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Luyben: Distillation Design and Control Using ASPEN Simulation

ASPEN Simulation
Scenarios-Based Tutorial 1 Physical Properties

Cheng-Liang Chen
LABORATORY

PSE

Department of Chemical Engineering National TAIWAN University

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Outline
Part 1:
Start-up ASPEN Plus Physical Properties of Pure Components (Benzene and Toulene) Binary Vapor-Liquid Equilibrium (Benzene and Toulene)

Part 2:
Distillation Short-cut Design: DSTWU (Benzene and Toulene) Rigorous Distillation Simulator: RadFrac
 Ex: Benzene and Toluene Separation  Ex: Propane and iso-Butane Separation

Part 3:
Simulation of Multicomponent Nonideal Systems
 Ex: Methyl Acetate / Methanol / Water  Ex: Ethanol Dehydration  Ex: Heat-integrated Columns (Methanol / Water)

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Start Up ASPEN Plus

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Start Up ASPEN Plus

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Start Up

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Start Up

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Physical Properties of Pure Components

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

Int. system units (SI); English eng. units (ENG); Metric eng. units (MET)

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene
Chao-Seader Pure Component Liquid Fugacity Model
The Chao-Seader model calculates pure component fugacity coecient, for liquids. It is used in the CHAO-SEA property method. This is an empirical model with the Curl-Pitzer form. The general form of the model is: 0 1 ln (i) = ln i + i ln i
0 1 i , i = fcn (T, Tci; p, pci)

References K.C. Chao and J.D. Seader, A General Correlation of Vapor-Liquid Equilibria in Hydrocarbon Mixtures, AIChE J., Vol. 7, (1961), p. 598.

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Physical Properties of Pure Components

Benzene and Toulene

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Pure Component Properties

On the Pure Component Properties Analysis dialog box, most of the required information is set to defaults, including:
Item Property Method Information The global property method is used, as specied on the Properties Specications Global sheet. You can select any Property Method that appears on the Properties Specications form. The default is a temperature range from 0 to 25o C. You can enter a new range by modifying lower and upper temperatures, or you can change from a temperature range to a temperature list, and specify a list of discreet temperature values. The default is 41 points. You can change the number of points, or enter a temperature increment The default is 1 atm. You must change the default for vapor properties, for liquid properties near the critical point, and properties generated from EOS property methods

Temperature

Number of points to be tabulated Pressure

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Available Thermodynamic/Transport Properties

Item AVAIL CP CPCV CV DG DGPC DH DHPC DHVL DS K MU Property Availability, H T0S Constant pressure heat capacity Heat capacity ratio Constant volume heat capacity Free energy departure Free energy dep, pressure cor. Enthalpy departure Enthalpy dep, pressure cor. Enthalpy of vaporization Entropy departure Thermal conductivity Viscosity Item GIG H PHI PHIPC PL RHO S V SONVEL U SIGMA Property (Ideal gas) Free energy Enthalpy Fugacity coecient Fugacity coef, pressure cor. Vapor pressure Density Entropy Volume Sonic velocity Internal energy Surface tension

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Physical Properties of Pure Components

Benzene

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Physical Properties of Pure Components

Benzene

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Physical Properties of Pure Components

Benzene

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Physical Properties of Pure Components

Benzene

ln P

D =C+ T

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Physical Properties in Aspen Physical Property System

The following properties may be required by Aspen Physical Property System calculations: Thermodynamic Properties Fugacity coecients (for K values) Enthalpy Entropy Gibbs energy Molar volume Transport Properties Viscosity Thermal conductivity Diusion coecient Surface tension

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Physical Properties in Aspen Physical Property System

The properties required by unit operation models in the Aspen Physical Property System are called major properties and are listed in the table labeled Major Properties in Aspen Physical Property System. A major property may depend on other major properties. In addition, a major property may depend on other properties that are not major properties. These other properties can be divided into two categories: subordinate properties and intermediate properties. Subordinate properties may depend on other major, subordinate or intermediate properties, but are not directly required for unit operation model calculations. Examples of subordinate properties are enthalpy departure and excess enthalpy. The table labeled Subordinate Properties in Aspen Physical Property System lists the subordinate properties.

