Computers and Chemical Engineering 30 (2005) 343–356

New approach to the characterisation of petroleum mixtures used

in the modelling of separation processes
Egon Eckert ∗ , Tomáš Vaněk
Department of Chemical Engineering, Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic
Received 15 March 2005; received in revised form 26 September 2005; accepted 3 October 2005

Abstract
Characterisation of complex mixtures is a common tool especially in oil processing industry. Characterisation procedures result in experimentally
gained characterisation curves, but for the simulation of industrial processes the definition of a substitute mixture is required. Traditionally, a system
of pseudocomponents is derived from the True Boiling Point (TBP) characterisation curve, but there are a number of disadvantages, e.g. the physical
properties of pseudocomponents must be estimated by unreliable empirical methods. The new approach to the characterisation of complex mixtures
is based on representing the original mixture by a system of real components. Such substitute mixture is fully defined, it has a chemical character,
and physical properties can be simply retrieved from databases. Utilisation of a substitute mixture of real components in the simulation of crude
oil processing proved that the new approach could replace the traditional one in normal boiling temperature ranges where real components are
available. Both approaches could be also easily combined.
© 2005 Elsevier Ltd. All rights reserved.

Keywords: Refinery processes; Oil processing; Characterisation procedures; Complex mixtures; Pseudocomponents

1. Introduction (Briesen & Marquardt, 2003, 2004a, 2004b). While continuous

Mixtures containing an extremely large number of various
components can be often encountered in industrial chemical
technologies, particularly in oil processing and refining. Briesen
and Marquardt (2003, 2004a, 2004b) analysed thoroughly the
past, present and future trends in this branch of industry and
pointed out the need to increase the accuracy in the modelling of
oil refining processes. There are direct economical and environ-
mental consequences of any progress in this point and improved
treatment of complex mixtures is probably the most promising
direction. In order to deal with such mixtures in modelling and
simulation calculations, it is necessary to simplify the problem
by utilising a substitute mixture possessing reasonably lower
number of components or to use an alternative representation of
the mixture. For this purpose, the continuous thermodynamics
can be employed (see, e.g. Rätzsch & Kehlen, 1983), or, more
recently, the wavelet-Galerkin discretisation has been proposed
∗ Corresponding author.
E-mail addresses: Egon.Eckert@vscht.cz (E. Eckert),
Tomas.Vanek@vscht.cz (T. Vaněk).
thermodynamics has received only a little attention in indus-
trial practice, the adaptation of wavelet-Galerkin discretisation
method for the modelling of unit operations, where complex
mixtures are processed, is intensively being studied. Its main
advantage is the possibility to tune the representation of the mix-
ture by means of adaptive control of the problem discretisation.
On the other hand, this approach uses a non-trivial mathematical
background and also the standard models of unit operations must
be reformulated in order to incorporate the continuous represen-
tations (distributions) of some model variables, e.g. of the vector
of composition (Briesen & Marquardt, 2003, 2004a, 2004b).
Moreover, physical properties dependent on the composition
(e.g. K-values) must be also converted to distribution-based
functions. Such methods can be employed only for physical
processes as distillation or absorption, but not for processes
with chemical reactions. Since the last decade of 20th century,
methods for the “reconstruction” of the chemical composition
have been developed presuming that some other information
was available beside the usual distillation curve. It might be
data from elemental analysis, gas chromatography, mass spec-
trometry, 1 H and 13 C NMR analyses, etc. (e.g. Whitson & Brulé,
2000).

