SIM4ME Thermodynamics

Dynamic Simulation
Suite
SIM4ME
Thermodynamics
Invensys SimSci-Esscor
5760 Fleet Street, Suite 100,
Carlsbad, CA 92008
Dynsim 4.2 : SIM4ME

Thermodynamics
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Table of Contents
Table of Contents
Components and Thermodynamics Overview............................1
Components and Thermodynamics Window ..............................2
Library Tab.. ...................................................................................3
Petro Tab4
Cut Set Tab ....................................................................................5
Assay Tab ...................................................................................6
Blend Tab....................................................................................8
Property Tab ................................................................................10
Slate Tab. ..................................................................................11
Method Tab ..................................................................................12
Local Thermo Tab........................................................................13
Local Flash Tab ...........................................................................14
Default Tab. ..................................................................................15
Special Packages ........................................................................17
GLYCOL Package ......................................................................................... 17
Field Descriptions/Miscellaneous ..............................................19

Component Family List.................................................................................. 20
Component Full Name................................................................................... 21
SIMSCI Name................................................................................................ 22
Formula.......................................................................................................... 23
Filter............................................................................................................... 24
Most Commonly Used ................................................................................... 25
PROCESS Databank..................................................................................... 26
SIMSCI Databank.......................................................................................... 27
Hydrocarbon Lightends ................................................................................. 28
Standard Liquid Density ................................................................................ 29
Molecular Weight........................................................................................... 30
Characterization Options ............................................................................... 31
Default ........................................................................................................... 32
Lee-Kesler ..................................................................................................... 33
Cavett ............................................................................................................ 34
SIMSCI .......................................................................................................... 35
Extended API................................................................................................. 36
Distillation Data Type..................................................................................... 37
Pressure ........................................................................................................ 38
Volume (Weight) Percent Distilled vs. Temperature Table ........................... 39
Average Value ............................................................................................... 40
SIM4ME Thermodynamics
Contents - 1
Table of Contents
Volume Percent Distilled vs. Gravity Table ................................................... 41

Extrapolation to end points ............................................................................ 42
Lightends Data Amount ................................................................................. 43
Basis .............................................................................................................. 44
Library Component vs. Relative Amount table .............................................. 45
Normalize Lightends...................................................................................... 46
Average Value ............................................................................................... 47
Volume Percent Distilled vs. Inspection Property ......................................... 48
Watson K Factor............................................................................................ 49
Assay vs. Relative Amount table ................................................................... 50
Equilibrium Methods ...................................................................................... 51
Enthalpy Calculations .................................................................................... 52
Entropy Calculations...................................................................................... 53
Density Calculations ...................................................................................... 54
Transport Data............................................................................................... 55
Kinematic Viscosity Calculation Methods...................................................... 56
Thermal Conductivity..................................................................................... 57
Petroleum Correlation Viscosity Estimation .................................................. 58
Petroleum Correlation Thermal Conductivity Estimation............................... 59
Refinery Inspection Properties ...................................................................... 60
Calculation Mode for Local Flash .................................................................. 61
Use Model Prediction .................................................................................... 62
Force Local Thermo ...................................................................................... 63
Force Rigorous Thermo ................................................................................ 64
Use Model Prediction .................................................................................... 65
Force Local Flash .......................................................................................... 66
Force Rigorous Flash .................................................................................... 67
Component Slate........................................................................................... 68
Cut Set........................................................................................................... 69
Method Slate ................................................................................................. 70
Standard Conditions ...................................................................................... 71
Peng-Robinson.............................................................................................. 72
Peng-Robinson - Modified Panagiotopolous-Reid ........................................ 73
Peng-Robinson-Panagiotopoulos-Reid......................................................... 74
Soave-Redlich-Kwong ................................................................................... 75
SRK-Kabadi-Danner...................................................................................... 76
SRK-Modified Panagiotopoulos-Reid............................................................ 77
SRK-SIMSCI.................................................................................................. 78
Redlich-Kwong .............................................................................................. 79
Braun K10...................................................................................................... 80
Grayson-Streed ............................................................................................. 81
Curl-Pitzer method......................................................................................... 82
Johnson-Grayson .......................................................................................... 83
API Liquid Density ......................................................................................... 84
Ideal ............................................................................................................... 85
SIMSCI Databanks ........................................................................................ 86
User-Prepared Databanks............................................................................. 87
User-Defined Petroleum Components .......................................................... 88
Assay ............................................................................................................. 89
IUPAC............................................................................................................ 90
Normal Boiling Point (NBP) ........................................................................... 91
Assay Name .................................................................................................. 92
Cut Set........................................................................................................... 93
Enter Data For ............................................................................................... 94
Cubic Spline .................................................................................................. 95
Quadratic Polynomials................................................................................... 96
Contents - 2
Table of Contents
Probability Density Function .......................................................................... 97

API 1987 ........................................................................................................ 98
API 1963 ........................................................................................................ 99
Edmister-Okamoto....................................................................................... 100
Constant Watson K from TBP Curve........................................................... 101
Constant Watson K from D86 Curve ........................................................... 102
Liquid Volume Average ............................................................................... 103
Temperature Midpoint ................................................................................. 104
Initial and Final Points ................................................................................. 105
PDF.............................................................................................................. 106
Temperature Profile..................................................................................... 107
Start Temp/End Temp Table ....................................................................... 108
API Method .................................................................................................. 109
Index Mixing Method ................................................................................... 110
SimSci Mixing Method ................................................................................. 111
Summation Mixing Method .......................................................................... 112
Average Value ............................................................................................. 113
Volume Percent Distilled vs. Molecular Weight Table................................. 114
Default ......................................................................................................... 115
Modular Thermo - Transport Data............................................................... 116
Normal Melting Point ................................................................................... 117
Customize the Property Tab........................................................................ 118
Distillation Data............................................................................................ 119
Temp............................................................................................................ 120
Fluid Flowrate .............................................................................................. 121
Distillation Types ......................................................................................... 122
Pressure () ................................................................................................... 123
Pressure Basis ............................................................................................ 124
Cracking ...................................................................................................... 125
Rate ............................................................................................................. 126
Fraction........................................................................................................ 127
Percent ........................................................................................................ 128
Match TBP Curve ........................................................................................ 129
COSTALD.................................................................................................... 130
RACKETT .................................................................................................... 132
Contents - 3
Components and Thermodynamics Overview
Components and Thermodynamics Overview

Dynsim provides considerable flexibility for defining components and allows you to construct
customized thermodynamic method slates.
The component data can originate from various sources such as the following:
SIMSCI databanks
User-prepared databanks
User-defined petroleum components
Cut Sets
Components derived from petroleum assay data
Assay blends
There is no limit to the number of components that you can select for a flowsheet; however,
solution time improves when you keep the component slate size to a minimum.
You can assign different component slates and thermodynamic methods to specific unit
operations, but you must use a Basis Changer unit operation to connect unit operations using
different thermodynamic methods.
The current version of SIM4ME does not support component slate or thermodynamic method
propagation. When you place a new unit operation on the flowsheet, the new unit is assigned the
default component slate and thermodynamic method (as specified in the Defaults window). If you
assign a non-default component slate to a unit operation, units downstream do not automatically
inherit the slate and method of the upstream unit.
Note: There are no preset defaults for thermodynamic methods and correlations.
When you first construct a SIM4ME flowsheet, you must specify the individual thermodynamic
methods and correlations to be used to calculate the various properties.
Version 4.2, October 2006
Components and Thermodynamics Window
Components and Thermodynamics Window

The Components and Thermodynamics window contains the Selected Components Tree and a
set of nine tabs. These tabs and their functions are:
Library
Petro
Cut Set
Assay
Property
Slate
Method
Local Flash
Default
The Selected Components Tree shows all of the components that have been selected. These can
include the following:
SIMSCI databanks
User-prepared databanks
User-defined petroleum fractions
Petroleum pseudocomponents derived from assay data, and blends of petroleum
pseudocomponents.
There is no limit to the number of components that can be included in this tree. A few operations
simple operations can be performed directly on the tree:
Drag components around to change their order.

Delete or rename components by selecting, clicking the right mouse button, and choosing
either Delete or Rename.
The majority of the data entry operations take place on the individual tabs.
There is an Apply button on the window along with the normal OK, Cancel, and Help buttons.
Pressing Apply saves all of the data entered thus far (like clicking OK), but you will remain in the
GUI so you can make additional changes. You can think of Apply as being the same as clicking
OK, then immediately entering the thermo GUI again. Any changes you made before clicking
Apply will NOT be undone if you subsequently click Cancel; only changes made after clicking
Apply will be undone.
Library Tab
Library Tab
This tab allows you to enter components from preexisting libraries to the Selected Components
Tree.
Library Components are represented in the Selected Components Tree by the benzene ring icon.
To select a component from a preexisting list:
1. Use the Component Family pull down list to select a family type.
2. Double-click on a Component Full Name, or select one or more components and drag them
to the Selected Components Tree.
To add a component directly to the Selected Components list, enter the SIMSCI name in the Add
Library Component box, then hit Enter or click Add.
Use the Filter function to assist you in limiting the Component Full Names shown.
You can delete and rename items in the Selected Components list by right-clicking them.
Petro Tab
Petro Tab
Use this window to add Petro Components (petroleum fractions) to the Selected Components
Tree. Define at least two of the thermodynamic properties for each petro component you add.
Petro components are represented in the Selected Components Tree by the oil drum icon. A red X
appears on the icon when data are incomplete.
1. Enter values for at least two of the following:
Normal Boiling Point

Standard Liquid Density
Molecular Weight
Characterization Option
2. Click Characterize All Petro Components.

