Reactor Process Simulation with Equilibrium

Reactions

Maurice Politis

February 19, 2025

Table of Contents

Introduction to Reactor Process Simulation

Fundamentals of Chemical Equilibrium

Modeling Equilibrium Reactions in Reactors

Limiting Conversion Due to Chemical Equilibrium

Practical Considerations in Reactor Design

Step-by-Step Example: Ammonia Synthesis

1. Introduction to Reactor Process Simulation
▶ Purpose of Reactor Simulation:
▶ Predict reactor performance before building it.
▶ Optimize reactor design (size, shape, operating conditions).
▶ Improve safety and efficiency.
▶ Reduce costs and development time.
▶ Troubleshoot existing reactors.
▶ Example, Using Aspen Hysys we can select a proper reactor
(i.e. CSTR, PFR) for a specific process and optimize the
operating conditions.
▶ Equilibrium Reactions: Reactions that proceed in both
forward and reverse directions, eventually reaching a state of
dynamic equilibrium. This equilibrium limits the maximum
achievable conversion.
▶ Importance in Reactor Design: Understanding equilibrium
is crucial for predicting the maximum yield of a desired
product and for designing reactors that approach this
maximum.
2. Fundamentals of Chemical Equilibrium

▶ Chemical Equilibrium: A dynamic state where the rates of

the forward and reverse reactions are equal. The net change in
concentrations of reactants and products is zero. It’s dynamic
because reactions are still happening, just at equal rates.
▶ Equilibrium Constant (K):
▶ A quantitative measure of the equilibrium position.
▶ For a general reaction: aA + bB ⇌ cC + dD
▶ The equilibrium constant is expressed as:

[C ]c [D]d
K=
[A]a [B]b

where [] denotes equilibrium concentrations (or

activities/fugacities for non-ideal systems).
▶ A large K indicates that the equilibrium favors products; a
small K favors reactants.
2. Fundamentals of Chemical Equilibrium (Continued)

▶ Significance of K:
▶ Predicts the direction a reaction will shift to reach equilibrium.
▶ Determines the extent of reaction (how much product can be
formed).
▶ K is temperature-dependent (van’t Hoff equation).
▶ Example Equilibrium Reactions:
▶ Haber Process (Ammonia Synthesis): N2 (g) + 3H2 (g) ⇌
2NH3 (g)
▶ Esterification: CH3 COOH(aq) + C2 H5 OH(aq) ⇌
CH3 COOC2 H5 (aq) + H2 O(l)
▶ Steam Reforming of Methane: CH4 (g) + H2 O(g) ⇌ CO(g)
+ 3H2 (g)
3. Modeling Equilibrium Reactions in Reactors

▶ Modeling in Process Simulators:

▶ Simulators use thermodynamic models (e.g., equations of
state, activity coefficient models) to calculate equilibrium
constants and phase behavior.
▶ Equilibrium reactors are often modeled as ”Gibbs Reactors” or
”Equilibrium Reactors.”
▶ Gibbs Free Energy Minimization:
▶ The fundamental principle: At equilibrium, the total Gibbs free
energy (G) of the system is at a minimum.
▶ The simulator adjusts the composition of the reactor contents
until the minimum G is achieved, subject to mass balance
constraints.
▶ Mathematically: Minimize G = i ni µi , where ni is the
P
number of moles of component i, and µi is the chemical
potential of component i.
3. Modeling Equilibrium Reactions in Reactors (Continued)
▶ Assumptions and Limitations:
▶ Equilibrium Assumption: The reaction reaches equilibrium
within the reactor. This is valid for fast reactions relative to
the residence time.
▶ Ideal Mixing: Perfect mixing within the reactor (often
assumed for CSTRs).
▶ Accurate Thermodynamic Data: The accuracy of the
simulation depends on the accuracy of the thermodynamic
models and data used.
▶ No Kinetic Limitations: Equilibrium models do not consider
reaction rates.
▶ Relationship between conversion, equilibrium constant
and equilibrium composition:
▶ Consider the generic reversible reaction: aA + bB ⇌ cC + dD
▶ Let ’x’ be the conversion of reactant A.
▶ The equilibrium constant (K) is defined in terms of the
equilibrium concentrations (or activities) of the reactants and
products.
▶ Stoichiometric Table (ICE Table - Initial, Change, Equilibrium):
ICE Table

Species Initial (mol) Change (mol) Equilibrium (mol) Equilibrium

A NA0 -a*x NA0 (1-x) NA
B NB0 -b*x NB0 − (b/a)NA0 x (NB0 − (
C NC 0 +c*x NC 0 + (c/a)NA0 x (NC 0 + (
D ND0 +d*x ND0 + (d/a)NA0 x (ND0 + (

Table: Stoichiometric Table (ICE Table)

▶ V is the volume of the reacting mixture.

