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BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p.

001-009 | 2009 | ISSN 1982-0593

ATMOSPHERIC DESTILATION RESIDUUM EXTRACTION WITH


SUPERCRITICAL PROPANE: A STUDY OF THE PROCESS VARIABLES
INFLUENCE
a
a

Mehl, A.;

Nogueira, L. S. C.;

Pessoa, F. L. P. 1; Silva, S. M. C.

Federal University of Rio de Janeiro Chemistry School DEQ

ABSTRACT

Supercritical propane is a powerful solvent in the extraction of light hydrocarbons from crude oil residues.
The extraction efficiency is a function of pressure, temperature, oil composition and the ratio between
solvent and oil rates. This work presents the results of computer simulation studies in the investigation of
the capabilities of supercritical propane in the extraction of a light fraction from the atmospheric
distillation residuum (RAT). The experimental physical-chemical characterization of the feed was used to
generate a mixture of pseudo-components representing the RAT. It was observed that the extraction
efficiency increases with the solvent/oil ratio and the pressure, whereas it decreases with the increasing
temperature. A practically complete recovery of the light fraction was reached at 100 bar, with propane
feed at 100 C and a solvent/oil ratio of 15:1 in volumetric basis.

KEYWORDS

supercritical fluid extraction; propane; simulation; heavy oil

To whom all correspondence should be addressed.


Address: Av. Athos da Silveira Ramos, 149 - Edifcio Centro de Tecnologia, Bloco E, Sala 201, Rio de Janeiro/RJ, Brazil
CEP: 21941-909 | Telephone: +55 21 2562-7315 | E-mail: pessoa@eq.ufrj.br

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

1. INTRODUCTION

2. LITERATURE REVIEW

The atmospheric distillation residuum (RAT) is a


crude oil fraction with boiling point above 420 C,
which is obtained as bottom stream in the
atmospheric distillation of the crude oil. It is a
residuum of high molecular weight, high viscosity,
high pour point and low commercial value. Solvent
extraction is a separation process based on the
selective solubility capacity of the components of a
mixture by a specific solvent and is commonly used
to recover fractions of high commercial value
present in the RAT.

The supercritical fluid extraction may be a viable


alternative for the conventional separation process
of heavy hydrocarbons in the petroleum industry.
The performance of the supercritical fluid
extraction in the fractionation of multi-component
mixtures depends on several factors, such as the
solvent density, differences in volatility and
intermolecular forces between the solute and
supercritical solvent (Hwang et al., 1996).

In the supercritical extraction a solid or liquid


substrate is separated from the mixture through a
dense pure gas or a mixture of dense gases
employed as extraction agent. Downstream the
extractor, the desired are separated from the
supercritical solvent by means of depressurization
of the product stream. This technique represents a
promising alternative concerning the recovery of
high-quality products. Moreover this technique is
considered a clean technology due to the
possibility of energy consumption minimization in
the solvent recovering that is recycled to the
process.
This work analyses the supercritical fluid
extraction of the RAT as an alternative process
used to remove the undesirable compounds
present in this fraction to obtain a fraction with
commercial interest, as the extract stream.
Furthermore it should be mentioned that the
residual stream has a useful destination as
asphaltic residuum in asphalt production.
Hydrocarbons with low molecular weight
simultaneously solubilize paraffinic and isoparaffinic compounds and promote the
precipitation of resins and asphaltenes. As a low
molecular weight hydrocarbon, propane exhibits
excellent solvency power added to a good
selectivity. For this reason, it is usually chosen as
the solvent in vacuum residuum desasphalting
units.
The aim of this work is to evaluate the influence
of process variables such as solvent/oil ratio,
operational pressure and solvent temperature on
the process efficiency.

