UniSim Clean Fuels

Property Package

Reference Guide
Copyright
June 2005 R350 Release

The information in this help file is subject to change over time. Honeywell may make
changes to the requirements described. Future revisions will incorporate changes,
including corrections of typographical errors and technical inaccuracies.

For further information please contact

Honeywell
300-250 York Street
London, Ontario
N6A 6K2
Telephone: (519) 679-6570
Facsimile: (519) 679-3977

Copyright Honeywell 2005. All rights reserved.

Prepared in Canada.
 Table of Contents
1 Introduction ......................................................... 1-1
1.1 Meeting New Sulphur Levels in Motor Gasoline ..... 1-3

2 Gasoline Fractionation.......................................... 2-1

2.1 Gasoline Sulphur Species Distribution ................. 2-2
2.2 Light/Medium Gasoline Fractionation................... 2-5
2.3 Improve Fractionator Design.............................. 2-8

3 Clean Fuels Property Package............................ 3-1

3.1 Introduction .................................................... 3-2
3.2 Thermodynamic Model ...................................... 3-2

4 Clean Fuels Pkg Extension .................................... 4-1

4.1 Using the Clean Fuels Pkg Extension ................... 4-2
4.2 Clean Fuels Pkg Extension User Interface ............ 4-3
4.3 Clean Fuels Pkg View ........................................ 4-4

5 Clean Fuels Pkg Tutorial ....................................... 5-1

5.1 Introduction .................................................... 5-2
5.2 Flowsheet Setup .............................................. 5-3
5.3 Modeling the Gasoline Fractionator ....................5-10
5.4 Plot Utility ......................................................5-15

A References ...........................................................A-1

Index.................................................................... I-1

iii
iv
 Introduction 1-1

1 Introduction

1.1 Meeting New Sulphur Levels in Motor Gasoline .............................. 3

1-1
1-2

The increasing environmental concern of sulphur content in

petroleum products mean refiners are needing to find better
ways of managing sulphur pool target levels in gasoline. The
complexity of modeling these processes with the accuracy in the
very low ppm region requires highly accurate thermodynamic
methods for modeling and optimization. To meet the need for
increased model reliability, a new property package, the Clean
Fuels Pkg, has been developed specifically for systems of thiols
and hydrocarbons. The new property package features new
methods, estimation routines as well as extensive new
databases of pure component properties and mixtures.

This user manual is a comprehensive guide that provides the

steps needed to use the Clean Fuels Pkg in a UniSim Design
flowsheet. To apply the Clean Fuels Extension efficiently, the
manual describes the property package views as well as its
capabilities. A simple flowsheet model of a gasoline fractionator
is constructed using the Clean Fuels Pkg and the steps of its
construction are given in the tutorial. The tutorial presents the
basic steps needed to build the flowsheet model. Each view is
explained on a page-by-page basis to give a complete
description of the data requirements in order to use the property
package efficiently. This User Guide does not detail UniSim
Design procedures and assumes the user is familiar with the
UniSim Design environment and its conventions. Here you will
find the information required to build a UniSim Design flowsheet
and work efficiently within the simulation environment.

1-2
 Introduction 1-3

1.1 Meeting New Sulphur

Levels in Motor
Gasoline
With new strict global-wide legislation regulating undesirable
emissions from internal combustion engines, refineries are
facing challenging design decisions to meet lower sulphur
targets in motor gasoline. With these regulations continuing to
evolve, reducing sulphur to target levels will likely involve some
of the highest capital costs for refiners.

During the early 1990s gasoline sulphur levels were

approximately 340 ppmw [1]. With new levels set in 2000,
refiners are reducing sulphur to 150 ppmw. By 2006, the US
EPA proposes to reduce sulphur to 30 ppmw with phased
reductions beginning in 2004. European regulations call for
reductions to 50 ppmw by 2005 while Canadian regulations
require 30 ppmw by 2004 [1]. Farther ahead, the US EPA has
called for even lower targets of 10 ppmw. Continuously lower
levels of gasoline sulphur present new challenges to develop and
identify viable low cost solutions for reduced gasoline sulphur
content in motor gasoline.

Effective solutions to manage gasoline sulphur content involve

choosing the best technology options for sulphur removal, as
well as selecting designs that best fit the operating philosophy
for refiners. Important to gasoline sulphur management
strategies is understanding how the various sulphur species are
distributed in fractionator gasoline cuts which is critical in
determining the optimum operating conditions of gasoline
fractionators.

As sulphur content of gasoline is reduced, gasoline fractionation

will become increasingly important. Key in the optimum design
of new or existing equipment is the construction of accurate
flowsheets of gasoline fractionation processes. Fundamental to
the construction of flowsheet models is the accurate VLE
representation of thiol containing mixtures of hydrocarbons.

1-3
1-4 Meeting New Sulphur Levels in Motor

1-4
 Gasoline Fractionation 2-1

2 Gasoline
Fractionation

2.1 Gasoline Sulphur Species Distribution............................................ 2

2.2 Light/Medium Gasoline Fractionation ............................................ 5

2.3 Improve Fractionator Design ......................................................... 8

2-1
2-2 Gasoline Sulphur Species Distribution

2.1 Gasoline Sulphur

Species Distribution
Various sulphur compounds are distributed throughout the
gasoline TBP range. The amount of sulphur species in motor
gasoline depends on a number of factors including the crude
source, treating methods and gasoline cut point. The boiling
range of FCC gasoline does not change significantly with sulphur
levels2. Therefore knowing the temperature range where the
various sulphur species distil and how much of each sulphur
species is present at a given TBP temperature is important in
operating fractionation equipment that meet sulphur pool target
levels. A list of sulphur compounds is shown in the table below
together with the hydrocarbon boiling point ranges and UniSim
Design component information.

