Topic 1: Fundamentals of ideal homogeneous chemical

reactors design.

In the previous course, a chemical reactor was defined as "all that process equipment in which a
chemical reaction takes place" and the design objectives of this type of process equipment were
established:
1. To maximize the conversion of the reactants into the desired products.
2. To maximize selectivity regarding a desired product.
3. To maximize the yield of the chemical reaction.

1.1 Reaction coordinates.

Chemical reactors performance is usually measured in terms of the following variables, called
“reaction coordinates”
 Conversion: fraction of the fed molar amount of reactant (usually the limiting reactant) that is
converted into products, it is a ratio of the quantity of the reactant that has reacted.
Mathematically it is defined as:

Eq. (1)

 Selectivity: ratio of the obtained moles of the desired product regarding the moles obtained of
the undesired products at the outlet of the reactor, mathematically it is expressed as:

Eq. (2)

 Yield: refers to the amount of a specific product (commonly the desired one) formed per mole
of reactant consumed, mathematically it is expressed as:

Eq. (3)

1.2 Design variables.

Design variables are those parameters that define the bases for the theoretical and mechanical
design of a chemical reactor. They are:

 Reactor volume (V): physical space occupied by the reaction medium (homogeneous system)
or by the solid catalyst (packed bed system). It does not include agitation or mixing systems,
 heat exchange systems such as coils, jackets or tube bundles, measurement or control
instruments, empty or safety spaces.
 Reactor length (L): vertical or horizontal distance over which the chemical reaction carries
out, it is usually preferred as a design parameter in tubular reactors. It does not include the
length to feed the reactants or to remove the products. For packed bed reactors, it corresponds
to the height or length that the solid particles must occupy.
 Catalyst mass (W): mass of catalyst required to achieve the desired conversion in a packed or
fluidized bed reactor.
 Retention time (t): the span of time that the feed mixture is allowed to react in a batch or
semi-continuous reactor; it does not include the necessary time to feed the reagents, to remove
the products, to modify the conditions of the reaction medium till the operating conditions
(such as temperature or pressure), cleaning and reconditioning for the next batch.
 Residence time (tR): it is the average time it takes for a differential volume element of
feeding to pass through the reactor.

Eq. (4)

 Space-time (): ratio of the reactor volume and the volumetric flow rate of the feeding, it
represents the time required to process one reaction volume in a continuous reactor.

Eq. (5)

 Space velocity (SV): it is the inverse quantity of space-time, it represents the number of
reactor volumes that are processed per unit of time in a continuous reactor.

Eq. (6)
There are different types of space velocities:
 Gas hourly space velocity (GHSV): it is the ratio of volumes of gas present in feed gas at
standard conditions to the volume of the reactor or catalyst denoted as:

Eq. (7)

 Liquid hourly space velocity (LHSV): it is the ratio of the volume of liquid present in feeding at
60 °F to the volume of reactor or catalyst, it is expressed as:
 Eq. (8)

 Weight hourly space velocity (WHSV): it is the ratio of the mass flowrate of the feeding to the
mas of the catalyst, it is defined mathematically as:

Eq. (9)

1.3 Design factors for ideal chemical reactors.

When designing an ideal chemical reactor, six fundamental factors must be taken into account:
1. Mode of operation: it refers to the material flow regime under which the reactor will
operate; this allows establishing the composition of the system based on the general molar
balance. The possible regimes are:

The reagents are loaded at the beginning of the operation and once the
Batch
necessary retention time is reached, the products are unloaded.

One or more chemical species are charged or discharged continuously,

Semi-continuous
while the rest of the components are charged intermittently.

Continuous at steady The reaction medium is continuously fed and removed, keeping the total
state molar flow rate constant (without accumulation of matter).

The reaction medium is continuously fed and removed, but there is

Continuous at
accumulation of matter inside the reactor, so the total molar flowrate at
unsteady state
the inlet and outlet of the reactor are different.