SIM4ME uses internal correlations to estimate the third parameter if missing.
To add a component to the Selected Components Tree:
Enter a name in the New Petro Component field and hit Enter or click Add.
The name appears in the left column of the table and is automatically included in the Selected
Components Tree.
Cut Set Tab
Cut Set Tab

Use this window to add or modify True Boiling Point Cut Sets.
To add a new Cut Set:
1. Enter a name in the New Cut Set field and hit Enter or click Add.
2. Select a method for entering the Temperature profile.
3. Enter the data in the grid.
To select or update a Cut Set:
1. Use the Cut Set Name pull down list to select a name.
2. Change the Temperature profile and/or the data.
3. Click Update Selected Cut Set to see a real-time update of the input values. The values are
updated under any circumstances once you leave the tab.
Assay Tab
Assay Tab
Use this window to enter assay characterization data.
For many petroleum feedstocks, the composition is not completely known in terms of defined
components. Thus, laboratory assay curves must be used to represent these streams by
pseudocomponents (boiling point cuts) for which the necessary thermophysical properties can be
estimated.
Assay curves can include laboratory distillation, gravity, molecular weight, predefined special
properties, such as pour point and viscosity, and user-defined special properties. Assay curves can
be supplied on either a liquid volume % or weight % distilled basis.
The minimum information required to characterize any stream is a laboratory distillation and the
average gravity or Watson K Factor.
For many petroleum streams, the composition of the lightest portion is determined from a
chromatographic analysis. The known components can be supplied as Lightends data and used
directly to characterize the front portion of the distillation curve.
The number of pseudocomponents to use in characterizing a petroleum stream is defined with a
TBP Cut Set (Cutpoint set), where the number of components is defined for one or more
temperature intervals on the TBP curve.
Assays are represented in the Selected Components Tree by the Assay Curve icon.
To create a new assay:
Enter the assay name in this field and hit Enter or click Add.
The assay name appears in the Assay Name field and in the Selected Components Tree.
To enter assay data:
1. Use the pull down list to select the Assay Name.
2. Optionally modify the:
Cut Set
Method Slate
3. Enter data for:
Distillation
Type
Pressure
Volume (Weight) Percent Distilled vs. Temperature Data. Right-click on the Percent
Distilled column header to switch between Volume and Weight percent.
Gravity
Average Value (required)
Percent Distilled vs. Gravity Table (optional)
Molecular Weight (optional)
Average Value
Percent Distilled vs. Molecular Weight Table
Assay Tab
Lightends
Drag one or more library components from the Selected Components Tree and drop
them into the table.
Enter relative amounts for each.
By default, the assay will match your lightends composition to the assay data. You
can also select Fraction (or Percent) to indicate that your amounts are actual fractions
(percents). If you do this you can also enter the overall lightends fraction (percent).
Inspection Properties
Select one of the inspection properties.
Enter either an Average Value, or enter a property curve in the table.
4. Click Process Selected Assay to perform the assay cutting and characterization. You can
then see the properties of the individual cuts in the Property tab.
Blend Tab
Blend Tab
Use this tab to create Blends of Petroleum Assays.
A Blend can be used to configure and blend one or more assays in the desired proportions to
generate pseudo-components that would match in their characteristics with a stream obtained
from mixing the specified assays in the same proportion. The pseudo-components for petroleum
assays based on a given TBP Cut-Set can be averaged to produce a single set of blend
components that may then be used to represent the streams in the simulation.
The Components and Thermodynamics GUI allows multiple cut-point sets to be used in any
simulation to define multiple blends of pseudo-components. This is useful when petroleum
streams are dissimilar and one set of blend components is not adequate to represent all streams.
Assays are represented by the Assay curve icon in the selected components list.
Blends are represented in the Selected Components list by the Blend icon.
Incompletely specified a Blend icon represents Blends with a Red cross on it.
Note: To create a Blend, it is required to have a defined Cut-set and a minimum of one Assay in
the Selected Component list. The user may create separate Method slates to be used for different
Blends.
To create a new blend:
Enter the name for the new blend in the New Blend field and click Add or press Return. The
blend name appears in the Blend Name field and in the Selected Components list.
From the Cut-Set drop-down list, select a Cut-Set upon which the new blend is to be based.
Drag one or more Assays from the Selected Components list and drop them into the first cell
in the Assay or Blends column. Additional rows are automatically created to accommodate
the number of Assays being added.
Specify whether the Blend Basis is to be by Weight or Liquid Volume.
Enter the fractional relative amounts of each Assay in the cells in the Relative Amount
column. The amounts should total to 1.00. Otherwise, the relative amount values will be
normalized.
To delete/rename a blend:
Right-click on the Blend in the Selected Components list to display a menu of options.
Blend Name (drop-down)

Use this drop-down list to select the Blend Name to be used for the current simulation.
Cut-Set (drop-down)
Use this drop-down list to select the Cut-Set to be used for the current blend.
Blend Tab
Method Slate (drop-down)

Use this drop-down list to select the Method slate to be used for the current blend.
An illustration of the Blends Tab after creating a Blend:
Blend Basis
Choose whether the Blend Basis is to be by Weight or Liquid Volume.
Normalize
Check this option to normalize the amounts of Assays if they do not sum to 1.00.
Assay and Relative Amounts Table
Use this table to add Assays to a Blend and to specify their relative amounts.
Initially, this table contains only a single row.
To enter data for this table:
Drag one or more Assays from the Selected Components list and drop them into the first cell
in the Assay or Blend column. Additional rows are automatically created to accommodate the
number of Assays being added.
Enter the fractional relative amounts of each Assay in the cells in the Relative Amounts
column. The amount should total to 1.00. If not, Thermo will normalize the amounts.
To delete an Assay:
Right-click on the cell containing the name of the Assay and click Delete.
Property Tab
Property Tab
This tab allows you to view the values of the fundamental properties of the components. For
Library and Petro components, you can also change these values.
Properties are arranged in tables. The drop down list at the top allows you to select the table to
view.
To change the units-of-measure, right-click on a column header. To change a property value,
enter a new value. User entered values are blue bordered. Delete the cell contents to restore the
original.
The Customize button is use to create or modify your own tables. Drag properties from the list at
the bottom of the tab into the column headers in the dummy grid. Then save the table. The name
you choose when you save will now appear in the drop-down list at the top of the tab. Click
Close to exit customize mode and return to the normal tab.
Note that you CANNOT modify or delete the tables provided in the install, but you can load
them, modify them, and save them under another name.
10
Slate Tab
Slate Tab
Use this tab to create or modify component slates.
New Component Slate
To create a new Component Slate:
1. Enter the name for the new slate in the New Component Slate field and click Add or press
Return.
The slate name appears in the Slate Name field.
2. Drag one or more Components, Assays or Blends from the Selected Components list and
drop them into Components in Slate list. A tree structure similar to that in the Selected
Components list is replicated.
To remove a Component, Assay or Blend from the Components in Slate list:
1. Select the item in the list.
2. Right-click on the item and click Remove.
To remove a fraction from an Assay:
Expand the Assay to display its fractions.
1. Select the fraction in the list.
Slate Name
This drop-down list contains the names of the currently defined Component Slates.
Components in Slate
To add Components, Assays or Blends to a Component Slate:
Drag one or more Components, Assays or Blends from the Selected Components list
and drop them into the Components in Slate list.
To remove a Component, Assay or Blend from the Components in Slate list:

1. Select the item in the list.
To remove a fraction from an Assay:
Expand the Assay to display its fractions.
1. Select the fraction in the list.
11
Method Tab
Method Tab
Use this window to modify or create thermodynamic method slates. There are no defaults for
thermodynamic methods and correlations. Specify the individual thermodynamic methods and
correlations to be used to calculate the various properties.
For example, if you expand the tree, the following subcategories are displayed:
Thermodynamic Data
Equilibrium
Enthalpy
Entropy
Density
Transport Data
Viscosity
Thermal conductivity
Inspection Property Data
Content Properties
Point Properties
To create a New Method Slate:
Enter the name in the New Method Slate field and hit Enter or click Add.
The new slate name appears in the Method Slates drop down list.
To select a Method Slate:
Use the Method Slate Name pull down list that contains the names of the currently
defined Thermodynamic Method Slates.
To select an Enthalpy (or other) calculation method for all phases at once:
Select the subcategory Enthalpy and right-click to display the options.
To select an Enthalpy (or other) calculation method for each phase individually:
1. Expand the Enthalpy subcategory.
2. Specify a different method for each phase by selecting it, then right clicking to display the
appropriate options.
When you select a method for calculating an RIP, additional data entry fields may appear at the
bottom of the tab.
12
Local Thermo Tab
Local Thermo Tab