Supercritical fluid extraction technique can be


used to treat heavy feeds and obtain products of
lower viscosity. It represents a cleaner technology
wherein it is not necessary to use toxic solvent and
the final cuts containing most of the contaminants
and asphaltenes can be conveniently discarded
(Zhao et al., 2005).
With respect to the simulation studies of such
process, Mendes et al. (2005) used the PRO-II
software to simulate the extraction of deasphalted
oil from the vacuum residue using supercritical
propane as solvent. The results concerning the
separation efficiency combined with its economical
evaluation reveal a promising future for such
technique. Similarly, Concha et al. (2008) used the
PRO-II software to simulate the vacuum residuum
deasphaltation in a pilot plant scale using propane
as solvent in near critical conditions, to verify the
effects of propane-to-residuum ratio and
operational temperature in the process and
concluded that the column pressure is not an
important variable, the high temperature favors
the quality and the efficiency of the process.
Additionally, propane was found to be a great
solvent due to its high solubility and selectivity
capacity.

3. RESULTS AND DISCUSSION


The simulation of the RAT extraction with
supercritical propane was performed using the
UNISYM simulator by HONEYWELL. The
atmospheric residuum used as the feed of the
extraction was obtained from a 35.6 API crude oil.
The characterization of the RAT is shown in Table 1.

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

Table 1. Characterization of RAT obtained from a 35.6 API crude oil.


Viscosity at 82.2 C, mm2/s
Viscosity at 100.0 C, mm2/s
Pour Point, C
Relative Density at 20/4 C
Density (API)
Destilation Curve 760 mmHg, %vol
IBP
5/10
15/20
25/30
35/40
45/50
55/60
65/70
80/85
FBP
(% Recovered)
Asphaltenes (insolubles in n-heptane), %m/m
Ramsbottom Carbon Residuum, %m/m
Sulphur content, %m/m
Nitrogen content, %m/m
Basic nitrogen content, %m/m
Elementary Analysis, %m/m
Carbon
Hydrogen
Nitrogen
Metals, mg/kg
Nickel
Vanadium
Iron
Copper
Lead
Zinc

As in the case of the crude oil, the exact


chemical composition of the RAT is unknown.
Therefore the process simulator uses the
distillation curve to define a mixture of pseudocomponents to represent the RAT in the
simulation. For each pseudo-component the
physical and chemical properties were estimated
and the results are presented in Table 2. The
critical temperature and pressure, the acentric
factor and the enthalpy were estimated by the LeeKesler correlation and the molecular weight by the
Twu correlation. To model the phase behavior of
this system the Peng-Robinson cubic equation was
selected since it has been extensively used for
modeling systems composed by hydrocarbons and
light gases. The quadratic mixing rule was used. In
order to facilitate the data analysis, the pseudocomponents were segregated into three groups,

Result
44.34
24.70
42
0.9193
21.8
C
382.2
410.8/427.2
441.8/457.5
475.4/493.9
512.3/530.9
568.2/587.3
607.1/627.6
649.1/673.0
700.8/726.7
750
87.8
2
5.4
0.28
0.28
0.09
86.1
12.9
0.5
8
<3 (*)
9
<1 (*)
<1 (*)
2

Method
ASTM D445
ASTM D445
ASTM D97
ASTM D 1298
ASTM D 1298
ASTM D2287

IP 143
ASTM D524
UOP 864 (LECO)
UOP384 (Kjeldahl)
UOP 269
ASTM D5291

N 2440
(*) lower than the
method quantification
limit.

according to their volatility, as shown in Table 2.


The module chosen to represent the
supercritical fluid extraction process was a liquidliquid extraction column allowing the definition of
the number of theoretical stages (N), where the
number of inlet and outlet streams may vary from
two (top and bottom) to N. It is necessary to define
the pressure profile throughout the column, but in
this study the pressure was considered to be
constant as a simplification. The RAT feed
temperature used in the simulation was 370 C
since RAT usually leaves the atmospheric
distillation column under this condition.
Firstly the solvent/oil ratio and the pressure
were investigated and the influence of propane
feed temperature was verified with the best

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

Table 2. Pseudo-components properties.