2. Thermodynamic operation: it refers to the thermal effects that must be taken into account,
hence three possible regimes are defined:
The temperature of the reaction system is kept constant (usually by the
use of an appropriate heat exchange system), so it is not necessary to
Isothermal
consider the thermal effects on the reaction kinetics or the energy
balance for the reactor design.
The reactor is considered as thermally isolated from its surroundings, so
there will be temperature gradients in the reactor, depending on whether
Adiabatic
the reaction is endothermic or exothermic; these effects must be
estimated through the energy balance in the reactor.
 The reactor has a heat exchange system that does not keep the
temperature of the reaction medium constant, so it will present
Non-isothermal
temperature gradients, which must be estimated based on the energy
balance for the reactor and for the heat exchange medium.

3. Hydraulics of the process: it is necessary to take into account the flow pattern of the
reaction medium inside the reactor, which will affect the pressure drop inside the
equipment. In general, for stirred tank reactors the pressure drop is negligible, for tubular
reactors it is very small, while for packed bed and fluidized bed reactors it is significant.

4. Number and type of reactive phases: chemical reactions are generally carried out in fluid
phases (solids are not very reactive), so the number and type of fluid phases involved in the
reaction must be taken into account, since this will define the equipment hydrodynamics
and density behavior.
Density of the reaction medium is considered to be constant, except in
Liquid phase specific cases such as polymerization reactions where there are significant
changes in density.

It is necessary to consider the variation of the density of the reaction

Gas phase medium with pressure and temperature through an appropriate equation of
state and the molar expansion factor ().

If more than two phases are present, it is necessary to use equations of

state to describe the behavior of the gas phase and liquid-gas and solid-
Multiphase systems
fluid contact models based on the mass transfer coefficients to describe
the interfacial behavior.

5. Complexity of the reaction system: this parameter determines the kinetic laws and the
stoichiometric relationships that must be considered in the design of the reactor. In general,
all reactive systems involve more than one simultaneous reaction, however, under the
appropriate reaction conditions it is possible to simplify them to the occurrence of a single
main reaction; otherwise all chemical reactions involved in the system must be considered.

6. Chemical reaction activation method: it will determine the proper operation of the
reactor. It is necessary to consider whether the reaction requires thermal, photochemical,
catalytic, biochemical, electrochemical, or other activation.

Topic 1: Fundamentals of the design of ideal homogeneous

1.4 General mole balance.
The material balance in a chemical reactor, in which "j" chemical reactions occur, is usually stated
on a molar basis as:
For the design of a chemical reactor, a mole balance equation must be established for each of the
independent species of the reaction system (defined in the stoichiometric analysis).
In the Equation (10), two different cases can be possible for the generation/consumption term:

 Reaction system with homogeneous properties: the process variables (temperature,

concentration of chemical species and catalytic activity) are spatially uniform throughout the
volume of the system, as it occurs in reactors with perfect mixing (batch and continuous
stirred tank reactors), so the generation term can be established as:

Eq. (11)

 Reaction system of heterogeneous properties: the process variables (temperature,

concentration of chemical species and catalytic activity) vary with the position throughout the
volume of the system, as occurs in plug-flow and packed bed tubular reactors, hence the term
of generation is expressed as:

Eq. (12)

1.5 General energy balance.

In a similar way, the energy balance can be established for a thermodynamic system in which a
chemical reaction is carried out, according to the First Law of Thermodynamics:
In this course, the IUPAC convention for the sign of heat and work terms in thermodynamic
systems will be used:

 Heat and work are considered to be positive when the energy flow is from the sourradings
to the reaction system (energy inlet), which effect is an increase in the internal energy of
the system; that is, the work done on the system and the heat supplied to the reaction
medium.
 Heat and work are considered to be negative when the energy flow is from the system to
the surrounding, so the internal energy of the system decreases; that is, the work done by
the system and the heat dissipated by the reaction medium.