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Physical Properties in Aspen Physical Property System

The properties required by unit operation models in the Aspen Physical Property System are called major properties and are listed in the table labeled Major Properties in Aspen Physical Property System. A major property may depend on other major properties. In addition, a major property may depend on other properties that are not major properties. These other properties can be divided into two categories: subordinate properties and intermediate properties. Intermediate properties are calculated directly by property models, rather than as fundamental combinations of other properties. Common examples of intermediate properties are vapor pressure and activity coecients. The table labeled Intermediate Properties in Aspen Physical Property System lists the intermediate properties. Major and subordinate properties are obtained by a method evaluation. Intermediate properties are obtained by a model evaluation.

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Major Properties in Aspen Physical Property System

Prop Name PHlV PHIL PHlS PHlV PHlLMX PHlSMX HV HL HS HVMX HLMX HSMX GV GL GS GVMX GLMX GSMX SV SL SS SVMX SLMX SSMX Symbol ,v i ,l i ,s i v i l i s i ,v Hi ,l Hi ,s Hi v Hm l Hm s Hm ,v i ,l i ,s i Gv m l Gm Gs m ,v Si ,l Si ,s Si v Sm l Sm s Sm Description Vapor pure component fugacity coecient Liquid pure component fugacity coecient Solid pure component fugacity coecient Vapor fugacity coecient of a component in a mixture Liquid fugacity coecient of a component in a mixture Solid fugacity coecient of a component in a mixture Vapor pure component molar enthalpy Liquid pure component molar enthalpy Solid pure component molar enthalpy Vapor mixture molar enthalpy Liquid mixture molar enthalpy Solid mixture molar enthalpy Vapor pure component molar Gibbs free energy Liquid pure component molar Gibbs free energy Solid pure component molar Gibbs free energy Vapor mixture molar Gibbs free energy Liquid mixture molar Gibbs free energy Solid mixture molar Gibbs free energy Vapor pure component molar entropy Liquid pure component molar entropy Solid pure component molar entropy Vapor mixture molar entropy Liquid mixture molar entropy Solid mixture molar entropy

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Major Properties in Aspen Physical Property System

Prop Name VV VL VS VVMX VLMX VSMX MUV MUL MUVMX MULMX KV KL KS KVMX KLMX KSMX DV DL DVMX DLMX SIGL SIGLMX Symbol ,v Vi ,l Vi ,s Vi v Vm l Vm s Vm ,v i ,l i v l ,v i ,l i ,s i v l s v Dij l Dij v Di l Di ,l i l Description Vapor pure component molar volume Liquid pure component molar volume Solid pure component molar volume Vapor mixture molar volume Liquid mixture molar volume Solid mixture molar volume Vapor pure component viscosity Liquid pure component viscosity Vapor mixture viscosity Liquid mixture viscosity Vapor pure component thermal conductivity Liquid pure component thermal conductivity Solid pure component thermal conductivity Vapor mixture thermal conductivity Liquid mixture thermal conductivity Solid mixture thermal conductivity Vapor binary diusion coecient Liquid binary diusion coecient Vapor diusion coecient of a component in a mixture Liquid diusion coecient of a component in a mixture Pure component surface tension Mixture surface tension

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Subordinate Properties in Aspen Physical Property System

Prop Name DHV DHL DHS DHVMX DHLMX DHSMX DHVPC DHLPC DHSPC DGV DGL DGS DGVMX DGLMX DGSMX DGVPC DGLPC DGSPC DSV DSL DSS Symbol Description
,ig

