Department of Chemical Engineering

College of Engineering
Xavier University – Ateneo de Cagayan

Final Design Project

Reactors with Multiple Reactions

In partial fulfillment to the requirements of the course

CHE 37
Chemical Reaction Engineering

by

Ocho, Joli Andrea

Padel, Vince Nixau
Polito, Elijah Ramm

BS ChE – 3

to

Engr. Jayhiel S. Malila, MS

Course Instructor

November 24, 2022

CHE 37 – Chemical Reaction Engineering Page 1

 SECTION I
From a realistic perspective, what occurs in a chemical reactor does not have only
one reaction, most of the time multiple reactions occur. Although some of these reactions
are desired, some are undesirable reactions. The reduction of undesirable reactions that
occur with the desired reaction contributes to a chemical plant's economic success. A
single reaction differs from multiple reactions in such a way that a single reaction requires
only one rate expression to describe its kinetic behavior, whereas multiple reactions
require multiple rate expressions. The four basic types of multiple reactions are series,
parallel, independent, and complex reactions. Series reactions is also called consecutive
reactions

CHE 37 – Chemical Reaction Engineering Page 2

 SECTION II
A. Establishing the General Schematic Diagram and Mathematical Equations
Before we begin solving the problem, we will first identify the nomenclature of the given
problem. A is the K-benzoate, R is the lumped intermediates, and K-terephthalate is represented
by S. The k1 and E1 are the rate constant and the activation energy in the reaction of A to R in the
series reaction. The k2 and E2 are the rate constant and activation energy in the reaction of R to
S in the series reaction. Lastly, k3 and the E3 are the rate constant and activation energy in the
autocatalytic reaction. The Ci is the concentration of the i constituent. The
P, R, T, and t are the Pressure, Universal Gas Constant, Temperature,
and time. To start with solving the problem, we will establish the
foundation of all CRE’s problems, the General Mole Balance Equation.
𝑉 𝑑𝑁𝑖
𝐹𝑖𝑂 − 𝐹𝑖 + ∫0 𝑟𝑖 𝑑𝑉 = 𝑑𝑡
[equation 1]

For the batch reactor, which is the reactor in the first two conditions, there
is no inflow or outflow. From the General Mole Balance Equation, the
equation for the batch reactor in terms of the moles is as follows:
𝑑𝑁𝑖
= 𝑟𝑖 𝑉 [equation 2]
Figure 1. Batch Reactor 𝑑𝑡
𝑁𝑖
The equation 2 can be expressed in terms of the concentration as 𝐶i = 𝑉
.
𝑑𝑁𝑖
𝑑𝑡
= 𝑟𝑖 𝑉

𝑑(𝑁𝑖 )
= 𝑟𝑖
𝑑𝑡𝑉
𝑑𝐶𝑖
𝑑𝑡
= 𝑟𝑖 𝑉 [equation 3]

For the CSTR, there is no accumulation, and it is perfectly mixed. The equation for the continuous
stirred tank reactor is as follows:
𝐹𝑖 −𝐹𝑖𝑂
𝑉
= 𝑟𝑖 [equation 4]

In terms of concentration 𝐹𝑖 = 𝐶𝑖 ∅𝑣 ,
𝐶𝑖 ∅𝑣 − 𝐶𝐴𝑂 ∅𝑣𝑜
= 𝑟𝐴
𝑉
For liquid phase, the volumetric flow rate is constant.
Figure 2. Continuous Stirring Tank Reactor
𝐶𝐴 ∅𝑣 − 𝐶𝐴𝑂 ∅𝑣
= 𝑟𝐴
𝑉
∅𝑣 (𝐶𝐴 − 𝐶𝐴𝑂 )
= 𝑟𝐴
𝑉
∅𝑣 (𝐶𝐴 − 𝐶𝐴𝑂 )
=𝑉
𝑟𝐴

CHE 37 – Chemical Reaction Engineering Page 3

 (𝐶𝐴 − 𝐶𝐴𝑂 ) 𝑉
=
𝑟𝐴 ∅𝑣
(𝐶𝐴 −𝐶𝐴𝑂 )
𝑟𝐴
= 𝜏 [equation 5]