0098-1354/$ – see front matter © 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compchemeng.2005.10.005
344 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356
Nomenclature
C number of candidate components in the primary
temperature interval
F objective function
I total number of real components
K number of measured properties
KW Watson factor
M molecular weight
S standard specific gravity
T temperature
x volume or mass fraction
w weight in criterion (11)
Greek letters
Φ volume or mass fraction distilled
η viscosity
ρ density
ζ symbol for property
Superscripts
L left edge of an interval
R right edge of an interval
– mean value
Subscripts
b at boiling point
c index of a candidate component
HE index of the first heavy-end component
i index of a component or temperature interval
j index of a component
k index of a property in criterion (11)
LE index of the last light-end component
m measured value
r value calculated or retrieved from the database
When using substitute mixtures in steady state or dynamic
simulation, the classical unit operation models can be employed.
In fact, in simulation programs the solution engine deals equally
with real components as well as with pseudocomponents if
properly defined during the data input phase. The number of
components used for the substitute mixture is usually up to 102 ,
which is considerably lower than for original complex mixtures,
i.e. 104 –107 or more in case of crude oils. It might be felt that in
the age of powerful computing machinery the number of compo-
nents in chemical engineering calculations could be practically
unlimited. Nevertheless, there are at least two good reasons why
to keep lower number of components. First, the dimension of unit
operation models is dependent on the number of components
involved and especially equation-oriented simulators could still
run into troubles according to memory requirements and internal
limits. Second, it is very hard to analyse the results of simula-
tion run when the number of components is high, e.g. thousands
or more, and no new information could be obtained. Probably,
there would be subsets of components behaving almost equally,
the content of each being on the ppm level. It could be noticed
that also for well-defined mixtures in practical calculations it
is often desired to decrease the number of components or even
pseudocomponents. The method called lumping is based on rep-
resenting groups of components with close boiling points and/or
some other properties by a selected single member component
inheriting in the mixture the “weight” of the entire group (Riazi,
2005). Montel and Gouel (1984) suggested to optimise the lump-
ing scheme for the substitution of a group of known components
in order to preserve the PVT behaviour.
The approach based on pseudocomponents had been devel-
oped quite a long time ago (Edmister, 1955; Katz & Brown,
1933) and first was used for flash calculations on an early com-
puter (Hariu & Sage, 1969). As the main advantage it was appre-
ciated that the characterisation procedure was non-iterative. It is
still widely accepted as a convenient method in the simulation
of separation equipment, but a number of problems arise. Above
all:
• The chemical character of components forming the mixture
could also play a role in chemical reactions occurring in the
studied processes. For pseudocomponents, we cannot define
any chemical character.
• A pseudocomponent is primarily defined only by its (pseudo)
boiling point and by some additional parameters, mostly by
specific gravity, molecular weight or viscosity. All other phys-
ical properties, e.g. needed for simulation calculations, must
be estimated. Unfortunately, the reliability of common esti-
mation methods (listed, for example, by Whitson & Brulé,
2000) for critical properties, the acentric factor, etc. is rather
low according to the results of testing published, for exam-
ple, by Lindqvist, Markkanen, and Happonen (1994), Riazi
(2005) and Twu (1984).
• For pseudocomponents, we cannot use group contribution
methods (e.g. UNIFAC) requiring information about the
molecular structure of compounds in order to estimate
some parameters (e.g. binary interaction parameters for
vapour–liquid equilibrium).
• The information about the type of the mixture, e.g. if paraffinic
or aromatic compounds are prevailing, or about the type of
some of its important components (e.g. polar compounds)
could not be easily utilised.
• Arbitrary combinations of pseudocomponents and com-
pounds identified in the original mixture are not supported
in commercial simulation programs. That is, it is not possible
to place a real component into the middle of the temperature
range used for the definition of pseudocomponents without
knowing its content.
When modelling distillation and absorption processes for
complex hydrocarbon mixtures within simulation programs, the
original mixture is traditionally substituted by a mixture com-
prising two different groups of components. For the light-end,
real components usually up to C5 are employed if they are
present and if their content can be determined. For the remain-
ing part, a system of pseudocomponents is derived from certain
global characterisations of the mixture based on its distilla-
tion behaviour. This approach is implemented in recent major
 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356
commercial simulation programs as ASPEN Plus, HYSYS and
PRO/II (ASPEN Plus and HYSYS are registered trademarks of
Aspen Technology and PRO/II is a trademark of SimSci-Esscor).
Besides these standard features, there are most recent attempts to
implement other approaches to oil and gas processing, e.g. avail-
able with HYSYS 3.2 onwards as HYSYS UpstreamTM Option.
The usage of pseudocomponents has after all one impor-
tant advantage: when defined and equipped by a set of esti-
mated physical (pseudo) properties, pseudocomponents could
be in simulation programs treated as any other real compo-
nents (except in processes with chemical reaction). This is also
the main presumption for the alternative way how to establish
a feasible substitute mixture as suggested by Ba, Eckert, and
Vaněk (2003). It has been shown that the substitute mixture com-
posed of suitable real components can be used in simulation
calculations instead of an alternative mixture of pseudocom-
ponents with comparable results (Eckert & Vaněk, 2003). The
primary intention was to overcome the main disadvantages of
pseudocomponents mentioned above, namely the need to esti-
mate their properties. It is possible to retrieve property data from
the database, which is used as the source of real components.
At the same time, wide variety of thermodynamic models and
packages of compatible methods, typically within simulation
programs, can be used. There is no need to limit to equation-
of-state (EOS) models but other types of models, especially for
the description of the phase equilibrium, can be employed, even
those requiring some interaction parameters. Moreover, the mix-
ture of real components exhibits a chemical character, which
can be utilised when modelling complex reaction schemes. For
example, Bělohlav, Zámostný, Herink, Eckert, and Vaněk (2005)
recently used substitute mixtures of real components for the pre-
diction of yields from pyrolysis reactors.
Despite the simplicity of the new approach, it has not been
used before, e.g. no attempt to employ real components for this
purpose is mentioned even in the most current Riazi’s (2005)
monograph. The principles of the new approach make it directly
usable in simulation programs with current content of their
databases of physical properties and for current models of unit
operations.
Further in this text, we shall recapitulate the two approaches
employing substitute mixtures in order to explain the differ-
ence between the appropriate algorithms. The verification of
the new approach is then provided on a non-trivial simulation
case—crude oil refining.
2. Characterisation of mixtures using
pseudocomponents
Normally, two steps are needed to define a system of pseu-
docomponents for a complex mixture. First, some standard
characterisation curve must be experimentally obtained, prefer-
ably the True Boiling Points (TBP) curve, which is directly
used in the next step. The TBP curve represents the depen-
dence of temperature measured in the head of a laboratory
batch column on mass or volume fraction distilled. The col-
umn should have a high number of stages and perform at large
reflux ratio (API, 1992). There are other possibilities, e.g. the
345
Fig. 1. Definition of a pseudocomponent and of its content in the substitute
mixture from the TBP curve.
TBP curve can be substituted by its more accurate chromato-
graphic equivalent SIMDIST or by transformation of curves
resulting from some other characterisation procedures (ASTM
D86, EFV—Equilibrium Flash Vapour) using empirical correla-
tions (API, 1992). The later case is not too reliable and can lead
to a considerable deviation of the calculated TBP curve from
the experimental curve (Ba et al., 2003). In the second step, the
range of boiling points of the TBP curve is cut in order to obtain
non-overlapping temperature intervals (Ti , Ti+1 ), for i = 1, . . ., I,
continuously covering the entire temperature range. There are
various possibilities how to choose these intervals—some rec-
ommendations were published, for example, in Whitson and
Brulé (2000). Usually, it is sufficient to use about 15 K for
normal boiling points up to 700 K, about 30 K within 700 and
950 K and about 50 K for higher boiling mixtures as it is done in
the HYSYS simulation program when using automatic cutting
option (see Hyprotech, 2003). Each temperature interval rep-
resents one pseudocomponent with normal boiling point given
by the arithmetic or, more precisely, the integral mean temper-
ature over the corresponding interval of fraction distilled (see
Fig. 1). The relevant definitions of arithmetic and integral mean
temperatures are given by Eqs. (1) and (2), respectively.
i ) + Tb (Φi )
Tb (ΦR L
Tbi = , i = 1, . . . , I (1)
2

