Process Simulation using ASPEN PLUS

Karthikeyan Marimuthu Graduate Research Assistant

January 20, 2011

Outline
 Introduction  Motivation  Principles of flow sheet simulation  Thermodynamic Models  Examples  Conclusion

Introduction

Complex Ammonia Plant

A Simple flow sheet of Ammonia Plant

Process Flow Sheets are the language of Chemical Processes and Plants1 Modeling converts the flow sheet in to equations. Software Simulations solve the equations.
1. Seider et al (2004)

Process Modeling
Modeling

Modeling is an art of deriving inter relationships between process variables.

Model

A process model is a set mathematical equations that express the behavior of the system under the various assumptions.
Examples 1) Expected travelling time from Guindy to A.C.Tech when the Chief Minister is expected to arrive Governor bungalow. 2) The rate of diffusion of a drug molecule inside blood.

Notion of a Model

This slide is taken from the lecture notes of Dr. Niket Kaisare, CH 512, IIT Madras

Classification of Models
Linear Steady State Non Linear Deterministic Lumped Parameter Non linear Model Dynamic Linear Empirical Correlations Stochastic Difference Equations Distributed Parameter Non linear Linear

This model classification is biased towards deterministic modeling in Chemical Engineering. Otherwise, one can classify models in many ways.

Model Development Procedure

1) Define the objectives of the model?
The purpose of the model? Type of the model?

2) Identify and classify different variables

Model inputs are not same as the process inputs

3) Flow diagram and the control volume (helps for step 1 and 2)

Model Development Procedure

4) Conservation of Momentum/Mass/Energy/Species
rate rate rate rate of of of of generation/ ! - s accumulation input output disappearance

5) Additional Constitutive Relationships

Mass Transfer/Thermodynamics : Equation of state, Equilibrium relationships (VLE), etc Reaction Engineering : Reaction Kinetics Heat Transfer : Empirical equations for heat/mass transfer coefficients, etc Fluid Mechanics : Coefficient of discharge, friction factor, drag coefficient, etc Design : Pump specification, Valve behavior etc

Model Development Procedure

6) Check for the consistency
   of 7) Model should be mathematically consistent. Units of the variables should be consistent. How many variables are needed to be specified (Degrees Freedom).

Solve the model equations

Check whether analytical solution is possible ( Mostly not possible). Identify an appropriate numerical scheme to solve differential equation/algebraic equations.

8)

Validation
 Check whether the results are physically realizable.  Check whether the results matches the experimental data.

Example Flash Drum

Fv
v

Gas

yj Vv P yj F0 P0 T0
0

Feed

VL T
L

x0j

xj

FL xj

liquid

Binary Flash Drum

Flash Drum
1) Objectives of the model?
For a given input mixture, find out amount and concentration of outlet. Deterministic Steady state and Dynamic model

2) Identify and classify different variables

Input : Feed composition (x0j ), Pressure inside the vessel (P), Inlet temperature and temperature inside the vessel (Isothermal expansion). Output : Final liquid and gas compositions.

3) Flow diagram and the control volume

Steady State Model

4) Steady State Model
0 rate rate rate rate of of of of generation/ ! - s accumulation input output disappearance 0

Over all Balance

V 0 F0 ! V v Fv  V L FL
Component Balance

V 0 F0 V v Fv V L FL xj yj  x0 j ! av av av ML Mv M0

Steady State Model

Energy Balance

h0 V 0 F0 ! HV v Fv  hV L FL h0 ! f1  0 j , T h ! f 2  j , T x , x , H ! f 3 y j , T , P
Vapor Liquid Equilibrium

y j ! f  j ,T , P x
This is very important and we will discuss this in detail.