1.4.1 Work in chemical reactors.

In the chemical reactors, the energy flow in the form of work is often separated into shaft work
(done by a stirrer or turbine) and flow work (needed to introduce and remove matter from the
system):

Eq. (14)
1.4.2 Input and output of energy by flow of matter.
The energy of the material streams that enter and leave a chemical reactor is established using the
molar energies of each component of the reaction medium as:

Eq. (15)

In general, for reactive systems, the contribution of the kinetic energy and the potential energy of
the chemical species is negligible compared to the internal energy (U), so they are usually omitted:

Eq. (16)
Since the measurement of internal energy is not possible in a thermodynamic system, the flow of
energy related with material streams is usually estimated in terms of enthalpy:

Eq. (17)
 1.4.3 Accumulation of energy within the system.
The energy accumulation can be estimated by deriving equations (16) and (17) in function of time,
and assuming ideal behavior of the fluids, it is as follows:

Eq. (18)

In the previous equation, the fluid expansion factor has been introduced, which is a dimensionless
number that takes the following values:

 fe = 0, for fluids that do not undergo volume changes during the reaction (liquids and
gases without change in the number of moles of reaction)
 fe = 1, for systems in the gas phase with a change in the number of moles of reaction.

1.4.4 Heat transfer in chemical reactors.

In stirred tank reactors, heat is exchanged through
jackets or coils; a specific mass (n a) of the
exchange fluid flows through them (such as water,
steam, oil), which enters at a temperature T a1 and
leaves the exchanger at a temperature T a2. In these
cases the heat transfer rate is stated in terms of the
general heat exchange equation as:

Eq.
(19)

By rearranging the previous equation, for the heat

flux:

Eq. (20)

If the molar flowrate of the exchange fluid is high,

it is possible to consider that the fluid temperature
remains constant (Ta) and it is possible to simplify
as:

Ea. (21)
 In tubular reactors, the rate of heat transfer varies
along the length of the reactor, so the heat flux
equation must be integrated in order to determine
the amount of heat transferred to the reactor:

Eq.
(22)

For a PFR:

Eq. (23)

For a PBR:

Eq. (24)

1.4.5 General Energy Balance Equation.

Combining equations (13), (17) and (18) the General Energy Balance Equation is obtained,
applicable to chemical reactors:

Eq.
(25)

References.

 Fogler, H.S. (2022). Elements of Chemical Reaction Engineering (6 th Edition). New

Jersey: Pearson.
 Levenspiel, O. (1998). Chemical Reaction Engineering (3rd Edition). New York: Wiley.

Topic 2: Thermal effects in chemical reactors.

Temperature and pressure have influence over the rate and progress of chemical reactions and the
equilibrium conditions and these effects must be considered in the design of chemical reactors; this
allows establishing the optimal design conditions and the calorific effects to be taken into account
to achieve the ideal design.

1.6 Heat of reaction.

In the previous course, it was established that the heat of reaction for a chemical reaction "j", at
standard conditions (25°C and 1 bar), can be determined from the standard heats of formation of the
reactants and products as:

Eq. (1)

If the value is referred to one of the "i-th" chemical species that participate in the chemical reaction,
the standard molar heat of reaction is obtained:

Eq. (2)

Most of the industrial chemical reactions are carried out at a temperature different than the standard,
in these cases the molar heat of reaction at the operating temperature must be calculated using the
Kirchoff’s Equation (shown as follows) using the heat capacities of the chemical species:

Eq. (3)

Where heat capacity of reaction is estimated as follows:

Eq. (4)

If heat capacity of the chemical species are supposed to be constant, such as in condensed phase
(liquid and solid phases) reaction systems and ideal gases with small temperature difference (<100
K or 180 R), an average heat capacity can be used and the molar heat of reaction at reaction
temperature is calculated as:

Eq. (5)

If the heat capacity of the chemical species depends strongly on temperature, polynomial functions
for heat capacities must be used and the molar heat of reaction is estimated by:

Eq. (6)
 Eq. (7)

1.7 Equilibrium constants.

The equilibrium constant, and hence, the equilibrium compositions in reacting systems at standard
conditions can be calculated from the Second Law of Thermodynamics by the following
expression:

Eq. (8)

The value of the equilibrium constant is strongly dependent on temperature and pressure; the Van’t
Hoff’s Equation can estimate this effect:

Eq. (9)

