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Nemati Rouzbahani, A.1; Bazri, M.2
1, 2
Department of Petroleum Engineering, Amirkabir industrial university of technology
1
Iran, Bandar-Abbas, Jomhori Eslami St. Fakhar 4 Alley No.24
PO: 79136-43675
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*
Tel: +98 93 5248 1033 Email: ali_nematy@aut.ac.ir
ABSTRACT
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In this article asphaltene precipitation models are described and in a case study the precipitated asphaltene is
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represented by an improved solid model. The main purpose of this study is to model and anticipate the effects
of major parameters on formation of asphaltene precipitation and deposition at reservoir conditions, in order to
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provide a better understanding of the factors that may enhance asphaltene precipitation or deposition. The oil
and gas phases are modeled with Peng-Robinson equation of state. The effect of several factors such as solid
molar volume and injected solvent gas composition as well as thermodynamic condition variations (such as
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pressure and temperature) on the predictions made by this model will be investigated too. Eventually, with
regard to the experimental data that has been obtained from one of the oil wells located at the South Oil Zones
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of Iran’s oilfields, the accuracy of modeling and anticipating of asphaltene precipitation will be checked. All of
the related calculations have been done by Winprop software from CMG package.
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NOMENCLATURE
INTRODUCTION
𝑅 = Gas global constant (8.314 kPa.m3 /kmol.K)
𝑇 = Temperature (K)
(m3/kmol) A
𝑣𝑎 = Molar volume of asphaltene (m3/kmol)
vl = Non oil asphaltene–solvent mixture molar volume
oil and forming a single solid phase whereas asphaltene solubility parameter is reported as the
Precipitation occurs when asphaltene sticks to a solid asphaltene dissolution on the best solvent. This
surface like pipes or oil stone surfaces. Therefore the parameter also can be defined as a linear function of
problems which are made by asphaltene precipitation temperature as equation 2:
can be removed by proper anticipation and exact
controlling of asphaltene deposition. On the other δ̅ = a + bT (2)
words, asphaltene precipitation can be formed only
when asphaltene deposition occurs. Since that Where ‘a’ and ‘b’ are constants (Pan and
recognizing asphaltenes behavior, need complete and Firoozabadi, 1998) [3].
comprehensive information about crude oil
compositions, first of all we will pay attention to 2-2. Thermodynamic model of collision
expression generalities about crude oil compositions
(1987)
properties.
With assuming asphaltene as a suspended solid
2. REVIEWING THE THERMODYNAMIC
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particle within crude oil which is surrounded by
MODELS FOR ASPHALTENE resins; Mansoori presented a thermodynamic model.
PRECIPITATION
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In this model, according to experimental data about
initial point of asphaltene forming, a critical
chemical potential is estimated for resins and then
this critical chemical potential can be used for
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anticipation of the initial deposition point in other
conditions (Leontaritis and Mansoori, 1987) [4].
2-1. Dissolving model (1984)
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asphaltene deposition. Hirschberg et al presented a According to formation method of asphaltene
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model by using these definitions and assumptions [1]. sediment cells which known as micellars and
In this model, the related calculations to liquid and minimizing Gibbs energy, Firozabadi&Pen
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gas phases equilibrium and flash calculation has been presented thermodynamic model for asphaltene
done by SRK equation of state [2]. In this model it is deposition. This model is highly accurate and can
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assumed that asphaltene deposition (if formation has confirm the experimental data with high precision.
Nevertheless some efforts for improving this model
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done) has no effect on gas liquid equilibrium. By
defining the maximum volume of (𝜑𝑎 )max solved are in progress that has had no success so far
asphaltene in the oil in form of; this model can be (Leontaritis and Mansoori, 1987) [4].
presented as equation 1:
v v
A v 2
ln(φa )max = v [1 − v − RT (δ̅a − δ̅l ) ]
satisfactory for a part of these data (Escobedo and Tables 1, 2 and 3 are showing overall properties of
Mansoori, 1995) [5]. The other presented models for crude oil and thermodynamic conditions of reservoir
asphaltene deposition are generally complex and have during oil extraction.