𝑉
𝜏 = ∅ is termed space time.
𝑣

For the rate of reactions, multiple reactions can be accounted for a one species. In the reaction
of K-benzoate (A), there are no multiple reactions. The rate of reaction is as follows:
−𝑟𝐴 = 𝑘1 𝐶𝐴 [equation 6]
The reaction rate for the lumped intermediates accounts the reaction happened in the series
reaction and the autocatalytic reaction.
𝑟𝑅 = 𝑟𝑅 𝑠𝑒𝑟𝑖𝑒𝑠 1 + 𝑟𝑅 𝑠𝑒𝑟𝑖𝑒𝑠 2 + 𝑟𝑅𝑎𝑢𝑡𝑜𝑐𝑎𝑡𝑎𝑙𝑦𝑡𝑖𝑐

𝑟𝑅 = 𝑘1 𝐶𝑅 − 𝑘2 𝐶𝑅 − 𝑘3 𝐶𝑅 𝐶𝑆 [equation 7]
For the reaction rate of the K-terephthalate,
𝑟𝑆 = 𝑟𝑆𝑠𝑒𝑟𝑖𝑒𝑠 + 𝑟𝑆 𝑎𝑢𝑡𝑜𝑐𝑎𝑡𝑎𝑙𝑦𝑡𝑖𝑐

𝑟𝑆 = 𝑘2 𝐶𝑅 − 𝑘3 𝐶𝑅 𝐶𝑆 [equation 8]
As the rate constant is a function of temperature, changing the temperature affects the value of
the rate constant. To obtain the new rate constant when the temperature changes, we use:
𝐸
−
𝑘(𝑇𝑜 ) = 𝐴𝑒 𝑅𝑇𝑜

This is for the initial temperature. For the new temperature:

𝐸
𝑘(𝑇) = 𝐴𝑒 −𝑅𝑇
Taking the ratio:
𝐸
𝑘(𝑇) 𝐴𝑒 −𝑅𝑇
= 𝐸
𝑘(𝑇𝑜 ) −
𝐴𝑒 𝑅𝑇𝑜
𝐸
𝑘(𝑇) 𝑒 −𝑅𝑇
= 𝐸
𝑘(𝑇𝑜 ) −
𝑒 𝑅𝑇𝑜
𝑘(𝑇) 𝐸 1 1
− ( − )
= 𝑒 𝑅 𝑇 𝑇𝑜
𝑘(𝑇𝑜 )

1 1
Taking the -1 in (𝑇 − 𝑇 )
𝑜

CHE 37 – Chemical Reaction Engineering Page 4

 𝑘(𝑇) 𝐸 1 1
( − )
= 𝑒 𝑅 𝑇𝑜 𝑇
𝑘(𝑇𝑜 )
𝐸 1 1
( − )
𝑘(𝑇) = 𝑘(𝑇𝑜 )𝑒 𝑅 𝑇𝑜 𝑇 [equation 9]

B. Derivation of the Mathematical Equation

For this derivation let us use the Chemical Reaction Engineering Algorithm.

Schematic
Let us start with our General Mole Balance Equation
GMBE:
𝑉 𝑑𝑁𝐴
𝐹𝐴0 − 𝐹𝐴 + ∫0 𝑟𝐴 𝑑𝑉 = [equation 1]
𝑑𝑡

Now let us derive for a batch reactor

We will make the following assumptions

Assumptions:
1) No in and out flow rate(𝐹𝐴0 = 𝐹𝐴 = 0), therefore

𝑉 𝑉
𝑑𝑁𝐴 𝑑𝑁𝐴
𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑑𝑉 = → ∫ 𝑟𝐴 𝑑𝑉 =
0 𝑑𝑡 0 𝑑𝑡

𝑉
2) Perfectly mixed (∫0 𝑟𝐴 𝑑𝑉 = 𝑟𝐴 𝑉 ), therefore

𝑉
𝑑𝑁𝐴 𝑑𝑁𝐴
∫ 𝑟𝐴 𝑑𝑉 = → 𝑟𝐴 𝑉 =
0 𝑑𝑡 𝑑𝑡
𝑉
𝑑𝑁𝐴 𝑑𝑁𝐴
∫ 𝑟𝐴 𝑑𝑉 = → 𝑟𝐴 𝑑𝑉 =
0 𝑑𝑡 𝑑𝑡
Performance equation of Batch reactor

