Lecture 05

- Continue…….. ( non-ideal reactors)

Concept of “pockets” and criteria for macro-mixing:

1) Contents of individual pockets are well mixed with themselves, but do not mix with
second pockets.
2) Pockets should represent chemical reaction conditions. For 𝐴 + 𝐵 → 𝐶, one cannot,
therefore, reduce the size of a pocket to one molecule; then the reaction will not occur.
Pockets should have a finite volume.

3) Pocket-contents should have same residense time, but different pockets may have

different residense times.

⇒ Macro- mixing → macro – fluids (segregated fluids) → macro - reactor

Ideal PFR is a good example of macro – reactors

𝑖𝑛𝑑𝑖𝑣𝑖𝑑𝑢𝑎𝑙 𝑝𝑜𝑐𝑘𝑒𝑡𝑠
(𝑠𝑎𝑡𝑖𝑠𝑓𝑦 𝑐𝑟𝑖𝑡𝑒𝑟𝑖𝑎)

 Fast fluidized bed reactor and liquid-liquid emulsion (LLE) membrane-based reactive
continuous separation processes are examples of industrial or practical reactors. In the
former rector, particles do not mix with each other and a spatially constant concentration
may be assumed within the micron-sized particles. In the second case, small globules (or
droplets) are dispersed and immiscible in a continuous phase without mixing.

⇒ Micro – mixing → micro – fluids (non – segregated fluids) → micro – reactor

1. Ideal CSTR is a good example of micro – reactors.

2. Ideal CSTR cannot be a macro – fluid reactor because residense times are
different for different fluid elements. However, for 𝐴 → 𝐵 (1st order
reaction), an ideal CSTR can be treated as a macro –reactor. In other words,
it makes no difference for first-order kinetics whether one assumes non-
segregated or segregated flow, or micro- or macromixing in an ideal CSTR.
Time of reaction alone and not degree of micromixing determines
conversion. This is expected because a first-order process depends upon
time of reaction of the reacting species and not on the interaction of
molecules (See Carberry).

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 Design of a non – ideal flow reactor (∈= 0)

1. Segregated flow model (a real/non – ideal reactor is modeled as a segregated or macro

reactor) V
2. CA0 𝑋𝐴 = ?

 Each pocket is a batch reactor (well-mixed) within themselves. 𝑋 = 𝑋(𝑡) is known a

priori for all types of reaction.
 Each pocket has a residense time (some pockets can exit early and some can exit late).

RTD
(We should be able to determine RTD of each pocket or volume – element of the reactor)

Definition (there are two types of RTDs):

volume size x (Δt) = fraction of fluid

J’(t) having residense time between
t & (t + Δt)

0
𝑡 𝑡 + Δ𝑡 time

Δ𝑡

𝐽′(𝑡)
defined in such a way that
J′ (t)δt ≡ fraction of fluid
having RT
t < RT < t + δt
(area under the curve = 1)

δ𝑡 ∞
∫0 𝐽′ (𝑡)𝑑𝑡 = 1
0 𝑡 𝑡 + δ𝑡 time
2
or,
𝐶𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑣𝑒 − 𝑏𝑎𝑠𝑖𝑠

1.0
J(t)
𝐼𝑡 𝑖𝑠 𝑐𝑙𝑒𝑎𝑟 𝑡ℎ𝑎𝑡
𝑡

𝐽(𝑡) = ∑ 𝐽′ (𝑡)Δ𝑡
Δ𝐽
𝑜𝑟 𝐽′ (𝑡) =
0 Δ𝑡 }
𝑡1 𝑡𝑖𝑚𝑒, 𝑡

1.0

𝑡
𝐽(𝑡) 𝐽(𝑡) = ∫ 𝐽′ (𝑡)𝑑𝑡
(0 < 𝑡 < 𝑡1 ) 0
𝑑𝐽(𝑡)
𝑜𝑟 𝐽′ (𝑡) =
𝑑𝑡 }

0 𝑡1 time, t

Thus, for a non – ideal reactor: 𝑙𝑖𝑡𝑡𝑙𝑒 𝑝𝑜𝑐𝑘𝑒𝑡𝑠 (𝑏𝑎𝑡𝑐ℎ) 𝑟𝑒𝑎𝑐𝑡𝑜𝑟𝑠

V

v, CAO 𝑋 =?