RAT Composition
PseudoNBP (C)
components Mass Fraction (%)
0.48
NBP421
421.40
Light
Fraction
1.74
NBP444
444.23
(16.04%)
4.33
NBP473
473.17
9.49
NBP496
495.95
8.45
NBP524
523.53
Medium Fraction 551.69
7.77
NBP552
(31.59%)
7.66
NBP580
579.53
7.70
NBP607
607.22
7.59
NBP635
634.90
15.56
NBP678
678.11
Heavy Fraction 736.96
11.82
NBP737
(52.36%)
8.11
NBP791
790.97
3.76
NBP861
861.47
2.90
NBP919
919.45
1.39
NBP984
984.35
1.21
NBP1049
1048.87

solvent/oil ratio obtained. The extraction


fluxogram with the recovery and recycle of
propane is shown in Figure 1.
The parameter representing the relative
quantity of the recovered fraction of interest from
the original feed, as represented by equations (1),
(2) and (3), was chosen to evaluate the extraction
efficiency. The simulation condition and the
corresponding results are showed in Table 3.

MW
388.10
411.75
461.98
494.63
535.01
577.11
619.16
664.68
712.82
786.66
886.37
983.43
1080.3
1160.23
1219.08
1271.89

mfle
.100
mflRAT
mfme
%Medium_Re c. =
.100
mfmRAT
mfpe
%Heavy_Rec . =
.100
mfpRAT
%Light_Rec. =

(1)
(2)
(3)

where:
mfle - mass flow rate of pseudo-components in the
light fraction of the extract stream;

Figure 1. Process Fluxogram.

PC
Acentric
TC (C)
(kPa)
Factor
578.50 1102.09
1.02
596.66 1017.27
1.08
621.50 939.46
1.14
639.80 872.21
1.20
661.08 791.37
1.26
683.20 720.80
1.32
705.77 662.82
1.38
728.09 609.74
1.44
750.24 560.51
1.49
784.53 490.65
1.57
830.67 407.39
1.68
873.30 344.68
1.77
926.31 268.63
1.89
970.39 219.40
1.98
1017.10 168.78
2.08
1064.14 130.00
2.18

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

Table 3. Simulation results.


Propane/RAT
ratio (vol/vol.)
3:1
3:1
3:1
3:1
5:1
5:1
5:1
5:1
9:1
9:1
9:1
9:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1
15:1

Pressure
(bar)
60
75
90
92.8
60
75
90
100
60
75
90
100
60
75
90
100
130
150
200
130
150
200
130
150
200
130
150
200

Propane Feed
Temperature (C)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
125
125
125
150
150
150
175
175
175

%Light_Rec.
(% mass)
1.01
1.85
3.49
3.92
0.44
2.38
8.30
15.08
2.63
17.46
45.99
68.67
18.60
67.50
99.42
99.98
100.00
100.00
100.00
99.90
100.00
100.00
98.60
100.00
100.00
78.60
99.80
100.00

mfme - mass flow rate of pseudo-components in


the medium fraction of the extract stream;
mfpe - mass flow rate of pseudo-components in
the heavy fraction of the extract stream;
mflRAT - mass flow rate of pseudo-components in
the light fraction of the RAT;
mfmRAT - mass flow rate of pseudo-components in
the medium fraction of the RAT;
mfpRAT - mass flow rate of pseudo-components in
the heavy fraction of the RAT.
The efficiency of the separation is related to the
amount of the light fraction recovered from the
RAT. According to the results presented in Figures
2, 3 and 4, the higher the solvent/oil ratio the
higher the separation efficiency.
Regarding to the process pressure, a direct
dependence was observed since the relative
quantity of the light fraction recovered increases
with pressure as shown in Figures 5 and 6.

