Topic 3 – Reaction Kinetics and Reactor

Theory

Chapter 2
Spring 2012
Kazi Parvez Fattah
 Reaction Rate

 A mathematical expression describing the rate at which the

mass or volume of some material A is changing with time t
is:

 Reaction rate can be a function of (one or a combination of

the following)
 Temperature

 Pressure

 Reacting components or products

 pH

 Other environmental factors

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 Reaction Order

 The reaction rate is given as

r = ±kCn
Where, k = reaction rate constant (in s-1 or d-1)
C = concentration of the substance
n = exponent of reaction order
 The ± sign in the equation indicates that the

substance or chemical species is either consumed

(decreasing) or being formed (increasing)

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 Types of Reaction Rates

Zero order (n=0)

Inorganic sleeve fouling for UV
𝑑𝐶
reactors
= ±𝑘; 𝐶𝑡 = 𝐶0 ± 𝑘𝑡
𝑑𝑡
Reaction not a factor of the
chemical/substance

First order (n=1) 𝑑𝐶

BOD decay = ±𝑘𝐶; 𝐶𝑡 = 𝐶0 𝑒 ±𝑘𝑡
Radioactive decay 𝑑𝑡

Second order (n=2) 𝑑𝐶 2

1 1
Ozone generation
= ±𝑘𝐶 ; = ± 𝑘𝑡
𝑑𝑡 𝐶𝑡 𝐶0
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 Zero Order Reaction - Example

 Typical Figure  Example

 Nitrogen gas strips oxygen
from water before an
aeration test is performed.
Initial oxygen concentration
was 9.5 mg/L and a zero
order reaction rate coefficient
was 0.075/s. How long until
the oxygen concentration
reaches below 0.5 mg/L?

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 First Order Reaction - Example

 Typical Figure  Example

 A wastewater has an
initial BOD of 220
mg/L. BOD is decayed
with a first order rate
constant of 0.011/hr.
 How long will it take to
reduce BOD to 30 mg/L?
 What will the BOD be
after 5 days?

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 Second Order Reaction - Example

 Typical Figure  Example

 Ozone generation has
second order kinetics. If
the ozone concentration
in a container is 0.0015
g/m3 before a generator
is turned on and 0.002
g/m3 after 1 minute,
what is the ozone
concentration after 3
minutes?
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 Steady State

 When a system has operated in such a way that the

following is true:
Rate of input = Rate of output
 Therefore, the rate of accumulation is zero
(i.e. dM/dt = 0)
 Steady state does not imply equilibrium

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 Reactor
 Reactions are often required as part
of an engineered system
 Reactors are tanks in which
physical, chemical and biochemical
reactions occur
 Key aspects of reactors
 Flow characteristics

 Mixing conditions

 Control volumes

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 Determination of Flow Characteristics

 A tracer used in a reactor

to understand the flow
dynamics and mixing
behavior
 Conservative, that is,
does not react
 Non-conservative, that is,
it reacts
 For monitoring practice
conservative tracer is
used
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 Types of Reactor

 Batch Reactor

 Completely Mixed Flow Reactor (CMFR)

 Plug Flow Reactor (PFR)

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 Batch Reactor

 They are of the fill-and- Material added

draw type to the reactor

 Materials added are mixed

for sufficient time to react
and then drained.
Mixing and
 Composition within the reacting
tank changes with time as
reaction proceeds
 A batch reaction is Reactor is
unsteady drained

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 Completely Mixed Flow Reactor (CMFR)

 Also known as
continuous-flow stirred
tank reactor (CSTR)
 Contents in the tank are
ideally uniform
throughout
 Composition of the
effluent is the same as
the composition in the dM d(in) d(out)
tank = − − kCV
dt dt dt
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 Plug Flow Reactor (PFR)

 Fluid particles pass

through the tank in
sequence
 Assumed that no
mixing occurs in the
lateral direction
(direction of flow)

