Conversion in Non-ideal reactors

Zero adjustable • Segregation Model

Parameter
Model • Maximum Mixedness Model

One Adjustable • Tanks in series Model

Parameter
Model • Dispersion Model

Two adjustable
• Real Reactors are modeled as
Parameter
combination of ideal reactors
Model
Mixing-1
■ RTD tells us how long the various fluid elements have been in the reactor, but it does not tell us
anything about the exchange of matter between the fluid elements (i.e., the mixing)
■ Mixing of reacting species is one of the major factors controlling the behavior of chemical
reactors
■ First order reactions are independent of the concentration hence mixing is of no importance and
knowledge of the length of time each molecule spends in the reactor is all that is needed to predict
conversion. For first-order reactions conversion can be given as -
𝑑𝑋
= 𝑘(1 − 𝑋)
𝑑𝑡

■ For reactions other than first order, knowledge of the RTD is not sufficient to predict conversion.
For reactions other than first order, the degree of mixing of molecules must be known in addition
to how long each molecule spends in the reactor
■ The model needs to be developed which takes care of mixing which occur at 2 different levels –
– Micromixing
– Macromixing
Mixing-2
■ Macromixing produces a distribution of residence times without specifying how molecules of different
ages encounter one another in the reactor
■ Micromixing describes how molecules of different ages encounter one another in the reactor. There are
two extremes of micromixing:
1. all molecules of the same age group remain together as they travel through the reactor and are not
mixed with any other age until they exit the reactor (i.e., complete segregation);
2. molecules of different age groups are completely mixed at the molecular level as soon as they enter
the reactor (complete micromixing or Maximum Mixedness).
■ For a given state of macromixing (i.e., a given RTD), these two extremes of micromixing will give the
upper and lower limits on conversion in a non-ideal reactor.
■ For single reactions with orders greater than one the segregation model will predict the highest
conversion.
■ For reaction orders between zero and one, the maximum mixedness model will predict the highest
conversion
Mixing-3
■ Define a globule as a fluid particle containing millions of molecules all of the same age.
■ A fluid in which the globules of a given age do not mix with other globules is called a macrofluid. A
macrofluid could be visualized as non-coalescent globules where all the molecules in a given globule
have the same age.
■ A fluid in which molecules are not constrained to remain in the globule and are free to move everywhere
is called a microfluid
■ There are two extremes of mixing of the macrofluid globules—early mixing and late mixing. The
extremes of late and early mixing are referred to as complete segregation and maximum mixedness,
respectively.

Macrofluid Microfluid
Conversion in Non-ideal reactors
■ Zero adjustable Parameter Model
– Segregation Model (Late Mixing)
– Maximum Mixedness Model (Early Mixing)

■ Segregation Model - complete segregation, no interaction between elements

■ Consider a CSTR the flow through the reactor to consist of a continuous series of
globules/elements
■ These globules/spheres retain their identity; they do not
interchange material with other globules in the fluid during
their period of residence, i.e., they remain segregated.
■ These globules spend a different amount of time in the
reactor. So, lumping all the molecules that have exactly the
same residence time in the reactor into the same globule.
■ The principles of reactor performance in the presence of
completely segregated mixing were first described by
Danckwerts and Zwietering
Segregation Model
■ Consider fluid elements dropping as spheres
or drops into the reactor
■ There are three equally sized drops acting as
reactor,
■ Each drop or reactor will spend a different
amount of time in the reactor
■ The drops are spaced similar time apart (say
1 min) as they leave the pipe on the way to
the reactor.
■ The reaction does not begin until the drop
1 3 hits the reactor
3 2
■ At the exit all three drops merge (late mixing)
Segregation Model
■ Since the elements do not interact, it can be
visualized as a PFR, each exit stream
corresponds to a specific residence time in the
reactor.
3 2 1
■ The molecules removed near the entrance to the
reactor correspond to those molecules having
short residence times in the reactor.
■ Batches of molecules are removed from the
reactor at different locations along the reactor in
such a manner as to duplicate the RTD function
E(t).
■ The points at which the various groups or
batches of molecules are removed correspond to
the RTD function for the reactor.
■ Batch of molecules removed near entrance corresponds
to shorter residence time meaning bypass or channeling
Segregation Model…
▪ There is no molecular interchange between globules, each acts as batch reactor.
▪ The reaction time in any one of these tiny batch reactors is equal to the time that the particular drop
has spent in the reaction environment after exiting

1 3
3
2

Sum it for all globules for mean conversion

First Order Reactions

■ If we have the RTD, the reaction-rate law and parameters, then

for a segregated flow model we have sufficient information to
calculate the conversion.
■ Using the batch reactor equation for X(t) and the RTD, we can
find the mean conversion in the exit stream.