UniSim
UniSim Design BPT Range
Component name NPB °F Design Comp Formula
Sim Name °F
ID
Sulphur Components in Light Gasoline
Ethyl Mercaptan E-Mercaptan 95.09 70-90 354 C2H6S
Dimethyl Sulfide diM-Sulphide 99.23 75-80 380 C2H6S
Iso-propyl Mercaptan 2C3Mercaptan 126.61 110-130 3162 C3H8S
Tert-butyl Mercaptan t-B-Mercaptan 147.59 120-150 524 C4H10S
Methyl Ethyl Sulphide M-E-Sulfide 151.97 130-140 381 C3H8S
n-Propyl Mercpatan nPMercaptan 150.89 115-130 389 C3H8S
Thiophene Thiophene 183.29 140-200 384 C4H4S
Iso-Butyl Mercaptan 2-M-1C3Thiol 191.21 180-200 732 C4H10S
n-Butyl Mercaptan nBMercaptan 209.23 185-200 390 C4H10S
Dimethyl disulfide diMdiSulphid 229.53 190-200 385 C2H6S2
2-Methyl Thiophene 2MThiophene 234.59 200-250 733 C5H6S
3-Methyl Thiophene 3MThiophene 239.81 210-270 734 C5H6S
Tetrahydrothiophene Thiolane 250.01 220-260 526 C4H8S
1-Pentyl Mercaptan 1Pentanthiol 259.95 245-255 525 C5H12S
Hexyl Mercaptan 1Hexanethiol 306.77 290-340 847 C6H14S
Benzothiopene ThioNaphtene 427.81 400+ 3116 C8H6S

Essential for the accurate prediction of azeotropes occurring

between thiols and hydrocarbons is the accurate calculation of

2-2
 Gasoline Fractionation 2-3

pure component vapor pressures. For this, the most up to date

pure component data (DIPPR) was used in the development of
the Clean Fuels Property Package methods. A list of sulphur
species supported in UniSim Design for the Clean Fuels Property
Package is shown in the table below.

UniSim
Formula Component Name DIPPR ID
Design ID
CH4S METHYL MERCAPTAN 1801 353
C2H6S ETHYL MERCAPTAN 1802 354
C3H8S n-PROPYL MERCAPTAN 1803 389
C4H10S tert-BUTYL MERCAPTAN 1804 524
C4H10S ISOBUTYL MERCAPTAN 1805 732
C4H10S sec-BUTYL MERCAPTAN 1806 731
C6H14S n-HEXYL MERCAPTAN 1807 847
C9H20S n-NONYL MERCAPTAN 1808 3068
C8H18S n-OCTYL MERCAPTAN 1809 871
C3H8S ISOPROPYL MERCAPTAN 1810 3162
C3H8S ISOPROPYL MERCAPTAN 1810 695
C6H12S CYCLOHEXYL MERCAPTAN 1811 3280
C7H8S BENZYL MERCAPTAN 1812 3319
C3H8S METHYL ETHYL SULFIDE 1813 381
C4H10S METHYL n-PROPYL SULFIDE 1814 730
C6H14S DI-n-PROPYL SULFIDE 1817 846
C4H10S DIETHYL SULFIDE 1818 382
C2H6S DIMETHYL SULFIDE 1820 380
C4H4S THIOPHENE 1821 384
C8H6S BENZOTHIOPHENE 1822 3116
C4H10S2 DIETHYL DISULFIDE 1824 383
C11H24S UNDECYL MERCAPTAN 1825 958
C10H22S n-DECYL MERCAPTAN 1826 945
C5H12S n-PENTYL MERCAPTAN 1827 525
C2H6S2 DIMETHYL DISULFIDE 1828 385
C6H14S2 DI-n-PROPYL DISULFIDE 1829 848
C12H26S n-DODECYL MERCAPTAN 1837 3013
C8H18S tert-OCTYL MERCAPTAN 1838 3373
C7H16S n-HEPTYL MERCAPTAN 1839 865
C4H10S n-BUTYL MERCAPTAN 1841 390
C6H6S PHENYL MERCAPTAN 1842 391
C4H8S TETRAHYDROTHIOPHENE 1843 526
C2H6OS DIMETHYL SULFOXIDE 1844 950

2-3
2-4 Gasoline Sulphur Species Distribution

UniSim
Formula Component Name DIPPR ID
Design ID
C3H6O2S 3-MERCAPTOPROPIONIC ACID 1873 3153
COS CARBONYL SULFIDE 1893 355
H2S HYDROGEN SULFIDE 1922 15
CS2 CARBON DISULFIDE 1938 364
C12H8S DIBENZOTHIOPHENE 2823 3441
C12H26S tert-DODECYL MERCAPTAN 2838 3460
C5H6S 2-METHYLTHIOPHENE 2844 3216
C5H6S 2-METHYLTHIOPHENE 2844 733
C5H6S 3-METHYLTHIOPHENE 2845 3217
C5H6S 3-METHYLTHIOPHENE 2845 734
C2H4O2S THIOGLYCOLIC ACID 2872 3134
C5H9NS N-METHYLTHIOPYRROLIDONE 3888 3223
C4Cl4S TETRACHLOROTHIOPHENE 4877 3169
C4H10O2S THIODIGLYCOL 6855 3195
C2H6OS 2-MERCAPTOETHANOL 6858 3138
C4H10OS ETHYLTHIOETHANOL 6859 3192
C2H6S2 1,2-ETHANEDITHIOL 6860 3139

Quantifying sulphur species by hydrocarbon boiling range

requires fractionating 20-30 narrow boiling range (10-20°F)
using an ASTM D2892(TBP) column or TBP column with 15
theoretical stages and a 5/1 reflux ratio2. A highly fractionated
gasoline sample will be discontinuous up to about 390°F due to
the different sulphur species boiling point ranges. Sulphur
distribution, sulphur species and hydrocarbon TBP can then be
plotted using this information. Sulphur species content in
gasoline change from primarily mercaptans in the low boiling
range IBP-140°F material to thiophenic compounds in the 140-
390°F, and benzothiophenes and substituted benzothiophenes in
the 390-430°F heavy gasoline. Above 390°F the total sulphur
increases significantly with temperature.

