹࡱࢀࡴࡻࡰ

Recall,
C A 0 − C A1
τ1 =
−rA1

C A0 − C A1 −C A1 CA0
−rA1 = = +
τ1 τ1 τ1
rAi = f(Cai) The equation generated is linear
with a slope of 1/߬
Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ: ࡳࡾ࡭ࡼࡴࡵ࡯࡭ࡸ ࡹࡱࢀࡴࡻࡰ
EXAMPLE 1

Consider the Diels-Alder reaction between benzoquinone (B)

and cyclopentadiene (C):

B + C → adduct r = kC BCC
If the reaction occurs in the liquid phase at 25℃, determine
the reactor volume requirements for cascades of one and
three identical CSTRs that operate at the same temperature.
The rate at which liquid feed is supplied is 0.278 m3/ks. The
following constraints are applicable: k=9.92 m3/(kmol-ks);
CC0 = 0.1 kmol/m3; CB0 = 0.08 kmol/m3; conversion
desired = 87.5%
ANSWER KEY 1

• The graphical approach requires a plot of reaction

rate versus the concentration of the limiting
reactant (benzoquinone). To prepare this plot it is
necessary to relate the two reactant concentrations
to one another. From the initial concentrations and
the stoichiometric coefficients:

C B 0 − C B 
CC = 0.1 − C B 0X B = 0.1 − C B 0   = 0.02 + C B
 C B0


r = 9.92C BCC = 9.92C B (0.02 + C B )

ANSWER KEY 1

• For 87.5%, conversion the concentration of B in

the effluent from the last reactor in the cascade
will be:

C B = C B 0 (1 − X B )
C B = 0.08(1 − 0.875)
3
C B = 0.01 kmol/m
ANSWER KEY 1

• For the case where the cascade consists of just

one reactor, only a single straight line is involved in
the graphical solution.

• One merely links the point on curve M (see next

slide) corresponding to the effluent concentration of
B (CB = 0.01) with the point on the abscissa
corresponding to the feed concentration (CB0 = 0.08)
 Mixed Flow Reactor
ࡳࡾ࡭ࡼࡴࡵ࡯࡭ࡸ ࡹࡱࢀࡴࡻࡰ

1 CSTR
−࢘࡮ = ૢ. ૢ૛࡯࡮ ࡯࡮ + ૙. ૙૛ = ࢉ࢛࢘࢜ࢋ ࡹ

࡯࡮૚ ࡯࡮૙
ANSWER KEY 1

• The slope of this line is equal to:

1 v0
slope = − = −
τ V

• In the present instance, the slope is

(2.976 − 0) × 10−3
slope = −
(0.01 − 0.08)
−1
slope = −0.0425 ks
ANSWER KEY 1

• Thus,

1 v0
slope = − = −
τ V
3
m
0.278
−1
−0.0425 ks =− ks
V

3
V = 6.54 m
ANSWER KEY 1

• For the case where the cascade consists of three

identical reactors, a trial-and-error approach is
necessary to determine the reactor size required.

• One starts at the inlet concentration (CB0) and draws a

line linking this point on the abscissa with some point J
on curve M.
• One then draws a straight line parallel to the first
(because same ߬), but passing through the point on
the abscissa corresponding to the benzoquinone
concentration at point J. This straight line intersects
curve M at some point K.
ANSWER KEY 1

• One then repeats the procedure by drawing yet another

parallel line through the point on the abscissa
corresponding to the benzoquinone concentration at K.

• If the intersection of this straight line with curve M

occurs at a CB = 0.01, the initial choice of slope was
correct. If not, one must choose a new point J and
repeat the procedure until such agreement is obtained.

• The figure in the next slide indicates the construction

for this case.
 Mixed Flow Reactor
ࡳࡾ࡭ࡼࡴࡵ࡯࡭ࡸ ࡹࡱࢀࡴࡻࡰ

3 EQUAL SIZED CSTR IN SERIES

−࢘࡮ = ૢ. ૢ૛࡯࡮ (࡯࡮ + ૙. ૙૛)

ࡶ = ࡯࡮૚
ࡷ = ࡯࡮૛
࡯࡮૜ ࡯࡮૙
ANSWER KEY 1

• The slope of the lines is equal to:

1 v0
slope = − = −
τ V
(18.2 − 0) × 10−3
slope = −
(0.034 − 0.08)
−1
slope = −0.396 ks
ANSWER KEY 1

• Thus:

1 v0
slope = − = −
τ V
3
m
0.278
−1
−0.396 ks =− ks
V
3
V = 0.70 m
3
Vtot = 3 × 0.70 = 2.1 m
ANSWER KEY 1

• Using analytical approach:

• Case 1: Single CSTR

C B 0 ∆X B C B 0 (X B − 0)
τ= =
−rB −rB

−rB = 9.92C BCC

−rB = 9.92C B 0 (1 − X B )(0.1 − C B 0X B )
ANSWER KEY 1

• Hence,

C B 0 (X B − 0)
τ=
9.92C B 0 (1 − X B )(0.1 − C B 0X B )

0.08(0.875 − 0)
τ=
9.92(0.08)(1 − 0.875)[0.1 − (0.08)(0.875)]

τ = 23.5215 ks
ANSWER KEY 1

• From the definition of space time:

V
τ=
v0
V
23.5215 =
0.278

V = 6.5389785 m 3
ANSWER KEY 1

• Case 2: Two-identical CSTR in series

C B 0 ∆X B C B 0 (X B 1 − 0)
1st CSTR τ1 = =
−rB (−rB )1

C B 0 ∆X B C B 0 (X B 2 − X B 1 )
2nd CSTR τ2 = =
−rB (−rB )2
ANSWER KEY 1

• For identical reactors, the space times are identical.