If the molar heat of reaction is supposed to be constant in the temperature range between the
standard and the reaction temperature, the integration of Equation (9) results in:

Eq. (10)

If molar heat of reaction varies significantly with temperature, polynomial functions for heat
capacity must be used and integrate:

Eq.(11)

Integration of Equation (11) results in:

Eq. (12)

It is convenient to recall some additional aspects, previously discussed in the Chemical Reactors I
course, about chemical equilibrium constants:
 1. The value of the thermodynamic equilibrium constant does not depend on the pressure of
the system, the presence of inert materials and the kinetics of the reaction; it only depends
on the temperature.
2. The compositions and conversions at equilibrium are dependent on the pressure, the
presence of inert materials and the kinetics of the reaction.
3. If temperature increases, the equilibrium conversion increases for endothermic reactions
and decreases for exothermic reactions (see Figure 2.1).
4. If pressure increases in gas phase reactions, the conversion increases when the number of
moles decreases with the reaction and decreases when the number of moles increases with
the reaction.
5. A decrease in the concentration of inert materials acts in the same way as an increase in
pressure, for all reactions.

Figure 2.1. Behavior of equilibrium conversion with the temperature for

endothermic and exothermic reactions.

1.8 Effect of temperature on reaction rate.

Reaction rate depends directly on the temperature, which clearly affects the operation of a chemical
reactor. This effect is included into the rate law through the specific reaction rate constant (k) of the
reaction:

Eq. (13)

2.3.1 Arrhenius Theory for Chemical Kinetics.

There are numerous theories that attempt to explain (and quantify) the effect of temperature on the
specific reaction rate constant, the most used model is the Arrhenius Theory. This theory is based
on the postulate that all chemical reactions require a fixed amount of energy to be carried out, called
activation energy (Ea), which works as a barrier for the reactants to be transformed into the
products. Based on this concept, Arrhenius proposed the following equation:

Eq. (14)
 Equation (14) can be linearized to
obtain the values of the activation
energy and the pre-exponential factor
from a series of experimental data.

Eq. (15)

The previous equation allows

introducing the effect of temperature
on the reaction rate in the design
equations of any chemical reactor:

Eq. (16)

Figure 2.2. Energy curves for chemical reactions

(https://byjus.com/jee/activation-energy/).

2.3.2 Collision theory.

The collision theory is an attempt to explain from a solid theoretical basis the effect of temperature
over the reaction rate, its postulates are:
1. Chemical reactions take place by the effective collision between the molecules of the
reactants.
2. Effective collisions occur only between molecules with enough kinetic energy.
3. Activation energy is the amount of kinetic energy required to break the bonds of the
reactant molecules.
4. The effectiveness of collisions depends on the kinetic energy and the orientation of the
molecules; increasing the temperature increases the number of molecules with sufficient
kinetic energy for an effective collision to occur. Based on this, the specific rate constant is
defined as:

Eq. (17)
Where  is the collision frequency and  is the steric factor (related with molecules geometry and
shape).

Figure 2.3. Molecular collisions in chemical reactions (Atkins, Physical Chemistry,

10th edition, p. 578).
2.3.3 Transition State Theory.
The transition state theory explains the reaction rate of chemical reactions under the supposition of
the existence of a reaction intermediate called “transition state” or “activated complex” that is in
quasi-chemical equilibrium with the reactants, which is unstable due to its high energy. His
postulates are:
1. When the reactant molecules get close enough, they suffer a deformation that allows the
formation of a transition state (activated complex) of high energy and very short lifetime,
whose destabilization promotes the formation of the products.
2. The activation energy is the energy required for the formation of the activated complex.
3. The formation of the transition state depends on thermodynamic factors, such as enthalpy,
entropy and Gibbs free energy.
4. Reaction rate can be established by studying the energy of the activated complexes.
Dependence of the specific reaction rate constant on temperature can be stated in terms of Eyring's
Equation:

Eq. (18)

Thermodynamic parameters of the activated complex can be calculated as:

Eq. (19)
 Figure 2.4. Potential energy curve showing the formation of
transition state (Encyclopedia Britannica, Inc.)