2-4
 Gasoline Fractionation 2-5

2.2 Light/Medium Gasoline

Fractionation
As sulphur content of motor gasoline is mandatorily reduced,
gasoline fractionation will become increasingly more important.
Light gasoline thiophene content determines the total sulphur
content of a treated gasoline stream. The IBP-140°F
hydrocarbons contain primarily C2 and C3 mercaptans and up to
90% of these mercaptans can be extracted in caustic treating
processes. Thiophene however can not be extracted using these
methods. The thiophene NBP is 183.29°F. Due to strong
hydrocarbon-thiol molecular interactions, thiophene distils with
hydrocarbons between 140°F and 200°F. Peak thiophene
concentration occurs at about 165-170°F boiling range2.
Thiophene content varies with each crude and the amount of
hydrotreating, however it can represent up to 75% of the
sulphur in the 140-180°F hydrocarbons. Therefore 140°F+
material in light gasoline increases treated stream sulphur
content.

A simulated plot of an FCC naphtha and the distribution of

thiophene with increasing hydrocarbon boiling point is shown in
Figure 2.1. The plot was constructed using a simulation model
of an Oldershaw still with 70 theoretical stages at 20/1 reflux
ratio and equal narrow boiling range cuts of 5% volume distilled.
Results are shown in the table below. Qualitatively, the sulphur
distribution curve of FCC gasoline increases rapidly, with
thiophene beginning to boil with hydrocarbons at approximately
140°F as shown in Figure 2.1. The predicted peak sulphur
concentration occurs at 168°F. Sharp fractionation of the light/
medium gasoline can increase yield significantly while still
meeting treated product sulphur levels2.

2-5
2-6 Light/Medium Gasoline Fractionation

Figure 2.1: Simulated Thiophene Peak of FCC Gasoline

The table below shows the Simulated Distillation Data of

Thiophene Distribution in a FCC Gasoline.

Percent Distilled Volume Temperature °F Sulphur ppm wt

20% 95.60 0.00
25% 117.15 0.00
30% 142.28 0.11
35% 151.77 10.9
40% 168.61 1354.0
45% 182.07 36.8
50% 196.67 0.00
55% 220.88 0.00

Fractionation of light/medium gasoline fractionation requires a

dedicated gas plant column. The column efficiency will
determine light gasoline yield and thiophene concentration in
gasoline. Medium/heavy gasoline fractionation is performed in
the main fractionator with heavy gasoline produced as a side cut
product, to minimize energy consumption and capital costs.

2-6
 Gasoline Fractionation 2-7

The table that lists the Light/medium gasoline fractionation separates feed to the
sulphur compounds casuistic extraction process from the medium boiling range
together with the
hydrocarbon boiling point gasoline. The caustic extraction process converts mercaptans to
ranges and UniSim disulfides, which are easily extracted. Caustic extraction can
Design component
information in Section
remove between 80-90% of the C2/C3 mercaptans.
2.1 - Gasoline Sulphur
Species Distribution, The amount of thiophene entering the feed caustic extraction
lists the sulphur species
process or its equivalent leaves with the treated product stream.
that are present in light
gasoline. Thiophene begins to distil with C6 hydrocarbons boiling above
140°F. Thiophene content peaks in the 165-170°F boiling range
so increasing levels of 140°F+ material increases the treated
product stream sulphur level. If thiophene content and not the
mercaptan extraction efficiency controls the treated product
sulphur level, then the light gasoline 140-160°F boiling material
must be controlled to meet product stream sulphur targets. The
140-160°F boiling range hydrocarbons make up 7-9 wt% of the
total FCC gasoline2, light gasoline yield can be increased
significantly with good fractionation by lowering the amount of
140-170°F boiling material in light gasoline product which allows
higher light gasoline yield. Sharp fractionation is achieved
through an appropriate number of column trays, controlling
reflux and energy input.

2-7
2-8 Improve Fractionator Design

2.3 Improve Fractionator

Design
Here the fractionation objective is to determine the optimum
number of trays and reflux that will result in sharp fractionation
of light and medium gasoline. The optimum values are achieved
using accurate VLE models.

Understanding how sulphur is distributed in gasoline is the first

step in determining the gasoline cut point to achieve the
necessary sharp fractionation between light and medium
gasoline. In designing a gasoline fractionation column, the
design objective is to ensure that thiophene is controlled in the
gasoline distillate. Even small amounts of thiophene contained
in the light fraction can add significantly to gasoline sulphur
levels.