Hi Hi ,l ,ig Hi Hi ,s ,ig Hi Hi v ig Hm Hm l ig Hm Hm s ig Hm Hm ,v ,v Hi (p) Hi (p i) ,l ,l Hi (p) Hi (pi ) ,s ,s Hi (p) Hi (p i) ,v ,ig i i ,l ,ig i i ,s ,ig i i ig Gv m Gm ig Gl m Gm ig Gs m Gm ,v ,v i (p) i (p i) ,l ,l i (p) i (p i) ,s ,s i (p) i (pi ) ,v ,ig si si ,l ,ig si si ,s ,ig si si

,v

Vapor pure component molar enthalpy departure Liquid pure component molar enthalpy departure Solid pure component molar enthalpy departure Vapor mixture molar enthalpy departure Liquid mixture molar enthalpy departure Solid mixture molar enthalpy departure Vapor pure component molar enthalpy departure pressure correction Liquid pure component molar enthalpy departure pressure correction Solid pure component molar enthalpy departure pressure correction Vapor pure component molar Gibbs energy departure Liquid pure component molar Gibbs energy departure Solid pure component molar Gibbs energy departure Vapor mixture molar Gibbs energy departure Liquid mixture molar Gibbs energy departure Solid mixture molar Gibbs energy departure Vapor pure component molar Gibbs energy departure pressure correction Liquid pure component molar Gibbs energy departure pressure correction Solid pure component molar Gibbs energy departure pressure correction Vapor pure component molar entropy departure Liquid pure component molar entropy departure Solid pure component molar entropy departure

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Subordinate Properties in Aspen Physical Property System

Prop Name DSVMX DSLMX DSSMX HNRY HLXS HSXS GLXS GSXS PHILPC PHISPC GAMPC GAMPC1 HNRYPC XTRUE MUVLP MUVPC MUVMXLP MUVMXPC KVLP KVLP KVMXLP KVMXPC Symbol ig sv m sm ig sl m sm ig ss m sm HiA E,l Hm E,s Hm GE,l m E,s Gm ,l ,s E E Pc iA xt ,v i (p = 0) ,v ,v i (p) i (p = 0) v (p = 0) v (p) v (p = 0) ,v i (p = 0) v (p) v (p = 0) ,v i (p = 0) v (p) v (p = 0) Description Vapor mixture molar entropy departure Liquid mixture molar entropy departure Solid mixture molar entropy departure Henrys constant of supercritical component i in subcritical component A Liquid mixture molar excess enthalpy Solid mixture molar excess enthalpy Liquid mixture molar excess Gibbs energy Solid mixture molar excess Gibbs energy Pure component liquid fugacity coecient pressure correction Pure component solid fugacity coecient pressure correction Liquid activity coecient pressure correction, symmetric convention Liquid activity coecient pressure correction, asymmetric convention Henrys constant pressure correction for supercritical component i True composition. in subcritical component A Pure component low pressure vapor viscosity Pure component vapor viscosity pressure correction Low pressure vapor mixture viscosity Vapor mixture viscosity pressure correction Pure component low pressure vapor thermal conductivity Pure component vapor thermal conductivity pressure correction Low pressure, vapor mixture thermal conductivity Vapor mixture thermal conductivity pressure correction

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Intermediate Properties in Aspen Physical Property System

Prop Name GAMMA GAMUS GAMMAS WHNRY PL PS DHVL DHLS DHVS VLPM Symbol s w ,l pi ,s pi vapHi fusHi subHi Vil Description Liquid phase activity coecient Liquid phase activity coecient, unsymmetric convention Solid phase activity coecient Henrys constant mixing rule weighting factor Liquid pure component vapor pressure Solid pure component vapor pressure Pure component enthalpy of vaporization Pure component enthalpy of fusion Pure component enthalpy of sublimation Partial molar liquid volume

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Vapor Pressure Models for Pure Liquids

The Aspen Physical Property System has several submodels for calculating vapor pressure of a liquid. It uses parameter THRSWT/3 to determine which submodel is used. If THRSWT/3 is 0 200 301 302 400 401 501 502 Then this equation is used Extended Antoine BARIN Wagner PPDS Modied Wagner PML IK-CAPE NIST TDE Polynomial NIST Wagner 25

See Pure Component Temperature-Dependent Properties for details.