We require the following: (𝑁𝑜𝑡𝑒: 𝑡 ≡ 𝑅𝑇𝐷 𝑡𝑖𝑚𝑒

≠ 𝑟𝑒𝑎𝑙 𝑡𝑖𝑚𝑒)
1) 𝑋(𝑡) for a batch reactor
2) 𝑅𝑇𝐷 (𝐽 𝑜𝑟 𝐽′ ) of the reactor under consideration

∞
𝑋 = ∫0 𝑋(𝑡)𝐽′ (𝑡)𝑑𝑡 𝑜𝑟 ∑ 𝑋(𝑡)𝐽′ (𝑡)Δ𝑡 : Performance/design equation of a
segregated/macro reactor
(averaged over 𝑅𝑇)

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 Similarly, any intrinsic property, 𝑟 𝑎𝑡 𝑜𝑢𝑡𝑙𝑒𝑡
∞
= ∫0 𝑟(𝑡)𝐽′ (𝑡)𝑑𝑡

𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑙𝑢𝑖𝑑
𝑖𝑛𝑡𝑟𝑖𝑛𝑠𝑖𝑐 ℎ𝑎𝑣𝑖𝑛𝑔 𝑅𝑇 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑡 & 𝑡 + Δ𝑡
𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦

The average residence time always holds good as follows:

∞
(𝜏) 𝑜𝑟 𝑡 = 𝑅𝑇𝐷 = ∫ 𝑡 𝐽′(𝑡) 𝑑𝑡
0

Determining RTD experimentally (two methods)

(𝑡𝑟𝑎𝑐𝑒𝑟 𝑎𝑛𝑎𝑙𝑦𝑠𝑖𝑠: no reaction)
𝑀 (𝑑𝑜𝑠𝑒/𝑑𝑒𝑙 𝑓𝑛 )
output

𝒐𝒓, 𝐶𝑖𝑛 𝑠𝑡𝑒𝑝 − 𝑖𝑛𝑝𝑢𝑡 𝐴𝑟𝑒𝑎 ≡ 𝑀(𝑑𝑜𝑠𝑒)

time

output

𝑜𝑟 𝐶𝑖𝑛

time

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 Either of the two methods of injecting a tracer will work. It is a question of convenience in the
experiment. ′𝑄′, flow rate must be the same as that used in the real reactor; however, without
reaction (i.e., reaction is switched off !)

Method 1: Step Tracer Injection

Input Output
𝑣 (𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒)
𝐶𝑖𝑛
𝐶𝑖𝑛
V
𝐶𝑜𝑢𝑡 (𝑡)
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒
0 𝐶𝑜𝑢𝑡 (𝑡)
𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑙𝑢𝑖𝑑
ℎ𝑎𝑣𝑖𝑛𝑔 𝑅𝑇 ( 0, 𝑡)
𝑪𝒂𝒍𝒄𝒖𝒍𝒂𝒕𝒊𝒐𝒏𝒔:
0 𝑡 𝑡𝑖𝑚𝑒
By the very definition of 𝐽(𝑡):

𝐶𝑜𝑢𝑡 (𝑡)
𝐽(𝑡) = ⇒ J’(t) = d(J(t))/dt
𝐶𝑖𝑛

Now, turn on the reaction (no tracer!)

∞ ∞
𝑋 = ∫0 𝑋(𝑡)𝐽′ (𝑡)𝑑𝑡 = ∫0 𝑋(𝑡)𝑑(𝐽(𝑡))

𝐵𝑎𝑡𝑐ℎ 𝐵𝑎𝑡𝑐ℎ

Method 2: Pulse Injection

Input

𝑣 (𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒) 𝐶𝑒𝑥𝑖𝑡 (𝑡)

𝑀 = 𝑡𝑜𝑡𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 V
𝑡𝑟𝑎𝑐𝑒𝑟 (𝑑𝑜𝑠𝑒) 𝑣
′𝑑𝑒𝑙𝑡𝑎′
𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛

0 𝑡𝑖𝑚𝑒

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 𝐶𝑒𝑥𝑖𝑡 (𝑡)

Output

t (t + 𝜟t)

Species balance (use definition of 𝐽′(𝑡))

𝑀𝐽′ (𝑡)𝑑𝑡 = 𝐶𝑒𝑥𝑖𝑡 (𝑡)𝑣𝑑𝑡

𝐶𝑒𝑥𝑖𝑡 𝑣 𝐶𝑒𝑥𝑖𝑡 (𝑡) 𝐶𝑒𝑥𝑖𝑡 (𝑡) 𝐶𝑒𝑥𝑖𝑡 (𝑡)
𝐽′ (𝑡) = = 𝑀⁄ = ∞ = ∞ Type equation here.
𝑀 𝑣 ∫0 𝑣𝐶𝑒𝑥𝑖𝑡 (𝑡)𝑑𝑡⁄𝑣 ∫0 𝐶𝑒𝑥𝑖𝑡 𝑑𝑡

∞
J(t) = ∫0 𝐽′(𝑡)𝑑𝑡

Again, turn on the reaction (no tracer)

∞ ∞
𝑋 = ∫0 𝑋(𝑡)𝐽′ (𝑡)𝑑𝑡 = ∫0 𝑋(𝑡)𝑑(𝐽(𝑡))

Either of the two methods will work: by determining J(t), J’(t) can be determined, or vice-versa.
∞
Also, be careful in evaluating or calculating such integrals: ∫0 𝑋(𝑡)𝐽′(𝑡)𝑑𝑡, which contain two
different functions that may span over different time-domains, thus having different limits of
integrations. See the examples and questions in the examinations that follow in the next lectures.