INTRODUCTION TO CHEMICAL

PROCESS SIMULATORS
DWSIM Chemical Process Simulator

A. Carrero, N. Quirante, J. Javaloyes

October 2016
Introduction to Chemical Process Simulators

Contents
Monday, October 3rd 2016
 Introduction to Sequential – Modular Steady State Process
Simulators
 Get used to working with DWSIM and COCO
Monday, October 10th 2016
 Simulation of Chemical Reactors
Monday, October 17th 2016
 Simulation of Distillation Columns
Monday, October 24th 2016
 Case studies

2 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Tips to introduce inlet data in DWSIM

1. Introduce the composition and accept the changes

2. Introduce the rest of the inlet information by pressing Enter after writing each data

Pressure
Temperature
Mass o molar flow

For any simulator!

3. Review the thermodynamic model

4. Review the units

3 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactions
• Conversion: specify the conversion (%) of the limiting reagent as a
function of temperature.

• Equilibrium: specify the equilibrium constant (K) as a function of

temperature, a constant value or calculated from the Gibbs free energy
reaction (DG/R).

• Kinetic: specify the frequency factor (A) and the activation energy (E)
for the direct reaction (optionally for the reverse reaction), including the
orders of reaction of each component.

• Heterogeneous catalytic: specify the kinetic terms of the kinetic

reaction as well as the activation energy, frequency factor, and
component exponent terms of the adsorption kinetics.

4 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Conversion Reaction
• It is assumed that the user has information regarding the conversion of
one of the reactants as a function of temperature.
• By knowing the conversion and the stoichiometric coefficients, the
quantities of the components in the reaction can be calculated.
• Considering the following reaction:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶
where a, b and c are the stoichiometric coefficients of reactants and
product, respectively. A is the limiting reactant and B is in excess. The
amount of each component at the end of the reaction can be calculated
from the following stoichiometric relationships:
𝑏 𝑐
𝑁𝐴 = 𝑁𝐴𝑜 − 𝑁𝐴𝑜 𝑋𝐴 𝑁𝐵 = 𝑁𝐵𝑜 − 𝑁𝐴𝑜 𝑋𝐴 𝑁𝐶 = 𝑁𝐶𝑜 + 𝑁𝐴𝑜 𝑋𝐴
𝑎 𝑎

5 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Conversion Reaction
DWSIM COCO

6 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Equilibrium Reaction
• The quantity of each component at the equilibrium is related to
equilibrium constant by the following relationship:
𝑛
𝜐𝑗
𝐾= 𝑞𝑗
𝑗=1

where K is the equilibrium constant, q is the basis of components (partial

pressure in the vapor phase or activity in the liquid phase), ν is the
stoichiometric coefficient of component j and n is the number of
components in the reaction.
• The equilibrium constant can be obtained:
• Considering it as a constant.
• Considering it as a function of temperature.
• Calculating it automatically from the Gibbs free energy at the
temperature of the reaction.

7 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Equilibrium Reaction
DWSIM COCO

8 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Kinetic Reaction
• It is defined by the parameters of the equation of Arrhenius (frequency
factor and activation energy) for both the direct order and for reverse
order.
• Considering the following kinetic reaction:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
• The reaction rate for the A component can be defined as:
𝑟𝐴 = 𝑘 𝐴 𝐵 − 𝑘 ′ [𝐶][𝐷]
where:
𝑘 = 𝐴 𝑒𝑥𝑝(−𝐸/𝑅𝑇) 𝑘′ = 𝐴′ 𝑒𝑥𝑝(−𝐸′/𝑅𝑇)

• The kinetic reactions are used in Plug-Flow Reactors (PFR) and in

Continuous-Stirred Tank Reactors (CSTR).
𝑉
• FA is the molar flow of the A component.
𝐹𝐴 = 𝐹𝐴𝑜 + 𝑟𝐴 𝑑𝑉 • V is the reactor volume.

9 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Kinetic Reaction
DWSIM COCO

10 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Heterogeneous Catalytic Reaction

• It is described the rate of catalytic reactions involving solid catalyst.
• Considering the following reaction:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶

• Depending on the reaction mechanism, the reaction rate expression can

be generally written as:
𝑅𝑒𝑎𝑐 𝛼𝑖 𝑃𝑟𝑜𝑑 𝛽𝑗
𝑘𝑓 𝑖=1 𝐶𝑖 − 𝑘𝑟 𝑗=1 𝐶𝑗
𝑟= 𝛾 𝑛
𝑀 𝑀 𝑘𝑔
1+ 𝑘=1 𝐾𝑘 𝑔=1 𝐶𝑔

where kf and kr are the rate constants of the forward and reverse kinetic
rate expressions, K is the absorption rate constant, and M is the number of
absorbed reactants and products plus absorbed inert species.

11 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactions
• Chemical reactions in DWSIM are managed through the Chemical
Reactions Manager and in COCO through Settings – Reaction packages .

• The user can define various reactions which are grouped in Reaction
Sets. This reaction sets list all chemical reaction, and the user must
activate only those we wants to become available for one or more
reactors.
• In the reaction set configuration window we define the reaction
ordering.