too many configurable parameters that lead to a more
complicated model. An overall comparison between the
presented models will be discussed in next section of Table 1
this article. Reservoir oil properties
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Table 2
Heavy components properties
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asphaltene deposition. So that in model 1 the oil
phase is divided into two components which
Value
asphaltenes contain one of these components and the
other component includes non-asphaltenes. In models
2 and 3 an extra component for including the
micellars and along resins effect on simulating has
been applied. Although that deposition rate clearly
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Molecular weight of heavy components C12+
Molecular weight of C12+
330
0.9636
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has influence on oil and gas phase equilibrium, model 4-1. Specifying asphaltene component
3 neglects this effect, which this ignoring may lead to
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(note that heavy components like asphaltene have
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occurring some errors in oil-gas phase calculations
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vapor solution).
us to reach this goal. C12+ components can be
Briefly, if the purpose of simulation is applying
broken up to C21+ or C31+, in both case those
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thermodynamic model with a multi-components
modeling, using model 4 is recommended. This
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exclusive property makes model 4 (solid model) one
of the best possible choice for usage in related
components will mark as Ultra heavy or asphaltene
part of oil. Therefore, if we want to divide the
components up to C21+ by using the approved
methods, it is necessary to have an estimate about
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simulating programs like Winprop.
critical and physical conditions of divided
hydrocarbon groups such as IC4-NC4 ،IC5-C6، C7-
4. CASE STUDY C15، C16-C20 and C21+. The critical conditions
estimate for heavy components with having some
In this section according to experimental data that is data about special mass and molecular weights of
gained from one of the oil reservoirs in south of Iran, C21+ component, is calculating by Lee-Kesler
suggested thermodynamic models in Winprop equations [6] (Lambourn and Durrieu, 1983) [7].
software (from CMG software package) will be Physical conditions of mixture are estimated by Teo
investigated and the results will be compared with equations. Applying regression analysis on
experimental data. Eventually to anticipate the hydrocarbon heavy group’s data for achieving more
amount of thermodynamic equilibrium conditions accurate and valid results seems essential of course.
(such as temperature, pressure, oil molar fraction and This analysis applies by Winprop software itself. It
…) effects on increasing or decreasing of asphaltene should be mentioned that the oil and gas phase have
deposition, these results will be used too. been modeled by Peng-Robinson equation of state
[8]. Table 4 shows the crude oil sample data after
regression and dividing the heavy component up to
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C21+. Similarly these divisions are applicable up to of asphaltene will sediment for certain, we need to
C31+ group. Table 5 shows these results after divide heavy component (such as C21+ or C31+) into
regression analysis. To determine which components
Table 3
Crude oil composition in one of the southern Iranian oilfield
Oil reservoir
19 7.1 5.21 1.11 2.9 1.1 1.1 5.4 4.1 3.4 3.07 2.95 2.59 39.62 0.3 0.9
(%mol)
Table 4
Crude oil component’s properties (after lumping to C21+)
Components
CO2
N2
Pc(atm)
72.8
33.5
Tc(K)
304.2
126.2
ω
0.225
0.04
Mw
44.01
28.013
Z
0.2736
0.2905
0.094
D
Vc(l/mol)
I
0.0895
SG
0.818
0.809
Mol%
0.93
0.3
C1
C2
C3
45.4
48.2
41.9
190.6
305.4
369.8
0.008
0.098
0.152
16.043
30.07
44.097 S
0.2876
0.2789
f
0.2763
0.099
0.148
0.203
0.3
0.356
0.507
18.91
7.2
5.21
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IC4-NC4 36.679 422.805 0.208199 58.124 0.27182 0.2582 0.57827 4.04
IC5-C6 31.792 499.214 0.260697 81.1134 0.26541 0.3446 0.66932 7.66
28.26942 614.7636 0.466133 117.8796 0.25672 0.5485 0.80087 29.16
e
C7-C15
C16-C20 19.48304 735.1288 0.731515 198.5777 0.24694 0.8634 0.8743 15
C21+ 12.14509 875.1478
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1.106591
Table 5
347.3872 0.22982 1.4187 0.94981 11.59
c ω Mw Z Vc(l/mol) SG Mol%
CO2
N2
C1
C2
C3
72.8
33.5
45.4
48.2
41.9
A r
304.2
126.2
190.6
305.4
369.8
0.225
0.04
0.008
0.098
0.152
44.01
28.013
16.043
30.07
44.097
0.2736
0.2905
0.2876
0.2789
0.2763
0.094
0.0895
0.099
0.148
0.203
0.818
0.809
0.3
0.356
0.507
0.93
0.3
18.91
7.2
5.21
IC4 36 408.1 0.176 58.124 0.275 0.263 0.563 1.11
NC4 37.5 425.2 0.193 58.124 0.2728 0.255 0.584 2.93
IC5 33.4 460.4 0.227 72.151 0.2716 0.306 0.625 1.05
NC5 33.3 469.6 0.251 72.151 0.2685 0.304 0.631 1.14