This tab allows you to enter a new Local Thermo Option or edit an existing Local Thermo
Option. The existing Local Thermo Options can be seen in the pull down list Local Thermo
Options Name.
To add a new Local Thermo Option:
1. Enter a name in the New Local Thermo Options field.
2. Click Add.
This will add the new Local Thermo Option entered to the Local Thermo Options Name list.
Each Local Thermo Option is associated with one of the following three Calculation Modes:
Use Model Prediction - the model will determine when to use the rigorous flash and when to
use a local approximation.
Force Local Thermo - to force use of the local approximation always.
Force Rigorous Thermo - to force use of the rigorous flash always.
By default Use Model Prediction will be associated with any new Local Thermo Option created.
The user has to exclusively select, if desired so, the other two options.
To edit an existing Local Thermo Option:
1. Select the Local Thermo Option from the Local Thermo Options pull down list.
2. Modify the relative and absolute tolerances for Temperature and Pressure in the Windows
Check Size window.
3. Modify "Second Order Error" to specify the maximum error and also select an option from
the drop down list in the Use Composition Effect column for composition effect.
4. Click Apply.
13
Local Flash Tab
Local Flash Tab

This tab allows you to create a new Local Flash Option or edit an existing Local Flash Option.
The existing Local Flash Options can be seen in the pull down list Local Flash Options Name.
To add a new Local Flash Option:
1 Enter a name in the New Local Flash Options field.
2 Hit Enter or click Add.
This will add the new Local Flash Option entered to the Local Flash Options Name list.
Each Local Flash Option is associated with one of the following three Calculation Modes:
Use Model Prediction the model will determine when to use the rigorous flash and
when to use a local approximation.
Force Local Flash - to force use of the local approximation always.
Force Rigorous Flash - to force use of the rigorous flash always.
By default Use Model Prediction will be associated with any new Local Flash Option created.
The user has to exclusively select, if desired so, the other two options.
To edit an existing Local Flash Option:
1 Select the Local Flash Option from the Local Flash Options Name pull down list.
2 Modify Second order error to specify the maximum error before a model update will
occur.
14
Default Tab
Default Tab
Use this tab to set default Pseudocomponent and Assay Characterization options, Distillation
Boundaries, Data and Methods options. Also use it to choose the Standard Conditions for the
flowsheet.
This tab consists of the following areas:
Pseudocomponent Characterization Option
Choose one of the following as the default characterization method to predict a missing third
parameter of a pseudocomponent:
SIMSCI
Cavett
Lee-Kesler
Extended API
Unless changed locally on the Petro tab, the default method is used automatically in subsequent
pseudocomponent characterization.
Assay Characterization Options
These include:
Fitting Procedure
Distillation Curve Interconversions
Gravity Curve Generation Method
Calculation of NBP for Cuts.
Fitting Procedure
Curve fitting procedures are used to extrapolate and interpolate distillation data supplied for an
assay. Curve fitting produces a smoothed distillation curve that can be integrated to determine the
average boiling points for the pseudocomponents.
The following three curve fitting methods are available:
Cubic Spline
Quadratic Polynomials
Probability density function
Distillation Curve Interconversions
All assay distillation curves must be converted to a 760 mm Hg TBP basis before use in
determining the pseudocomponent normal boiling points. Modular Thermo provides three
Interconversion options:
API 1987
API 1963
Edmister-Okamoto
Gravity Curve Generation Method
When a gravity curve is not provided for an assay stream, the gravities for the pseudocomponents
must be generated using one of the techniques described below.
Constant Watson K from TBP Curve
Constant Watson K from D86 Curve
Calculation of NBP for Cuts
15
Default Tab
Choose this option to determine which method is used to calculate the Normal Boiling Point of
narrow cuts.
Liquid Volume Average
Temperature Midpoint
Distillation Boundaries
These include:
Initial and Final Points
PDF (Probability Density Function)
Default Selections
Component Slate
Method Slate
Cut Set
The default Component Slate and Method Slate will be assigned to any new unit operations
you create. The default Cut Set will be used by any new assays you create.
Standard Conditions
The definition of standard conditions is the basis for some of the Thermo calculations. These
parameters are used for stream special property calculations such as calculating Standard Vapor
flow rates and Density. They do not represent actual atmospheric conditions. Select from the
drop-down list either:
Pre-defined standard conditions, or
Custom option and enter your standard T and P directly.
16
Special Packages
Special Packages
GLYCOL Package
The glycol data package uses the SRKM equation of state to calculate phase equilibria for glycol
dehydration applications. This system uses a special set of SRKM binary interaction data and
alpha parameters for systems containing glycols, water, and other components. The binary
parameters and alpha parameters have been obtained by the regression of experimental data for
glycol systems. The recommended temperature and pressure ranges for the GLYCOL package
are:
Temperature: 80-400 F
Pressure: up to 2000 psia
Other thermodynamic properties such as the vapor and liquid enthalpy, entropy, and vapor
density are calculated using the SRKM equation of state, while the liquid density is calculated
using the API method.
Table below shows the components present in the GLYCOL databank for which there are binary
interaction parameters available.
Components Available for GLYCOL Package
Components
Formula
LIBID
Hydrogen
Nitrogen
Oxygen
Carbon Dioxide
Hydrogen Sulfide
Methane
Ethane
Propane
Isobutane
N-butane
Isopentane
Pentane
Hexane
Heptane
Cyclohexane
Methylcyclohexane
Ethylcyclohexane
Benzene
Toluene
O-xylene
M-xylene
P-xylene
Ethylbenzene
Ethylene Glycol
Diethylene Glycol
H2
N2
O2
CO2
H2S
CH4
C2H6
C3H8
C4H10
C4H10
C5H12
C5H12
C6H14
C7H16
C6H12
C7H14
C8H16
C6H6
C7H8
C8H10
C8H10
C8H10
C8H10
C2H6O2
C4H10O3
H2
N2
O2
CO2
H2S
C1
C2
C3
IC4
NC4
IC5
NC5
NC6
NC7
CH
MCH
ECH
BNZN
TOLU
OXYL
MXYL
PXYL
EBZN
EG
DEG
17
Special Packages
Triethylene Glycol
Water
C6H14O4
H2O
TEG
H2O
Figure below shows the binary interaction parameters, denoted by x, present in the glycol
databank. Interaction parameters denoted by o are supplied from the SRK databank. It should
be noted that for all pairs not denoted by x or o, the missing binary interaction parameters are
estimated using a molecular weight correlation, or are set equal to 0.0.
Figure - BINARY Interaction Data in the Glycol Databank
18
Field Descriptions/Miscellaneous
19
Component Family List

Categorizes components similarly to an organic chemistry textbook. If you know the structure of
a desired component, look for its family name in the family list. The component family can be
selected from the Component Family pull down list.
The Modular Thermo databanks contain the following general component collections:
Most Commonly Used
Hydrocarbon Light Ends
PROCESS Databank
SIMSCI Databank
In addition, the following specific chemical families have been grouped to allow you to quickly
create component slates:
Acids
Alcohols
Aldehydes
Amides
Amines
Aromatic Hydrocarbons
Elements
Esters
Halogenated Derivatives
Ketones
Miscellaneous
Naphthenic Hydrocarbons
Other Nitrogen Derivatives
Paraffin Hydrocarbons
Salts and Minerals
Silicon Derivatives
Sulfur Derivatives
Unsaturated Hydrocarbons.
20
Component Full Name

Typically either the common name or IUPAC name for a component.
21
SIMSCI Name
Used as a variable for process stream and thermodynamic calculations.
Enter a name of up to eight characters in length.
22
Formula
This is a nonstructural chemical formula for the component, when appropriate.
Formulas for isomers are not unique.
23
Filter
Enter alphanumeric text to limit the components shown in the Selected Components Tree list.
24
Most Commonly Used

This component family comprises approximately 100 components representing the pure
components commonly encountered in natural gas and petroleum processing.
25
PROCESS Databank
The PROCESS databank is the SIMSCI original databank of component physical properties. It
has only VL components and contains no VLS property data.
The SIMSCI Databank is newer.
26
SIMSCI Databank
The SIMSCI database contains property data for about 1750 pure components.
It is newer than the PROCESS databank.
27
Hydrocarbon Lightends
This list contains low molecular weight hydrocarbons and gases commonly found in oil refinery
streams. Compounds up to decane are included
28