12 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactors
DWSIM COCO
• Conversion Reactor
CONVERSION

• Equilibrium Reactor
EQUILIBRIUM

• Gibbs Reactor
GIBBS REACTOR

• CSTR
CSTR

• PFR PFR

13 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactors

Reaction type Reactor type

Conversion Conversion

Equilibrium Equilibrium, Gibbs

Kinetic PFR, CSTR

Heterogeneous catalytic PFR, CSTR

14 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactors

Conversion Reactor

• The conversion reaction is a vessel in which conversion reactions are

performed.
• You can only attach reaction sets that contain conversion reactions.
• It should be specified the stoichiometry of all reactions and the
conversion of the limiting reactant.
• This reactor calculates the composition of the outlet streams.

15 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactors

Equilibrium Reactor

• The equilibrium reactor is a vessel which models equilibrium reactions.

• The outlet streams of the reactor are in a state of the chemical and
physical equilibrium.
• The reaction set can contain an unlimited number of equilibrium
reactions, which are simultaneously or sequentially solved.

16 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactors

Gibbs Reactor

• Gibbs reactors can work with equilibrium reactions or without any

reaction information (Gibbs minimization mode).
• In this case, it will respect the element mass balance and try to find a
state where the Gibbs free energy will be at a minimum.

17 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactors

CSTR

• The CSTR (Continuous-Stirred Tank Reactor) is a vessel in which Kinetic

and Heterogeneous catalytic reactions can be performed.
• The conversion in the reactor depends on the rate expression of the
reactions associated with the reaction type.
• The inlet stream is assumed to be perfectly (and instantaneously) mixed
with the material already in the reactor, so that the outlet stream
composition is identical to that of the reactor contents.
• To simulate the CSTR we need to know the volume of the reactor.

18 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Reactors

PFR

• The PFR (Plug Flow Reactor, or Tubular Reactor) generally consists of a

bank of cylindrical pipes or tubes.
• The flow field is modeled as plug flow, implying that the stream is
radially isotropic (without mass or energy gradients). This also implies
that axial mixing is negligible.
• To simulate the PFR we need to know the volume and the length of the
reactor.

19 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Butyl Acetate Production

The following system is used to produce Butyl-acetate from Methyl acetate
and Methanol.
MeAC  BuOH MeOH  BuAc
Use Peng-Robinson (PR) thermodynamic package
Reactor
DP = 0 atm
BuOH Feed Liquid phase reaction
100 kmol/h
T = 305 K
P = 15 atm

R in R out
P = 5 atm T = 305 K
P = 5 atm
MeAc Feed
150 kmol/h
T = 305 K
P = 15 atm

20 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Butyl Acetate Production

The following system is used to produce Butyl-acetate from Methyl acetate

and Methanol.

MeAC  BuOH MeOH  BuAc

Use Peng-Robinson (PR) thermodynamic package

The reaction follows the next kinetic law:
𝑘𝑚𝑜𝑙
𝑟 = 𝑘𝐹 𝐶𝑀𝑒𝐴𝑐 𝐶𝐵𝑢𝑂𝐻 − 𝑘𝑅 𝐶𝑀𝑒𝑂𝐻 𝐶𝐵𝑢𝐴𝑐 𝑠·𝑚3

71960
− 𝑅𝑇
𝑘𝐹 = 7 · 106 𝑒𝑥𝑝
72670
6 − 𝑅𝑇
𝑘𝑅 = 9.467 · 10 𝑒𝑥𝑝

21 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Butyl Acetate Production

The following system is used to produce Butyl-acetate from Methyl acetate

and Methanol.
MeAC  BuOH MeOH  BuAc
Use Peng-Robinson (PR) thermodynamic package

Molar flow and composition of the reactor outlet stream, for different
types of reactors:

• Conversion reactor, assuming 10% of methyl acetate

• Gibbs reactor.
• Plug Flow Reactor (PFR), 4 m length and 0.5 m diameter.
• Continuous-Stirred Tank Reactor (CSTR), 2 m3 volume.

22 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Ethylene Glycol Production

monoetilenglicol

Dietilenglicol

Trietilenglicol
Óxido de etileno

Agua

Reciclado
Pesados

23 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Ethylene Glycol Production

Simulate with COFE (COCO) a reactor to produce ethylene glycol considering
that we know the conversion for each reaction.

Reactions:

Use Peng-Robinson (PR) thermodynamic package

24 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Ethylene Glycol Production

Parametric study varying length of the PFR

Kinetics

Kinetics in COCO
R1 = exp(13.62-8220/T)/60/1000*C(Water)*C("Ethylene oxide")
R2 = exp(15.57-8700/T)/60/1000*C("Monoethylene glycol")*C("Ethylene oxide")
R3 = exp(16.06-8900/T)/60/1000*C("Diethylene glycol")*C("Ethylene oxide")

25 A. Carrero , N. Quirante & J. Javaloyes

Introduction to chemical process simulators

Ethylene Glycol Production

Parametric study varying length of the PFR
0.3

0.25

0.2

Mole f raction Ethy lene oxide stream 2

Mole f raction Ethy lene gly col stream 2
Mole f raction Diethy lene gly col stream 2
Mole fraction

Mole f raction Triethy lene gly col stream 2

0.15

0.1

0.05

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

Length of PFR / m

26 A. Carrero , N. Quirante & J. Javaloyes