Mid-Semester Examination

CL-451: Chemical Process Design

Closed Book, Closed Notes Examination

Tuesday, February 18, 2014

0830 1030 hrs
Overall Weight: 30%

Attempt Questions 1-4. Questions do not have equal weights. AR stands for
Attainable Region throughout. Do not seek any clarifications/interpretations. If you
make any assumptions, state the same clearly. To plot graphs, make suitable grids in
your answer book itself. No graph paper will be provided separately. The x-y data
that you plot should be tabulated in a table for more accurate quantitative feel.
QUESTION 1: Construct an AR for the following series-parallel reactions.
A + R B, Zero order in R, First order in A, Irreversible, rate constant = 2 hr-1.
B + R C, Zero order in R, First order in B, Irreversible, rate constant = 1 hr-1.
The feed is a mixture of A and R with concentrations of 1.0 and 1.2 kmol/m3 respectively.
Design a reactor system to obtain 10 m3/hr of product with A, B and C concentrations of
0.4, 0.3 and 0.3 kmol/m3 respectively. What will be the concentration of R in this
product?
Derive all relevant equations from first principle. Show equations of all edges of the AR
as well as appropriate reactor lines and coordinates of vertices if any.
Show your AR on CB vs CA and CC vs CA plots.

(12)

Answer: A B C was considered in the class and AR created. The reactor line for
PFR was entirely above that for CSTR and area under it was the AR. In the present case,
maths is the same for the reactor line. However, the lines abruptly end when R is
consumed. R is the limiting reactant. The reactor lines are thus only a part of the inverse
dome lines derived earlier.
The mathematical model needs to be derived for CSTR and PFR for CA v Tau, CB vs Tau,
CA vs CB. The CR can be calculated as CR0 (CB-CB0) 2 (CC CC0). With no B and C in
the feed, this is simply CR0 CB 2 CC. Tau when CR becomes 0 needs to be determined.
This gives CA at that value of Tau. The reactor lines end there. A line joining end point of
PFR line to that of CSTR line and a line joining end point of CSTR line to the feed point
complete the construction of AR.
The desired composition cannot be obtained by PFR as it is outside the AR made by PFR
only. However, the point is within the AR made from CSTR alone. The composition can
be obtained by a CSTR with bypass.
Calculations of the reactor size and the fraction that needs to go through bypass line and
CSTR need to be done. This involves geometry only once reactor lines are drawn.

QUESTION 2: Irreversible series reaction A B C is to be carried out for maximum

value creation. The feed is pure A with molar density of 8 kmol/m3. The rate constants for
the first and second reaction are 16 and 8 kmol/m3/hr respectively. Its availability is
restricted to a maximum of 50 m3/hr. Two identical stirred tank reactors, each of capacity
12.5 m3, are available for deployment.
Mixture of A, B and C is priced in terms of concentrations of A, B and C as per the
following formula.
P = 36 + 4 CB.CC - 2 CA Rs/kg.
For example, the given feed will cost 20 Rs/kg. Density of any mixture of A, B, C is 1000
kg/m3.
Construct an AR for the case clearly showing the boundaries of the AR and reactor lines.
Display AR on all 3 possible 2-D concentration plots.
Suggest your design of the reactor system which creates maximum value. Indicate the
flow rates passing through one or more reactors arranged in series or parallel
combinations with or without bypass.
(9)
Answer: This was done in the class and is a simple variation of that. It is also similar to
the 10%-Quiz problem.
The type of reactor does not matter as reactions are zero order. In any case, available
reactors are CSTRs only. The reactor line is in two parts. One joins feed point to point
(0,4) on CB v CA plot. Another part joins (0,4) to (0,0). The first part is for space time of
0-30 minutes and the other for space times of 30 minutes to 60 minutes and above.
If one deploys only one of the two CSTRs available and pushes entire feed through it, the
possible space time is 15 minutes. Space time below this is thus not possible. It means
that reactor line between (8,0) and (4,2) on CB v CA plot is not attainable.
Similarly, if one uses only one CSTR and pushes 12.5 m3/hr through it, it will produce C
entirely by providing space time of 60 minutes. That leaves 37.5 m3/hr of feed to mix as
bypass stream. This will produce a net product of (6,0,2).
If less is sent through the reactor and the balance bypassed, one can even attain any
composition between CA > 6, CB = 0 and CC = 8 - CA. The entire x axis is thus attainable.
The attainable region is thus a quadrilateral (6,0,2), (4,2,2), (0,4,4) and (0,0,8) with a line
segment (6,0,2) to (8,0,0) attached to it.
The given pricing formula suggests that the product should not have A. Therefore, CB +
CC = 8. The formula then suggests that CB = CC will maximize product value (=100). That