Degrees of Freedom
Total Number of Variables
Number of variables in the system Input : Gas : Liquid :
0

3NC + 16

, F0 , M0av , x01, x02, , Fv , Mvav , H,y1, y2, , FL , MLav ,h,x1, x2,

..xNC, T0, h0 & Po - NC + 6 ..yNC - NC +4 T&P -2 ..xNC - NC +4

Degrees of Freedom
Total Number Equations
Over all Mass balance Energy Balance Component Mass Balance Mole fraction constraints (Feed, Gas and Liquid) Equilibrium Relationships (for all components) Average Molecular weight Density of Feed vapor and liquid Enthalpies of Feed, Vapor and Liquid Total Number of Equations 1 1 NC-1 3 NC 3 3 3 2NC + 13

Degrees of Freedom
Degrees of Freedom = Total Number of Variable Total number of Equations = 3NC + 16 (2NC+13) = NC + 3 Need to specify NC + 3 variables to solve this problem Feed Composition of NC-1 components Initial Pressure P0 Pressure inside the vessel P Initial Temperature T0 Initial flow rate - F0 NC-1 1 1 1 1

Dynamic Model
Unsteady State Model
0 rate rate rate rate of of of of generation/ ! - s accumulation input output disappearance

Over all Balance

d  L VL V ! V 0 F0  V v Fv  V L FL dt

Dynamic Model
Component Balance

V L x jVL d M av L dt

V F ! 0 0 x  V v Fv y  V L FL x 0j j j av av av M0 Mv ML

Energy Balance

d  L V L h V ! h0 V 0 F0  HV v Fv  hV L FL dt

Thermodynamic Models
Equilibrium Relationship
In addition to Mass and Energy balance we need thermodynamic relationship (VLE) Several Thermodynamic models are available to generate equilibrium relationship between vapor and liquid phase. Wrong selection of thermodynamic will result in a poor estimation of output variables. The problem is further complicated when there are several operations happening.

Mixture

Reproduced from Hill and Justice (2011), CEP.

K Model

yi ! Kxi
No universal model to predict the values of K. Different mixture have different dominant behavior. Different models have been developed to predict the values of K of a mixture based on it s dominant behavior. VLE for a mixture of water and Ethanol is dominated by the liquid phase behavior, while the mixture of hexane and propane dominated by vapor.

Determination of K

yi K i Pi !K ! xi Ji P

Sat

Generalized VLE relation ship For Ideal mixture Ki = Pisat / P(T) Activity Coefficient Fugacity Coefficient Not all the mixtures of Ideal Need to determine Activity coefficient and fugacity coefficients for a given mixture. Based on the behavior the mixture, one should use the appropriate thermodynamic model

Thermodynamic Models
Equation of State (PVT relationship) Approach Ideal gas - Light gases (at low pressure and high temperature) Real gas Compressibility factor Combustion gases, alkane mixtures Cubic Equation of state - Van der Waals Redlich-Kwong Soave-Redlich-Kwong (Petroleum) Peng Robinson (Hydro Carbons)

Thermodynamic Models
Activity Coefficient Models Based on the thermodynamic constraint on the liquid Based on the Excess Gibbs free energy of a mixture. Includes the binary interaction parameter. Examples (Commonly used) NTRL (BIP) UNIFAC & UNIQUAC NRTL

Comparison of Models

Reproduced from Hill and Justice (2011), CEP.

Summary of Thermodynamic Models

Model Category Equation of State Most Commonly used System Type models SRK, PR Real gas + ideal liquid Examples Petroleum pseudo components, Similar hydrocarbons Light gases

Activity coefficient(BIP)

NRTL Wilson

Ideal gas + Polar liquid Water + Organics Dissimilar Hydrocarbons(Benzen e and cyclohexnane Ideal gas + Polar liquid Mineral acids and water Dissimilar organics (Ester and alcohols) Aqueous Electrolyte Water + Acid, base or solids

Predictive Activity

UNIFAC UNIQUAC

Electrolyte

NRTL

Hill and Justice (2011), CEP.

Validation

Hill and Justice (2011), CEP.

Example - 1
Problem Statement A liquid mixture of 25 mol % n pentane, 45 mol % n-hexane and 30 mol % n-heptane, initially at 69 deg C and a high pressure, is partially vaporized by isothermally lowering the pressure to 1 bar. Find the relative amounts of vapor and liquid in equilibrium and their components.

