Chemical Reaction Engineering -I

Autumn 2024

Instructor:

Dr. Sushant Kumar

Department of Chemical and Biochemical Engineering
Indian Institute of Technology, Patna 1
Thu, 24.10.24

Design for Parallel Reactions

Qualitative Discussion About Product Distribution
!!
𝐴 → 𝑅 (𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡)
!"
𝐴 → 𝑆 (𝑈𝑛𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡)
With corresponding rate equations

𝑑𝐶" % (4.1)
𝑟" = = 𝑘# 𝐶$ !
𝑑𝑡

𝑑𝐶& %
𝑟& = = 𝑘' 𝐶$ " (4.2)
𝑑𝑡

Dividing eqn. (4.1) and (4.2) gives a measure of the relative rates of formation of R and S. Thus,

𝑟" 𝑑𝐶" 𝑘# %!(%"

= = 𝐶 (4.3)
𝑟& 𝑑𝐶& 𝑘' $

And, this ratio has to be as large as possible.

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Ways to keep low 𝐶$ : (a) Using a MFR
(b) Maintaining high conversions
(c) Increasing inerts in the feed
(d) Decreasing the pressure in gas-phase systems

Ways to keep high 𝐶$ :

(a) Using a batch or PFR
(b) Maintaining low conversions
(c) Removing inerts from the feed
(d) Increasing the pressure in gas-phase systems

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 𝑟" 𝑑𝐶" 𝑘# %!(%"
= = 𝐶 (4.3)
𝑟& 𝑑𝐶& 𝑘' $

Cases:
1. 𝐼𝑓 𝑎# > 𝑎' : A high reactant concentration is desirable since it increases the R/S ratio. As a result, a batch or PFR
would favour formation of product R and would require a minimum reactor size.

2. 𝐼𝑓 𝑎# < 𝑎' : A low reactant concentration to favour formation of R. But this would also require large MFR.

!
3. 𝐼𝑓 𝑎# = 𝑎' : The product distribution is fixed by !! alone and is unaffected by type of reactor used.
"

!!
Note: the product distribution is controlled by varying . This can be done by:
!"
!
1. By changing the temperature level of operation. If the activation energies of the two reactions are different, !! can be
"
made to vary.
2. By using a catalyst to manipulate selectivity.

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Note: The use of proper contacting pattern is the critical factor in obtaining a favourable distribution of products for multiple
reactions.

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Q. 4.1

The desired liquid-phase reaction

!! 𝑑𝐶" 𝑑𝐶)
𝐴 + 𝐵 → 𝑅 + 𝑇, = = 𝑘# 𝐶$#.+ 𝐶,-..
𝑑𝑡 𝑑𝑡

Is accompanied by the unwanted side reaction

!" 𝑑𝐶& 𝑑𝐶/

𝐴 + 𝐵 → 𝑆 + 𝑈, = = 𝑘' 𝐶$-.+ 𝐶,#.0
𝑑𝑡 𝑑𝑡

From the standpoint of favourable product distribution, order the contacting schemes from the most desirable to
the least desirable.

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Mon, 28.10.24

Qualitative Treatment of Product Distribution and of Reactor Size

Let, 𝜑 be the fraction of A disappearing at any instant which is transformed into desired product, R.

12345 26 " 627148 8;# (4.4)

Instantaneous fractional yield of R, 𝜑 = =
12345 26 $ 74%9:48 (8;$

%33 " 627148 ;#% ;#%

Overall fractional yield of R, Φ = = = = 𝜑=> 74%9:27 (4.5)
%33 $ 74%9:48 ;$&(;$% (∆;$

For plug flow, where 𝐶$ changes progressively through the reactor,

;$% ;$%
−1 1
For PFR: Φ? = G 𝜑𝑑𝐶$ = G 𝜑𝑑𝐶$ (4.6)
𝐶$- − 𝐶$6 ;$& ∆𝐶$ ;$&

For mixed flow, the composition is 𝐶$6 everywhere, so 𝜑 is likewise constant throughout the reactor, and we have

For MFR: Φ1 = 𝜑4@%3%A%:48 %: ;$% (4.7)

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The over-all fractional yields from mixed and plug flow reactors processing A from 𝐶$- to 𝐶$6 are related by
;$%
𝑑Φ? 1
Φ1 = and Φ? = G Φ 𝑑𝐶 (4.8)
𝑑𝐶$ ∆𝐶$ ;$& 1 $
%: ;$%

These expressions allow us to predict the yields from one type of reactor given the yields from the other.