𝑑𝑁𝐴
= 𝑟𝐴 𝑉 [Equation 2]
𝑑𝑡

Now let us derive for a Continuously stirred tank

Assumptions:
𝑑𝑁𝐴
1) Steady State( = 0)
𝑑𝑡

𝑉 𝑉
𝑑𝑁𝐴
𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑑𝑉 = → 𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑑𝑉 = 0
0 𝑑𝑡 0

CHE 37 – Chemical Reaction Engineering Page 5

 𝑉
2) Perfectly mixed(∫0 𝑟𝐴 𝑑𝑉 = 𝑟𝐴 𝑉)

𝑉
𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑑𝑉 = 0 → 𝐹𝐴0 − 𝐹𝐴 + 𝑟𝐴 𝑉 = 0
0

Isolate V

Algebraic form of performance equation

𝐹 −𝐹
𝑉 = 𝐴 𝑟 𝐴0[equation 4],
𝐴

After acquiring the performance equations using the General Mole Balance
Equation (GMBE). Let us get the Stoichiometry:

Stoichiometry:
We will be expressing our performance equations in terms of concentration
Batch reactor
𝑑𝑁𝐴
= 𝑟𝐴 𝑉 [Equation 2]
𝑑𝑡
𝑁𝐴
Recall: 𝐶𝐴 = 𝑉

𝑑𝑁𝐴
= 𝑟𝐴 𝑉
𝑑𝑡

𝑑(𝑁𝐴 )
= 𝑟𝐴
𝑑𝑡(𝑉)

𝑑𝐶𝐴
= 𝑟𝐴 [Equation 3]
𝑑𝑡

CSTR
𝐹𝐴 −𝐹𝐴0
𝑉= [Equation 4]
𝑟𝐴

Recall:𝐹𝑖 = 𝐶𝑖 𝜙𝑉

𝐶𝐴 𝜙𝑉 − 𝐶𝐴0 𝜙𝑉0
𝑉=
𝑟𝐴

For liquid phase, Volumetric flow rate is constant (𝜙𝑉 = 𝜙𝑉0 )

𝐶𝐴 𝜙𝑉 − 𝐶𝐴0 𝜙𝑉0 𝜙𝑉 (𝐶𝐴 − 𝐶𝐴0 )

𝑉= → 𝑉=
𝑟𝐴 𝑟𝐴

CHE 37 – Chemical Reaction Engineering Page 6

 1 𝜙𝑉 (𝐶𝐴 − 𝐶𝐴0 )
(𝑉 = )
𝜙𝑉 𝑟𝐴

𝑉 𝐶𝐴 − 𝐶𝐴0
=
𝜙𝑉 𝑟𝐴

𝑉
Where 𝜙 = 𝜏
𝑉

𝑉 𝐶𝐴 − 𝐶𝐴0 𝐶𝐴 − 𝐶𝐴0
= → 𝜏=
𝜙𝑉 𝑟𝐴 𝑟𝐴

𝐶𝐴 −𝐶𝐴0
𝜏= [equation 5]
𝑟𝐴

The next step after deriving our stoichiometry would be to derive our rate law

Rate Law

For A:
−𝑟𝐴 = 𝑘1 𝐶𝐴
For lumped intermediates:
𝑟𝑅 = 𝑟𝑅𝑠𝑒𝑟𝑖𝑒𝑠 1 + 𝑟𝑅𝑠𝑒𝑟𝑖𝑒𝑠 2 + 𝑟𝑅𝑎𝑢𝑡𝑜𝑐𝑎𝑡𝑎𝑙𝑦𝑡𝑖𝑐
𝑟𝑅 = 𝑘1 𝐶𝑅 − 𝑘2 𝐶𝑅 − 𝑘3 𝐶𝑅 𝐶𝑆
For S:
𝑟𝑆 = 𝑟𝑆𝑠𝑒𝑟𝑖𝑒𝑠 + 𝑟𝑆𝑎𝑢𝑡𝑜𝑐𝑎𝑡𝑎𝑙𝑦𝑡𝑖𝑐
𝑟𝑆 = 𝑘2 𝐶𝑅 − 𝑘3 𝐶𝑅 𝐶𝑆