Enter Standard Liquid Density data in terms of specific gravity or API gravity.
29
Molecular Weight
Enter the molecular weight.
The molecular weight is the most difficult property to predict accurately from generalized
correlations and should be supplied when possible for the most accurate characterization of a
Petro Component.
30
Characterization Options
Select one of the following characterization methods to predict a missing third parameter:
Default
SIMSCI
Cavett
Lee-Kesler
Extended API.
The Default method is established in the Defaults tab of this window by selecting one of the four
methods.
31
Default
The Default method is established in the Defaults dialog box by choosing one of the four listed
methods.
SIMSCI
Cavett
Lee-Kesler
Extended API.
32
Lee-Kesler
Method developed for Mobil Oil Company by B. I. Lee and M.G. Kesler.
Predicts pseudocomponent properties based on the component normal boiling point, gravity and
molecular weight.
33
Cavett
Uses a nomogram from the 1967 API Technical Data Book that relates molecular weight, normal
boiling point and specific gravity. The molecular weight prediction for compounds with normal
boiling points lower than 300 F is predicted with a method developed by SIMSCI, based on pure
component data.
34
SIMSCI
Estimates molecular weight for each petroleum component, based on its normal boiling point and
gravity. The molecular weights are derived by application of a correction factor to the molecular
weight for normal alkanes.
35
Extended API
Uses an improved nomogram published in the 1980 API Technical Data Book, which relates
molecular weight, normal boiling point and specific gravity. The molecular weight prediction for
compounds with normal boiling points lower than 300 F is predicted with a method developed
by SIMSCI based on pure component data.
36
Distillation Data Type

Select the distillation data analysis type from the following standard options:
True Boiling Point (Volume %)
ASTM D86 (Volume %)
ASTM D86 Cracking (Volume %)
ASTM D1160 (Volume %)
ASTM D2887 (Weight %)
The heading of the Percent Distilled column of the data entry table changes to reflect whether the
data is reported on a liquid volume % (TBP, D86 and D1160) or weight % (D2887) basis.
37
Pressure
Enter the pressure at which the data for the distillation curve was collected if other than the
default pressure.
Default pressures are:
TBP
760 mm Hg
ASTM D86
760 mm Hg
ASTM
10 mm Hg
D1160
ASTM
Chromatographic analysis
D2887
38
Volume (Weight) Percent Distilled vs. Temperature Table

Enter data pairs for liquid volume (weight) % distilled vs. temperature in the respective columns.
The default upper and lower distillation boundaries for volume (weight) % distilled are 1% to
98%. The default distillation boundaries can be changed in the Defaults window.
If the distillation basis is other than the default for the method, you can change the basis from
volume % to weight % (or vice versa) by right clicking on the Percent Distilled column heading
to display a menu of options.
39
Average Value
Enter the average gravity (as a specific gravity, API Gravity, or Watson K-Factor) for each assay.
If a Watson K is given, it is converted to a gravity using the TBP data for the curve. Entry of a
gravity curve is recommended but not required.
You can change the basis for the average gravity by right clicking on the heading of the Gravity
column in the data entry table to display a menu of options.
40
Volume Percent Distilled vs. Gravity Table

Enter the % distilled (the mid-volume or mid-weight % of the data point) and corresponding
gravity values in the table.
The percents must be on the basis chosen for the distillation data (liquid volume or
weight %)
The gravity values correspond to the gravity type selected (specific gravity, API
Gravity, or Watson K-Factor).
At least three gravity points must be supplied to define the gravity curve.
You can change the basis for the gravity data entries by right clicking on the heading of the
Gravity column to display a menu of options.
Options for the Gravity Curve Generation Method are found in the Defaults window.
For details, see Extrapolation to end points.
41
Extrapolation to end points

If a user-supplied gravity curve does not extend to the 95% point, quadratic extrapolation is used
to generate an estimate for the gravity at the 100% point. Gravity for each cut is determined at its
mid-point, and an average gravity for the stream is computed. If this average does not agree with
the specified average, the program either normalizes the gravity curve (if data are given up to
95%) or adjusts the estimated 100% point gravity value to force agreement. Since the latter could
in some cases result in unreasonable gravity values for the last few cuts, consider providing an
estimate of the 100% point gravity value and letting the program normalize the curve, particularly
when gravity data is available to 80% or beyond.
42
Lightends Data Amount

Select one of the following Specification options to determine the amount of lightends in the
assay:
Match TBP (default)
Fraction
Percent
By default, SIM4ME matches user-supplied lightend data to the TBP curve. The user-specified
rates for all lightend components are adjusted up or down, all in the same proportion, until the
NBP of the highest-boiling lightend component exactly intersects the TBP curve. All of the cuts
from the TBP curve falling into the region covered by the lightends are then discarded and the
lightend components are used in subsequent calculations.
Alternatively, you can specify the lightends as a fraction or percent (on a weight or liquid volume
basis) of the total assay or as a fixed lightend flowrate. In these cases, the supplied numbers for
the lightend components can be normalized to determine the individual component flowrates.
43
Basis
Select one of the following Specification options to determine the amount of lightends in the
assay:
Weight
Volume
44
Library Component vs. Relative Amount table

Use this table to add Library Components to the assay and to specify their relative amounts.
To enter data for this table:
1. Drag one or more Library Components from the Selected Components Tree and drop them
into the cells in the Library component column.
Additional rows are automatically created to accommodate the number of components being
added. All Windows 95/NT selection options are supported.
2. Enter the fractional relative amounts of each lightend component in the cells in the Relative
Amounts column.
The amount should total 1.00. If not, SIM4ME normalizes the amounts.
45
Normalize Lightends
Select this option to normalize the relative amounts of the lightend components if the amounts do
not sum to 1.00. The Normalize option does not become available until you have entered a value
in the Lightends Amount data field.
46
Average Value
Enter a value for the average for the particular inspection property.
47
Volume Percent Distilled vs. Inspection Property

Enter the mid-volume % distilled and corresponding Inspection Property values for the cuts.
The curve generated from these data pairs is quadratically interpolated and extrapolated to cover
the entire range of pseudocomponents.
If you also supply an average molecular weight in addition to the data pairs, the Inspection
Property value for the last cut is adjusted so that the curve matches the given average.
48
Watson K Factor
The Watson K Factor is defined as:
where
NBP = component or stream average normal boiling point (R)
Sp.Gr. = component or stream average normal boiling point at 60F
relative to water at 60F
49
Assay vs. Relative Amount table

Use this table to add assays to a blend and to specify their relative amounts.
To supply data for this table:
1. Drag one or more assays from the Selected Components Tree and drop them into the last cell
in the Assay column.
Additional rows are automatically created to accommodate the number of assays being added.
2. Enter the fractional relative amounts of each assay in the cells in the Relative Amounts
column.
The amount should total to 1.00. If not, Modular Thermo normalizes the amounts.
To delete an assay:
Right-click on the cell containing the name of the assay and click Delete.
50
Equilibrium Methods
Modular Thermo offers the following options for equilibrium calculation methods:
Peng-Robinson
Peng-Robinson-Modified Panagiotopolous-Reid
Peng-Robinson-Panagiotopoulos-Reid
Soave-Redlich-Kwong
SRK-Kabadi-Danner
SRK-Modified Panagiotopoulos-Reid
SRK-SIMSCI
Redlich-Kwong
Braun K10
Grayson-Streed
51
Enthalpy Calculations
Modular Thermo offers the following options for enthalpy calculations:
Soave-Redlich-Kwong
Curl-Pitzer
Johnson-Grayson
52
Entropy Calculations
Modular Thermo offers the following options for entropy calculation methods:
Soave-Redlich-Kwong
Curl-Pitzer
53
Density Calculations
Modular Thermo offers the following options for Density calculation methods:
Soave-Redlich-Kwong
API Liquid Density
Ideal
54
Transport Data
Most pure library components include saturated vapor and liquid values for viscosity and thermal
conductivity as part of the general thermodynamic properties database.
Pure-Component Average
Petroleum Correlation Method
Transport Data Pure-Component Average

Choose this method to compute transport properties as a weighted average of pure-component
values. This method requires that the property in question be available for each component in the
mixture with the exception of petroleum pseudocomponents.
The pure-component properties at the temperature of interest are combined to calculate stream
average properties according to the mixing rules.
Transport Data - Petroleum Correlation Method
Choose this method to apply a petroleum correlation method to all components in the stream.
Modular Thermo estimates the above properties from correlations for pseudocomponents.
55
Kinematic Viscosity Calculation Methods