ΦR
1 i
Tbi = R Tb (Φ) dΦ, i = 1, . . . , I (2)
Φi − Φi ΦLi
L
As also illustrated by Fig. 1, the interval of fraction distilled
i − Φi ), i = 1, . . ., I determines at the same time the relative
(ΦR
L
contribution of each pseudocomponent to the mixture, which is
used to define its composition.
For the consequent usage of the substitute mixture of pseu-
docomponents it is necessary to supply the same structure of
physical properties as for real components. Usually, it is not
346 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356
difficult to measure besides the TBP curve also the density and/or
viscosity of individual fractions collected in the laboratory col-
umn during the distillation test. Moreover, for each fraction the
mean molecular weight can be estimated. Therefore, if we use
pseudocomponents to represent these fractions then two to four
data items are available for each pseudocomponent: the mean
normal boiling point and one to three other properties, which
can be used to trigger a series of empirical estimation procedures
delivering the remaining set of properties—critical properties,
acentric factor, etc. (see, e.g. Riazi, 2005; Whitson & Brulé,
2000). Unfortunately, we should be aware of low reliability of
such methods as it was mentioned in the introductory part of this
contribution.
It is relatively simple to measure global parameters of a
complex mixture, i.e. bulk properties as the density, molecular
weight, refraction index or viscosity, and this is often delivered
with other measurements. Unfortunately, their direct use for the
derivation of a substitute or model mixture is known only for the
density where it is possible to construct under certain conditions
an approximation of the characterisation curve from the Watson
factor (Wauquier, 1995). When the global density of the mixture
is known and the Watson factor
1/3
(1.8Tb )
KW = (3)
S will be discussed further.
can be assumed to be constant then it is possible to get an approx-
imation of the density characterisation curve (Wauquier, 1995).
This could be an alternative to density data measured for each
fraction during the characterisation experiment.
3. Characterisation of mixtures using real components
The main disadvantages of the approach based on pseudo-
components can be overcome if we employ real components
to form the substitute mixture. Of course, the selection of suit-
able real components and the derivation of the substitute mixture
must follow certain criteria and an appropriate algorithm must be
defined. We shall use two consecutive phases, i.e. a set of compo-
nents to be present in the substitute mixture must be first selected
and then the composition of their mixture will be adjusted. The
prerequisites for the algorithm are as follows:
a. The TBP curve measured for the original complex mixture
is available
Tb = Tb (Φ) (4)
where Tb is the measured “True Boiling Point” temperature
and Φ is the mass or volume fraction distilled.
b. Some other characterisation curve is available, e.g. all or
some of dependencies
M = M(Φ) (5)
ρ = ρ(Φ) (6)
η = η(Φ) (7)
where M is the molecular weight, ρ the liquid density (even-
tually specific or API gravity) and η is the liquid viscosity.
The liquid density curve can be also obtained approximately
using the Watson factor as mentioned above. Instead of using
Eqs. (5)–(7) directly, it is better to convert them into “phase
portraits” by eliminating the mass or volume fraction distilled
and establishing direct relation between these properties and
the boiling point temperature:
M = M(Tb ) (8)
ρ = ρ(Tb ) (9)
η = η(Tb ) (10)
c. The overall temperature range is divided (cut) into a sys-
tem of non-overlapping temperature intervals continuously
covering the range. There are several possible approaches
similarly to the definition of pseudocomponents – an equidis-
tant grid, adaptive grid taking into account the shape of the
curve or a grid based on boiling points of homological series
of alkane compounds – see, e.g. Table 5.2 in Whitson and
Brulé (2000).
d. A sufficiently large database of chemical components and
their physical properties is available. Detailed requirements
3.1. Selection of components
The basic assumption is that a suitable database is available.
The “quality” of such database can be expressed not only by the
reliability of data included but also by the extent of the database.
Here, we take primarily into account the number of components
but on its own this is not sufficient. It is important to have satis-
factory representation for important families of chemical com-
pounds, in our case especially hydrocarbons or detailed groups
as, e.g. paraffines or aromatics. At the same time, the range of
normal boiling points for these compounds must be wide and
the normal boiling points should cover the range uniformly and
densely. This is, of course, an ideal situation, which is more or
less fulfilled by databases from various sources. In “open” lit-
erature we can find, for example, the API database (API, 1992)
with 478 hydrocarbons up to C30 , normal boiling points up to
720 K and molecular weights up to 420 kg/kmol. Generally, nor-
mal boiling points of higher hydrocarbons are very difficult to
obtain as the thermal decomposition takes place (Kopsch, 1995).
Accordingly, data for higher hydrocarbons (C18+ ) in databases
are frequently estimated or their origin is ambiguous. Neverthe-
less, their long-term usage in many chemical engineering cal-
culations giving realistic results gives certain guaranty that also
the substitute mixture of real components selected from such
databases can sufficiently model the original complex mixture.
The internal database of the HYSYS simulation program
(Hyprotech, 2003), which we used for test calculations, incor-
porates 521 hydrocarbons and covers approximately the same
range of normal boiling points and molecular weights as the
API database. The source of data is not explicitly specified and
probably the same limitations can be expected as for API data.
 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356
Fig. 2. Plot of molecular weights vs. normal boiling points of hydrocarbon
components from the HYSYS database.
Thermal decomposition is also one of the reasons why the
number of available hydrocarbon compounds rapidly decreases
with increasing normal boiling point as demonstrated by
Figs. 2 and 3. This situation leads to a poor chance to find
a suitable real component to represent higher boiling point
temperature ranges. Unfortunately, the mixtures in oil pro-
cessing contain a significant portion of higher boiling com-
pounds forming the so-called “heavy-end”. Some components
can exhibit normal boiling point higher than 1000 K and molec-
ular weight exceeding 800 kg/kmol. Normal boiling points and
densities, as the minimum information needed, can be found,
e.g. in Beilstein database (MDL Information Systems, 2005),
for about 1850 hydrocarbons up to C42 , where only two com-
ponents are available—1-cyclohexyl-hexatriacontane and 1-
phenyl-hexatriacontane. Figs. 2 and 3 show another interesting
feature. With increasing temperatures the range of molecular
weights of components having approximately the same boiling
point is getting wider, see, for example, the region around 700 K
in Fig. 3.
Fig. 3. Plot of API gravities vs. normal boiling points of hydrocarbon compo-
nents from the HYSYS database.
