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www.elsevier.com/locate/ces

Damien Hudebine, Jan J. Verstraete

Development Division, IFP-Lyon, BP3, 69390 Vernaison, France

Received 1 March 2004

Available online 2 November 2004

Abstract

Reconstruction of petroleum fractions comprises the group of methods that allow to create mixtures of molecules from partial analytical

data. In this article, a two-step reconstruction algorithm will be presented. The rst step, called stochastic reconstruction step, assumes

that oil mixtures can be described by distributions of structural blocks. The choice of the blocks and distributions is based on expert

knowledge. The transformation from a set of distributions into a mixture of molecules is obtained by Monte-Carlo sampling, while a

simulated annealing procedure adjusts the parametric distributions. The second step, termed reconstruction by entropy maximization,

improves the representativeness of the set of constructed molecules by adjusting their molar fractions. The estimation of these molar

fractions is carried out by maximizing an information entropy criterion under linear constraints. The proposed two-step reconstruction

algorithm allows to rebuild mixtures that resemble the petroleum fractions more closely than the approaches used previously. The technique

is validated by comparing the properties of the rebuilt mixtures to analytical data that have not been used for the molecular reconstruction.

2004 Elsevier Ltd. All rights reserved.

Keywords: Complex uids; Mixing; Modeling; Monte-Carlo; Molecular reconstruction; Petroleum

1. Introduction

In petroleum rening, both the accurate design and optimization of hydrocarbon conversion processes require the

development of rigorous and reliable kinetic models. To establish an extensive kinetic model, the composition of the

feedstock should be known with great detail. For the lightest

products (gas, liqueed gas, gasoline), this characterization

can be obtained by gas chromatography. For heavier cuts,

however, no analytical technique is yet powerful enough to

detect and quantify the thousands of different compounds

that compose an oil fraction. Consequently, it is necessary to

numerically reconstruct a mixture from partial analytical

data, model hypotheses and expert knowledge.

Allen and Liguras (1991) proposed to select a set of

predened molecules and to modify their molar fractions

in order to obtain a mixture whose properties are close

to the desired analytical data. The analyses used are gas

Corresponding author. Tel.: +33 4 78 02 20 53; fax: +33 4 78 02 20 08.

0009-2509/$ - see front matter 2004 Elsevier Ltd. All rights reserved.

doi:10.1016/j.ces.2004.09.019

up 190 linear equality constraints as a function of the molar

fractions. The problem solution is obtained by minimizing

a specic criterion.

Quann and Jaffe (1996) suggested a similar method but

the molecules are replaced by vectors of structural blocks,

called structure oriented lumping (SOL) vectors. The reconstruction of the mixture of SOL vectors from analytical

data has not been detailed by the authors for commercial

reasons.

Zhang (1999) characterized petroleum cuts by a matrix of

pseudo-compounds classied by chemical family and carbon number. Such a matrix can be obtained by coupling gas

chromatography with mass spectrometry (GC/MS) but these

analyses are long and complex. Another method consists of

collecting a library of matrices associated with their overall

mixture properties and calculating a new matrix by interpolation.

Others authors chose to dene the petroleum fractions by

an average model molecule in 2D (Hirsch and Altgelt, 1970;

Speight, 1970) or 3D (Faulon et al., 1990). The analyses

4756

to provide information on chemical functions, e.g. via infrared and NMR spectrometry.

Finally, Neurock et al. (Neurock, 1992; Neurock et

al., 1994) have developed a method called stochastic

reconstruction (SR). The main hypothesis of this approach

resides in the characterization of petroleum cuts by a set of

distributions of molecular structural attributes. These distributions are sampled by a Monte-Carlo method in order to

obtain a mixture of molecules. The method thus provides

both a set of pseudo-compounds (molecule mixture) and

a statistical average description (distributions). When coupled to an optimization loop on the distribution parameters,

the method has been proven able to yield mixtures that

closely mimic the original properties of heavy asphaltene

feedstocks (Trauth, 1993; Trauth et al., 1994).