Modular Thermo offers the following options for Kinematic Viscosity calculation methods:
Petroleum Correlation
Kinematic Viscosity - Pure-Component Average
This method computes the kinematic viscosity of a stream as a weighted average of
pure-component viscosities. The pure-component method requires that the viscosity be available
for each component in the stream with the exception of petroleum pseudocomponents.
Saturation values are used and no pressure corrections apply.
This method is available for both vapor and liquid viscosity calculations.
Kinematic Viscosity - Petroleum Correlation
This method employs predictive correlations that apply to bulk hydrocarbon mixtures. The
correlations are applied to pure components as well as pseudocomponents. Pressure corrections
apply.
This method is available for both vapor and liquid kinematic viscosity calculations.
For details, see Petroleum Correlation Viscosity Estimation.
56
Thermal Conductivity
Modular Thermo offers the following options for thermal conductivity calculation:
Thermal Conductivity - Pure-Component Average
Applies simple mixing rules to the temperature-dependent values of pure components to calculate
thermal conductivity properties of mixtures.
Saturation values are used and no pressure corrections apply.
This option is available for both vapor and liquid viscosity calculations.
Thermal Conductivity - Petroleum Correlation
Uses predictive correlations that apply to bulk hydrocarbon mixtures.
This option is available for both vapor and liquid conductivity calculations.
For details, see Petroleum Correlation Thermal Conductivity Estimation.
57
Petroleum Correlation Viscosity Estimation

Vapor Viscosity
See:
Thodos, G., and Yoon, 1970, Viscosity of Nonpolar Gaseous Mixtures at Normal Pressures,
AIChE J., 16, 300-304.
Dean, D.G., and Stiel, L.S., 1965, The Viscosity of Nonpolar Gas Mixtures at Moderate and High
Pressures, AIChE J., 11, 526-532.
Liquid Viscosity
When the system is near the critical point (0.98<Tr<1.0), the method developed by Letsou
and Steil is used.
0.76<Tr<0.98
For this range, equations relating viscosity to reduced temperature and acentric factors
developed by Letsou and Steil (see section 9-12 in Reid, Prausnitz and Poling) are used.
These methods were developed from data on simple liquid hydrocarbons.
(Tb<T<0.76Tc)
For intermediate ranges, the Andrade equation is used to determine the viscosity, based on
reference values at the NBP and a reduced temperature of 0.76. The reference values are
computed by the methods described above.
Temperatures below the normal boiling point
For temperatures below the normal boiling point, SIMSCI has developed a method based on
the Arrhenius relation and the Thomas equation. This method relates liquid density at the
NBP, the critical temperature, and the system temperature. The density at the NBP is
estimated using the equation of Gunn and Yamada.
After the mixture viscosity has been estimated using one of the above methods, it is corrected for
the effects of pressure using the method of Kouzel (also given in the API Technical Data Book,
pp. 11-47, 2nd edition). The vapor pressure needed for this method is estimated with the Reidel
equation.
58
Petroleum Correlation Thermal Conductivity Estimation

Vapor Thermal Conductivity
Modular Thermo employs the Roy-Thodos method to determine vapor thermal
conductivities.
The function of temperature used is the one that is presented by the authors for saturated
hydrocarbons. This method is corrected for pressure effects using the equations of Stiel and
Thodos.
Liquid Thermal Conductivity
The Sato and Reid method is used to calculate liquid thermal conductivity.
59
Refinery Inspection Properties

Modular Thermo offers calculation methods for the following Refinery Inspection Properties:
Property
Available Methods
Carbon Content
Summation, Index, SimSci
Hydrogen Content
Nitrogen Content
Oxygen Content
Iron Content
Summation, Index
Nickel Content
Wax Content
Sulfur Content
Freeze Point
Cloud Point
Flash Point
Summation, Index
Summation, Index
Summation, Index
Summation, Index, User Formula
Index, SimSci, User Formula
Index, SimSci, API, User Formula
There are many more properties available. Select a property and provide a method.
For details on the methods listed above, refer to:
API
Index
SimSci
Summation
User Formula
60
Calculation Mode for Local Flash

There are three Calculation Modes available for Flash:
Use Model Prediction

Use Local Flash
Use Rigorous Flash
61

When the Use Model Prediction option is selected, the model based on certain criteria selects
either Local Thermo or Rigorous Thermo during the simulation run time. For the Use Model
Prediction option, check for the following:
Window Check Size
The Window Check Size defines an operating region for Local Flash around a reference point.
Relative and Absolute tolerances for Pressure and Temperature are used to define the operating
range. During execution, if the local property deviation crosses the operating region, a Check
is made if the property is still continuous with respect to the reference. If a discontinuity is
detected, then the property is updated by making a rigorous call. If the property is still
continuous, then the window is extended to the next deviation interval.
The default values for relative tolerance for both Pressure and Temperature are 0.1. The default
values for absolute tolerance for Pressure and Temperature are 30 K and 100 kPa respectively.
The user is free to modify these values. However, the greater the window check size, the less
number of checks are made by the local model. This results in a higher probability of not
detecting a discontinuity and greater risk for flowsheet instability. The smaller the window check
size, the more number of checks are made by the local model. However, this will enable to detect
a discontinuity faster. Hence it is a trade off between model speed and model stability. The user
needs some level of experience for setting these tolerance limits. However, the default values
work quite well under most situations.
Defining Second Order Fraction and Use Composition Option
Local Thermo uses a Second Order Taylor series expansion to predict local properties. The
differences between the first order terms and the second order terms in the expansion give an
excellent approximation of the true error in the model. The update criterion is triggered if the
second order terms exceed the specified second order fractional error with respect to the first
order terms.
The tolerance limit for second order fractional error can be defined in the Second Order column.
The default value is 0.15 for this fractional error. However, the user can modify this value.
The user also has the choice as whether to include or not composition effect in the Taylor Series
Expansion. The user can make this choice by selecting either on or off option from the pull
down menu in the Use Composition Effect column.
62
Force Local Thermo

When this option is selected, Local Thermo is forced all the time during the simulation run.
63
Force Rigorous Thermo

When this option is selected, Rigorous Thermo is forced all the time during the simulation run.
64

When this option is selected, the model uses its own judgment based on certain criteria to select
between Local Flash and Rigorous Flash at a particular point of time during the simulation run.
When Use Model Prediction is used as the Calculation Mode, the user needs to define a tolerance
limit on the second order fractional error for Temperature, Pressure and Composition.
The tolerance limit for second order fractional error can be defined in the Second Order column.
The default value is 0.15 for this fractional error. However, the user can modify this value.
65
Force Local Flash

When this option is selected, Local Flash is forced all the time
66
Force Rigorous Flash

When this option is selected, Rigorous Flash is forced all the time.
67
Component Slate
Use this drop down list to choose a default component slate from the list of previously defined
slates.
The default component slate is automatically applied to all units and streams subsequently placed
on the flowsheet.
You can also change the component slate at the local level when creating new units and streams.
68
Cut Set
Use this drop down list to choose a default Cut Set from the list of previously defined Cut Sets.
The default Cut Set automatically is applied to all subsequent blends.
You can also change the Cut Set at the local level when creating new blends.
69
Method Slate
Use this drop down list to choose a default thermodynamic method slate from the list of
previously defined slates.
The default method slate is automatically applied to all units and streams subsequently placed on
the flowsheet.
You can also change the method slate at the local level when creating new units and streams.
70
Standard Conditions
Choose from the three predefined options for Standard Temperature and Pressure Conditions for
the standard molar volume calculations or manually add temperature and pressure conditions.
The default temperature is 60 F (English) and the default pressure is 1.0 atmosphere.
The standard volume occupied by one mole of vapor at standard temperature and pressure.
The default values are:
English
379.49 ft3/lb Mole at 60 F, 1.0 atmosphere
Metric, SI
22.414 m3/Kg Mole at 0.0 C, 1.0 atmosphere (Metric, SI)
71
Peng-Robinson
The Peng-Robinson (PR) equation of state (EOS) is a 1976 modification of the Redlich-Kwong
EOS. PR is similar to the Soave-Redlich-Kwong equation and was designed to improve the poor
liquid density predictions for the SRK method.
Peng-Robinson has been found to give accurate predictions for non-polar mixtures of
hydrocarbons. It does not give accurate predictions for polar components.
Hydrogen phase behavior is approximated by Peng-Robinson using a modified acentric factor.
In addition to K-values, the PR equation can be used to predict the enthalpies, entropies and
densities for the liquid and vapor phases. The predicted liquid phase densities are not very
accurate and the API method is suggested when the PR system is chosen.
72
Peng-Robinson - Modified Panagiotopolous-Reid