means a product (0,4,4) should be achieved. This is one of the vertices of the AR
corresponding to space time of 30 minutes.
It is also natural to process maximum feed using both reactors which can get 30 minutes
space time.
Given the feed limitations and reactors, entire feed can be processed using available
volume of 25 m3 reactor which gives exact 30 minutes space time.
In one option, each reactors processes 25 m3/hr in parallel. In another option, entire feed
passes through reactors in series, each providing a space time of 15 minutes.
QUESTION 3: Consider zero order reactions as shown below with feed available as a
equimolar mixture of A and B with individual concentrations as 1 kmol/m3, and
possibility to carry out reaction at any temperature between 100 to 160 C in isothermal
reactors. The rate constants k1, k2, k3 are given as 3, 2 and 1 kmol/m3/hr at 100 C and 6, 8
and 2 kmol/m3/hr at 160 C respectively. The rate constants vary linearly over the given
temperature range.
k1
k2
k3
A C, B C, C D
Construct an AR for this case in CC vs CA and CD vs CC concentration plots. What is the
dimensionality of the AR?
Suggest a simple possible reactor network to obtain a product with mole fractions of A,
B, C as 1/5, 1/5, 1/3 respectively. Indicate space time and temperature for the reactor(s).
If there is a stream split, indicate the split fractions clearly. If it is not possible to achieve
such a product concentration without a separation system, say so and justify your answer
quantitatively
(6)
Answer: The reactor lines can be easily obtained for the two extreme temperatures; 100
and 160 C. The AR is a convex region made from these lines.
The desired composition is a point within this AR and can be certainly achieved. One
should try to see if it can be achieved by a single reactor without a bypass. This will be
possible if a reactor line for some temperature between 100-160 exactly passed through
the desired point.
The feed has equal concentration of A and B. The desired product also must have equal
concentrations of A and B (2/5, 2/5). Therefore, the reactor must consume A and B at the
same rates. This is possible if k1 and k2 are the same at the temperature we are
contemplating to operate the reactor. Given the data, this is possible only at temperature
120 C when k1 and k2 are both 4. k3 at this temperature is 4/3. If concentration of A and B
must drop from 1 kmol/m3 to 2/5 kmol/m3, the reactor space time must be 3/20 hr or 9
minutes for a rate constant value of 4. This would also ensure B concentration to be 2/5.

Given the rate constant of the reaction forming D as 4/3 at 120 C, Concentration of D will
be 1/5 in the product. Concentration of C will then be 1. This is not what we want. We
want (6/15, 6/15, 10/15, 8/15), considering that A + B + C + D must be 2 and the desired
mole fractions are (1/5, 1/5, 1/3) for A, B, C.
Therefore, a reactor operating at some space time should produce a product where C:D
ratio is 5:4. The concentration of A and B can then be raised to the desired level by the
bypass stream.
What reactor gives a C:D ratio of 5:4? It will have to be a reactor which consumes entire
A and B and then further depletes C. It can be at any temperature. Let us say it operates at
100 C. It should produce 8/9 kmol/m3 of D and 10/9 kmol/m3 of C. With k3 as 1, tau
should be 8/9 hrs. This reactor will give a product with (0, 0, 10/9, 8/9) concentration
vector.
This vector should change to (6/15, 6/15, 10/15, 8/15) vector after mixing with feed. Or C
should drop from 10/9 to 10/15. If fraction x goes through reactor and (1-x) as bypass,
x . 10/9 + (1-x) . 0 = 10/15
Or x = 90/150 = 6/10 = 0.6.
Thus passing 60 % through a reactor of space time 8/9 hrs and mixing with 40% feed
should give the desired product.
Similarly, one could operate the reactor at 160 C. k3 is now double and hence reactor
space time of 4/9 hrs should be enough. 60:40 split remains the same.
QUESTION 4: Suggest a suitable reactor, separator and recycle scheme to process 240
m3/day of feed which is an equimolar mixture of three isomers (say, A, B, C) to obtain
240 m3/day of isomer A. Any mixture of isomers can be catalytically treated in an
isomerization reactor to reach equilibrium composition by providing space time of 2
minutes. The equilibrated product mixture of isomers has equimolar composition of the
three isomers. Similarly, an adsorption based system such as SMB (Simulated Moving
Bed) can separate isomer A entirely and in pure form as extract and a mixture of other
two isomers (B and C) as raffinate stream. Draw a flowsheet showing the reactor,
separation system and recycle (if any). Indicate flow rate and compositions of all streams
in your flowsheet.
(3)
Answer: The SMB produces 2 product streams. One is pure A and the other is a mixture
of B and C without A. SMB also treats an equimolar mixture of A, B, C exiting the
reactor. Therefore, SMB extract stream is 240 m3/day of A and 480 m3/day of equimolar
mixture of B and C is raffinate stream. This stream must be sent to the reactor for
isomerization. The feed is already an equilibrated isomer mixture and need not be sent
through the reactor. It will only increase reactor volume. It should therefore bypass the
reactor. 240 m3/day of fresh feed should thus directly mix with 480 m3/day of equilibrated

product from the reactor. The SMB thus treats 720 m3/day of equimolar mixture of A, B
and C.
The 480 m3/day of equimolar mixture from SMB should be treated in a reactor providing
2 minutes space time. Thus, reactor volume be such as to give 2 minutes space time to a
feed of 20 m3/hr or 1/3 m3/min. The reactor volume should thus be 2/3 m3.
ASM/IITB/CL/451/2014