During a previous work (Hudebine et al., 2002), two algorithms for molecular reconstruction have been developed

in order to rebuild light cycle oil (LCO) gasoils from overall

petroleum analyses. The rst method was based on stochastic

sampling of statistical distributions (SR), the other was a new

approach, termed reconstruction by entropy maximization

(REM). During validation, both methods have been applied

to LCO gasoils because a larger number of analytical data

was available for this type of feeds and the properties of

the resulting mixture could thus be compared with the original data. The results have shown a reasonably good agreement, but they also illustrated some of the drawbacks of

each method. Hence, coupling the SR and REM methods

had been proposed. In the present work, this combination

of both approaches will be tested on various LCO gasoils to

illustrate the improvement of the coupled method compared

to each approach taken separately.

2. General description of the two-step reconstruction

algorithm

In the present work, a two-step algorithm for molecular

reconstruction was developed. In a rst step, a large representative set of molecules is created, containing several

thousands of species. This is done via a SR method. The

second step in the algorithm aims at improving the composition of this set of molecules by adjusting the mole fractions

of the various species via the REM method.

2.1. The Stochastic Reconstruction step

The SR step creates an initial set of molecules, which is

then successively modied until a mixture is obtained that

mimics the properties of the experimental data. To achieve

this, the SR method uses parametric distributions of structural blocks (polycyclic cores, rings, chains, etc.) in order to

characterize the oil fraction to be reconstructed. The transition from a set of distributions into a molecule is performed

N times by a Monte-Carlo sampling method, generating a

diagram and chemical rules are applied to avoid the creation of unfeasible or unlikely molecules. The building diagram is a decision tree that describes the sampling steps of

the different distributions in the correct order. The chemical

rules are criteria that discard molecules based on thermodynamic or likelihood grounds. For each molecule, pure compound properties are also calculated, either directly by inspection of the structure (e.g. chemical formula, molecular

weight, NMR), or numerically by group contribution methods (e.g. specic gravity, normal boiling point). The MonteCarlo sampling creates a mixture of N molecules, each with

a molar fraction of 1/N . This mixture is therefore called

equimolar, even if a same structure may have been generated several times. The average properties of this equimolar

mixture are obtained through mixing rules and compared to

the available analyses through an objective function. This

objective function is then minimized by means of an optimization method, which modies the parameters of the distributions. The basic algorithm of the SR step is depicted in

Fig. 1.

2.2. The Reconstruction by Entropy Maximization step

The second step of the algorithm starts from the set of N

molecules dened previously and modies their molar fractions in order to obtain a mixture whose properties are more

closely aligned to those of the petroleum cut. To adjust the

molar fractions, the model maximizes the information entropy, hence the name of the method. This criterion guarantees that a given molecule cannot be preferred to others

if no information is available. In other words, without constraints or information, the distribution of the predened set

of molecules is uniform. When constraints are introduced,

the uniform distribution is distorted in order to match this

information. If the constraints are linear as a function of

the molar fractions, the resolution of the problem is semialgebraic and can be reduced to a maximization problem of

a non-linear equation with J parameters, with J the number

of constraints to verify (Hudebine, 2003). The basic algorithm of the REM step is shown in Fig. 2.

2.3. Advantages of the two-step algorithm

Each of the two steps described above could be used

as a stand-alone reconstruction method. SR has previously

been applied to rebuild various LCO gasoils (Hudebine et

al., 2002; Hudebine, 2003). The results have shown a good

agreement between the properties of the reconstructed mixtures and the analytical data. However, some shortcomings

also appeared, especially concerning the t to some analyses. For example, in the mass spectrometry analysis, monocycloparafns (Cn H2n ) are systematically underestimated,

while the family of indanes/tetralins (Cn H2n8 ) is overestimated. This mismatch has been attributed to internal con-

Building diagram

4757

and building of a molecule

N times

Distributions

Calculation of the

equimolar mixture

properties

pure component properties

of the distributions

No

Simulated annealing

Close

enough ?

Analytical data

Predefined set of

molecules

Maximization of the

information entropy

associated to the constraints

Linear constraints

Mixing rules

Optimization of the

parameters {j}

fractions of the set of molecules

the molecule construction scheme. Consequently, the problem is intrinsic to the SR method and cannot be eliminated

easily. As a Monte-Carlo technique is used, the SR method

is also computationally intensive.

As opposed to the SR method, the computational effort

of the REM method is much smaller. Moreover, this method

allows to obtain a mixture whose properties are very close

to the analytical data. However, this approach also exhibits

some difculties when used as a stand-alone method. Firstly,

the method strongly depends on the initial set of molecules.