This method, PRM, is a modification of the mixing rule for the PR-Panagiotopoulos-Reid by
SIMSCI in which two more adjustable parameters, cij and cji are introduced. This improves the
prediction for polar-nonpolar systems, where the nonideality is large or strongly asymmetric.
SIMSCI has fit many binary systems of chemicals to this equation and the parameters are
supplied in Modular Thermo.
The PRM method in Modular Thermo uses an improved correlation developed by SIMSCI that
provides more accurate vapor pressure predictions than the original PR formulation for a wide
range of components.
In addition to K-values, the PRM equation can be used to predict the enthalpies, entropies and
accurate and the API method is suggested when this system is chosen.
73
Peng-Robinson-Panagiotopoulos-Reid
This method (PRP) is a modification of the Peng-Robinson method in which an asymmetric
mixing rule containing two parameters is used in determination of the "a (T)" term in the PR
equation. Two adjustable interaction parameters are used, kij and kji. This significantly improves
the accuracy of predictions for mixtures of polar and non-polar components. The mixture rule is
flawed, however, in that it is not invariant to dividing a component into a number of identical
pseudocomponents.
The PRP method in Modular Thermo uses an improved alpha correlation developed by SIMSCI.
The improved correlation provides more accurate vapor pressure predictions than the original PR
formulation for a wide range of components.
In addition to K-values, the PRP equation can be used to predict the enthalpies, entropies and
74
Soave-Redlich-Kwong
The Soave-Redlich-Kwong equation of state (SRK) is a modification of the Redlich-Kwong
equation of state (which is based on the van der Waals equation) and was published by Georgi
Soave in 1972.
This equation has been found to give accurate predictions for non-polar mixtures of
hydrocarbons. It does not give accurate predictions for polar components.
Modular Thermo contains correlations for kij's for systems with hydrocarbons and N2, H2S
and O2. Some kij's are also provided for hydrocarbon splits such as ethane-ethylene and
propane-propylene. Hydrogen phase behavior is approximated by SRK using a modified acentric
factor. Other methods, which modify the alpha formulation, give more accurate predictions for
hydrogen than the original SRK formulation.
In addition to K-values, the SRK equation can be used to predict the enthalpies, entropies and
accurate and the API method is suggested when the SRK system is chosen.
75
SRK-Kabadi-Danner
This method (SRKKD) is a modification of the Soave-Redlich-Kwong method to improve the
prediction of vapor-liquid-liquid phase equilibria for hydrocarbon systems with water. To achieve
this, Kabadi and Danner proposed a two parameter-mixing rule for calculation of the "a (T)" term
in the SRK equation. They also developed a means to provide estimates for water-hydrocarbon
equilibria when no data is available.
The SRKKD method in Modular Thermo uses an improved alpha correlation developed by
SIMSCI that provides more accurate vapor pressure predictions than the original SRK
formulation for a wide variety of components.
In addition to K-values, the SRKKD equation can be used to predict the enthalpies, entropies and
76
SRK-Modified Panagiotopoulos-Reid
This method (SRKM) is a modification of the mixing rule for the SRK-Panagiotopoulos-Reid by
SIMSCI, in which two more adjustable parameters cij and cji are introduced. This improves the
prediction for polar-nonpolar systems, where the nonideality is large or strongly asymmetric.
SIMSCI has fit many binary systems of chemicals to this equation and the parameters are
supplied in PRO/II.
The SRKM method in Modular Thermo uses an improved alpha correlation developed by SimSci
that provides more accurate vapor pressure predictions than the original SRK formulation for a
wide variety of components.
In addition to K-values, the SRKM equation can be used to predict the enthalpies, entropies and
77
SRK-SIMSCI
This method (SRKS) uses a new mixing rule to eliminate the flaw in the original
Panagiotopoulos-Reid mixing rule. Four adjustable parameters are used, with the mixing
rule designed to produce good results for mixtures of polar and nonpolar compounds.
The SRKS method in Modular Thermo uses an improved alpha correlation developed by
SIMSCI. The improved correlation provides more accurate vapor pressure predictions than the
original SRK formulation for a wide variety of components.
In addition to K-values, the SRKS equation can be used to predict the enthalpies, entropies and
Suitable for three phase separators for water-hydrocarbon systems such as those found in FCC
gas plants and hydrocrackers, lube oil and solvent dewaxing units, natural gas systems containing
polar compounds such as methanol and any chemical operations for which the parameters can be
determined by regression.
78
Redlich-Kwong
Redlich-Kwong is a specific case of the generalized two-parameter cubic equation of state of the
form:
where
P = pressure
T=
absolute temperature
v=
moral volume
u, w = constants (typically integers)
By setting u = 1 and w = 0, the Redlich-Kwong equation is obtained.
For derivation of the values for a and b, see the Redlich-Kwong in the Technical Reference.
79
Braun K10
The Braun-K10 method (BK10) is based on the charts developed by Cajander, ET. Al., in 1960.
The chart for a convergence pressure of 5000 psia is used to predict the component K-values at a
system pressure of 10 psia. The K-values at 10 psia are ratioed to the desired pressure.
This method has limited capability to predict the K-values for light components and uses gross
approximations for H2, N2, O2, CO, CO2 and H2S. For aromatic compounds, a vapor pressure
correlation is used for K10 values of 2.5 or less. Pseudocomponents are estimated using a
correlation of K10 values and boiling points.
This method usually gives reasonable results for refinery heavyend columns operating at low
pressures. If the lightends distribution in the column is important, another method should be used.
The method should never be used for systems at pressures higher than 70 psia or temperatures
outside the range 100 to 900 F. Because the composition effect on K-values is ignored, it can be
expected to yield poor results for mixtures of aromatics with paraffins, naphthenes and olefins.
80
Grayson-Streed
This method (GS) is based on the Chao-Seader method and represents an attempt by Grayson and
Streed to extend the Chao-Seader approach to the higher temperatures and pressures encountered
in oil refining. Grayson and Streed also fit special equations for the liquid fugacities of methane
and hydrogen, using data available from hydrocracking operations.
Suitable for the refinery heavyend columns such as crude, vacuum, FCC main fractionators and
coker columns. It can also be used for most refinery gas plant operations and hydrogen processes
such as reforming and hydrocracking. For hydrocracking, more accurate hydrogen solubilities are
predicted by using one of the SRK modifications. General limits are pressures less than 3000 psia
and temperatures less than 800 F, although the method usually extrapolates reasonably well with
temperature.
81
Curl-Pitzer method
The Curl-Pitzer method (CP) predicts the enthalpies and entropies for liquids and vapors. The
enthalpy deviation is computed by using the principle of corresponding states, i.e., in terms of the
reduced temperature, reduced pressure and the acentric factor. The critical temperature and
pressure for the mixture are computed using the mixing rules of Stewart, Burkhart and Voo.
The method is limited to nonpolar mixtures and can be used for Pr up to 10.0, Tr for liquids in the
range 0.35 to 4.0, and Tr for vapors in the range 0.6 to 4.0. Curl-Pitzer can be used to predict the
enthalpies and entropies for liquids and vapors.
The enthalpy deviation is computed using the principle of corresponding states, i.e., in terms of
the reduced temperature, reduced pressure and the acentric factor. The critical temperature and
pressure for the mixture is computed using the mixing rules of Stewart, Burkhart and Voo.
Curl-Pitzer is suitable for most hydrocarbon applications including natural gas and refinery
processes. The method must extrapolate for vacuum columns; Lee-Kesler method is
recommended for this application.
For heavyends, the saturated vapor Tr is less than 0.6 and the method must extrapolate.
Extrapolation usually produces reasonable results.
82
Johnson-Grayson
The Johnson-Grayson method (JG) can be used to predict enthalpies for hydrocarbon liquids and
vapors. It is essentially an ideal enthalpy correlation, using saturated liquid at -200 F as the
datum. Vapor phase corrections are computed with the Curl-Pitzer method. The pressure effects
on the liquid phase are ignored.
The method is useful for heavy hydrocarbons over the temperature range 0 to 1200 F. It can be
extrapolated with reasonable results. This method should not be used for mixtures lighter than
carbon number five.
This method is suitable for refinery heavyend systems such as vacuum systems and synthetic fuel
applications with heavy oils.
83
API Liquid Density

The API method (API) can be used to predict liquid densities at flowing conditions. A standard
liquid density is computed at 60 F, using the weight average of the component densities. The
reduced temperature and pressure of the mixture at 60 F and 14.696 psia are computed with the
Kay rule and used to determine a density factor, C, from Figure 6A2.21 in the API Technical
Data Book. A second factor is determined at the flowing temperature and pressure for the mixture
and the flowing density is computed from the equation below:
The method is applicable to most hydrocarbon systems, provided that the reduced temperature is
less than 1.0.
84
Ideal
The Ideal method obtains liquid densities from pure component liquid density correlations.
This method is suitable for systems of similar components at low pressures and temperatures.
85
SIMSCI Databanks
The SIMSCI databanks, SIMSCI and PROCESS, contain more than 1700 components and are
adequate for nearly all flowsheet models.
86
User-Prepared Databanks
You can prepare custom component databanks using the SIMSCI LIBMRG and DATAPREP
programs.
87
User-Defined Petroleum Components

You can define petroleum components by supplying two of the three following properties for
each component:
Normal Boiling Point
Molecular Weight
SIM4ME uses internal correlations to estimate the third parameter, when missing.
88
Assay
Components derived from petroleum assay data.
89
IUPAC
International Union of Pure and Applied Chemistry.
90
Normal Boiling Point (NBP)