Relationship Between Conversion and K

▶ Substitute the equilibrium concentrations into the expression

for K:
 c  d
NC 0 +(c/a)NA0 x ND0 +(d/a)NA0 x
c
[C ] [D] d V V
K= a b
= a  b
[A] [B]

NA0 (1−x) NB0 −(b/a)NA0 x
V V

▶ This equation relates K (a thermodynamic property) to the

equilibrium conversion (x). Solving this equation (often
numerically) gives the equilibrium conversion. The equilibrium
composition is then found by substituting ’x’ back into the
”Equilibrium (mol)” column of the ICE table.
4. Limiting Conversion Due to Chemical Equilibrium

▶ Limiting Conversion: The maximum conversion of a reactant

achievable under given conditions, dictated by the equilibrium
constant. You can’t get 100% conversion if K is finite.
▶ Why it Occurs: As products form, the reverse reaction rate
increases. Eventually, the forward and reverse rates become
equal, and the net conversion stops, even if reactants are still
present.
▶ Effect of Equilibrium Constant (K):
▶ Large K: High limiting conversion (reaction goes almost to
completion).
▶ Small K: Low limiting conversion (reaction hardly proceeds).
4. Limiting Conversion (Continued)

▶ Influence of Conditions:
▶ Temperature: Affects K (van’t Hoff equation). For
endothermic reactions, increasing temperature increases K and
limiting conversion. For exothermic, it’s the opposite.
▶ Pressure: Affects K for gas-phase reactions with a change in
the number of moles. Increasing pressure favors the side with
fewer moles of gas.
▶ Initial Reactant Concentrations: Using an excess of one
reactant can shift the equilibrium towards the products,
increasing the conversion of the limiting reactant.
▶ Example: Consider A ⇌ B. If K = 1, and you start with pure
A, the limiting conversion is 50%. If K = 100, the limiting
conversion is much closer to 100%.
5. Practical Considerations in Reactor Design

▶ Strategies to Overcome Equilibrium Limitations:

▶ Excess Reactants: Increase the concentration of one reactant
to drive the reaction further to the right (Le Chatelier’s
Principle).
▶ Product Removal: Continuously remove products (e.g., by
distillation, membrane separation) to shift the equilibrium
towards product formation.
▶ Optimal Conditions: Choose temperature and pressure to
maximize K (and thus conversion) while considering reaction
kinetics.
▶ Reactive Distillation: Combine reaction and separation in a
single unit.
▶ Membrane Reactors: Use selective membranes to remove
products.
5. Practical Considerations (Continued)

▶ Trade-offs between Equilibrium and Kinetics:

▶ Equilibrium Conversion: Tells you the maximum possible
conversion.
▶ Reaction Kinetics: Tells you how fast the reaction proceeds.
▶ Reactor Design: Must consider both equilibrium and kinetics.
A fast reaction may still have a low yield if equilibrium is
unfavorable. A favorable equilibrium may be useless if the
reaction is too slow. Reactor size and residence time are key
parameters.
6. Step-by-Step Example: Ammonia Synthesis

Reaction: N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

Scenario: We have a reactor operating at 400°C and 200 atm.
The feed contains a stoichiometric ratio of nitrogen and hydrogen
(1:3). We want to find the equilibrium conversion of nitrogen and
the equilibrium composition.
Steps:
1. Obtain K: Find the equilibrium constant (K) for the reaction
at 400°C and 200 atm. This typically involves using
thermodynamic data (e.g., Gibbs free energy of formation)
and potentially an equation of state to account for non-ideality
at high pressure. For this example, let’s assume we’ve
calculated K = 0.01 (This is a simplified value for illustration).
6. Example (Continued)

2. Set up ICE Table:

Species Initial (mol) Change (mol) Equilibrium (mol)
N2 1 -x 1-x
H2 3 -3x 3-3x
NH3 0 +2x 2x
Here, ’x’ represents the conversion of N2 .
6. Example (Continued)

3. Express K in terms of x:
▶ In terms of mole fraction K is:
2
yNH3
Ky = 3
yN2 yH2
▶ Where, yi is the mole fraction of component i.
6. Example (Continued)

4. Calculate total number of moles:

Ntotal = (1 − x) + (3 − 3x) + 2x = 4 − 2x

5. Calculate Partial Pressures and K:

1 (2x/(4 − 2x))2 1
K = Ky · 2
= 3
· 2
P ((1 − x)/(4 − 2x))((3 − 3x)/(4 − 2x)) P

(2x)2 (4 − 2x)2
0.01 = 3
·
(1 − x)(3 − 3x) P2
6. Solve for x: This equation can be solved numerically to find
the equilibrium conversion x.