That is why the molecules must be chosen with care, i.e. corresponding to the type of feedstock studied. Secondly, the

search of a solution gets increasingly more difcult when

the properties of the initial set of molecules (which is considered to be equimolar) are too far from the analytical data.

In extreme cases, if the initial mixture is very different, the

dispersion of the molar fractions is so important that the

optimized mixture is composed of a very small number of

highly concentrated compounds, while the remaining compounds have a near-zero mole fraction. The REM method is

also very sensitive to inconsistencies in the analytical data,

in contrast to the SR method that has intrinsic data reconciliation properties.

To summarize the individual approaches and underline

their advantages and drawbacks, the SR method is a very

only roughly approaches the analytical data. On the other

hand, the reconstructed molecules are always typical of the

studied oil fraction due to the use of specic building rules

based on analytical and expert knowledge. Opposed to the

SR method, the REM method is a nishing method that allows to nd a mixture with properties that are very close to

analytical data, but it needs a particularly well-dened initial set of molecules. For these reasons, coupling both methods seems an excellent solution to eliminate their respective

drawbacks.

to a LCO gasoil

3.1. Construction of the initial set of molecules by the SR

step

The SR method can be applied to any type of feedstock

with a limited number of modications. In the case of LCO

gasoil reconstruction, only the type of the distributions and

the building diagram must be specied.

The choice of the set of distributions is very important and

needs some expert knowledge of the chemical structure of

LCO gasoils. For example, due to the cut point of classical

4758

Table 1

Distributions used for the reconstruction of LCO gasoils by the SR step

Initial value

Optimized value

Distribution 1

Number of polycyclic cores

Probability to have 1 core:

0.200

Complement to 1

0.283

Complement to 1

Distribution 2

Number of aromatic rings per core

Probability

Probability

Probability

Probability

to

to

to

to

have

have

have

have

0

1

2

3

ring:

ring:

ring:

ring:

0.400

0.200

0.200

Complement to 1

0.178

0.223

0.451

Complement to 1

Distribution 3

Number of naphtenic rings per core

Probability

Probability

Probability

Probability

to

to

to

to

have

have

have

have

0

1

2

3

ring:

ring:

ring:

ring:

0.400

0.200

0.200

Complement to 1

0.476

0.327

0.076

Complement to 1

Distribution 4

Number of thiophenic rings per core

Probability to have 1 ring:

0.800

Complement to 1

0.772

Complement to 1

Distribution 5

Does an aromatic CH accept a chain?

Probability for yes:

0.700

Complement to 1

0.780

Complement to 1

Distribution 6

Does a naphtenic CH2 accept a chain?

Probability for yes:

0.700

Complement to 1

0.428

Complement to 1

Distribution 7

Type of the chain

Probability to have an ethyl:

Probability to have an isopropyl:

0.700

0.150

Complement to 1

0.314

0.481

Complement to 1

Distribution 8

Size of the parafns

Value for :

Value for :

2.000

4.000

2.088

4.438

Distribution 9

Do a parafnic CH2 accept a chain?

Probability for yes:

0.700

Complement to 1

0.996

Complement to 1

than one polycyclic core. A histogram with two bins, 0 or

1, is then enough to describe this structural part of gasoil

molecules. Analogously, the maximum length of the alkyl

chains is necessarily limited because of the cracking reactions in the catalytic cracking process. The distribution of

the alkyl chain length can be described by a histogram with

only 3 possibilities: 1, 2 or 3 carbon atoms. Table 1 lists

the 9 distributions and the 15 associated parameters used to

build LCO gasoils.

To dene the hierarchic relationships between distributions and identify the sampling steps, a specic building diagram is also needed. This operation is relatively simple for

LCO gasoils. For each molecule to rebuild, the distribution

1 is sampled rst. If the number of cores is equal to 0, the

molecule is a parafn and distribution 8 is used to determine

its length. If the number of cores is equal to 1, distributions

24 are successively used to select the number of aromatic,

cyclohexanic and thiophenic rings in the core. Depending

from a library of predened cores. After that, each aromatic

and naphtenic carbon atom is tested to dene whether an

alkyl chain is inserted or not (distributions 5 and 6). Finally,

if a chain is accepted, distribution 7 is used to determine its

length.

