Environmental engineering

CE 475
2- Types of Reactors

PREPARED BY DR. A. H. BIRIMA 1

 Reactions
A general mathematical expression describing a rate at which the mass or
volume of some material A is changing with time t is

Where r = reaction rate

Zero-order reactions are defined as those in which r is a constant so that

…………………….(2.1)

The unit for the reaction rate constant in zero-order reactions is mass/time,
such as kg/s.
First-order reactions are defined as those wherein the change of the component
A is proportional to the quantity of the component itself so that
and …………………….(2.2)

PREPARED BY DR. A. H. BIRIMA 2

Note that the unit of the reaction rate constant in the first order
reaction is time -1, such as d-1.

Second-order reactions are ones wherein the change is proportional to the

square of the component, or

and …………………….(2.3)

Note that in second-order reactions, the reaction rate constant has the
unit of (time x mass) -1 .

In environmental engineering applications, Equations 2.1, 2.2, and 2.3 are

usually written in terms of the concentration, so for zero-order reactions,

…………………….(2.4)

for first-order reactions,

…………………….(2.5)

PREPARED BY DR. A. H. BIRIMA 3

and for second-order reactions,
…………………….(2.6)

Defining A = Ao at time t = to and integrating:

…………………….(2.7)

PREPARED BY DR. A. H. BIRIMA 4

when the constituent of interest is a concentration, C, which it very often, the
rate constant in a zero-order reaction has units of mass /volume/time, or
mg/L/s if C is in mg/L and t in seconds.

The integrated form of the zero-order reaction when the concentration is

increasing is

…………………….(2.8)

and if the concentration n is decreasing, the equation is

…………………….(2.9)

Plot of o zero-order reaction in which the

concentration is decreasing.

PREPARED BY DR. A. H. BIRIMA 5

Example 2.1

An anteater that all he has to do is finds an anthill and starts

eating. The ants are so plentiful that all he has to do is flick out his
tongue and gobble them up at a rate of 200 per minute. How long
will it take to have a concentration of 1000 ants per anteater in
the anteater?

PREPARED BY DR. A. H. BIRIMA 6

First Order Reactions

The first-order reaction of a material being consumed, or destroyed, can be

expressed as

…………………….(2.10)

PREPARED BY DR. A. H. BIRIMA 7

Example 2.2

An owl eats frogs as a delicacy, and his intake of frogs is

directly dependent on how many frogs are available. There
are 200 frogs in the pond, and the rate constant is 0.1 day-l.
How many frogs are left at the end of 10 days?

PREPARED BY DR. A. H. BIRIMA 8

 Second Order and Noninteger Order Reactions
The second-order reaction is defined as

Which plots as a straight line as shown in

Figure below

PREPARED BY DR. A. H. BIRIMA 9

 Second Order and Noninteger Order Reactions

The noninteger-order (any number reaction is defined as

where n is any number. Integrated, it is

These reactions are not as common in environmental engineering.

PREPARED BY DR. A. H. BIRIMA 10

Types of Reactors
What is the reactor?
 It is the tank in which physical, chemical and biological
reactions occur.
 These reactors are classified based on their flow
characteristics and their mixing conditions.

1. Batch Reactor
2. Flow reactor

PREPARED BY DR. A. H. BIRIMA 11

  Types of Reactors
Batch reactor
 Batch reactor are of the fill and draw type: water and chemical are
added to the tank , mixed for sufficient time to allow the reaction
occur and then drained.
 Although the reactor is well mixed and the contents are uniform at
any instant in time, the composition within the tank changes with
time as the reaction proceeds.
 A batch reaction is unsteady. Because there is no flow into or out of
a batch reactor.

Figure 1 Batch reactor operation. (a) Materials added to the reactor. (b)
Mixing and reaction. (c) Reactor is drained. (source: intro. to EE- Davis)
Note: There is no influent or effluent during the reaction.

PREPARED BY DR. A. H. BIRIMA

  Types of Reactors
 Batch reactor
For batch reactor
𝑑 (𝑖𝑛) 𝑑 (𝑜𝑢𝑡) 𝑑𝑀
𝑑𝑡
= 𝑑𝑡
=0 But, = −𝑘𝐶∀
𝑑𝑡

𝑑𝑀 𝑑𝐶
Also, = ∀ So, for the first – order reaction in batch reactor
𝑑𝑡 𝑑𝑡

𝑑𝐶
= −𝑘𝐶 …………………..(2.11)
𝑑𝑡

Where C = concentration of substance

k = reaction rate constant, s-1 or d-1
∀ = volume of fluid in the reactor, m3

PREPARED BY DR. A. H. BIRIMA 13

 Flow reactors
 Flow reactor have a continuous type of operation: material
flows into, through and out of the reactor at all times.

 Flow reactors are classified by mixing condition into:

1. Completely mixed flow reactor (CMFR) also called continuous-

flow stirred tank reactor (CSTR).
2. Plug-flow reactor

PREPARED BY DR. A. H. BIRIMA 14

 Flow reactors
 Completely mixed flow reactor (CMFR)
The contents of CMFR ideally are uniform throughout the tank.
The composition of the effluent is the same as the composition in
the tank.
If the mass input rate into the tank remains constant, the
composition of the effluent remains constant.

Figure 2 Schematic diagram of (a) continuous-flow stirred tank reactor (CSTR) and (b)
the common diagram. The propeller indicates that the reactor is completely mixed.
(source: intro. To EE, Davis)

PREPARED BY DR. A. H. BIRIMA 15

 Flow reactors
 Plug flow reactor
• In plug flow reactor (PFR), fluid particles pass the tank
in sequence. Those that enter first leave first.
• In the ideal case, it is assumed that no mixing occur in
the lateral direction.
• Although composition varies along the length of tank,
as long as the flow conditions remain steady, the
composition of the effluent remains constant.