347
There are a number of other databases, which could be poten-
tially used for the same purpose, e.g. DIPPR (Design Institute
for Physical Properties at Brigham Young University, 2000) or
the suite of internal databases attached to the ASPEN Plus. The
reasons why we did not employ these databases are technical
as the program providing the selection of components needs a
self-standing “flat” data file. Our approach, initially designed for
exclusive usage of real components in the substitute mixture, can
be extended to combine real components for lower and moder-
ate boiling point temperatures with pseudocomponents for the
heavy-end. Nevertheless, this demonstrates the potential of the
new approach.
The procedure for the selection of real components for the
substitute mixture can be made flexible in order to exploit all
information about the original mixture. As stated above, if the
chromatographic analysis of the mixture is available it could be
also a basis for the formation of a substitute mixture. Certain
components can be clearly identified and directly added to the
list of components in the substitute mixture. If no chromato-
graphic analysis is available but the TBP curve is known, all
components for the substitute mixtures can be selected accord-
ing to the following algorithm:
Step 1. For each primary temperature interval (prerequisite c)
a set of candidate components is selected from the database.
The criterion is that each component selected must have its
normal boiling point within the considered temperature inter-
val. If needed, filtration conditions can be set, e.g. reflecting the
requirements to include only some families of components or, on
contrary, to exclude another components or families. For exam-
ple, it is known that no olefin components are present in crude
oils (Petrov, 1987). On the other hand, at least one component
should be available for each interval. If not, then either a set of
wider intervals must be used or the interval can be represented by
a pseudocomponent. The combination of real components and
pseudocomponents is necessary for higher boiling mixtures.
Step 2. Exactly one component is selected for each primary
temperature interval from the set of candidate components by
comparing their physical properties. We know the normal boil-
ing point of each candidate component and from phase portraits
(8)–(10) the “desired” values can be derived and compared
with values retrieved from the database. The simplest way how
to combine the deviations for different properties is to use a
weighted sum of relative differences. The criterion for the selec-
tion is then defined by
K
 |ζr,k,c − ζm,k,c |
wk → minc (11)
ζm,k,c
k=1
where K is the number of measured properties and ζ m,k,c and ζ r,k,c
are the measured and from database obtained (calculated or sim-
ply retrieved) values of property ζ, respectively. The expression
is calculated for each candidate component, c = 1, . . ., Ci and the
component with the lowest value of criterion (11) is chosen to
represent the interval. There are degrees of freedom in the choice
of weight factors wk , which can reflect the precision of measure-
ments or some other demands. It should be noted that measured
348 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356
Fig. 4. Situation after the selection of a real component in the ith primary tem-
perature interval (Ti , Ti+1 ).
viscosity and density in fact represent properties of discrete mix-
tures (fractions), which can be hardly derived from properties of
contained pure components according to non-trivial and unreli-
able mixing rules.
Sometimes no other curves than the TBP curve are available.
Step 2 of the algorithm can be then replaced by choosing a com-
ponent with its normal boiling point being closest to the mean
temperature of the appropriate temperature interval. This is an
emergency solution but it can be expected that the selected real
component would be close to a pseudocomponent defined tradi-
tionally while all properties of the real component are directly
available from the database.
The result of this phase of the algorithm is simply a list of
real components together with their normal boiling points and
other properties. If it is desired for some reason to include other
components into the substitute mixture, it can be done now. Such
an obvious reason is, for example, the confirmed presence of a
particular component or component type in the original mixture.
Especially polar compounds are in the focus since they strongly
affect the phase equilibrium in multiphase systems. A compound
can be added to the substitute mixture with or without informa-
tion about its amount in the original mixture. Both possibilities
are aided in the second phase of the algorithm.
3.2. Determination of the composition of a substitute
mixture
The problem is that the normal boiling point of each selected
component can fall anywhere in the primarily defined temper-
ature interval (Ti , Ti+1 ) (see Fig. 4), and no longer it is a mean
temperature of this interval. If a model of the experimental char-
acterisation procedure were available then we could abandon
the principle of mean temperatures and this step would consist
in a repeated evaluation of the characterisation curve from the
Fig. 5. Construction of intervals of fraction distilled in the second phase of the
algorithm attached to real components selected in the first phase.
model for varying composition of the mixture until a satisfactory
match with the experimental characterisation curve is reached.
This kind of an optimisation can be easily employed, for exam-
ple, for the EFV curve (Eckert, 1999).
When the TBP curve is available then the procedure sug-
gested by Ba et al. (2003) can be used. Fig. 5 illustrates the
principles of the procedure, which at first glance could be found
similar to the method used to derive the composition of a mixture
of pseudocomponents. The presumption that each component
should represent an interval of fraction distilled, where its nor-
mal boiling point is the mean temperature according to Eq. (1)
or (2), is preserved. The difference is that we cannot expect
that the intervals could be generally chosen to cover the whole
range without gaps and/or overlapping. This is automatically
fulfilled for pseudocomponents where the procedure starts from
the other end—the mean temperatures are calculated for temper-
ature intervals initially chosen to continuously cover the entire
temperature range without overlapping. Nevertheless, in the case
of real components the idea is to distribute the intervals to make
them cover the range as much as possible with minimum gaps
and overlapping. This is an optimisation task where the objective
function can be defined as follows:
I+1
 2
F (ΦL ) = i−1 − Φi ) → min
(ΦR L
(12)
i=LE+1
For each interval the starting and end fractions distilled are
denoted by the superscript ‘L’ (=left) and ‘R’ (=right). Gener-
ally, we can utilise the information about light-end components,
which can be usually identified in the original mixture together
with their composition, and incorporate them into the substitute
mixture. The index of the last light-end component is there-
fore denoted by ‘LE’ and the corresponding fraction distilled
by ΦR LE . On the other end of the range, I + 1 can be denoted by
 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356 349