We need to equate the two equations to solve the
intermediate concentrations, XB1

C B 0 (X B 1 − 0) C B 0 (X B 2 − X B 1 )
=
−rB −rB

C B 0 (X B 1 − 0) C B 0 (X B 2 − X B 1 )
=
9.92C B 0 (1 − X B 1 )(0.1 − C B 0X B 1 ) 9.92C B 0 (1 − X B 2 )(0.1 − C B 0X B 2 )
ANSWER KEY 1

• Solving for XB1 where XB2 = 0.875

C B 0 (X B 1 − 0) C B 0 (X B 2 − X B 1 )
=
9.92C B 0 (1 − X B 1 )(0.1 − C B 0X B 1 ) 9.92C B 0 (1 − X B 2 )(0.1 − C B 0X B 2 )

X B 1 = 0.6894

X B 2 = 0.875
ANSWER KEY 1

• Solving for the space time:

1st CSTR

C B 0 (X B 1 − 0) C B 0 (X B 1 − 0)
τ1 = =
(−rB )1 9.92C B 0 (1 − X B 1 )(0.1 − C B 0X B 1 )

(0.08)(0.6984 − 0)
τ1 =
9.92(0.08)(1 − 0.6984)[0.1 − (0.08)(0.6984)]

τ1 = 4.989 ks
ANSWER KEY 1

• Solving for the space time:

2nd CSTR

C B 0 (X B 2 − 0) C B 0 (X B 2 − X B 1 )
τ2 = =
(−rB )2 9.92C B 0 (1 − X B 2 )(0.1 − C B 0X B 2 )

(0.08)(0.875 − 0.6984)
τ2 =
9.92(0.08)(1 − 0.875)[0.1 − (0.08)(0.875)]

τ2 = 4.989 ks
ANSWER KEY 1

• From the definition of space time:

V
τ1 = τ 2 =
v0
V
4.989 =
0.278
3
V1 = V2 = 1.387 m
3
Vtot = 2 ×V1 = 2.774 m
ANSWER KEY 1

• Case 3: Three-identical CSTR in series

C B 0 ∆X B C B 0 (X B 1 − 0)
1st CSTR τ1 = =
−rB (−rB )1
C B 0 ∆X B C B 0 (X B 2 − X B 1 )
2nd CSTR τ2 = =
−rB (−rB )2
C B 0 ∆X B C B 0 (X B 3 − X B 2 )
3rd CSTR τ3 = =
−rB (−rB )3
ANSWER KEY 1

• For identical reactors, the space times are identical.

We need to determine the intermediate conversions
XB1 and XB2 by solving three equations simultaneously

C B 0 (X B 1 − 0) C B 0 (X B 2 − X B 1 ) C B 0 (X B 3 − X B 2 )
= =
−rB −rB (−rB )3

X B 1 = 0.575
X B 2 = 0.781
X B 3 = 0.875
ANSWER KEY 1

• Solving for the space time:

1st CSTR

C B 0 (X B 1 − 0) C B 0 (X B 1 − 0)
τ1 = =
(−rB )1 9.92C B 0 (1 − X B 1 )(0.1 − C B 0X B 1 )

(0.08)(0.575 − 0)
τ1 =
9.92(0.08)(1 − 0.575)[0.1 − (0.08)(0.575)]

τ1 = 2.5266 ks
ANSWER KEY 1

• From the definition of space time:

V
τ1 = τ 2 = τ 3 =
v0
V
2.5266 =
0.278
3
V1 = V2 = V3 = 0.7023948 m
3
Vtot = 3 ×V1 = 2.107 m
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ ࡯ࡻࡺࡲࡵࡳࢁࡾ࡭ࢀࡵࡻࡺ

GENERALIZATIONS:

1 Optimum size for CSTRs in series

is found to be dependent on the
kinetics of the reaction and
conversion level.
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ ࡯ࡻࡺࡲࡵࡳࢁࡾ࡭ࢀࡵࡻࡺ

GENERALIZATIONS:

1 For general nth order kinetics,

࢔ = ૚ equal – size reactors

࢔ > ૚ smaller before larger reactor
૙ < ࢔ < ૚ larger before smaller reactor
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ ࡯ࡻࡺࡲࡵࡳࢁࡾ࡭ࢀࡵࡻࡺ

GENERALIZATIONS:

2 An examination of 1/(-rA) versus

CA or XA curve is a good is a good
way to find the best arrangement
of units.
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ ࡯ࡻࡺࡲࡵࡳࢁࡾ࡭ࢀࡵࡻࡺ

GENERALIZATIONS:

3 For any nth – order reactor (n > 0), the

reactors should be connected in series.

Reactant concentration should be kept as high

as possible if n > 1

Reactant concentration should be kept as low

as possible if n < 1
 Mixed Flow Reactor
ࡿࡱࡾࡵࡱࡿ ࡯ࡻࡺࡲࡵࡳࢁࡾ࡭ࢀࡵࡻࡺ

GENERALIZATIONS:

4 For reactions whose rate –

concentration curve passes through a
maximum or minimum, the
arrangements of units depends on the
shape of the curve, conversion level,
and the units available
 REFERENCES

Hill Jr., C. G. (1977) ‘An Introduction to
Chemical Engineering Kinetics & Reactor
Design’, John Wiley & Sons, Inc. USA.

Fogler, H. S. (1999) ‘ Elements of Chemical
Reaction Engineering: 3rd Edition’, Prentice-
Hall International, Inc. USA.
QUESTIONS?