The above-described operations are applied N times so as

to obtain a mixture of N molecules that is statistically representative of the distributions. For each molecule, the elemental composition, molecular weight, mass spectrum, 1 H

NMR spectrum and 13 C NMR spectrum are easily obtained.

For the specic gravity and the normal boiling point, novel

group contribution methods are used (Hudebine, 2003). The

properties of the equimolar mixture are subsequently calculated by linear mixing rules (elemental analysis, average

molecular weight, average specic gravity, simulated distillation, mass spectrometry, 1 H and 13 C NMR analyses). In

the case of the average specic gravity and the distillation,

this is equivalent to the assumption of an ideal mixture be-

4759

Table 2

Properties of rebuilt mixtures compared to the analytical data for a LCO gasoil

Petroleum analyses

Analytical data

Set L

Set L+

Global analyses

Carbon content

Hydrogen content

Sulfur content

Specic gravity

(wt%)

(wt%)

(wt%)

(g/cm3 )

88.05

10.42

1.53

0.9407

87.80

10.69

1.51

0.9333

88.06

10.42

1.52

0.9537

Simulated distillation

5 wt%

10 wt%

20 wt%

30 wt%

40 wt%s

50 wt%

60 wt%

70 wt%

80 wt%

90 wt%

95 wt%

Final boilingpoint

( C)

( C)

( C)

( C)

( C)

( C)

( C)

( C)

( C)

( C)

( C)

( C)

( C)

135

207

231

264

286

305

323

342

361

381

403

418

454

134

171

208

245

269

298

327

356

377

396

416

433

459

134

153

223

250

281

302

318

336

357

376

401

443

458

Mass spectrometry

Cn H2n+2

Cn H2n

Cn H2n(2,4)

Cn H2n6

Cn H2n8

Cn H2n10

Cn H2n12

Cn H2n14

Cn H2n16

Cn H2n18

Cn H2n20 and more

Cn H2n10 S

Cn H2n16 S

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

13.1

9.9

5.4

7.1

7.0

2.0

16.7

10.7

6.9

7.0

5.1

4.5

4.6

18.6

6.0

6.3

4.3

7.1

2.0

18.1

9.6

10.0

7.6

0.3

2.4

7.7

13.1

9.9

5.4

7.1

7.0

2.0

16.7

10.7

6.9

7.0

5.1

4.5

4.6

13 C NMR

Saturated CH3

Saturated CH2

Saturated CH

Saturated C

Aromatic CH

Condensed aromatic C

Substituted aromatic C

(mol%)

(mol%)

(mol%)

(mol%)

(mol%)

(mol%)

(mol%)

16.7

32.0

7.7

0.4

22.3

7.6

13.3

19.0

26.7

10.0

0.0

24.8

7.7

11.8

17.5

29.3

7.5

0.0

22.4

8.0

15.3

1 H NMR

Diaromatic H

Monoaromatic H

H (type alpha)

H (type beta)

H (type gamma)

(mol%)

(mol%)

(mol%)

(mol%)

(mol%)

13.6

2.3

23.1

43.9

17.1

14.7

2.4

13.9

48.3

20.7

13.8

2.1

22.9

45.9

15.3

in order to adjust the equimolar mixture until the desired

mixture properties are found. The difference between experimental and calculated data is mathematically described by

an objective function, which is minimized by a simulated

annealing algorithm.

The SR step was applied to a LCO gasoil whose properties are given in Table 2. For this sample, the available

analyses were the elemental analysis, simulated distillation,

mass spectrometry, 13 C NMR analysis and 1 H NMR analysis. The number of molecules to be sampled was set to

5000. The equimolar mixture obtained after simulated annealing is called Set L. Its calculated mixture properties

are also given in Table 2. Comparison to the experimental

analyses shows a good agreement between the properties of

the generated mixture and the analytical data of the LCO.

Table 1 provides the initial and optimized parameters of the

distributions used.