heavy-end (HE), even if no heavy-end components were present Table 1

and by definition ΦLHE = ΦLI+1 = 1. The reason why only the Light-end components and their liquid volume (%)

elements of the vector ΦL = {ΦLLE+1 , . . . , ΦLI } are considered No. Component Liquid volume (%)
as independent optimisation variables in (12) is that Eqs. (1) 1 i-Butane 0.19
or (2) can be treated as implicit equations for ΦR i , i = LE + 1, 2 n-Butane 0.11
. . ., I, i.e. ΦRi = Φ R (ΦL ). Alternatively, the reversed relation
i i 3 i-Pentane 0.37
ΦLi = ΦLi (ΦR i ) could have been used with Φi as the set of opti-
R 4 n-Pentane 0.46
misation variables. It is reasonable to define bounds for the
values of ΦLi in order to avoid getting some unreal solutions
and the following set of constraints was considered: (Eckert & Vaněk, 2003) we used the concept of a “theoretical
TBP curve” as curve of a staircase shape reflecting the distribu-
ΦLi ≤ ΦLi+1 , i = LE + 1, . . . , I tion of normal boiling points of individual components from the
(13) mixture. Such curve we could get in a batch distillation column
Φi−1 ≤ ΦLi ≤ Φi+1 , i = LE + 1, . . . , I
with the number of stages approaching infinity and very high
Optimisation problem (12) together with constraints (13) can be reflux ratio. In its discrete version the  theoretical TBP curve is
j=i−1
solved using some standard package. composed of points with co-ordinates ( j=1 (xj + xi )/2; Tbi )
In order to obtain a consistent composition of the substitute for i = 1, . . ., I, taking into account for simplicity the arithmetic
mixture it is necessary to convert the intervals (ΦLi , ΦR
i ) resulting mean values defined by Eq. (1). Analogical theoretical curves
from the optimisation to mass or volume fractions. In ideal case, can be constructed for molecular weight and density, eventually
the intervals would exactly cover the entire range, the value of the API gravity or some other properties.
object function (12) would be zero and the following condition Theoretical TBP curves were constructed for examples of
would be fulfilled: separations in a distillation and absorption columns (Eckert &
I
 Vaněk, 2003) and the match between results obtained by both
i − Φi ) = ΦHE − ΦLE
(ΦR L L R approaches was excellent, thus showing that substitute mixtures
(14)
i=LE+1 of real components can replace mixtures of pseudocomponents
with all the extra benefits, which this approach brings. For these
Then, the length of each interval can be directly taken as the examples only the measured TBP curves were available as input
appropriate mass or volume fraction. Nevertheless, this is not information.
usually true according to possible overlapping of the intervals The example presented further is based on the “Refining
and existence of areas not covered with any interval. The sim- Tutorial” case delivered with the simulation program HYSYS
plest way how to get a consistent composition derived from the (Version 3.2) and at the same time this program has been used
lengths of intervals (ΦLi , ΦR
i ) is to “normalise” the vector of for all calculations. The advantage is that HYSYS incorporates a
mass or volume fractions: relatively extensive database of hydrocarbons and it also enables
j − Φj )(ΦHE − ΦLE )
(ΦR L L R to define pseudocomponents in a built-in tool called “Oil Envi-
xj = I , j = LE + 1, . . . , I (15) ronment”.
i=LE+1 (Φi − Φi )
R L

Example (Hyprotech, 2003). Crude oil is processed in a frac-

A similar procedure can be used when some of the real compo-
tionation facility to produce naphtha, kerosene, diesel, atmo-
nents were identified in the original mixture and their relative
spheric gas oil and atmospheric residue products. The crude oil
amounts, i.e. mass or volume fractions, are known.
is characterised by laboratory assay data in Tables 1–3. The TBP
The second phase of the algorithm was implemented as
curve is accompanied by the dependence of molecular weight
self-standing program incorporating the MINOS (Murtagh &
on the liquid volume fraction distilled and a separate assay on
Saunders, 1995) optimisation package.
API gravity is also available. A light-end is considered and its
4. Application of the method
Table 2
TBP distillation assay
In order to approve the suggested approach it was reason-
able to simulate real industrial processes employing substitute Liquid volume (%) Temperature (◦ C) Molecular weight (kg/kmol)
mixtures. Unfortunately, the data measured, for example, on dis- 0 26.7 68
tillation columns and published in open literature are almost 10 123.9 119
always for binary mixtures and small-scale columns. Data from 20 176.1 150
30 221.1 182
major distillation columns in crude oil processing are very rarely 40 275.0 225
available. Therefore, an alternative way is to compare at least 50 335.0 282
the two different approaches to substitute mixtures on the same 60 399.4 350
simulation problem, once using a substitute mixture composed 70 490.6 456
of pseudocomponents and then a mixture of real components. 80 590.6 585
90 691.7 713
An important point is to define some methodology how to 98 765.6 838
compare different substitute mixtures. In a former contribution
350 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356

Fig. 6. Simplified flowsheet for the crude oil processing example.