Combine the rate law and stoichiometry

For Batch:
= 𝑟𝐴 [Equation 3]
𝑑𝐶𝐴
𝑑𝑡
For A:
= −𝑘1 𝐶𝐴[Equation 10]
𝑑𝐶𝐴
𝑑𝑡
For Lumped Intermediates:
𝑑𝐶𝑅
= 𝑘1 𝐶𝑅 − 𝑘2 𝐶𝑅 − 𝑘3 𝐶𝑅 𝐶𝑆
𝑑𝑡
[Equation 11]
For S:
= 𝑘2 𝐶𝑅 − 𝑘3 𝐶𝑅 𝐶𝑆 [Equation 12]
𝑑𝐶𝑆
𝑑𝑡

CHE 37 – Chemical Reaction Engineering Page 7

For CSTR:
𝜏 = 𝐴 𝑟 𝐴0 [Equation 5]
𝐶 −𝐶
𝐴

For A:
𝜏=
𝐶𝐴 −𝐶𝐴0
−𝑘1 𝐶𝐴
[Equation 13]
For Lumped Intermediates:
𝐶 −𝐶𝐴0
𝜏 = 𝑘 𝐶 −𝑘𝐴 𝐶 −𝑘 𝐶 𝐶
[Equation 14]
1 𝑅 2 𝑅 3 𝑅 𝑠

For S:
𝜏=𝑘
𝐶𝐴 −𝐶𝐴0
[Equation 15]
2 𝐶𝑅 −𝑘3 𝐶𝑅 𝐶𝑠

CHE 37 – Chemical Reaction Engineering Page 8

 SECTION III

As mentioned, reactors with multiple reactions are common in the industry. In a study by Van
Woezik, & Westerterp (2002), a semi-batch reactor was used in the nitric acid oxidation of 2-
octanol. The runaway behavior and its thermally safe operations of the process was studied.
The study focuses on the thermal dynamics of a semi-batch reactor that performs multiple
exothermic liquid-liquid reactions. During the reaction, 2-octanone is formed, which can then
be oxidized to form undesirable carboxylic acids. The runaway behavior of 2-octanol nitric
acid oxidation to 2-octanone and subsequent oxidation products such as carboxylic acids has
been experimentally studied. When the reaction transitions towards acids is accompanied by
a temperature runaway, a dangerous situation can occur. The operation conditions, such as
dosing time and coolant temperature, are studied and discussed in order to achieve a high
yield under safe conditions. The oxidation of 2-octanol (A) to 2-octanone (P) and further
oxidation products (X) can be described with the following reaction equations:

where B is the nitrosonium ion, which also causes an autocatalytic behavior. The reaction
rates in the acid phase can be expressed on the basis of a second order reaction:

where CA,Org, CP,Org and CB,Aq are the bulk concentrations of 2-octanol (A), 2-octanone (P) and
nitrosonium ion (B) in the organic phase (Org) and Aqueous phase (Aq), respectively. The
kinetic constants knol and knone can be described with:

where k∞, E/R and mH0 are the pre-exponential factor, the activation temperature and the
Hammett’s reaction rate coefficient, respectively. H0 is Hammett’s acidity function.

CHE 37 – Chemical Reaction Engineering Page 9

Solving the heat and mass balances over the reactor with the appropriate initial conditions
yields the temperature in the reactor as well as the concentrations of the reactants and
products as a function of time. The following conditions are assumed in the model for the
semi-batch reactor considered in this work: uniform reaction temperature, heat capacities and
volumes are additive, only the aqueous nitric acid phase is involved in the reactions, the nitric
acid phase is the continuous phase; no phase inversion occurs, there is no change in the
volume of the individual phases, and the reactants' mutual solubility is low.

CHE 37 – Chemical Reaction Engineering Page 10

References:

Van Woezik, B. A. A., & Westerterp, K. R. (2002). Runaway behavior and thermally safe
operation of multiple liquid–liquid reactions in the semi-batch reactor. Chemical
Engineering and Processing: Process Intensification, 41(1), 59–77.
doi:10.1016/s0255-2701(01)00106-4

CHE 37 – Chemical Reaction Engineering Page 11