Because of the strong molecular interactions between

hydrocarbons and sulphur containing compounds these mixtures
are non-ideal and can form azeotropes that are difficult to model
accurately. Typically an activity coefficient model would best
represent a non-ideal system. However because of the presence
of alkanes, olefins and oils as well as non-condensable
components in systems of gasoline, an equation of state is
always preferred for calculation of hydrocarbon binaries. An
equation of state however is not suitable for thiol-hydrocarbon
binary pairs. By combining the equation of state with an activity
model through a new Helmholtz Excess Energy AE mixing rule
and using an accurate vapor pressure model, the VLE
representation of hydrocarbon-thiol systems is possible,
representing both ideal and non-ideal binaries equally well. The
new mixing rule model is able to predict accurately thiol-
hydrocarbon azeotropes as well as the azeotrope temperature
and composition.

The new Clean Fuels property package methods also include a

binary interaction parameter database regressed for 101 thiol-
hydrocarbon binary pairs. To fill in missing parameters for
systems of binaries forming azeotropes, a newly developed

2-8
 Gasoline Fractionation 2-9

thiol-hydrocarbon binary estimation method is available which

will predict the azeotrope composition and temperature. All the
new methods developed are based on experimental data.
Figure 2.2 compares the Clean Fuels property package results
for the system nPropylMercapatn-Hexane with other methods.
As can be seen, the conventional equation of state (EOS)
methods fail while the effect of vapour pressure on the
calculation of the azeotrope for the activity model is highlighted
clearly. Although, the activity model performs fairly well in this
instance, its performance deteriorates with increasing
temperature and pressure. Selecting the correct thermodynamic
model for modeling gasoline fractionation is important.

Figure 2.2 VLE Diagram for nPropylMercapatn and Hexane at 1 atm

With a highly accurate VLE thermodynamic model, up to date

binary and pure component databases as well as reliable
estimation routines, the simulation of gasoline fractionation
towers can be used to better optimize new designs. For existing
equipment, towers can be rated accurately for performance

2-9
2-10 Improve Fractionator Design

changes where ultra low sulphur levels are required.

In the optimization of a gasoline fractionator, two design

variables are considered. Increasing the column number of
trays2 and the amount of reflux. Both have the same affect of
reducing the gasoline end point, however as Figure 2.3
illustrates, the effect of increasing the reflux is more dramatic in
controlling the end point temperature of gasoline.

Figure 2.3: Effect of Fractionator Design on Gasoline End Point

For existing gasoline fractionation towers, increasing reflux may

increase column tray traffic, so tower internals need to be
considered to handle the added capacity.

2-10
 Clean Fuels Property Package 3-1

3 Clean Fuels Property

Package

3.1 Introduction................................................................................... 2

3.2 Thermodynamic Model ................................................................... 2

3.2.1 Estimation Methods .................................................................. 7

3-1
3-2 Introduction

3.1 Introduction
The Clean Fuels Property Package is a specially designed
property package for the accurate VLE representation of thiol-
hydrocarbon containing systems. The Clean Fuels Pkg contains
the latest advances made in the development of cubic equations
of state and mixing rules. A new vapour pressure alpha function
is available that is correlated against DIPPR vapour pressure
data as well as DIPPR pure component properties for 1454
UniSim Design components. New databases are available
containing regressed coefficients for 101 thiol-hydrocarbon
binary pairs, and a new proprietary thiol-hydrocarbon
estimation method is able to predict the formation of azeotropes
and calculate the binary parameters from infinite dilution
activity coefficient data. The Clean Fuels Pkg allows User Data to
be supplied for azeotropes and infinite dilution activity
coefficient data as well as supporting 49 DIPPR thiol containing
components listed in the table of the sulphur species supported
in UniSim Design for the Clean Fuels Property Package in
Section 2.1 - Gasoline Sulphur Species Distribution.

3.2 Thermodynamic Model

Selecting an appropriate thermodynamic model to represent
Clean Fuels processes requires the selection of an appropriate
cubic equation of state that will allow better prediction of liquid
densities of mid-range to heavy hydrocarbons and polar
components. Also a highly accurate vapour pressure alpha
function is needed that extrapolates correctly beyond the critical
point. A suitable mixing rule is necessary that can allow
hydrocarbon-hydrocarbon binary pairs to be modelled with the
accuracy of an equation state while able to represent non-ideal
thiol-hydrocarbons as well as an activity model. Finally, the
selection of a suitable thermodynamic model involves choosing
an appropriate activity model that would allow the new mixing
rules to transition the van der Waals one-fluid mixing rules for
hydrocarbon binaries.

3-2
 Clean Fuels Property Package 3-3

The Clean Fuels Property Package uses an optimal two-

parameter cubic equation of state TST (Twu-Sim-Tassone)3 to
represent Clean Fuels Processes. The TST cubic equation is
represented as follows:

RT - a
P = ------------ – ------------------------------------------------------ (3.1)
v – b v 2 + 2.5bv – 1.5b 2

and can be rewritten in the form,

RT - – --------------------------------------------------
a
P = ------------ - (3.2)
v – b ( v + 3b ) ( v – 0.5b )

The values of a and b are at the critical temperature and are

found by setting the first and second derivatives of pressure
with respect to volume to zero at the critical point:

2 2
a ( T c ) = 0.427481R T c ⁄ P c (3.3)

b = 0.086641RT c ⁄ P c (3.4)

Z c = 0.296296 (3.5)

where:

c = critical point

The value of Zc from the SRK and PR equations are both larger
than 0.3 while Zc from the TST equation is slightly below it,
closest to the real one for many substances.

A prerequisite for the accurate VLE representation of thiol-

hydrocarbon systems in the entire composition range is the
accurate calculation of pure component vapour pressures.

3-3
3-4 Thermodynamic Model

You can use the Twu alpha correlation4.