Fig. 7. Subflowsheet for the atmospheric column.

composition is known. The main flowsheet for the process in in the HYSYS program further represented by an embedded
consideration is shown in Fig. 6. Preheated crude is initially fed flowsheet, i.e. subflowsheet in HYSYS terminology. The appro-
to a preflash drum to separate vapours from the liquids, which priate subflowsheet for our example is shown in Fig. 7. The
are further heated in a furnace. The preflash vapours are recom- Peng–Robinson property package was used in HYSYS for the
bined again with the hot crude from the furnace and the resulting calculation of physical properties. In the “Oil Environment” the
stream is then fed to the atmospheric crude column for frac- standard setting of estimation methods was used, i.e. Twu (1984)
tionation. Detailed description and specifications are presented critical property correlation for molecular weight, constant Wat-
in Appendix A. The icon of the distillation column in Fig. 6 son factor method for specific gravity and Lee–Kesler method for
represents in fact a complex separation process, which can be critical properties, the acentric factor and ideal enthalpy (Kesler
& Lee, 1976).
It was intended to solve the simulation case using both meth-
Table 3
ods for the characterisation of the process feed (Preheat Crude
API gravity assay
stream). Particularly, Table 4 globally summarises how the sub-
Liquid volume (%) API gravity stitute mixtures were assembled. Temperature ranges defined in
13 63.28 the first column of the table were for pseudocomponents divided
33 54.86 uniformly to intervals of the same width. For real components
57 45.91 this was also done but, as we know from the description of the
74 38.21
algorithm above, it serves only for the initial selection of subsets
91 26.01
of real components as candidates for representing these intervals.
 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356 351

Table 4 this interval. This primary selection was limited to hydrocar-

Characterisation of the process feed (Preheat Crude), basic temperature intervals bon compounds only but also compounds known to be missing
Temperature range (◦ C) Traditional method of New method of in oil fractions (e.g. olefins and cycloolefins) were excluded.
characterisation characterisation Technically, this is enabled by registering the chemical fam-
37.8–426.7 28 pseudocomponents, 28 real components ily of compounds and setting an “oil” flag on or off for each
uniformly component in the database. The most suitable component for
426.7–648.9 8 pseudocomponents, 8 pseudocomponents, each interval was found according to criterion (11) for K = 2, i.e.
uniformly uniformly taking into account the molecular weight and API gravity. The
648.9–760 2 pseudocomponents, 2 pseudocomponents,
uniformly uniformly
weight factors given to the contributions of both properties were
simply set to be one.
The resulting list of real components for the substitute mix-
For both substitute mixtures the same light-end (Table 1) was ture is presented in Table 5 and the comparison of the measured
supposed. Unfortunately, higher temperature ranges had to be and retrieved values of both considered properties are depicted
covered by 10 pseudocomponents, as there were only few hydro- in Figs. 8 and 9 as phase portraits. Table 5 contains also the
carbons in the HYSYS database with boiling points exceeding information about the number of candidate components for each
426.7 ◦ C. Our program used for the selection of real components, primary temperature interval. It is apparent that their number
accepts input data in various forms and physical units and pro- rapidly decreases when approaching higher temperatures. It is
vides necessary conversions. For our example, the conversions also interesting that starting from interval number 16 almost
of characterisation curves from Tables 2 and 3 to phase portraits all components selected belong to a monotone series of alka-
expressed by Eqs. (8) and (9) were done using a piece-wise nes. Only components number 18 (n-hexylbenzene) and 23
linear interpolation. The phase portrait for the API gravity has (n-decylbenzene) do not follow this fact and show larger devia-
been extended to include the light-end components. The reason tion from the phase portrait as documented by Figs. 8 and 9.
is that this curve bends at the boundary between light-end and Another component showing larger deviation in Fig. 9 is n-
the remaining part of the mixture, which affects interpolation or butylcyclohexane in interval 15. In order to improve the selection
extrapolation operations needed in the algorithm. Then, for each it could be possible, for example, to try larger temperature
temperature interval a set of candidate components was chosen intervals or their different distribution, but it would disable to
from the HYSYS database having normal boiling points within compare the new approach with the traditional one. Therefore,

Table 5
Resulting selection of real components (without the known light-end)
No. Temperature interval [K] Component Tb [K] M [kg/kmol] API gravity Number of candidate
components in interval

5 310.95–324.84 2,2-Dimethylbutane 322.88 86.18 84.90 3

6 324.84–338.73 2-Methylpentane 333.41 86.18 83.60 3
7 338.73–352.62 n-Hexane 341.88 86.18 81.60 3
8 352.62–366.51 2-Methylhexane 363.20 100.21 75.70 12
9 366.51–380.40 2,2-Dimethylhexane 379.99 114.23 70.70 9
10 380.40–394.29 2-Methylheptane 390.80 114.23 70.00 27
11 394.29–408.17 2,4-Dimethylheptane 406.05 128.26 65.20 23
12 408.17–422.06 2,3-Dimethylheptane 413.65 128.26 62.30 46
13 422.06–435.95 2,6-Dimethyloctane 433.56 142.29 61.80 62
14 435.95–449.84 5-Methylnonane 438.26 142.29 60.60 45
15 449.84–463.73 n-Butylcyclohexane 454.13 140.27 44.70 25
16 463.73–477.62 n-Undecane 469.04 156.31 58.60 12
17 477.62–491.51 n-Dodecane 489.43 170.34 56.50 8
18 491.51–505.40 n-Hexylbenzene 499.30 162.27 32.58 2
19 505.40–519.29 n-Tridecane 508.58 184.37 54.60 8
20 519.29–533.18 n-Tetradecane 526.66 198.38 53.60 6
21 533.18–547.07 n-Pentadecane 543.77 212.41 51.80 14
22 547.07–560.96 n-Hexadecane 559.94 226.43 50.60 7
23 560.96–574.85 n-Decylbenzene 571.10 218.37 33.12 6
24 574.85–588.74 n-Heptadecane 575.30 240.46 49.50 4
25 588.74–602.63 n-Octadecane 589.86 254.48 48.60 4
26 602.62–616.51 n-Nonadecane 603.80 268.51 47.80 8
27 616.51–630.40 n-Uneicosane 629.65 296.56 46.29 5
28 630.40–644.29 n-Dodecosane 641.76 310.59 45.74 3
29 644.29–658.18 n-Tricosane 653.37 324.61 45.04 6
30 658.18–672.07 n-Tetracosane 664.43 338.64 44.72 3
31 672.07–685.96 n-Pentacosane 675.04 352.67 44.27 2
32 685.96–699.85 n-Heptacosane 695.26 380.72 43.46 1
352 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356

