NON-ISOTHERMAL

REACTORS

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 Real Reactor

■ What non-ideality is to composition non-isothermal is to temperature

■ Most industrial reactors often operate under non-isothermal condition
■ Chemical reactions strongly depend on temperature by exchanging a large
amount of heat
– absorbing (i.e., endothermic) or generating (i.e., exothermic)

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Overview
■ Basics of Energy balances, concept of heat of reaction, effect of
Temperature considering CSTR and PFR
■ Design Algorithms for CSTR and PFR for specified conversion specified
reactor volume,
■ Adiabatic and non-adiabatic design procedures,
■ Unsteady-state Batch reactor design Procedures,
■ Non-isothermal endothermic and exothermic equilibrium limited
reactions and its reactor design procedures

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Background
■ Most chemical reactions are greatly affected by temperature. If the
temperature varies during the course of reaction it is called non-
isothermal operation
■ In an ideal gas mixture, the concentration of a component depends on the
temperature, Ci = pi/RT
■ The reaction rate also greatly affected by the temperature through the rate
constant (k = koe–E/RT)
■ Temperature affects the properties of the reaction mixture such as density,
specific heat, thermal conductivity and viscosity, enthalpy, as well as
mixing patterns and the energy for efficient mixing
■ In sort Temperature is the most important factor for reaction as well as
cost of the operation hence product.

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Background
■ The design of non-isothermal reactors involves both mass and energy
balances
■ Important reason to consider the non-isothermal reactor is because it is the
major cause of accidents in chemical plants.
■ Thermal runaway and consequent pressure buildup and release of chemicals is
an ever-present danger in any chemical reactor

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Operating Pressure
■ Consider reaction aA + bB ↔ rR + sS
■ The equilibrium constant K is independent of pressure with standard states.
■ When (r + s) > (a + b), the stoichiometric coefficients, an increase in pressure P results
in a decrease in conversion of the reactants to the products (When (r + s) < (a + b), an
increase in pressure P results in an increase in the equilibrium conversion.
■ In ammonia synthesis (N2 + 3H2 ↔ 2NH3), the reaction results in a decrease in the
number of moles. Therefore, an increase in pressure causes an increase in equilibrium
conversion due to this factor.
■ Le Chatelier's principle
– if a constraint (such as a change in pressure, temperature, or concentration of a reactant) is
applied to a system in equilibrium, the equilibrium will shift so as to tend to counteract the
effect of the constraint.

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Operating Temperature
■ So when high temperatures always favor, how high it should be kept?
■ The main factors affecting operating temperature are:
– Cost of maintaining the operating temperature (energy).
– Decomposition temperature of reactants and products.
– Possibility of operating at high pressures in the case of gas-phase reactions.
– Effect of temperature and pressure on equilibrium in the case of reversible
reactions.
– Effect of temperature on the rate constants associated with each elementary step in
a multiple reaction.
– Properties of materials of construction.
■ In irreversible reactions and in accordance with the Arrhenius equation it
is possible to operate at the highest possible temperature.

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Operating Temperature
■ In reversible reactions → aA + bB  rR + sS the equilibrium constant
is dependent on Gibbs Free Energy change

■ The van’t Hoff equation expresses as

■ ΔHR is the heat of reaction, which is a function of temperature.

Considering the case where ΔHR is constant and integrating the van’t
Hoff equation between the boundary limits

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Operating Temperature

■ For endothermic reactions, ΔHR has a positive numerical value if T2 > T1

and K2 > K1. The equilibrium constant K, therefore, increases as the
temperature increases. In this case, the reactor is operated at the highest
possible temperature.
■ For exothermic reactions, ΔHR has a negative numerical value if T2 > T1
and K2 < K1. The equilibrium constant K decreases as the temperature
increases. Here, the temperature is kept high so that the rate of reaction is
high, and then decreased as equilibrium is approached

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Energy Balance
▪ By First Law of Thermodynamics for a closed system, in which no mass crosses the system
boundaries, the change in total energy of the system, dE, is equal to the heat flow to the system,
δQ, minus the work done by the system on the surroundings, δW. For a closed system, the
energy balance is
𝑑𝐸 = 𝛿𝑄 − 𝛿𝑊
■ The continuous-flow reactors we have been discussing are open systems in which mass
crosses the system boundary. We shall carry out an energy balance on the open system.

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 Energy Balance
■ For an open system in which some of the energy exchange is brought about by the
flow of mass across the system boundaries, the energy balance for the case of only
one species entering and leaving becomes

Unsteady State Energy Balance

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 Work
■ Work term is divided in to two parts
– Flow work (W)
– Shaft work (Ws)
■ Total work is sum of flow work and Shaft work

Flow work

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Work
■ Mostly the flow-work term is combined with those terms in the energy balance that
represent the energy exchange by mass flow across the system boundaries

The energy Ei is the sum of the internal energy (Ui ), the kinetic energy , the potential energy (gzi ), and
any other energies, such as electric or magnetic energy or light

In almost all chemical reactor situations, the kinetic, potential, and “other” energy terms are negligible
in comparison with the enthalpy, heat transfer, and work terms, and hence will be omitted

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Work
■ the enthalpy, Hi (J/mol), is defined in terms of the internal energy Ui (J/mol), and the
product PV (1 Pa.m3 /mol = 1 J/mol):

Enthalpy carried into (or out of) the system can be expressed as the sum of the internal energy
carried into (or out of) the system by mass flow plus the flow work

The energy of the system at any instant in time, Esys , is the sum of the products of the number of
moles of each species in the system multiplied by their respective energies.

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Energy Balance
■ let the subscript “0” represent the inlet conditions. Unsubscripted variables
represent the conditions at the outlet

now consider flow systems that are operated at steady state. The steady-state energy balance
is obtained by setting RHS to 0

Consider a generic
reaction

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Energy Balance

the molar flow rates in terms of conversion. In general, the molar flow rate of species
I for the case of no accumulation and a stoichiometric coefficient

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Energy Balance

The term in parentheses that is multiplied by FA0 X is called the heat of reaction at temperature T
and is designated HRx(T).

All enthalpies (e.g., HA ,HB) are evaluated at the temperature at

the outlet of the system volume
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Energy Balance

The reference temperature at which is given is usually 25C. For any substance i that is being heated
from T1 to T2 in the absence of phase change

A large number of chemical reactions carried out in industry do not involve phase change.
Consequently, we shall further refine our energy balance to apply to single-phase chemical reactions.
Under these conditions, the enthalpy of species i at temperature T is related to the enthalpy of
formation at the reference temperature TR by

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Energy Balance
The heat capacity at temperature T is frequently expressed as a quadratic function of
temperature

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Energy Balance
Relating HRx(T ), H Rx(TR), and CP

the enthalpy of each species is given by

If we now substitute for the enthalpy of each species

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Energy Balance
The first term in brackets on the right-hand side of Equation is the heat of reaction at the reference
temperature TR

The enthalpies of formation of many compounds, , are usually tabulated at 25°C and can readily
be found in the Handbook

The second term in brackets on the right-hand side of Equation is the overall change in the heat
capacity per mole of A reacted,

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