1.9 Correlation between temperature and conversion.

Temperature, composition, and reaction rate are directly and uniquely related for any single
homogeneous reaction, this fact allows represents that correlation in terms of mathematical
equations and graphs (see Figure 2.5), which are useful in reactors design.

Figure 2.5. Different ways of representing the relationship of temperature,

composition and rate for a single homogeneous reaction (Levenspiel, O. (1998).
Chemical Reaction Engineering, 3rd Ed. p. 215).
In the design of chemical reactors, conversion-temperature curves (see Figure 2.6) are especially
useful; which will show a specific shape depending on the type of reaction. This plot can be either
prepared from a thermodynamically consistent model of the reaction rate or from a set of
experimental kinetic data.
 Figure 2.6. Shape of temperature-conversion plot for different reaction types (Levenspiel, O. (1998).
Chemical Reaction Engineering, 3rd Ed. p. 216).
If a thermodynamically consistent model is used, the following guidelines must be considered:
1. Stablish the stoichiometric chart for the reaction in terms of the conversion.
2. Deduce the rate law.
3. Determine the parameters of the thermodynamic model (usually the Arrhenius Equation is
used).
4. The three previous equations must be combined to obtain the mathematical correlation of
the conversion with the temperature.
5. Plot the T-X curves assigning custom values to reaction rate.

Figure 2.7. Example of temperature-conversion plot for a first order reversible

reaction (Levenspiel, O. (1998). Chemical Reaction Engineering, 3rd Ed. p. 219).

1.10 Optimum Temperature Progression.

Optimum temperature progression (OTP) is the sequence (of reactor temperatures) which
minimizes the value of V/FL0 for a given conversion of limiting reactant. This optimum may be an
isothermal or non-isothermal trajectory in time (batch reactor), along the length (tubular reactor), or
from stage to stage for a series of CSTR.
It is important to know this optimum progression because it is an ideal, which must be approached
by the real system; the OTP represents the operation line for the minimum reactor size.
The optimum temperature progression in any type of reactor is established by examining the points
in which reaction rate is a maximum (in the T-X plot).
  For irreversible single reactions, the rate always increases with temperature at any
composition, so the OTP must be defined by the highest allowable temperature (set by
materials of construction or by the possible side reactions).
 For irreversible endothermic reactions, a rise in temperature increases both the equilibrium
conversion and the reaction rate; thus, as with irreversible reactions, the highest allowable
temperature must be used.
 For exothermic reversible reactions two opposite factors are at work when temperature is
raised: the rate of forward reaction increases but the conversion decreases; thus for this kind
of reactions the OTP is obtained by connecting the maxima of the different rate curves, the
obtained line is called locus of maximum rates (see Figure 2.8).

Figure 2.8. Optimum temperature progression for different reaction types

(Levenspiel, O. (1998). Chemical Reaction Engineering, 3rd Ed. p. 220).

References.

 Fogler, H.S. (2022). Elements of Chemical Reaction Engineering (6 th Edition). New

Jersey: Pearson.
 Levenspiel, O. (1998). Chemical Reaction Engineering (3rd Edition). New York: Wiley.

Topic 3: Non-isothermal ideal batch reactors.

The main characteristic of batch reactors is the fact that they

operate in cycles: the reagents are introduced and mixed into
the reactor, the operating conditions (pressure and
temperature) are stabilized, and the reaction is allowed to
carry out for a set time (retention time).
They are usually used on a laboratory scale to study the
kinetics of chemical reactions and on an industrial scale when
the production of small quantities of a product is required or
in multi-product production situations. They are typically
made of steel, stainless steel, glass, glass-lined steel and other
specific alloys, depending on the type and conditions of the
 reaction.
Most of them are stirred-tank-type, although alternative
configurations such as piston-cilinder arrays and settlers can
be used for handling gases.
The basic design assumption is that the system works in a
perfect mixing regime, which implies that the properties are
especially homogeneous and that there is no variation in the
reaction rate. This is achieved using a suitable agitation
system, so that the H/DR and Da/DR ratios are adequate,
depending on the characteristics of the fluid. The type of
agitator paddle and the use of baffles to reduce vortex
formation should also be considered.