For a series of 1,2, …., N mixed flow reactors in which the concentration of A is 𝐶$# , 𝐶$' ….., 𝐶$B the overall fractional
yield is obtained by summing the fractional yields in each of the N vessels and weighting these values by the amount of
reaction occurring in each vessel. Thus,

𝜑# 𝐶$- − 𝐶$# + ⋯ + 𝜑B 𝐶$,B(# − 𝐶$B = 𝜑B 1=D48 𝐶$- − 𝐶$B

From which,
𝜑# 𝐶$- − 𝐶$# + ⋯ + 𝜑B 𝐶$,B(# − 𝐶$B (4.9)
ΦB 1=D48 =
𝐶$- − 𝐶$B

For any reactor type, the exit concentration of R is obtained directly from eqn. (4.5). Thus,

𝐶"6 = Φ 𝐶$- − 𝐶$6 (4.10)

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 (4.10) (4.10)
(4.10)
(4.9)
(4.6) (4.7)

Note: Shaded and dashed area gives total R formed

Note: the contacting pattern with the largest area produces most R: (a) plug flow is best
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(b) Mixed flow is best, (c) mixed flow up to CA1 followed by plug flow is best
Selectivity.

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑

𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑢𝑛𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑓𝑜𝑟𝑚𝑒𝑑

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Tue, 29.10.24

Q. 4.2

Consider the aqueous reactions

!! 𝑑𝐶"
𝐴 + 𝐵 → 𝑅, 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 = 1.0 𝐶$#.+ 𝐶,-.. , 𝑚𝑜𝑙/𝑙𝑖𝑡𝑒𝑟 P 𝑚𝑖𝑛
𝑑𝑡

is accompanied by the unwanted side reaction

!" 𝑑𝐶&
𝐴 + 𝐵 → 𝑆, 𝑢𝑛𝑤𝑎𝑛𝑡𝑒𝑑 = 1.0 𝐶$-.+ 𝐶,#.0 , 𝑚𝑜𝑙/𝑙𝑖𝑡𝑒𝑟 P 𝑚𝑖𝑛
𝑑𝑡

For 90% conversion of A, find the concentration of R in the product stream. Equal volumetric flow rates of the A and of B
streams are fed to the reactor, and each stream has a concentration of 20 mol/liter of reactant.

The flow in the reactor follows:

(A) Plug flow
(B) Mixed flow
(C) The best of the four plug-mixed contacting schemes of Q. 4.1 (assume that B is introduced in the reactor in a way
that CB= 1mol/l throughout)

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Q. 4.3

Often a desired reaction is accompanied by a variety of undesired side reactions, some of higher order, some of lower order.
To see which type of single reactor gives the best product distribution, consider the simplest typical case, the parallel
decomposition of A, CA0=2,

Find the maximum expected Cs for isothermal operations

(a) In a mixed flow reactor
(b) In a plug flow reactor
(c) In a reactor of your choice if unreacted A can be separated from the product stream and returned to the feed at CA0=2.

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Q. 4.4

For the reaction of Q. 4.3, determine the arrangement of reactors which would produce most S in a flow system where
recycle and reconcentration of unreacted feed is not possible. Find Cs, total for this arrangement of reactors.

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 Q. 4.5
Substance A in the liquid phase produces R and S by the following reactions:

𝐴 → 𝑅 , 𝑟" = 𝑘# 𝐶$'

𝐴 → 𝑆 , 𝑟& = 𝑘' 𝐶$#

The feed 𝐶$- = 1.0, 𝐶"- = 0, 𝐶&- = 0.3 enters two mixed flow reactors in series 𝜏# = 2.5 𝑚𝑖𝑛, 𝜏' = 10.0 𝑚𝑖𝑛 .

Knowing the composition in the first reactor 𝐶$# = 0.4, 𝐶"# = 0.2 , 𝐶&# = 0.7 , find the composition leaving the second reactor.

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