9
Segregation Model…

Reactor RTD Function Mean Conversion

𝐸 𝑡 = 𝛿(𝑡 − 𝜏)
PFR 𝑋ത = 1 − 𝑒 −𝑘𝜏 = 1 − 𝑒 −𝐷𝑎1
Dirac-Delta Function
1 𝑡 𝜏𝑘 𝐷𝑎1
CSTR 𝐸 𝑡 = 𝑒 − ൗ𝜏 𝑋ത = =
𝜏 1 + 𝜏𝑘 1 + 𝐷𝑎1
0, 𝑡 < 𝜏Τ2
Laminar FR 𝐸 𝑡 = ൞ 𝜏2
, 𝑡 ≥ 𝜏Τ2
2𝑡 3

■ Da is Damkohler number which relates the reaction time to residence time.

Problem1
■ Given that the Damkohler number values are – 0.1, 1, 2, 4, 10, find out the
conversion of first order reactions in PFR, CSTR and LFR using Segregation
Model.
Reactor RTD Function Mean Conversion
𝐸 𝑡 = 𝛿(𝑡 − 𝜏)
PFR 𝑋ത = 1 − 𝑒 −𝑘𝜏 = 1 − 𝑒 −𝐷𝑎1
Dirac-Delta Function
1 𝑡 𝜏𝑘 𝐷𝑎1
CSTR 𝐸 𝑡 = 𝑒 − ൗ𝜏 𝑋ത = =
𝜏 1 + 𝜏𝑘 1 + 𝐷𝑎1
0, 𝑡 < 𝜏Τ2
Laminar FR 𝐸 𝑡 = ൞ 𝜏2
, 𝑡 ≥ 𝜏Τ2
2𝑡 3

11
Da XPFR XCSTR XLFR
0.1
1
2
4
10

12
Maximum Mixedness Model
■ The maximum mixedness occur when
fluid is completely mixed radially (not
longitudinally) as soon as it enters the
reactor.
■ The entering fluid is fed into the reactor
through the side entrances in such a
manner that the RTD of the plug-flow
reactor with side entrances is identical to
the RTD of the real reactor.
■ Let t be the time it takes for the fluid to
move from a particular point to the end of
the reactor. In other words, t is the life
expectancy of the fluid in the reactor at
that point
Maximum Mixedness Model
■ Moving down the reactor from left to right, the life expectancy, t, decreases
and becomes zero at the exit. At the left end of the reactor, t approaches
infinity or the maximum residence time if it is other than infinite
[v0E(t)t]CA0
t→∞ t=0

t+t t

t+t t
14
Maximum Mixedness Model
■ The volumetric flow at the outlet can be given as

𝑣𝑡 = 𝑣𝑡+∆𝑡 + 𝑣0 𝐸(𝑡)∆𝑡

𝑣𝑡+∆𝑡 − 𝑣𝑡 = −𝑣0 𝐸(𝑡)∆𝑡

𝑣𝑡+∆𝑡 − 𝑣𝑡
= −𝑣0 𝐸(𝑡)
∆𝑡
𝑑𝑣𝑡
t → 0 = −𝑣0 𝐸(𝑡)
𝑑𝑡
∞
𝑣𝑡 = 𝑣0 න 𝐸 𝑡 𝑑𝑡 = 𝑣0 1 − 𝐹(𝑡)
𝑡
 Maximum Mixedness Model
■ Mole Balance - 𝐼𝑛 𝑎𝑡 𝐼𝑛 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑂𝑢𝑡 𝑎𝑡 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑏𝑦
+ − + =0
𝑡 + ∆𝑡 𝑆𝑖𝑑𝑒𝑠 𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑣𝐶𝐴 ቚ + 𝑣0 𝐶𝐴0 𝐸 𝑡 ∆𝑡 − 𝑣𝐶𝐴 ቚ + 𝑟𝐴 ∆𝑉 = 0