Fig. 3.1. Stirred tank batch reactor.

Heat released or absorbed by the reaction medium is removed by or added through heating
equipment such as jackets, coils or tube bundles, the former being the most commonly used. In
small reactors, single-pass jackets are usually used while for large reactors the use of multiple-pass
or half-coil jackets is recommended.

1.1 Design equations (molar balance).

From the General Molar Balance Equation (previously deduced), it can be established that the
molar balance in a batch reactor in which "j" reactions occur will be:

Eq. (3.1)
Fig. 3.2. Types of heat exchange systems for tank type reactors (a – jacketed vessel, b – external half-coil, c –
internal helical coil, d – internal baffle-type coil, e – external pipe bundle).

Molar balance can be written in terms of the conversion of the limiting reactant (only for single
reaction systems) as:

Eq. (3.2)
Integration of the previous equations leads to the called design equation, since it establishes the
basic design parameters based on the degree of conversion desired; for batch reactors that parameter
is the retention time. Depending on the operating conditions, there will be two cases:
 System at constant density: the volume and pressure of the reaction medium do not vary
with the progress of the reaction, as comes about in liquid and gas reaction systems at
constant pressure with no change in the number of moles in the reaction. The design
equation will be:

Eq. 3.3 (Multiple reactions)

Eq. 3.4 (Single reaction)

 System with variable density: it corresponds to systems in the gas phase where the volume
and pressure vary with the progress of the reaction; the volume variation with the
conversion must be taken into account by using equation 3.5, which must be joined with the
molar balance.

Eq. 3.5
Pressure change (if applicable) can be estimated by:

Eq. 3.6

3.2 Energy balance and thermodynamic operation.

Since the reaction rate is dependent on temperature, the energy balance should be involved
depending on the type of operation. Application of the corresponding simplifications to the General
Energy Balance Equation (reviewed previously) leads to the equation for the energy balance in a
batch reactor:
 Eq. 3.7
Last equation can be written in terms of conversion (for single reaction systems) as:

Eq. 3.8
For both equation (3.7 and 3.8) it is a common practice to assumed constant heat capacities for the
reaction species (an average value is usually taken over the range of operating temperatures).
Energy balance will be used in reactor design and optimization for various purposes, according to
the thermodynamic operation:
 Case 1. Isothermal operation: the energy balance is required to determine the amount of
heat that must be supplied to or removed from the reaction medium, in order to determine
the design of the appropriate heat exchange system.
 Case 2. Adiabatic operation: the energy balance allows establishing the relationship
between the temperature of the reaction medium and the conversion given the reacton
kinetics. For the case of a single reaction, the application of this condition leads to the
following equation, known as the adiabatic curve of the reaction, which will be almost
linear depending on the variation of the heat of reaction with temperature (Figure 3.3.).

Eq. 3.9

Fig. 3.3. Graphic representation of the energy balance for the reactor
adiabatic operation.
Case 3. Non-isothermal operation: when the amount of heat supplied to or removed from the
reaction medium is different from that necessary to achieve isothermal operation, the energy
balance in the reactor must be considered to establish the temperature profile of the reaction
medium and the energy balance in the exchange medium to establish the outlet temperature.

3.3 Operating parameters.

The operation and performance of batch reactors is measured in terms of three fundamental
operating parameters:
 Cycle time: it is the total time it takes to make a complete batch of a specific product, it is
obtained by adding the retention time (chemical reaction) and the conditioning times
(loading of reagents, discharge of products and cleaning).

Eq. 3.10
 Production rate: it is the relationship between the quantity of product obtained per
production batch and the cycle time:

Eq. 3.11
 Optimal conversion: the reaction rate varies with the progress of the reaction, increasing
quickly at the beginning until reaching a maximum value, after which it slows down,
causing the production rate to decrease, hence an optimal value of conversion can be
estimated, which maximizes production speed, given by:

Eq. 3.12

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