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 Batch Reactor

 Rate   Rate  Rate  Rate   Rate 

 Accumulated   in   out    produced   consumed 
         

No inflow and no outflow in a typical batch reactor

 Rate   Rate   Rate 
 Accumulated    produced   consumed 
     
dC
V  rV
dt
Typical reaction rate equations can be used to compute
• Retention time
• Effluent concentration
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 Detention (or Retention) Time

 It is the time that a fluid particle remains in the

reactor
 It is also known as hydraulic detention time (for
liquid systems), retention time or detention time
 The detention time in real tanks is generally less
than the theoretical detention time
 The time is calculated by the following equation
Volume(V )

Flow rate(Q )

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 Retention Time for Decay Reactions

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 Example
First order
 An industry wants to use a long
reaction
drainage ditch that can be C
assumed to act as a plug flow ln   kt
C0
reactor in removing odor from
their waste. The odor reduction 0.1C0
ln   kt
behaves as a first-order reaction, C0
with the rate constant k = 0.35 ln( 0.1)  (0.35)t
days-1. The flow rate is 1600
L/day. How long must the ditch t  6.57 days
be if the velocity of the flow is length of the ditch
0.5 m/sec and 90% odor
m sec
reduction is desired?  0.5  6.57 days  86400
sec day
 2.84 105 m
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 Reactor Analysis

 The selection of the reactor depend on the desired

behavior or model representation
 Important to understand the behavior of the reactor
system’s response to sudden increase or decrease
when a certain material is added to the reactor
 What is the response (effluent concentration) to a
step or pulse (or spike) change in the influent
concentration

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 Tracer Studies - Step or Pulse Increase

Step
Step decrease
increase

Pulse or spike
increase

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 Tracer Studies – Batch Reactor

Reactor response to a
step or pulse increase
in concentration of a
conservative
substance

Reactor response for (a) decay of a non-conservative substance

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 Tracer Studies – Batch Reactor contd.

 Inexpensive and easy to build

 Used in cases where the flow rate is less than
150 m3/d
 Easy to operate
 e.g. to check the wastewater for regulatory
compliance before discharge

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 Tracer Studies – Completely Mixed Flow
Reactors (CMFR)
General equation for a 𝑡 𝑡
𝐶𝑡 = 𝐶0 exp − + 𝐶1 1 − exp −
nonreactive contaminant 𝜃 𝜃

For flushing of a nonreactive 𝑡

𝐶𝑡 = 𝐶0 exp −
contaminant 𝜃

For flushing of a reactive 𝑡

𝐶𝑜𝑢𝑡 = 𝐶0 exp − + 𝑘 𝑡
contaminant 𝜃

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 Tracer Studies – Completely Mixed Flow
Reactors (CMFR) contd.

 Used for chemical mixing

 Flow rate is usually greater than 150 m3/d
 e.g. a) application of equalization tank to adjust pH
b) chemical precipitation to remove metals
 Ponds, lakes, streams and air mixing can be
modeled as a CMFR

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 Reactive Conservative
substance substance Step
response response increase

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Tracer Studies – Plug Flow Reactors (PFR)

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 Example Problem

 1) CMFR - Adapted from book example 2.9

 2) PFR
 A continuous PFR is to be designed to treat an influent
stream containing 250 mg/L of methanol at a flow rate of
300 L/min. a second order removal reaction is occurring.
The rate constant (k) was determined in the laboratory to
be 0.0090 L/mg.h.
 Determine (a) the detention time in hours and (b) the
volume of the reactor needed, in m3, to achieve 90%
removal of the methanol.

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 Review of Material Balance, Reaction
Kinetics and Reactors

 Material balance
 Mass balance
 Examples and problems
 Mass balance with transformation
 Reaction rates
 Zero, First and Second order
 Examples and problems
 Different types of reactors
 Batch, CMFR, Plug
 Examples and problems
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