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Vapor Pressure Models for Pure Liquids

Extended Antoine Equation
Parameters for many components are available for the extended Antoine equation from the Aspen Physical Property System pure component databank. This equation can be used whenever the parameter PLXANT is available. The equation for the extended Antoine vapor pressure model is:
,l ln(p i )

C2i = C1i + + C4i + C5i ln(T ) + C6iT C7i T + C3i

for C8i T C9i

Default values are zero for C3i, . . . , C8i; 1000 for C9i

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Thermodynamic Properties Model

Model Antoine/Wagner API liquid volume Aqueous Electrolyte NRTL Enthalpy Aqueous Electrolyte NRTL Gibbs Energy ASME Steam Tables Brelvi OConnell Bromley Pitzer Bromley Pitzer Enthalpy Bromley Pitzer Gibbs Energy BWR Lee Starling Cavett Liquid Enthalpy Departure Chao Seader Clarke Aqueous Electrolyte Density Constant Activity Coecient Costald Liquid Volume COSMO-SAC Debye Huckel Volume DIPPR Liquid Heat Capacity Electrolyte NRTL Electrolyte NRTL Enthalpy Electrolyte NRTL Gibbs Energy ENRTL-SAC (patent pending) Grayson Streed Hayden OConnell Model Name PL0XANT VL2API HAQELC GAQELC ESH2O0, ESH2O VL1BROC GMPT2 HAQPT2 GAQPT2 ESBWR0, ESCSTBWR DHL0CVT, DHL2CVT PHL0CS VAQCLK GMCONS VL0CTD,VL2CTD COSMOSAC VAQDH HL0DIP, DHL0DIP GMENRTL HMXENRTL GMXENRTL ENRTLSAC PHL0GS ESHOC0, ESHOC Phase L L1 L2 L L L VL L L L L VL L L L S L L L L L L1 L2 L L L L V Properties PL VLMX HLMX GLMX + VLPM GAMMA HLMX GLMX +,++ DHL,DHLMX PHIL VLMX GAMMA VL,VLMX GAMMA VLMX HL, DHL GAMMA HLMX GLMX GAMMA PHIL +, ++

+ A pure component equation of state model calculates: PHIL,PHIV,DHL,DHV,DGL,DGV,DSL,DSV,VL,VV ++ A mixture equation of state model calculates: PHILMX,PHIVMX,DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX +++ DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX

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Thermodynamic Properties Model

Model Henrys constant HF equation of state Ideal Gas Kent Eisenberg Lee Kesler Lee Kesler Plocker Modied UNIFAC Dortmund NBS/NCR Steam Tables Nothnagel NRTL (Non Random Two Liquid) NRTL-SAC (patent pending) Peng Robinson Boston Mathias Pitzer Pitzer Enthalpy Pitzer Gibbs Energy Polynomial Activity Coecient Predictive SRK Peng Robinson Wong Sandler Peng Robinson MHV2 Model Name HENRY1 ESHF0, ESHF ESIG0, ESIG ESAMIN ESLK ESLKP0, ESLKP GMUFDMD ESSTEAM0, ESSTEAM ESNTH0, ESNTH GMRENON NRTLSAC ESPR0, ESPR GMPT1 HAQPT1 GAQPT1 GMPOLY ESRKSV10, ESRKSV1 ESPRWS0, ESPRWS ESPRV20, ESPRV2 Phase L V V L VL VL L L1 L2 VL V L L VL L L L LS VL VL VL Properties HNRY,WHNRY +,++ +,++ PHILMX, GLMX, HLMX, SLMX +++ +,++ GAMMA +,++ +,++ GAMMA GAMMA +,++ GAMMA HLMX GLMX GAMMA +++ +++ +++

+ A pure component equation of state model calculates: PHIL,PHIV,DHL,DHV,DGL,DGV,DSL,DSV,VL,VV ++ A mixture equation of state model calculates: PHILMX,PHIVMX,DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX +++ DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX

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Thermodynamic Properties Model

Model Rackett / DIPPR Liquid Density Redlich Kister Redlich Kwong Redlich Kwong Soave Boston Mathias Redlich Kwong Aspen RKS MHV2 RKS Wong Sandler Schwartzentruber Renon Scatchard Hildebrand Solids Heat Capacity Polynomial Solids Volume Polynomial Standard Peng Robinson Standard Redlich Kwong Soave Three Sux Margules UNIFAC UNIQUAC Van Laar Wagner interaction parameter Watson / DIPPR Wilson Model Name VL0RKT, VL2RKT GMREDKIS ESRK0, ESRK ESRKS0, ESRKS ESRKA0, ESRKA ESRKSV20, ESRKSV2 ESRKWSWS0, ESRKSWS ESRKU0, ESRKU GMXSH HS0POLY VS0POLY ESPRSTD0, ESPRSTD ESRKSTD0, ESRKSTD GMMARGUL GMUFAC GMUQUAC GMVLAAR GMWIP DHVLWTSN GMWILSON Phase L LS V VL VL VL VL VL L S S VL VL LS L L1 L2 L L1 L2 L S L L Properties VL VLMX GAMMA +,++ +,++ +,++ +++ +++ +,++ GAMMA HS VS +,++ +,++ GAMMA GAMMA GAMMA GAMMA GAMMA DHVL GAMMA

+ A pure component equation of state model calculates: PHIL,PHIV,DHL,DHV,DGL,DGV,DSL,DSV,VL,VV ++ A mixture equation of state model calculates: PHILMX,PHIVMX,DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX +++ DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX

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Thermodynamic Properties Model

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Binary Vapor-Liquid Equilibrium

Phase Diagram

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Vapor Pressure
Vapor pressure is a physical property of a pure chemical component. It is the pressure that a pure component exerts at a given temperature when both liquid and vapor phases are present. Vapor pressure depends only on temperature. Figure 1.1a gives vapor pressure curves for benzene and toluene. ( P S : mmHg; [T ] : Kelvin)

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Vapor Pressure
Vapor pressure is a physical property of a pure chemical component. It is the pressure that a pure component exerts at a given temperature when both liquid and vapor phases are present. Vapor pressure depends only on temperature. Figure 1.1a gives vapor pressure curves for benzene and toluene. ( P S : mmHg; [T ] : Kelvin)

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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Binary VLE Phase Diagram

Benzene and Toulene

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VLE Nonideality
Liquid-phase ideality (activity coecients j = 1) occurs only when the components are quite similar. The benzene/toluene system is a common example. If components are dissimilar, nonideal behavior occurs. Consider a mixture of methanol and water. Water is very polar. Methanol is polar on the OH end of the molecule, but the CH3 end is nonpolar. This results in some nonideality.

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VLE Nonideality
Consider a mixture of ethanol and water. The CH3-CH2 end of the ethanol molecule is more nonpolar than the CH3 end of methanol.

Note that the activity coecient of ethanol at the x = 0 end (pure water) is very large (EtOH = 6.75) and also that the xy curve crosses the 45o line (x = y ) at 90 mol% ethanol. This indicates the presence of an azeotrope. Note also that the temperature at the azeotrope (351.0 K) is lower than the boiling point of ethanol (351.5 K).

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VLE Nonideality
The ethanol/water azeotrope is a minimum-boiling homogeneous azeotrope. Step 1: Setup Property Analysis, Property Estimation (UNIFAC)

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VLE Nonideality
The ethanol/water azeotrope is a minimum-boiling homogeneous azeotrope. Step 2: Components Specication (nd Water and Ethanol)

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VLE Nonideality
The ethanol/water azeotrope is a minimum-boiling homogeneous azeotrope. Step 3: Tools Conceptual Design Azeotrope Search

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VLE Nonideality
The ethanol/water azeotrope is a minimum-boiling homogeneous azeotrope. Step 4: Azeotrope Report

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Thank You for Your Attention

Questions Are Welcome