Normal Boiling Point (NBP) data can be supplied in any of the standard temperature systems
(R, K, F or C).
91
Assay Name
Contains the names of the currently defined assays.
From the drop down list, select the assay for which you wish to enter Distillation, Gravity,
Molecular Weight, Light Ends or Inspection Property data.
92
Cut Set
This list box displays the names of the currently defined Cut Sets.
From the drop down list, select the Cut Set for the newly defined assay. The fractions in the
Cut Set are included in the assay and can be seen in the Component Full Name list by expanding
the assay.
Modular Thermo automatically assigns names to the individual fractions according to their
mid-range boiling points expressed in Kelvins.
93
Enter Data For

This field contains a tree with branches for:
Distillation
Gravity
Molecular weight
Lightends
Inspection Property.
The Inspection Property branch can be expanded or collapsed by clicking on the box at the node.
Depending on the type of stream property data you wish to enter, click on the like-named branch
to open the appropriate data entry fields. The name of the adjacent data-entry area changes
accordingly.
94
Cubic Spline
All data points are fit to a cubic spline function. A normal probability function is used to
extrapolate beyond the first and last data point if necessary. When not provided, the initial point
and end point are defined as the 0.01 % and 99.99 % points, respectively. If only two points are
provided, the entire curve is defined with a probability fit.
The cubic spline method results in the best possible fit for nearly all laboratory curves, however,
curves with step functions may cause fitting problems. If this occurs, the validity of the data
should be checked.
95
Quadratic Polynomials
Successive quadratic approximations are applied to the shape of the input curve. This method is
not as elegant as the Cubic Spline method but does exhibit more stability for curves with step
functions.
96
Probability Density Function

PDF is a least squares probability density function that is fit to all supplied points on the curve.
This method is recommended when errors are suspected in the distillation data. Unlike the other
fitting methods, the generated curve does not actually pass through the supplied data points
except as noted below. The square of the errors in fitting the supplied data to a probability shaped
curve is, however, minimized.
The PDF curve may be forced through the initial point and/or the end point by using the Include
in PDF feature. Unless this feature is used, the initial and end points are handled similarly to the
other points on the curve.
When the Initial Point option is chosen and the initial point is supplied, the PDF curve is forced
through the supplied initial point. In similar fashion, the PDF curve can be forced through a
supplied end point by choosing the End Point option.
When the Initial Point option is chosen and the initial point is not supplied, the curve is first
extrapolated linearly to determine an initial point and then the point is held constant for the PDF
fitting. Undefined end points are handled similarly when the End Point option is used.
97
API 1987
This is the method published in the 1987 API Technical Data Book, which was developed by
Riazi and Daubert. The following equation is used to convert each D86 temperature to a TBP
temperature:
TBP = a (D86) b
where:
A, b = constants for each standard volume percent and TBP and D86 are Rankine.
For a table relating the constants a, b to standard volume percent, see the API 1987 Distillation
Curve Interconversion reference topic.
98
API 1963
This method is taken from the API Technical Data Book (prior to the 1987 Edition). This
technique provides a curve relating the D86 50% distilled point to the TBP 50% distilled point.
The API Technical Data Book also provides a series of curves that convert the D86 temperature
differences to TBP temperature differences.
Curves are provided for: IBP to 10 %, 10 to 30%, 30 to 50%, 50 to 70%, 70 to 90% and 90% to
EP. The TBP temperature differences are applied to the TBP 50% distilled point to generate the
complete TBP curve.
99
Edmister-Okamoto
This is an earlier version of the API 1963 method. This application is identical to that described
for API 1963.
100
Constant Watson K from TBP Curve

A Watson K Factor is estimated for the stream, based on its TBP and the supplied average
gravity. The gravity for each pseudocomponent is then back calculated from the stream average
Watson K factor using its average normal boiling point. The stream average Watson K Factor is
adjusted until the blended gravity for all of the stream components equals the supplied average
gravity for the stream.
101
Constant Watson K from D86 Curve

With this method, the stream average Watson K Factor is determined using the average of the
ASTM D86 temperatures at 10, 30, 50, 70 and 90 percent and the supplied average gravity. The
average K factor is next applied to each pseudocomponent at its normal boiling point to
determine its gravity. The entire gravity curve is normalized as required to match the supplied
average gravity.
102
Liquid Volume Average

The Normal Boiling Point (NBP) for the cuts is calculated from the volume average (or, in rare
cases where TBP, D86 or D1160 distillations are entered on a weight basis, as a weight-fraction
average) by integrating across the cut range. For small cut ranges, this closely approaches other
types of average boiling points.
This is the default calculation method.
103
Temperature Midpoint
The Normal Boiling Point (NBP) for the cuts is calculated from the midpoint of the initial and
final boiling points of the narrow cut.
104
Initial and Final Points

The initial boiling point (IBP) is defined as the temperature at which the first drop of liquid is
collected. The final boiling point or end point is defined as the maximum temperature reached
during the distillation.
The default values for initial and final point distillation points are 1% and 98%, respectively. You
can change the default initial and final points to match your distillation assay data.
105
PDF
The PDF curve can be forced through the initial point and/or the end point by using the Include in
PDF feature. Unless this feature is used, the initial and end points are handled similarly to the
other points on the curve.
When the Initial Point option is chosen and the initial point is supplied, the PDF curve is forced
through the supplied initial point. In similar fashion, the PDF curve can be forced through a
supplied end point by choosing the End Point option.
When the Initial Point option is used and the initial point is not supplied, the curve is first
extrapolated linearly to determine an initial point and then the point is held constant for the PDF
fitting. Undefined end points are handled similarly when the End Point option is used.
106
Temperature Profile
Choose a Temperature Profile option for a given range in a Cut Set. You can use different
temperature profiles for different ranges.
Number of Cuts
Fixes the number of cuts for a temperature range and automatically calculates the temperature
increment needed to make the number of cuts.
The temperature span for each cut in the range is identical.
Temperature Increment
Uses the specified temperature increment to determine the number of cuts for the range. If
necessary, Modular Thermo reduces the End Temp of the range so that the range contains an
integral number of cuts of the specified increment.
The temperature span for each cut in the range is identical.
Individual Temperature
Permits you to fix the temperature range for individual cuts.
Choose this option to specify cuts with different temperature spans.
107
Start Temp/End Temp Table

Enter the Start and End Temps for the Cut Set ranges in this table and specify the number of cuts
(or temperature increments) for each range.
To add or delete a range from an existing Cut Set:
1. Right-click on the row number of the Cut Set data table.
2. Choose the appropriate option from the menu.
You can add as many rows (temperature ranges) as you wish.
To change the temperature units of measure (UOM) or convert the temperature values for the
entire Cut Set:
1. Right-click anywhere in the Start Temp, End Temp or Temp Increment heading.
2. Choose the desired temperature UOM from the options.
Any change made in one column applies to all other columns.
108
API Method
API Flash Point Determination. This method uses API Procedure 2B7.1, which relates the flash,
point to the D86 10 percent distilled temperature. Flash points correspond to the Pensky-Martens
(D93) test procedure.
109
Index Mixing Method

The Index mixing method sums the individual component indices on a weight, molar or liquid
volume basis as appropriate for the property in question. The individual component index is
calculated from the property itself using the relationship:
The value of the constant C for a particular property is calculated from the values supplied at a
reference point.
To view the default reference index data:
1. Right-click on the Refinery Inspection Property.
2. Choose Index.
The Basis drop down list and data entry fields containing default values for Reference Index
Data appear.
3. Choose the appropriate basis (weight, liquid volume) from the Basis drop down list.
4. Supply your own values for the Reference Index, Reference Value or Gamma () or accept the
default values.
110
SimSci Mixing Method

The SIMSCI mixing method sums the component property index values. Different formulas than
the one used in the Index method convert data values to indices for the particular properties.
111
Summation Mixing Method

The Summation mixing method sums the actual individual component property values.
112
Average Value
Enter a value for the average molecular weight of the assay. If you do not supply molecular
weight data, SIM4ME estimates the molecular weights.
The default molecular weight estimation method is SIMSCI(Twu).
113
Volume Percent Distilled vs. Molecular Weight Table

Enter the mid-volume % distilled and corresponding molecular weight values for the cuts.
The curve generated from these data pairs is quadratically interpolated and extrapolated to cover
the entire range of pseudocomponents.
If you also supply an average molecular weight in addition to the data pairs, the molecular weight
value for the last cut is adjusted so that the curve matches the given average.
Alternatively, if you provide the value at 100% distilled, the entire molecular weight curve is
normalized to match the given average.
114
Default
The default method is established in the defaults dialog box and can be set to one of those listed.
115
Modular Thermo - Transport Data