4760

analyses

Partial analytical data of

Entropy

maximization

(REM)

Prediction of missing

Reconstruction of a new

REM step

To further improve the representativeness of this set of

molecules, the REM method is used to determine the molar

fractions of each of the molecules in the set. Table 2 also

lists the calculated properties of this new mixture (Set L+),

which is now no longer equimolar as each molecule has its

own molar fraction that has been dened via the information

entropy criterion. As can be seen, the REM step only adds

small improvements on more global analyses, such as the

elemental analysis. However, on more specic and detailed

analyses, such as NMR and mass spectrometry, the REM

step allows to rene the agreement between the mixture

properties and the analytical data in a signicant manner.

4. Reconstruction of various LCO gasoils using a

modied two-step reconstruction algorithm

As illustrated above, the two-step reconstruction algorithm can be applied to LCO gasoils to generate, for each

sample, a detailed mixture that adequately mimics the properties of the gasoil to be represented. However, as the rst

step of this reconstruction method uses a Monte-Carlo approach to generate its initial set of molecules, it still remains

a computationally intensive algorithm. A modied two-step

reconstruction algorithm was therefore derived and may be

applied when several LCO gasoils need to be represented.

two-step reconstruction algorithm.

To be representative of many LCO gasoils, a gasoil with

the widest boiling point range was chosen as reference gasoil

in order to be able to encompass all gasoils. The reference

gasoil chosen corresponds to the gasoil that was already presented in Table 2. The Set L+ from Table 2 is not equimolar,

however, a condition necessary for the information entropy

criterion. To return to an equimolar set of molecules, it is

necessary to multiply the molar fraction xi of each molecule

i by a constant factor K (50 000 for example) and to insert

this molecule K.xi times, rounded to the nearest integer, into

the new mixture set. Hence, an equimolar set of 50 000

molecules is obtained whose properties are exactly equal to

those of the non-equimolar mixture of 5000 molecules.

This new set constitutes an excellent starting point. Indeed, the constructed molecules are representative of LCO

gasoil molecules thanks to the building rules used by the SR

step. The properties of the corresponding equimolar mixture

are very close to the analytical data of the reference LCO

gasoil and are, by denition, also typical of analytical data

of any LCO gasoil. Consequently, this database of 50 000

molecules will be used to rebuild other LCO gasoils from

their analytical data by the REM step.

To further illustrate the information entropy maximization

step, the equations will now be developed. First, the entropic

criterion to be maximized is given by

H =

4.1. Description of the approach

A reference LCO is rst reconstructed through the abovedescribed two-step procedure. Hence, the resulting molecule

set can be considered as a reference mixture that is typical

for LCO gasoils. To reconstruct other LCO gasoils, only the

REM step is employed. It starts from the reference mixture

(instead of a specic Monte-Carlo generated mixture) to

obtain a new mixture whose properties are very close to

those of the LCO gasoil to represent. This mixture will now

contain the same molecules as the reference mixture but with

50

000

xi ln xi ,

(1)

i=1

of 50 000 molecules.

Associated with this criterion, various constraints must be

introduced. The rst one allows to ensure the normalization

of the molar fractions, which can be written as

50

000

i=1

xi = 1.

(2)

tted. As the mixing rules are considered to be linear, these

constraints can be written as follows:

50

000

i=1

exp

xi fi,j = fj

j J,

(3)

where J is the set of constraints, fi,j is the value of the property of the ith molecule associated to the jth constraint and

exp

fj is the experimental value of the analysis associated to

the jth constraint. The value of fi,j is determined for each

analysis. For example, in the case of the mass spectrometry analysis, fi,j = 0 when molecule i does not belong to

mass spectrometry class m corresponding to constraint j and

fi,j = Mi /Mmixture when molecule i belongs to mass spectrometry class m corresponding to constraint j. For the simulated distillation analysis, fi,j = 0 when the boiling point

of molecule i is above the experimental boiling BPexp (m)

and fi,j = Mi /Mmixture when the boiling point of molecule

i is lower than the experimental boiling BPexp (m). In these

formulas, Mi is the molecular weight of molecule i and

Mmixture is the average molecular weight of the mixture obtained from (xi .Mi ).

When these constraints are introduced into the entropy

criterion, Eq. (1) is modied and the new equation to maximize becomes

50

000

50

000

=

xi ln xi + 1

xi

i=1

J

j =1

1

2

exp

fj

50 000

i=1

i=1

xi fi,j

j

2

,

(4)

where is a Lagrange multiplier and j is a standard deviation associated to the jth constraint.