Fig. 8. Phase portrait for the molecular weight (—) compared with values Fig. 10. Measured TBP curve (䊉) compared with theoretical TBP curve for the
retrieved from the database for real components (
). substitute mixture gained by the new approach (
).

the actual result of selection was left unchanged and passed to

the second phase of the algorithm.
After selecting a unique component for each primary tem-
perature interval the actual intervals (ΦLi , ΦR
i ) attached to each
component were computed in the second phase of the algorithm
and the composition was derived using Eq. (15). Table 6 contains
the complete overview of resulting substitute mixtures including
the light and heavy-ends. Pseudocomponents were generated in
HYSYS Oil Environment and their names chosen by HYSYS
reflect the mean temperatures of appropriate intervals (in degree
Fahrenheit). For the new approach the interpretation accord-
ing to HYSYS could be that the four light-end components
(originally 1.13 vol.%) together with the system of selected real
components would form an extended light-end (in our example,
it will comprise 32 components and 63 vol.% of the mixture).
The measured and theoretical TBP curves of the Preheat Crude
are compared in Fig. 10. The comparison of experimental addi- Fig. 11. Measured characterisation curve for the molecular weight (䊉) com-
tional curves with properties of real components selected for pared with the theoretical curve for substitute mixture gained by the new
approach (
).
substitute mixture is depicted in Figs. 11 and 12. In these fig-

Fig. 9. Phase portrait for the API gravity (—) compared with values retrieved Fig. 12. Measured characterisation curve for the API gravity (䊉) compared with
from the database for real components (
). the theoretical curve for substitute mixture gained by the new approach (
).
 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356 353

Table 6
Resulting substitute mixtures
No. Substitute mixture of pseudocomponents Substitute mixture of real components and pseudocomponents

Real component/pseudocomponent Liquid volume (%) Real component/pseudocomponent Liquid volume (%)

1 i-Butane 0.19 i-Butane 0.19

2 n-Butane 0.11 n-Butane 0.11
3 i-Pentane 0.37 i-Pentane 0.37
4 n-Pentane 0.46 n-Pentane 0.46
5 NBP 109 1.05 2,2-Dimethylbutane 2.47
6 NBP 135 0.99 2-Methylpentane 0.00
7 NBP 161 1.25 n-Hexane 1.54
8 NBP 185 1.50 2-Methylhexane 3.04
9 NBP 210 1.64 2,2-Dimethylhexane 0.20
10 NBP 235 1.84 2-Methylheptane 2.22
11 NBP 261 2.10 2,4-Dimethylheptane 1.25
12 NBP 286 2.42 2,3-Dimethylheptane 2.90
13 NBP 311 2.81 2,6-Dimethyloctane 3.25
14 NBP 336 3.12 5-Methylnonane 0.00
15 NBP 361 3.14 n-Butylcyclohexane 5.17
16 NBP 386 3.14 n-Undecane 2.64
17 NBP 411 3.08 n-Dodecane 5.20
18 NBP 436 2.83 n-Hexylbenzene 0.00
19 NBP 461 2.64 n-Tridecane 3.23
20 NBP 486 2.55 n-Tetradecane 3.67
21 NBP 511 2.47 n-Pentadecane 2.45
22 NBP 536 2.41 n-Hexadecane 3.30
23 NBP 561 2.36 n-Decylbenzene 0.21
24 NBP 587 2.30 n-Heptadecane 1.40
25 NBP 612 2.28 n-Octadecane 2.65
26 NBP 637 2.31 n-Nonadecane 2.77
27 NBP 662 2.30 n-Uneicosane 4.54
28 NBP 687 2.22 n-Dodecosane 0.00
29 NBP 712 2.09 n-Tricosane 3.51
30 NBP 737 1.91 n-Tetracosane 0.00
31 NBP 762 1.73 n-Pentacosane 3.06
32 NBP 787 1.62 n-Heptacosane 1.19
33 NBP 825 3.03 NBP 821 2.78
34 NBP 875 2.90 NBP 868 3.02
35 NBP 925 2.84 NBP 919 2.90
36 NBP 975 2.80 NBP 970 2.86
37 NBP 1025 2.76 NBP 1021 2.81
38 NBP 1075 2.73 NBP 1072 2.79
39 NBP 1125 2.71 NBP 1123 2.77
40 NBP 1175 2.73 NBP 1175 2.78
41 NBP 1251 5.65 NBP 1251 5.65
42 NBP 1372 8.64 NBP 1372 8.64

ures, it can be also observed that in the region of higher boiling
temperatures program HYSYS is not so successful in the choice
of pseudocomponents and a considerable deviation between the
experimental and estimated values of the molecular weight as
well as API gravity is apparent.
The simulation calculations of the entire crude oil fractiona-
tion process employing both approaches to the characterisation
of complex mixtures run without any problems. The excel-
lent match between both approaches can be demonstrated by
Fig. 13, where the comparison is provided for all the prod-
ucts of fractionation, which have distinct mean boiling points.
The plotted theoretical TBP curves were recalculated in order
to eliminate water. In fact, the TBP curves reflect the match
in the composition of product streams, as the most important
parameter, after processing of a single feed stream in a num-
ber of unit operations within a relatively complex technology
with several recycle streams. Also for other parameters of the
product streams, as flowrates, temperatures and enthalpies, the
results of simulation proved very nice match. It can be noted
that these results were reached despite the fact that the database
used is relatively small compared to other data sources. More-
over, the content of some of the real components selected into
the substitute mixture resulting from the second phase of the
algorithm is practically negligible (see Table 6—components
numbers 6, 14, 18, 28 and 30). Results presented in Table 7
are restricted to the calculated values of temperatures and mass
flowrates of product streams and to calculated duties, i.e. energy
streams in the process. Presentation of complete set of cal-
culated parameters is here impossible according to its large
extent.
354 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356