NM
N ( M – 1 ) L ( 1 – Tr ) (3.6)
α = Tr e

Equation (3.7) has three parameters L, M, and N. These

parameters are unique to each component and are determined
from the regression of DIPPR pure component vapour pressure
data for 1454 components.

The generalized alpha function is used for non-library and

petroleum fractions:

(0) (1) (0) (3.7)

α = α + ω(α –α )

where:

α(0) is for ω=0

α(1) is for ω=1

Each alpha is a function of reduced temperature only.

To model both van der Waals fluids and highly non-ideal

mixtures using the same Gibbs excess energy model we use the
TST Zero-Pressure Mixing Rules3. The zero-pressure mixing
rules for the cubic equation of state mixture a and b parameters
are:

* E E
a vdw 1 - ⎛ -------
A 0 A 0vdw b vdw ⎞
⎜ - – ----------------- – ln ⎛⎝ --------------⎞⎠ ⎟
* *
a = b -------------
- + --------- (3.8)
b vdw C v0 ⎝ RT
* RT b ⎠

1
b = ∑ ∑ xi xj --- ( b i + b j )
2 (3.9)
i j

bvdw is used for b.

3-4
 Clean Fuels Property Package 3-5

avdw and bvdw are the equation of state a and b parameters

which are evaluated from the van der Waals mixing rules. The
Twu mixing rule given by Equation (3.8) is volume-dependent
through Cv0. Cv0 is a function of the reduced liquid volume at
zero pressure v0*=v0/b:

*
1 ⎛ v 0 + w⎞
C v0 = – ------------------- ln ⎜ -----------------
-⎟ (3.10)
( w – u ) ⎝ v* + u ⎠
0 vdw

Since the excess Helmholtz energy is a weak function of

pressure [5] we assume that the excess Helmholtz energy of the
van der Waals fluid at zero pressure can be approximated by the
excess Helmholtz energy of van der Waals fluid at infinite
pressure:

E E * *
A 0vdw A ∞vdw a vdw ai
----------------- - – ∑ x i ------*
- = C v0 -------------
= ----------------- (3.11)
RT RT *
b vdw i b i

A new versatile activity model NRTLTST 6 is used to describe

both a van der Waals fluid and a highly non-ideal mixture:

E
n ∑ xj τjiGji
G- = j
-------
RT ∑ xi ---------------------------
n
- (3.12)
i
∑ xk Gki
k

When τij and Gij are calculated using the parameters in

Equation (3.13) and Equation (3.14), the NRTL equation is
obtained.

A
τ ji = ------ji- (3.13)
T

G ji = exp ( – α ji τ ji ) (3.14)

3-5
3-6 Thermodynamic Model

However, Equation (3.12) can also recover the conventional

van der Waals mixing rules when the following expressions are
used for τij and Gij instead:

1 (3.15)
τ ji = --- δ ij b i
2

b
G ji = -----j (3.16)
bi

where:

2
C v0 ⎛ a i a⎞ ai aj
- ⎜ --------- – ---------j⎟ + 2k ij --------- ---------
δ ij = – – --------- (3.17)
RT ⎝ b i bj ⎠ b i bj

The TST mixing rules in Equation (3.8) are density dependent

through the function Cv0. Because of this density function, the
mixing rule is able to reproduce almost exactly the incorporated
GE model. Cv0 as defined by Equation (3.10) is calculated from
v0*vdw by solving the equation of state in Equation (3.1)at zero
pressure. This step can cause problems if there is no real root,
which may occur when non-condensable components are
present, for example. When this occurs, some sort of
extrapolation for v0* must be made. To omit the need for the
calculation of v0* from the equation of state, the zero-pressure
liquid volume of the van der Waals fluid, v0*vdw, is a constant, r:

*
v 0vdw = r (3.18)

Substituting Equation (3.18)into Equation (3.10), Equation

(3.10)becomes:

1 r+w
C r = – ------------------- ln ⎛ -------------⎞ (3.19)
(w – u) ⎝ r + u⎠

A universal value of r=1.18 has been determined from

information on the incorporated GE model and is recommended

3-6
 Clean Fuels Property Package 3-7

by Twu et al.7 for use in the phase equilibrium prediction for all
systems.

3.2.1 Estimation Methods

For systems containing thiols and hydrocarbons, some
hydrocarbons and petroleum fractions form azeotropes with
thiols. In cases were VLE data is not available for these systems,
reliable estimation methods are necessary to predict the
azeotrope and to calculate the binary interaction parameters.
The Clean Fuels Pkg contains an internal proprietary estimation
routine used to estimate the binary interaction parameters of
thiol and hydrocarbons that form azeotropes. Binary estimation
methods have been developed specifically for the thiols,
enthanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-
butanethiol, 2-methyl 1-propanethiol and 2-methyl 2-
propanethiol in mixtures of paraffins and naphthenes, while a
generalized estimation method is available to calculate the
binary parameters for all other thiols. The user is also allowed to
enter User applied azeotrope data or infinite dilution activity
coefficient data for calculation of binary parameters.

3-7
3-8 Thermodynamic Model

3-8
 Clean Fuels Pkg Extension 4-1

4 Clean Fuels Pkg

Extension

4.1 Using the Clean Fuels Pkg Extension.............................................. 2

4.1.1 Adding a Clean Fuels Pkg .......................................................... 2

4.2 Clean Fuels Pkg Extension User Interface ...................................... 3

4.3 Clean Fuels Pkg View ..................................................................... 4

4.3.1 NRTLTST Tab ........................................................................... 4
4.3.2 TST CEOS Tab.......................................................................... 5

4-1
4-2 Using the Clean Fuels Pkg Extension

4.1 Using the Clean Fuels

Pkg Extension
Refer to Chapter 2 - You can add a Clean Fuels Pkg Extension only if it exists as part
Fluid Package of the of a UniSim Design case. A Property Package Extension that is
UniSim Design
Simulation Basis part of an existing case can be accessed in the UniSim Design
manual for more Basis Environment. In the Basis Environment, you can view and
information on the adjust the extension variables as you would any UniSim Design
UniSim Design Property
Package. Property Package. Before creating a new Clean Fuels Pkg, the
user is required to be working within a UniSim Design case that
has a Fluid Package installed. The Fluid Package must consist of
a property package and associated flowsheet components.