Finally, the algebraic solution of the maximization problem is the following:

50000

J

fi,j

zi

zi , zi = exp

j , (5)

xi = , Z =

Z

j

i=1

j =1

where the vector of parameters {j } is calculated to maximize the non-linear Eq. (6):

exp

J

1 2 fj

(6)

E = ln Z +

j

2 j

j

j =1

Its maximization can be performed by a simple conjugate

gradient method. Once the parameters {j } are optimized,

the various molar fractions xi can be easily calculated from

Eq. (5). The mixture is now reconstructed.

4.2. Validation of the approach

Nine LCO gasoils have been reconstructed using the modied two-step reconstruction algorithm. The analyses used

4761

for the molecular reconstruction were the simulated distillation and mass spectrometry analyses. These analyses have

been chosen because they give some information in term

of molecule size (distillation) and chemical structure (mass

spectrometry). To validate the reconstruction, the best solution would be to compare the rebuilt mixtures to the real

gasoils molecule by molecule. However, this is impossible

as there are no analyses that allow to identify and quantify

the individual molecules present in gasoils. As a substitute

for a molecule-based validation, properties that were not

used during the reconstruction (elemental analysis, specic

gravity, molecular weight, 1 H NMR, 13 C NMR) were predicted from the rebuilt mixtures and compared to their corresponding experimental values. Fig. 4 gives the parity plots

for the predicted specic gravity, molecular weight, carbon

content, hydrogen content, sulfur content, as well as for the

distribution of hydrogen atoms by NMR type and for the

distribution of carbon atoms by NMR type.

The results show a good agreement between the predicted

and experimental analyses. Two problems have nevertheless been encountered. The rst one concerns the specic

gravity. If the ideal mixture hypothesis is directly used, a

constant bias is observed between analytical data and calculated mixtures properties. This bias has been evaluated

as +0.0113 g/cm3 and can be subtracted during the mixture calculations. The second problem concerns the average

molecular weight. The estimated molecular weights are always smaller than the experimental molecular weights,

which are obtained from a correlation based on specic

gravity and simulated distillation (API, 1987). The average bias equals 9 g/mol and is probably due to the hypothesis that the simulated distillation perfectly separates

molecules by increasing normal boiling points. In practice,

however, chromatographic columns are not strictly apolar

and separate to some extent according to the polarity of

the molecule. For example, the simulated distillation boiling

point for naphthalene is 11 C lower than its normal boiling

point, while for anthracene this difference already amounts

to 36 C (ASTM D2887, 2002). Hence, the reconstructed

polynuclear molecules are slightly smaller than their actual

counterparts, resulting in a slightly lower average molecular weight. For the other analyses (elemental analysis, NMR

analyses), the results are very consistent and, for most of the

evaluated properties, lie within the analytical condence intervals. Hence, the coupled SR/REM molecular reconstruction scheme can be used as alternative for the analyses themselves. This is particularly the case for the NMR analyses,

which are expensive and consequently hardly used.

5. Conclusion

Stochastic reconstruction (SR) is a method that yields

molecular sets whose mixture properties are very close to

those of the petroleum fraction that is represented, but the

achievement of a perfect-t solution is perturbed by the

4762

230

0.99

Molecular weight

0.97

0.96

0.95

0.94

0.93

Analytical confidence interval = 0.0005 g/cm3

0.92

0.91

0.91

0.92

0.93

0.94

0.95

0.97

0.96

0.98

210

200

190

180

170

160

160

0.99

(a)

220

0.98

Corrected specific gravity

90.0

220

230

Hydrogen content

89.5

89.0

88.5

88.0

Analytical confidence interval = 0.3 wt%

87.5

87.0

87.0

10.5

10.0

9.5

9.0

8.5

87.5

(c)

88.0

88.5

89.0

89.5

90.0

8.5

9.0

(d)

9.5

10.0

Experimental hydrogen content (wt%)

10.5

11.0

40

3.0

Secondary saturated CH2

Tertiary saturated CH

Aromatic CH

Condensed aromatic C

Substituted aromatic C

Sulfur content

Predicted sulfur content (wt%)

180

190

200

210

"Experimental" molecular weight (g/mol)

11.0

Carbon content

2.5

2.0

1.5

1.0

Analytical confidence interval = 5 % relative

0.5

35

30

25

20

15

10

5

0

0.0

0.0

(e)