The following transport properties for vapors and liquids are calculated by Modular Thermo:
Kinematic viscosity
Thermal conductivity
Most library components include saturated vapor and liquid values for viscosity and thermal
conductivity as part of the stored physical property data.
You can choose to compute transport properties as a weighted average of pure-component values.
The pure-component method requires that the property in question be available for each
component in the mixture with the exception of petroleum pseudocomponents.
The pure-component properties at the temperature of interest are combined to calculate stream
average properties according to the mixing rules described in detail in the Stream Average
Properties reference topic.
Modular Thermo also provides a Petroleum Correlation method that predicts the above properties
for pseudocomponents.
See also:
Petroleum Correlation Viscosity Estimation
Petroleum Correlation Thermal Conductivity Estimation
Modular Thermo offers the following options for Kinematic Viscosity calculation methods:
116
Normal Melting Point

Normal Melting Point data can be supplied in any of the standard temperature systems
(R, K, F or C).
117
Customize the Property Tab

This function allows you to select a set of properties dictated by a list of common scenarios, such
as API Gravity and carbon Number. Once selected, the set of properties populate the components
that can be configured. This can then be saved for use or for later modification as a new scenario.
To customize the Property tab:
1. Select a scenario in the list and click Customize.
The tab changes and a tab with a list and the New, Load, Save, Rename and Delete buttons
appear.
2. Either click:
New and build a new scenario by clicking on items in the pick list and dragging
them to the empty components fields labels.
Or
Load and select an existing item from the list in the Load dialog box that appears.
You can then modify this by clicking on items in the pick list and dragging them to
the empty components fields labels.
3. Click Save to name the item and click OK.
You cannot overwrite built-in tables.
Use the Delete button to delete customized tables and the Rename button to rename them in the
pull down list.
Customizations made here are saved to your local machine, NOT in the database you are working
on. As a result, customized table definitions are available with any database.
118
Distillation Data
Enter the following data:
Temp.
Assay Basis
Type
Pressure
Pressure basis
Cracking
To enter the distillation data:
1. Click New Assay and a data grid appear.
2. Enter the necessary data.
3. Click OK.
The name appears in the Assay Name field.
Corresponds to
STREAM DATA
TBP or D86 or D1160 or D2887
119
Temp.
Defines the units of the distillation curve temperatures.
The default is the same as the dimension you entered in the Input Dimensions dialog box.
Corresponds to
STREAM DATA
TBP or D86 or D1160 or D2887 STREAM= id,TEMP= C or F or K or R
120
Fluid Flowrate
The value of the fluid flowrate defines the basis for the assay data. The default is LV (liquid
volume).
Choose the WT (Weight) option only if the distillation analysis type is TBP.
Corresponds to
STREAM DATA
PROP ASSAY= LV or WT
121
Distillation Types
Select one of the following distillation types:
D86 Distillation: Atmospheric ASTM D86 distillation data.
D1160 Distillation: Vacuum ASTM D1160 distillation data.
TBP Distillation: True boiling point distillation data.
D2887 Distillation: ASTM D2887 simulated distillation curve data. Reported as TBP
and weight percentage.
Corresponds to
STREAM DATA
TBP or D86 or D1160 or D2887
122
Pressure ()
This is the pressure at which the analyses are to be performed.
By default, the distillation analyses are assumed to be at atmospheric pressure.
D1160 analyses are often performed in a vacuum of 10 mm Hg.
Corresponds to
STREAM DATA
TBP or D86 or D1160 or D2887 PRESS (pressure basis)= pressure
123
Pressure Basis
This is the basis for the pressure units.
The pressure unit defaults to the problem pressure units.
Corresponds to
STREAM DATA
TBP or D86 or D1160 or D2887 PRESS (pressure basis)= value
124
Cracking
Adds thermal cracking correlations for D86 analyses.
This option is enabled if the box is checked.
The cracking option is not available for TBP, D1160, and D2887 analyses.
Corresponds to
STREAM DATA
TBP or D86 or D1160 or D2887 CRACKING
125
Rate
Enter the total flowrate of the light hydrocarbons in the assay analysis.
Corresponds to
STREAM DATA
LIGHTENDS RATE (M or W or V or G)= value
126
Fraction
Enter the fraction of the total stream flowrate that is comprised of the light hydrocarbons.
Corresponds to
STREAM DATA
LIGHTENDS FRACTION (W or V)= value
127
Percent
Enter the percentage of the total stream flowrate that is comprised of the light hydrocarbons.
Corresponds to
STREAM DATA
LIGHTENDS PERCENT (W or V)= value
128
Match TBP Curve

Alter the lightends flowrate to match the TBP curve lightends.
Corresponds to
STREAM DATA
LIGHTENDS MATCH or NOMATCH
129
COSTALD
The COSTALD method (COSTALD) was developed to accurately predict the liquid densities of
LNG fluids. It is a corresponding states model and is 98.8 % accurate in predicting the densities
of light hydrocarbon mixtures.
This model uses two characteristic parameters for each pure component in the mixture - a
. The acentric factor is chosen
characteristic volume, V*, and a tuned acentric factor,
such that the SRK equation of state best matches the vapor pressure data. Typically, this tuned
acentric factor varies little in value from the standard acentric factor. The saturated volume is
given by:
where:
For mixtures, the following mixing rules are used:
where:
subscript m refers to mixture properties.
130
For compressed pure liquids and liquid mixtures, the original work was extended by Thomson et
al. in 1982, adding a pressure correction of the form:
where:
B, C are constants, dependent on composition
V
= saturated vapor pressure, obtained from a generalized vapor pressure relationship.

= molar volume
The COSTALD method is valid for aromatics and light hydrocarbons up to reduced temperatures
of 0.95. SIM4ME databanks contain COSTALD characteristic volume, V* for many components.
However, if the characteristic volume is not available, SIM4ME will use the critical volume of
the pure component, Vc. For petroleum and assay components, however, SIM4ME will back
calculate a characteristic volume, if missing, in order to provide a correct specific gravity for the
pseudocomponent.
References
1. Hankinson, R. W., and G. H. Thomson, 1979, A New Correlation for Saturated Densities of
Liquids and Their Mixtures, AIChE J., 25(4), 653.
2. Thomson, G. H., Brobst, K. R., and Hankinson, R. W., 1982, An Improved Correlation for
Densities of Compressed Liquids and Liquid Mixtures, AIChE J., 28(4), 671.
131
RACKETT
The Rackett method (RACKETT) may be used to predict liquid densities. The liquid density is
computed from equations relating the critical temperature, critical pressure and Rackett parameter
for the mixture. SIM4ME contains Rackett parameters for many components. If the Rackett
parameter is not available, the critical compressibility of the component will be used instead.
The saturated liquid density is obtained from:
(1)
where:
= saturated liquid volume
= Rackett parameter for component i
= critical temperature and pressure for component i
= reduced temperature for component i
The SIM4ME databanks contain Rackett parameters for many components. However, if Rackett
parameters are not available, SIM4ME will use the critical compressibility factor, zc. When the
Rackett parameter is missing for a petroleum or assay component, SIM4ME back-calculates the
missing parameter to ensure the specific gravity of the pseudocomponent is correct.
For mixtures, there are two ways to use the Rackett equation. The most straightforward, known as
the RACKETT method in SIM4ME, is to use equation (1) for the molar volume of each pure
component and then mix the volumes together linearly. A second approach is the "One-Fluid"
Rackett method (known as the RCK2 method), in which mixing rules are used to determine
effective critical parameters for the mixture and then equation (1) is used to determine the mixture
density. For most mixtures, the difference between these two methods will not be significant.
References
1. Rackett, H. G., 1970, Equation of State for Saturated Liquids, J. Chem. Eng. Data, 15, 514.
2. Spencer, C. F., and Danner, R. P., 1972, Improved Equation for Prediction of Saturated Liquid
Density, J. Chem. Eng. Data, 17, 236-241.
3. Spencer, C. F., and Adler, S. B., 1978, A Critical Review of Equations for Predicting
Saturated Liquid Density, J. Chem. Eng. Data, 23, 82-89.
132

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SIM4ME Thermodynamics

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Dynamic Simulation

Dynsim 4.2 : SIM4ME

The software described in this guide is furnished under a

2006 Invensys Systems, Inc. All rights reserved. No part

Field Descriptions/Miscellaneous ..............................................19

Volume Percent Distilled vs. Gravity Table ................................................... 41

Probability Density Function .......................................................................... 97

Components and Thermodynamics Overview

Components and Thermodynamics Overview

Version 4.2, October 2006

Components and Thermodynamics Window

Components and Thermodynamics Window

Drag components around to change their order.

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Normal Boiling Point

2. Click Characterize All Petro Components.

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Cut Set Tab

Cut Set Tab

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Blend Name (drop-down)

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Method Slate (drop-down)

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To remove a Component, Assay or Blend from the Components in Slate list:

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Local Thermo Tab

Local Thermo Tab

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Local Flash Tab

Local Flash Tab

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Component Family List

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Component Full Name

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Most Commonly Used

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Standard Liquid Density

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Distillation Data Type