4.1.1 Adding a Clean Fuels Pkg

To add a Clean Fuels Pkg to an existing UniSim Design case:
1. From the Simulation Basis Manager, click on the Fluid Pkgs
tab.
2. Click the Add button to add a Clean Fuels Pkg. The Fluid
Package view appears.
3. In the Property Pkg Filter group, click the Miscellaneous
Types radio button.

4-2
 Clean Fuels Pkg Extension 4-3

4. From the available property packages list select Clean Fuels

Pkg.

Figure 4.1

The View Property Package

button allows you to view
the Clean Fuels Pkg
parameters.
The Clean Fuels Pkg
parameters are shown on
the Clean Fuels Pkg
property view.

4.2 Clean Fuels Pkg

Extension User
Interface
The Clean Fuels Pkg Extension user interface is completely
integrated into the UniSim Design working environment and
conforms to all UniSim Design usage conventions for operations
and data entry. If you are an experienced user of UniSim
Design, you will already be familiar with all of the features of the
Property Package user interface. If you are a new user, begin by
reviewing the UniSim Design User Guide to familiarize
yourself with UniSim Design before using the Clean Fuels Pkg
Extension.

4-3
4-4 Clean Fuels Pkg View

4.3 Clean Fuels Pkg View

Like all UniSim Design property views, the Clean Fuels Pkg view
allows you access to all information associated with a particular
item, such as the interaction parameter view pages. You can
specify the binary interaction parameters or regress User data
on the Clean Fuels Pkg view.

Figure 4.2

The Clean Fuels Pkg view has two tabs (NRTLTST and TST
CEOS), and on each tab are groups of related parameters.

4.3.1 NRTLTST Tab

The NRTLTSTS tab as shown in Figure 4.2 contains the binary
parameters for the activity coefficient model NRTLTST (NRTL-
Twu-Sim-Tassone) used in the TST (Twu-Sim-Tassone) AE Mixing
Rules. This tab allows the user to view the binary parameters for
the activity model and to fill-in binary parameters not present in
the database or not calculated from the internal estimation
methods.

4-4
 Clean Fuels Pkg Extension 4-5

It is recommended that unknown parameters be filled-in at

all times using the UNIFAC VLE fill-in method.

User Data
The User Data button allows the user to provide either infinite
dilution activity coefficient data or azeotrope data per binary in
the calculation of interaction parameters for azeotrope
prediction of thiol-hydrocarbon binaries.

4.3.2 TST CEOS Tab

The TST CEOS tab contains the binary parameters for the TST
(Twu-Sim-Tassone) cubic equation of state (CEOS).

Figure 4.3

4-5
4-6 Clean Fuels Pkg View

The Twu Alpha Params button allows the user access to the Twu
vapor pressure alpha function parameters L, M and N, as well as
access to the DIPPR pure component properties Tc and Pc.

Figure 4.4

4-6
 Clean Fuels Pkg Tutorial 5-1

5 Clean Fuels Pkg

Tutorial

5.1 Introduction................................................................................... 2

5.2 Flowsheet Setup ............................................................................ 3

5.3 Modeling the Gasoline Fractionator.............................................. 10

5.3.1 Exercises .............................................................................. 14

5.4 Plot Utility.................................................................................... 15

5-1
5-2 Introduction

5.1 Introduction
The following example demonstrates how to use the Clean Fuels
Pkg to model a gasoline fractionator. In this example, a light/
medium gasoline is fractionated in a gas plant column. The
amount of sulphur is calculated in the light gasoline and the
gasoline endpoint is set to 150°F for design. The case will
consist of a FCC Gasoline feed stream to the tower and two
outlet streams, a light gasoline product stream and an
intermediate naphtha which is sent to an upstream hydrotreater
for further treating. The design objective is to maximize the
yield of light gasoline since hydrotreating of gasoline results in
severe octane loss.

Figure 5.1

5-2
 Clean Fuels Pkg Tutorial 5-3

5.2 Flowsheet Setup

Before working with the Clean Fuels Pkg Extension, you must
first create a UniSim Design case.
For more information on 1. In the Simulation Basis Manager, create a fluid package
adding library using the Clean Fuels Pkg. Add the UniSim Design Thiol
components, refer to library components 2C3Mercaptan, nPMercaptan and
Chapter 1 -
Components in the Thiophene.
UniSim Design
Simulation Basis Property Package Components
manual.
If you are unable to find Clean Fuels Pkg 2C3Mercaptan, nPMercaptan, Thiophene
the component using the
default Sim Name option Add the paraffins and olefins as shown in the table below,
on the Component List
view, click on the Full and then close the Component List view.
Name/Synonym radio
button. Then type the Component Name
component name in the
Match field. i-Butane
i-Butene
n-Butane
i-Pentane
1-Pentene
2M-13-C4==
Cyclopentene
3M1C5=
Cyclopentane
23-Mbutane
2-Mpentane
2M1C5=
1-Hexene
n-Hexane

2. Click on the Oil Manager tab of the Simulation Basis

Manager to install an oil with the TBP curve (light ends are
added in the main flowsheet).