170

(b)

0.5

1.0

1.5

2.0

2.5

10

15

20

25

30

35

40

Diaromatic H

Monoaromatic H

H alpha

H beta

H gamma

45

Predicted molar fractions (mole%)

(f )

50

3.0

40

35

30

25

20

15

10

5

0

0

(g)

10

15

20

25

30

35

40

45

50

Fig. 4. Parity plots between analytical data and estimated properties of the mixtures reconstructed by the coupled SR/REM algorithm. (a) specic gravity,

(b) molecular weight, (c) carbon content, (d) hydrogen content, (e) sulfur content, (f) 13 C NMR and, (g) 1 H NMR.

the generated molecules.

Reconstruction by entropy maximization (REM) is CPU

efcient and provides a very good agreement between sim-

very difcult to reconstruct and inconsistent if the initial

molecular set is not correct or very different from the feedstock type.

coupling both methods has been proposed and two variants have been developed and validated. The idea consists

in using a SR step to build a reference mixture. This set of

molecules thus obtained can be used in a second step either to improve its representativeness or to rebuild similar

petroleum fractions via the REM method. To validate the

latter approach, nine LCO gasoils have been reconstructed

with this technique from their simulated distillation and mass

spectrometry analysis. The results in terms of analysis prediction have shown a very good agreement. Consequently,

this two-step molecular reconstruction algorithm can be used

to predict missing analytical data or to generate molecular

mixtures that can serve as input to detailed kinetic models.

References

Allen, D.T., Liguras, D.K., 1991. Structural models of catalytic cracking

chemistry: a case study of a group contribution approach to lumped

kinetic modeling. In: Sapre, A.V., Krambeck, F.J. (Eds.), Chemical

Reactions in Complex Mixtures, Mobil Workshop. Van Nostrand

Reinhold, New York.

API, 1987. API procedure 2B2.1 for estimating the molecular weight of

a petroleum fraction. API Technical Handbook.

ASTM D2887, 2002. Standard test method for boiling range distribution

of petroleum fractions by gas chromatography. Annual Book of ASTM

Standards.ASTM, Philadelphia.

Faulon, J.L., Vandenbroucke, M., Drappier, J.M., Behar, F., Romero,

M., 1990. Modlisation des Structures Chimiques des Macromolcules

4763

Ptrole 45 (2), 161180.

Hirsch, E., Altgelt, K.H., 1970. Integrated structural analysis. A method

for the determination of average structural parameters of petroleum

heavy ends. Analytical Chemistry 42 (12), 13301339.

Hudebine, D., 2003. Reconstruction molculaire de coupes ptrolires.

Ph.D. Thesis, Ecole Nationale Suprieure de Lyon.

Hudebine D., Vera, C., Wahl, F., Verstraete, J., 2002. Molecular

representation of hydrocarbon mixtures from overall petroleum

analyses. A.I.Ch.E Spring Meeting, New Orleans, March 1014.

Neurock, M., 1992. A computational chemical reaction engineering

analysis of complex heavy hydrocarbon reaction systems. Ph.D. of the

University of Delaware.

Neurock, M., Nigam, A., Trauth, D.M., Klein, M.T., 1994. Molecular

representation of complex hydrocarbon feedstocks through efcient

characterization and stochastic algorithms. Chemical Engineering

Science 49 (24), 41534177.

Quann, R.J., Jaffe, S.B., 1996. Building useful models of complex reaction

systems in petroleum rening. Chemical Engineering Science 51 (10),

16151635.

Speight, J.G., 1970. A structural investigation of the constituents of

athabasca bitumen by proton magnetic resonance spectroscopy. Fuel

49 (1), 7690.

Trauth, D.M., 1993. Structure of complex mixtures through

characterization, reaction, and modeling. Ph.D. of the University of

Delaware.

Trauth, D.M., Stark, S.M., Petti, T.F., Neurock, M., Klein, M.T., 1994.

Representation of the molecular structure of petroleum resid through

characterization and Monte Carlo modeling. Energy and Fuels 8 (3),

576580.

Zhang, Y., 1999. A molecular approach for characterization and property

predictions of petroleum mixtures with applications to renery

modelling. Ph.D. of the University of Manchester.

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