Figure 3 Schematic diagram of a plug-flow reactor (PFR). Note; t3> t2 > t1.

PREPARED BY DR. A. H. BIRIMA 16

 Flow reactors

For the time – dependent reaction, the average time

that the fluid particle remains in the reactor,
(which called detention time or retention time or, for fluid
systems, Hydraulic detention time or hydraulic retention
time) is
Defined as

∀
𝑡0 = …………………….(2.12)
𝑄

Where 𝑡0 = theoretical detention time, s

∀ = volume of the fluid in the reactor, m3
𝑄 = flow rate into the reactor, m3/s

PREPARED BY DR. A. H. BIRIMA 17

 Reactor analysis
The selection of a reactor either as a treatment method or as a model
for a natural process depends on the behavior desired or recognized.
We will examine the behavior of batch, CSTR, and PFR reactors in
several situations.
Situations of particular interest are the response of the reactor to a
sudden increase (Figure 4 a) or decrease (Figure 4 b) in the steady-
state influent concentration for conservative and nonconservative
species (commonly called a step increase or decrease) and the
response to pulse or spike change in influent concentration (Figure 4c).
We will present the plots of the effluent concentration for each of the
reactor types for a variety of conditions to show the response to these
influent changes.

PREPARED BY DR. A. H. BIRIMA 18

 Reactor analysis

Figure 4 Example influent graphs of (a) step increase in influent concentration, (b) step
decrease in influent concentration, and (c) a pulse or spike increase in influent
concentration. Note: The size of the change is for illustration purposes only.

PREPARED BY DR. A. H. BIRIMA 19

  Reactor analysis
o Batch reactor
Laboratory experiments are often conducted in batch reactors
because they are inexpensive and easy to build.
Industries that generate small quantities of wastewater (less than 150
m3/d) use batch reactors because they are easy to operate and
provide an opportunity to check the wastewater for regulatory
compliance before discharging it.
In batch reactor, for nonconservative substance that decay as first order
reaction, the concentration of the substance at any time can be
obtained as,
𝐶𝑡
= 𝑒 −𝑘𝑡 …………………….(2.13)
𝐶0

Where 𝐶𝑡 = is the concentration of the substance at time t, mg/l

𝐶0 = the initial concentration of the substance, mg/l
PREPARED BY DR. A. H. BIRIMA 20
 Reactor analysis
o Batch reactor
Because there is no influent to or effluent from a batch reactor, the
introduction of a conservative substance into the reactor either as a step
increase or a pulse results in an instantaneous increase in concentration of
the conservative substance in the reactor (Fig. 5)

Figure 5 Batch reactor response to a step or pulse increase in concentration of a

conservative substance. C. = mass of conservative substance/volume of reactor.

The final concentration plot is shown in Figure 6 a. For the formation reaction,
where the sign in Equation 3 is positive, the concentration plot is shown in
Figure 6 b.

Fig. 6 Batch reactor response for (a) decay of a nonconseilative

substance and (b) for a formation reaction.

PREPARED BY DR. A. H. BIRIMA 21

Example 2.3

A contaminated soil is to be excavated and treated in a

completely mixed aerated lagoon at a Superfund site. To
determine the time it will take to treat the contaminated
soil, a laboratory completely mixed batch reactor is used to
gather the following data. Assuming a first-order reaction,
estimate the rate constant, k, and determine the time to
achieve 99 percent reduction in the original concentration.
Time (d) Waste concentration (mg/l)
1 280
16 132

PREPARED BY DR. A. H. BIRIMA 22

 Reactor analysis
When water flow rates are greater than 150 m3/d, a CSTR may be
selected for chemical mixing.
Examples of this application include equalization reactors to adjust
the pH, precipitation reactors to remove metals, and mixing tanks
(called rapid mix or flash mix tanks) for water treatment.
Some natural systems such as a lake or the mixing of two streams or
the air in a room or over a city may be modeled as a CSTR as a
approximation of the real mixing that is taking place.
For a step increase in a conservative substance entering a CSTR, the
initial level of the conservative substance in the reactor is C0 prior to t
= 0. At t = 0, the influent concentration (Cin ) is instantaneously
increases to C1 and remains at this concentration (Fig. 7).

PREPARED BY DR. A. H. BIRIMA 23

The mass balance for step increase is

…………..(2.14)

Figure 7 shows the effluent concentration plot.

Fig. 7 Response of a CSTR to (a) a step increase in

the influent concentration of a conservative
substance from concentration C0 to a new
concentration C1 . (b) Effluent concentration

PREPARED BY DR. A. H. BIRIMA 24

For flushing of a nonreactive contaminant from a CSTR by a
contaminant-free fluid, the mass balance is obtained by
……………(2.15)
Where𝑡0 = ∀Τ𝑄

Figure 8 shows the effluent concentration plot.

Flushing of CSTR resulting from (a) a step decrease in influent

concentration of a conservative substance from C0 to 0. (b) Effluent
concentration.

PREPARED BY DR. A. H. BIRIMA 25

 Example 2.4
Before entering an underground utility vault to do repairs,
a work crew analyzed the gas in the vault and found that it
contained}g mg/m3 of hydrogen sulfide. Because the
allowable exposure level is 14 mg/m3, the work crew
began ventilating the vault with a blower. If the volume of
the vault is 160 m3 and the flow rate of contaminant-free
air is 10 m3/min, how long will it take to lower the
hydrogen sulfide level to a level that will allow the work
crew to enter? Assume the manhole behaves as a CSTR
and that hydrogen sulfide is nonreactive in the time
period considered.

PREPARED BY DR. A. H. BIRIMA 26