5-3
5-4 Flowsheet Setup

3. Click the Enter Oil Environment button. The Oil

Characterization view appears.

Figure 5.2

4. Click the Add button. The Assay view appears.

Figure 5.3

5. In the Name field, type FCC Gas Oil.

6. From the Assay Data Type drop-down list on the Input
Data tab, select TBP.

5-4
 Clean Fuels Pkg Tutorial 5-5

7. In the Input Data group, click on the Edit Assay button. The
Assay Input Table view appears.

Figure 5.4

8. Add the assay input data as shown in the table below.

Assay Percent [%] Temperature [F]

0.0 108.6
5.0 167.3
15.0 190.2
20.0 201.4
25.0 213.6
30.0 226.3
35.0 239.3
40.0 252.7
45.0 266.2
50.0 279.5
55.0 292.4
60.0 305.5
75.0 348.3
90.0 407.9
95.0 425.5
98.0 458.3
100.0 490.2

5-5
5-6 Flowsheet Setup

9. After you have entered the assay input data, click the OK
button to return to the Assay view.

Figure 5.5

10. Close the Assay view to return to the Oil Manager property
view.
11. Click on the Cut/Blend tab to create a Blend object.
12. Click the Add button. The Blend view appears.

Figure 5.6

13. In the Name field, type FCC Gas Oil.

5-6
 Clean Fuels Pkg Tutorial 5-7

14. From the Cut Option Selection drop-down list of the Data
tab, select Auto Cut.
15. Click the Add button to select the assay.

Figure 5.7

The default Flow Unit is 16. Enter the data as shown in the table below.
Liquid Volume ensure that
you have selected Mass
from the drop-down list Flow Units Flow Rate
before specifying the flow Mass 364008 lb/hr
rate.

17. Close the Blend view to return to the Oil Manager property
view.
18. Click on the Install Oil tab, and in the Stream Name
column type FCC Gas Oil as shown in the figure below.

Figure 5.8

19. Click the Calculate All button to calculate the all the assays
and blends. Then click the Return to Basis Environment
button. The Simulation Basis Manager appears.

5-7
5-8 Flowsheet Setup

Ensure that you have 20. Click on the Fluid Pkgs tab, and then click the View button.
selected the Clean Fuels
Pkg in the Current Fluid 21. From Fluid Package view, click the View Property Package
Packages list. button. The Clean Fuels Pkg view appears.

Figure 5.9

Click the Unknowns Only button to specify the missing

Binary Interaction Parameters (BIPs) using the UNIFAC VLE
methods. Ensure that you have selected the UNIFAC VLE
radio button.
22. Close the Clean Fuels Pkg view and the Fluid Package view.
You can also press CTRL 23. From the Simulation Basis Manager, click the Enter
L to leave the Basis Simulation Environment to build your flowsheet.
Environment.
24. Create two streams named Sulphur Spike and Light Ends
For more information on
adding a stream, refer to in the Simulation Environment with the following stream
Chapter 3 - Streams in conditions and composition.
the UniSim Design
Operations Guide.
Conditions
Ensure that you have the
Mass Flow radio button Stream Name Sulphur Spike
selected in the Temperature [F] 100
Composition Basis group
of the Input Composition Pressure [psia] 114.6
from Stream view before Mass Flow [lb/hr] 219.6
specifying the stream
composition. Composition Mass Flow [lb/hr]
2C3Mercaptan 60.1
nPMercaptan 53.5
Thiophene 106.0

5-8
 Clean Fuels Pkg Tutorial 5-9

Conditions
Stream Name Light Ends
Temperature [F] 100
Pressure [psia] 114.6
Mass Flow [lb/hr] 1.705E+005
Composition Mass Flow [lb/hr]
i-Butane 392.2
i-Butene 13543.9
n-Butane 2318.5
i-Pentane 40094.1
1-Pentene 49783.6
2M-13-C4== 1475.2
Cyclopentene 2345.5
3M1C5= 2162.2
Cyclopentane 1138.2
23-Mbutane 5138.8
2-Mpentane 30575.8
2M1C5= 3221.3
1-Hexene 12306.8
n-Hexane 6004.2

25. Define the FCC Gas Oil stream conditions as shown in the
table below.

Conditions
Temperature [F] 100
Pressure [psia] 114.6
Mass Flow [lb/hr] 364008.7
Liq. Vol Flow [barrel/day] 32784.7

For more information on 26. Add a Mixer with the outlet stream named FCC Gasoline,
adding a Mixer, refer to and feed streams Sulphur Spike, Light Ends and FCC Gas
Section 5.1 - Mixer in
the UniSim Design
Oil.
Operations Guide. 27. Add a shell and tube Heat Exchanger with a 10 psi pressure
For more information on drop on both shell and tube sides.
adding a Heat Exchanger,
refer to Section 4.3 - The Shell side of the heat exchanger will heat the feed to the
Heat Exchanger in the column while the tube side cools the column bottoms
UniSim Design
Operations Guide. product.