FC6 32.46 507.5 0.27504 86 0.271261 0.344 0.69 5.44
C07-C15 25.90178 652.5765 0.451664 147.2724 0.265039 0.521218 0.827641 16.15
C16-C25 16.00509 809.8804 0.789045 279.2312 0.250012 0.927762 0.91395 2.572
C26-C30 12.07802 899.7084 1.014742 389.5274 0.239198 1.248509 0.959793 10.3
C31+ 6.808553 1075.737 1.423258 665.624 0.207435 2.197911 1.044126 6.758
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drawn. This diagram is comparable with experimental
data which is listed on table 6. Figure 1 shows this
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diagram versus table 6. It is clear that there is an
acceptable agreement between APP diagram and
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experimental data before the bubble pressure of oil,
while this agreement goes away after the bubble
pressure. Figure 2 shows App diagram for broken
components of oil up to C31+. After comparing the
diagram with experimental data, it can be realized
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that unlike the previous figure, in this case, there is a
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good agreement between APP
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diagram and
experimental data after the bubble pressure while this
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agreement is almost vanished for lower pressure than
bubble pressure.
Table 6
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Experimental data for asphaltene deposition
Figure 2
APP diagram after lumping to C31+
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4-3. Anticipation of molar volume of
Asphaltene
2.71 3.21 2.86 1.96 sediment component effect on solid
Deposition (Wt%)
precipitate
Pressure (Kpa) 6895 8963 13789 20684
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Figure 3
Effect of sediment component's molar volume
increment on APP diagram
Figure 5
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Temperature increment (380-434 K) effect on APP
diagram
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4-5. Anticipation of solvent gas injection
effect on solid precipitate
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point (380 to 434 K in here) temperature increment diagrams will be investigated. The major pure gases
has an inverse role and will lead to a growth in that their effects (in various volumes) on amount of
deposition (figure 5).
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parts toward extracted crude oil will be investigated.
These data are listed in table 7. It must be pointed
Figure 4 Table 7
Temperature increment (278-311 K) effect on APP Sample injected gas compositions
diagram
Components C1 C2 C3 iC4 nC4 iC5
Injected gas
50.6 18.45 12.72 2.17 6.26 1.9
(%mol)
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Figure 6
Effect of injected gas (in table 7) on APP diagram
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4-5-1. CO2 injection
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Effect of various amounts of N2 injection on APP
on figure 7. A very small increase in deposition
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increment before the bubble pressure is detectable
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while on pressures above the bubble point increase in
diagram
maximum amount reduction will take place and it
begins to stretch to the right side of diagram (higher
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deposition during injection even in low amounts of pressures) on figure 8.
CO2 is relatively high.
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of N2 gas leads to shrinkage on APP diagram at corresponding states," AIChE journal, vol. 21, pp.
pressures below the bubble point and will bring 510-527.
deposition reduction in these areas. APP diagrams
can be used for estimation of asphaltene deposition
7. G. A. Lambourn and M. Durrieu, 1983, "Fouling
details like when, how much and where (such as
inside of reservoir or around of reservoir edges in crude oil preheat trains," ICHMT DIGITAL
and…) it will happen inside oil wells. LIBRARY ONLINE, vol. 19.
To obtain high accuracy APP diagrams, at least three
points of APP graph should be studied and compared 8. D. Y. Peng and D. B. Robinson, 1976, "A new
by experimental data. These data are asphaltene two-constant equation of state," Industrial &
initial pressure point, weight percentage and a Engineering Chemistry Fundamentals, vol. 15, pp.
pressure between initial point and bubble point and 59-64.
eventually a weight percentage of the component that
will deposit and a pressure below bubble point.
KEYWORDS
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processes, storage, gas injection
REFERENCES
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3. H. Pan and A. Firoozabadi, 1998, "A
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thermodynamic micellization model for asphaltene
precipitation: Part I: Micellar size and growth," Old
Production & Facilities, vol. 13, pp. 118-127.
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