𝑡+∆𝑡 𝑡

∆𝑉 = 𝑣0 1 − 𝐹(𝑡) ∆𝑡

𝑣𝐶𝐴 ቚ + 𝑣0 𝐶𝐴0 𝐸 𝑡 ∆𝑡 − 𝑣𝐶𝐴 ቚ + 𝑟𝐴 𝑣0 1 − 𝐹(𝑡) ∆𝑡 = 0

𝑡+∆𝑡 𝑡

Similarly Substitute for v

𝑣0 1 − 𝐹(𝑡) 𝐶𝐴 ቚ + 𝑣0 𝐶𝐴0 𝐸 𝑡 ∆𝑡 − 𝑣0 1 − 𝐹(𝑡) 𝐶𝐴 ቚ + 𝑟𝐴 𝑣0 1 − 𝐹(𝑡) ∆𝑡 = 0

𝑡+∆𝑡 𝑡
 Maximum Mixedness Model
𝑣0 1 − 𝐹(𝑡) 𝐶𝐴 ቚ + 𝑣0 𝐶𝐴0 𝐸 𝑡 ∆𝑡 − 𝑣0 1 − 𝐹(𝑡) 𝐶𝐴 ቚ + 𝑟𝐴 𝑣0 1 − 𝐹(𝑡) ∆𝑡 = 0
𝑡+∆𝑡 𝑡

Divide by𝑣0 ∆𝑡 And take limit

∆𝑡 → 0

𝑑 1 − 𝐹 𝑡 𝐶𝐴 (𝑡)
𝐸 𝑡 𝐶𝐴0 + + 𝑟𝐴 1 − 𝐹(𝑡) = 0
𝑑𝑡

1 − 𝐹 𝑡 𝑑 𝐶𝐴 (𝑡) 𝐶𝐴 (𝑡)𝑑 1 − 𝐹 𝑡
𝐸 𝑡 𝐶𝐴0 + + + 𝑟𝐴 1 − 𝐹(𝑡) = 0
𝑑𝑡 𝑑𝑡

1 − 𝐹 𝑡 𝑑 𝐶𝐴 (𝑡)
𝐸 𝑡 𝐶𝐴0 + − 𝐸(𝑡)𝐶𝐴 (𝑡) + 𝑟𝐴 1 − 𝐹(𝑡) = 0
𝑑𝑡
Maximum Mixedness Model
1 − 𝐹 𝑡 𝑑 𝐶𝐴 (𝑡)
𝐸 𝑡 𝐶𝐴0 + − 𝐸(𝑡)𝐶𝐴 (𝑡) + 𝑟𝐴 1 − 𝐹(𝑡) = 0
𝑑𝑡

Rearrange and divide by [1 - F(t)]

𝑑𝐶𝐴 𝐸(𝑡)
= −𝑟𝐴 + 𝐶𝐴 − 𝐶𝐴0
𝑑𝑡 1 − 𝐹(𝑡)
CA = CA0(1-X)
𝑑𝑋 𝑟𝐴 𝐸(𝑡)
= + 𝑋
𝑑𝑡 𝐶𝐴0 1 − 𝐹(𝑡)

𝑑𝑋 𝑟𝐴 𝐸(𝑡)
= + 𝑋
𝑑𝑡 𝐶𝐴0 𝐼(𝑡)
Comparison of Model prediction
■ If Rate is represented by power law model

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Life Expectancy

■ Fluid elements lose their identity by the action of molecular diffusion, the
Einstein random walk analysis estimates this time
■ Ordinary fluids behave as microfluids except for very viscous materials and
for systems in which very fast reactions are taking place.
■ The concept of micro- and macro-fluids is of particular importance in
heterogeneous systems because one of the two phases of such systems
usually approximates a macro-fluid

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Multiple Components
■ When multiple reactions occur in reacting systems, it is best to work in
concentrations, moles, or molar flow rates rather than conversion

Segregation Model

Maximum Mixedness

21
Problem2
■ The liquid-phase reaction 𝐴 + 𝐵 → 𝐶 + 𝐷 is carried out isothermally in an
inert solution of N with 𝑀𝑁 = 28.9. The reaction follows an elementary rate
law. The feed is equal molar in A and B with CA0 = 0.75 mol/dm3, a
volumetric flow rate of 0.1 dm3/s, and a reactor volume of 100 dm3. Calculate
the conversion in (a) an ideal PFR, (b) a BR, and (c) an LFR.
■ Additional information: 𝑘 = 4.93 × 10−3 𝑑𝑚3 /𝑚𝑜𝑙. 𝑠 at 50°C with E = 13.3 kcal/mol, Δ𝐻𝑅𝑋 =
𝐹
– 10.5 𝑘𝑐𝑎𝑙/𝑚𝑜𝑙 Heat of mixing for 𝑀𝑁 = 𝐹 𝑁 , Δ𝐻𝑚𝑖𝑥 = – 0.44 𝑘𝑐𝑎𝑙/𝑚𝑜𝑙
𝐴0

22