5-9
5-10 Modeling the Gasoline Fractionator
For more information on a
distillation column, refer
to Chapter 8 - Column
in the UniSim Design
Operations Guide.
28. In the Heat Exchanger property view, name the tube side
feed Medium Gasoline and the outlet tube side to
Hydrotreater.
29. Specify the shell side feed FCC Gasoline, and name the
outlet shell side Feed to Fractionator.
30. Specify a stream temperature of 223°F for Feed to
Fractionator.
31. In the Parameters page of the Heat Exchanger property
view, change the Heat Exchanger Model to Exchanger
Design (Weighted).
5.3 Modeling the Gasoline
Fractionator
The Gasoline fractionator is modeled as a distillation column in
UniSim Design using a Partial Reflux Condenser.
1. Add a distillation column with a partial condenser. In the
Connections page, name the liquid distillate Light
Gasoline, the overhead vapor draw as Vent and the
bottoms liquid as Medium Gasoline. Cond-q and Reb-q
are the condenser and reboiler heat loads respectively.
2. The tower has 20 theoretical stages, and the feed to the
tower enters on Stage 13.
5-10
 Clean Fuels Pkg Tutorial 5-11

3. The pressure in the condenser is set at 240 kPa, the

pressure drop across the condenser is 55.16 kPa and the
bottom reboiler pressure is at 350 kPa.

Figure 5.10

4. On the Monitor page, enter a Reflux Ratio estimate of 1.0

and turn-off this specification. Set the Ovhd Vapor Rate to
0.0 MMSCFD, the distillate rate to 1.213e+004 barrel/
day (Volume).
5. Add a TBP End Point Volume Percent column specification for
Liquid Distillate at 150°F (65.56°C).

Figure 5.11

5-11
5-12 Modeling the Gasoline Fractionator

The figure below shows the Monitor page after adding a TBP
End Point Volume Percent column.

Figure 5.12

6. Click on the Parameters tab, and enter a top stage

temperature estimate of 140°F and a Tray 1 temperature
estimate of 180°F. Enter a bottoms reboiler temperature
estimate of 300°F.
7. Run the column and examine the column performance.

Before running the column, ensure that the outlet streams

are updated. Check the Update Outlets checkbox for the
column to automatically update the outlet streams. By
default the Update Outlets checkbox is checked.

5-12
 Clean Fuels Pkg Tutorial 5-13

Figure 5.13

Figure 5.14

5-13
5-14 Modeling the Gasoline Fractionator

5.3.1 Exercises
1. Add a UniSim Design Spreadsheet (Sulphur Calculations) to
calculate the total sulphur content in ppm wt of light
gasoline.

Spreadsheet Connections

Cell Object Variable

D2 Light Gasoline Comp Mass Flow, 2C3Mercaptan
D3 Light Gasoline Comp Mass Flow, nPMercaptan
D4 Light Gasoline Comp Mass Flow, Thiophene
B6 Light Gasoline Mass Flow
B7 Fractionator Spec Value TBP End Point

Figure 5.15

5-14
 Clean Fuels Pkg Tutorial 5-15

Figure 5.16

2. Find the Light Naphtha TBP End Point that corresponds to

less than 10 ppm wt and 1 ppm wt Thiophene Sulphur.

5.4 Plot Utility

1. Begin a new UniSim Design case, add a Fluid Package using
the Clean Fuels Pkg and add the two components 1-
Propanethiol and n-Hexane. Enter the Simulation
Environment.
2. Open the Excel Spreadsheet Txy Plot Utility, and connect
to UniSim Design.
3. Plot a Txy Diagram for system 1-Propanethiol-n-Hexane at
101.325kPa.
4. Find the azeotrope temperature and composition.
Ans. Experimental Data. (1PRSH) xazeo=0.5570,
Tazeo=147.83°F.

5-15
5-16 Plot Utility

Figure 5.17

5-16
 References A-1

A References
1
Halbert, T. R., Brignac, G. B., Greeley, J. P., Demmin, R. A. and
Roundtree, E. M., “Getting Sulfur on Target,” Hydrocarbon
Engineering, June 2000, pp.1-5.
2
Golden, S. W., Hanson, D. W. and Fulton, S. A., “Use Better
Fractionation to Manage Gasoline Sulphur Concentration,”
Hydrocarbon Processing, February 2002, pp. 67-72.
3
Twu, C.H., Sim, W.D. and Tassone, V., “A versatile liquid activity
model for SRK, PR and a new cubic equation-of-state TST”, Fluid
Phase Equilibria 194-197, 2002, pp. 385-399.
4
Twu, C.H., Bluck, D., Cunningham, J.R. and Coon, J.E., Fluid Phase
Equilibria, 69, 1991, pp. 33-50.
5
Wong, S.H. and Sandler,S.I., 1992, AIChE J., 38, 1992, pp. 671-680.
6
Twu, C.H., Wayne, D., and Tassone, V., “Liquid Activity Coefficient
Model for CEOS/AE Mixing Rules” Fluid Phase Equilibria, 183-184,
2001, pp. 65-74.
7
Twu, C.H., Coon, J.E. and Bluck, D., Fluid Phase Equilibria, 150-151,
1998, pp. 181-189.

A-1
A-2

A-2
 Index
C
Clean Fuels Pkg
adding 4-2
tutorial 5-1–5-15
Clean Fuels Pkg Extension
user interface 4-3
using 4-2
Clean Fuels Pkg View 4-4
NRTLTST tab 4-4
TST CEOS tab 4-5
E
Estimation Methods 3-7
F
Fractionator design
through accurate VLE models 2-8–2-10
G
Gasoline Sulphur species distribution 2-2–2-4
L
Light/Medium Gasoline fractionation 2-5–2-7
M
Modeling the Gasoline Fractionator 5-10
N
NRTLTST tab 4-4
User Data 4-5
P
Plot Utility 5-15
R
Requirements
system 4-2
T
Thermodynamic Model 3-2–3-7
estimation methods 3-7
TST CEOS tab 4-5
U
User Data 4-5
User Interface
Clean Fuels Pkg Extension 4-3

I-1
I-2 Index

I-2