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Graduate Seminars on

Chemical Reaction Engineering and Kinetics


October 15 - Nov 26, 2009

Lecture 2:
Energy Equation for Reactors
Brian G. Higgins
Department of Chemical Engineering and
Materials Science
University of California, Davis

Email: bghiggins@ucdavis.edu
Lecture notes posted at
http://www.ekayasolutions.com
Analysis of Chemical Reactors
and the Connecting Disciplines
Thermodynamics Fluid Mechanics

Kinetics
Chemical Mathematics
Reactor

Heat Transfer Mass Transfer

Chemical reactors are the linchpin in a chemical plant for


controlling, optimizing, manipulating
the transformation of matter through chemical reactions
Nonisothermal Reactors

Real reactors generate or absorb large amounts of heat

or

Rate coefficient is function of temperature

Advantage to operate exothermic reactors nonisothermally is:

Higher temperatures lead to higher reaction rates and smaller reactors

but
If temperature to high equilibrium can limit conversion
and
High temperatures can lead to hot spots and reactor failure
Analysis of Nonisothermal Reactors
Mass flow rate
Molar concentration

Reactor
Total energy
Control volume V

Rate of heat added


Rate of work done

The energy balance is an accounting of


rate of
•  heat flow into the reactor with reactants
•  heat flow out of the reactor with products
•  heat generated/absorbed by reaction
•  heat added/removed from reactor
•  work done by stirrers and friction
Energy Balance for Chemical
Reactors
Mass flow rate
Molar concentration

Reactor
Total energy
Control volume V

Rate of heat added


Rate of work done

Total energy per unit mass


Rate of Work Done on System

Inlet pressure

Exit pressure

Fluid density
Energy Terms

Convenient to work with enthalpy

reactor volume/mass

but composition

Complete energy analysis is complicated- simplifying assumptions often made!

Knowledge of thermodynamics important


Energy Equation for Batch
Reactor

Neglect kinetic energy, potential energy and shaft work


Rate of heat added
Rate of Enthalpy
change

Reactor volume
Definition for enthalpy

Rate of work due to change in volume


Expression for Enthalpy
Thermodynamic expression for enthalpy in terms of P, T, nj
Moles of species j

Heat capacity

Reactor volume Partial molar enthalpy

Coefficient of expansion
Constant Pressure Liquid Batch Reactor
Step 1

Rate of Enthalpy Rate of heat added


change

Enthalpy Expression Substitute


=0

or

Energy balance in terms of T and partial molar enthalpies


Constant Pressure Liquid Batch Reactor
Step 2

Use species balance to eliminate

Use heat of reaction to eliminate


Constant Pressure Liquid Batch Reactor
Example 1

At what rate must heat be removed to maintain reactor at 300 K to reach a conversion of 90%?

Solution:
Species balance:

For 90% conversion:

Time for 90% conversion:


Constant Pressure Liquid Batch Reactor
Example 1 continued

Energy balance for isothermal operation:


=0

Total heat removed:


Adiabatic Liquid Batch Reactor
Example 2

Species balance:

Stoichiometry:

Balance for species A:

Balance for species B:

Conservation of mass:
Adiabatic Liquid Batch Reactor
Example 2 continued

=0
Energy Balance:

Integrating:

Formula for calculating temperature rise in reactor


Adiabatic Liquid Batch Reactor
Example 2 continued

Reactor Parameters:

For 95% conversion:


Non-Isothermal Batch Reactors
Example 3

Ideal gas mixture

Case 1: Constant Pressure Reactor:


Reactor pressure is held constant; reactor volume therefore changes

Case 2: Constant Volume Reactor:

Reactor volume is held constant; reactor pressure therefore changes

Which reactor converts the reactant more quickly?


Analysis Constant Pressure Case
Example 3 continued

Species balance:

Energy balance constant pressure case:


Analysis Constant Volume Case
Example 3 continued

Species balance:

Energy balance constant volume case:


Ideal gas mixture Summary of Results
Example 3 continued

Case 1: Constant Pressure Reactor:

Case 2: Constant Volume Reactor:

By inspection

Reaction proceeds more quickly in constant volume case!


Energy Balance for CSTR
Material Balance for CSTR

Assumption: Perfectly mixed

General design equation for CSTR reactors


Energy Balance for Chemical
Reactors
Mass flow rate
Molar concentration

Reactor
Total energy
Control volume V

Rate of heat added


Rate of work done

Total energy per unit mass


Energy Balance for CSTR

Energy balance in terms of enthalpy:

Enthalpy relation:

Energy balance in terms of temperature:

Substituting the species balance

General design equation for CSTR reactors


Energy Balance for CSTR
Some special cases

Liquid phase reactor:

Steady State:

For liquid phase

Then
Steady State Energy Balance for CSTR
Example 1

What temperature must the reactor be operated at to achieve


80% conversion?

Solution:
Steady state species balances:

Adding and noting that cB0=0


Steady State Energy Balance for CSTR
Example 1 continued

Solution continued
Rate Expression
Steady State Energy Balance for CSTR
Example 1 continued

Solution continued
Rate Expression

Species balance

Working equation

Solve for T with cA1=0.2 cA0


Appendix
Derivation of key formulas
Energy Balance in terms of T and P
Step 1
Rate of heat added
Rate of Enthalpy
change

Reactor volume
Enthalpy Expression Substitute

or

Energy balance in terms of T and P and partial molar enthalpies


Energy Balance in terms of T and P
Step 2

Use species balance to eliminate

Use heat of reaction to eliminate