the possible number of all hydrocarbons. It is an interesting

fact that considering hydrocarbon molecules with 25 carbon
atoms, the number of possible configurations already exceeds
600 millions (Krambeck, 1991) and crude oil may contain a huge
number of distinct molecular species in the order 106 (Altgelt
& Boduszynski, 1994). Nevertheless, substitute mixtures allow
to deal with complex mixtures in modelling and simulation of
technological processes without need to dispose with data for
such extent of existing compounds. Systematic addition of miss-
ing data and inclusion of new components into databases are
continuously provided by the vendors of the main databases of
physical properties (e.g. Beilstein) and certainly it brings better
possibilities for the selection of real components into a substitute
mixture, but even current pallet of available compounds gives
good results. This was proved not only by the example presented
above but also by some other (Ba et al., 2003; Bělohlav et al.,
Fig. 13. Comparison of theoretical TBP curves for fractionation products (bot- 2005; Eckert & Vaněk, 2003, 2005).
tom to top: offgas, naphtha, kerosene, diesel, AGO and residue) employing the
traditional () and the new (
) approaches to characterisation.
There are many benefits when using real components for sub-
stitute mixtures instead of pseudocomponents:
Table 7
Selected simulation results for both substitute mixtures • The usage of substitute mixtures with real components can
be extended from usual calculations of separation processes
Stream Temperature (◦ C) Flowrate (kg/h)
to processes with chemical reactions (Bělohlav et al., 2005)
PC RC + PC PC RC + PC as the substitute mixture receives a chemical nature, even if
(a) Temperatures and flowrates for material streams only a “substitute” one.
Naphtha 75.3 74.6 92399 93614 • Empirical estimation methods for physical properties are gen-
Kerosene 231.4 229.7 64455 65446 erally not needed. The values retrieved from database are more
Diesel 249.2 247.8 86895 87533 reliable and precise despite the fact that for higher boiling
AGO 298.3 294.5 26264 26398
compounds (approximately C20 and higher) they are pre-
Residue 349.8 344.7 253426 255768
dicted only. On the other hand, the knowledge of the molecular
Unit/stream Duty (kW) structure allows us to use group contribution methods to esti-
mate various physical properties, e.g. the phase equilibrium
PC RC + PC
behaviour of the substitute mixture (and therefore of the orig-
(b) Duties—energy streams inal mixture as well).
Furnace/Duty 5.704 × 104 5.666 × 104
• The selection of components can be affected by partial infor-
AtmosTower/TrimDuty 1.157 × 104 0.936 × 104
AtmosTower/CondDuty 2.250 × 104 2.171 × 104 mation about components positively occurring in the mixture
or about the overall character of the mixture. Particularly, we
PC: substitute mixture of pseudocomponents and RC + PC: substitute mixture
can recognise in some mixtures components containing nitro-
of real components and pseudocomponents.
gen or sulphur, but there is certain problem with availability
of data. For example, the HYSYS database contains about 50
5. Conclusions sulphuric compounds the presence of which in oil could be
expected. On the other hand, the inclusion of such compo-
The results presented in this paper allow us to say that the new nents into the resulting substitute mixture is very important
simple approach to the characterisation of complex mixtures is when modelling separation processes having strong impact
fully acceptable even for simulation calculations of large-scale on the environment (Eckert & Vaněk, 2005).
and complex processes including various mass and heat transfer
operations. It can replace the traditional approach based on the The new approach could be also very convenient for the
definition of pseudocomponents for low and moderate normal implementation into standard commercial simulation programs
boiling points. Of course, there is an important assumption about where the combination with current proprietary databases and
the availability and sufficient number of real components with libraries of numerical methods, especially optimisation proce-
normal boiling points in the considered temperature range in the dures for the second phase of the algorithm, could be very
database. If necessary, we can always use a combined approach, profitable. There are also certain possible improvements in
as in the example above, adding pseudocomponents for higher the construction of the substitute mixture, e.g. the selection of
boiling temperature range where no real components are avail- components and/or the composition can be optimised in order
able in the database. We can remark that the number of real to get best match between experimental characterisation data
components not only in the HYSYS but also in other databases and results of the modelling of the appropriate characterisation
we have been dealing with is still extremely low compared to procedure.
 E. Eckert, T. Vaněk / Computers and Chemical Engineering 30 (2005) 343–356 355

Table A.1
Specifications of the parameters of material streams
Stream Temperature (◦ C) Pressure (kPa) Flowrate (kg/h) Flowrate (m3 /h) Composition

Preheated crude 232.2 517.1 662.4 (i.e. 100,000 bbl/day) See substitute mixtures (Table 6)
Bottom steam 190.6 1034 3402 H2 O only
Diesel steam 148.9 344.7 1361 H2 O only
AGO steam 148.9 344.7 1134 H2 O only
Hot crude 343.3
Naphtha 132.5
Offgas 0
Kerosene 86.12
Diesel 112.6
AGO 33.12
PA 1 Draw 331.2
PA 2 Draw 198.7
PA 3 Draw 198.7

Acknowledgement unknown parameters calculated further during the simulation

run. The overall connectivity and stream names are given by
Authors appreciate the support of the fund MSM Fig. 6 and within the subflowsheet by Fig. 7 from where also the
6046137306. location of feed stages as well as of side streams can be derived.

Appendix A. Detailed specifications for the example

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