Solution
Assumptions - Ideal mixture , yi /xi = Pivap /P - Vapor pressure can be determined using Antonie equation (ln(Psat )= A B/(T + C))
P5vap ! 2.721 bar, P6vap ! 1.024 bar & P7vap ! 0.389 bar

- Basis 1 mol/time units Equilibrium Relationships

y5 ! K 5 x5 where K 5 ! 2.7406 y6 ! K 6 x6 where K 6 ! 1.0109 y7 ! K 7 x7 where K 7 ! 0.3844

Solution
Constraint on the Mole fractions
x5  x6  x7 ! 1 y5  y6  y7 ! 1

Component Balances
x5 L  y5V ! 0.25 x6 L  y6V ! 0.45 x7 L  y7V ! 0.30

Over all Balance

L V ! 1

8 equations and 8 unknowns Relatively easy to solve

What if
The Mixture is non ideal - Need to use an appropriate thermodynamic model - May need to solve non linear algebraic equations ( Especially EOS method) - Developing an appropriate Numerical Method is very important - Convergence is critical. - Need to write your own software code to solve the problem.

What if
If your unit (Flash vessel) is connected to other units -You are required to do the mass balance for over all system - Not an easy task - Need to write a big & generalized code - You are required to replace one unit - Generalized code may not work.

ASPEN Solves for you

ASPEN Process Simulator

In 1970s the researchers at MIT s Energy laboratory developed a prototype for process simulation. They called it Advanced System for Process Engineering (ASPEN) This software has been commercialized in 1980 by the foundation of a company named ASPEN Tech. Build in Thermodynamic models, model library for distillation columns, separators, heat exchangers, reactors, etc. In build property data bank.

Process Simulators
Steady State Simulators ASPEN Plus, (We will study this alone in this work shop) ASPEN Hysys, HYSYS UNISIM(Honeywell), Pro II (Simulation Sciences) Dynamic Simulation ASPEN dynamics HYSIS Batch Processes BATCH Plus SUPERPRO Designer.

How to Start
Any Process Simulators does not model the process for you. You should know how to solve the problem. You Should know what thermodynamic model should be used. Simulator will generate equations based on how to you define the problem and then solve them. Using the instructions manual start with a simple problem (For example Flash vessel). Once you start solving the problem, you will learn all the available software features.

Example Main Window

To start with fresh flow sheet

You can select already developed flow sheet

User Interface

Equipment Choices

Streams that connect different equipments

Status of the flow sheet

Setting up a Simulation

Note the stream numbers

Output Flow Stream - Vapor

Input Flow Stream Click on this and drag to the main window Separators is checked

Flash Drum

Output Flow Stream - Liquid

Enter the details

Click on any stream, you will get the below data browser window

Click on Components Red indicated incomplete

Click on this and drag to the main window

Enter the details

Can see the component Window & Click on the space indicated

Enter the details

Components Data base. Type the component name & click find now

Search Results. Select your component and add.

You can see the new space for the next component. Repeat the same procedure.

Enter the details

Can see the color change from Red to Blue also there is tick OK.

All components are entered

Click next button, it will take you to next step

Enter the details

Changing the unit systems to SI and click next

Enter the details

Process Type The Category your component (Select)

Base Method Type of Thermodynamic Model that you think is the best

Enter the details

Ideal mixture is selected. You choose what you think is right!

Enter the details

Input conditions are entered

Enter the details

Flash conditions

Input is complete Simulation is ready to run. Click next to run.

Enter the details

Simulation is Completed

Enter the details

Click on Results and Summary, then Streams ( You can also generate the output summary).

Enter the details

Final Results!!! You are done!!!

Change the thermodynamic model and check whether the results are changing!!

Conclusion
A complex flow sheet can also be made and simulated as we have learned. Good modeling skill and basic knowledge in Simulations would be recommended to use ASPEN Plus. Before using ASPEN, it is recommended to simulate a simple flow sheet using your own code (Matlab).

THANK YOU