%Medium_Rec.
(% mass)
0.11
0.27
0.62
0.7
0.33
0.19
0.78
1.61
0.14
1.35
5.14
7.84
1.38
8.38
27.53
44.38
71.63
79.06
85.59
59.35
77.13
93.08
34.9
66.09
96.61
21.90
50.91
97.25

%Heavy_Rec.
(% mass)
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
Zero
3.45
4.94
5.98
2.95
5.06
9.73
2.10
4.56
13.10
1.80
3.92
15.33

Nevertheless it should also be noted that for the


highest value of the solvent/oil ratio used (15:1) at
an intermediate pressure (90 bar), total recovery of
the light fraction is achieved. Such a result
indicates that an optimal condition should be
defined based on both technical and economic
considerations.
According to the results presented in Figures 7,
8 and 9 discontinuities in the recovery results were
observed with respect to the influence of the
propane feed temperature gradient. At 130 bar
and 150 bar the relative amount of the recovered
fraction is decreased by increasing temperature,
whereas at 200 bar the increase of the
temperature leads to an increase in the quantity of
the recovered fraction.
This phenomenon can be explained as follows.
In an isobaric process the increase of temperature
results in the decrease of the solvent density

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

Figure 2. Influence of the solvent/oil ratio on the percentage of recovered material


(Pressure = 60 bar, Inlet Propane Temperature = 100 C).

Figure 3. Influence of the solvent/oil ratio on the percentage of recovered material


(Pressure = 75 bar, Inlet Propane Temperature = 100 C).

Figura 4. Influence of the solvent/oil ratio on the percentage of recovered material


(Pressure = 90 bar, Inlet Propane Temperature = 100 C)

yielding the reduction of its solvency power and


hence of the solute solubility in the solvent as well.
On the other hand, the increase in temperature
leads to an increase of the solute vapor pressure,

which yields an increase in its solubility. Thus, at


each point of pressure and temperature, it was
observed that one of these phenomena prevails.

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

Figura 5. Effect of pressure on the percentage of recovered material


(Propane/oil ratio = 15:1; Inlet propane temperature = 100 C).

Figura 6. Effect of pressure on the percentage of recovered material


(Inlet propane temperature = 100 C).

Figura 7. Influence of the inlet propane temperature


(Propane/oil ratio = 15:1; Pressure = 130 bar).

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

Figura 8. Influence of the inlet propane temperature


(Propane/oil ratio = 15:1; Pressure = 150 bar).

Figura 9. Influence of the inlet propane temperature


(Propane/oil ratio = 15:1; Pressure = 200 bar).

4. CONCLUSIONS

LIST OF ABBREVIATIONS

The propane in supercritical state has the ability


of separating the light fraction present in RAT with
good selectivity. The light fraction can be
completely separated from the heavy one.
Parameters like pressure and the solvent/oil ratio
showed a direct relation with the process
efficiency, but the solvent feed temperature
showed a reverse relation. An experimental study
in laboratory scale will be performed by our group
and the results will be compared with those
obtained in this work.

RAT atmospheric distillation residuum.


IBP initial boiling point.
FBP final boiling point.
Rec. recovered.
NBP normal boiling point.
Tc critical temperature.
Pc critical pressure.
MW molecular weight.
kPa kilo-Pascal.

ACKNOWLEDGMENTS
We thank ANP (PRH-13), CNPq and FAPERJ for
financial support.

BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 3 n. 1 | p. 001-009 | 2009 | ISSN 1982-0593

5. REFERENCES
Concha, V.; Quirino, F.; Koroishi, E.; Rivarola, F.;
Maciel, R.; Filho, R.M.; Medina, L.; Barros, R.
Simulao Computacional de Desasfaltao de
Resduo de Vcuo Realizada em Unidade Piloto.
In: RIO OIL & GAS 2008 EXPO and CONFERENCE,
Rio de Janeiro RJ, CD-ROM.
Hwang, J.; Milind, D. D.; Hanson, F. V. Dynamic
behavior of supercritical fluid extraction of a

crude oil and its vacuum residue. Fuel, v. 75


(13), p.1591-1595, 1996.
Mendes, M. F.; Ferreira, C. Z.; Pessoa, F. L. P.
Deasphaltation of Petroleum Using Supercritical
Propane. In: 2nd Mercosul Congress on Chemical
Engineering, Rio de Janeiro, 2005, v. 1, p. 1-10.
Zhao, S.; Xu, Z.; Xu, C.; Chung, K. H.; Wang, R.
Systematic characterization of petroleum
residua based on SFEF. Fuel, v. 84 (6), p.635645, 2005.