Al Qasim2017
Al Qasim2017
Al Qasim2017
OMAE2017
June 25-30, 2017, Trondheim, Norway
OMAE2017-62366
S As
CII , (1)
R Ar
Where S is the percentage of saturates, AS is the percentage of
asphaltenes, R is the percentage of resins, and Ar is the
FIGURE 1: GENERAL STRUCTURE MODEL OF percentage of aromatics in the oil. If the CII is greater than one,
ASPHALTENE [15] the amount of unfavorable components exceeds the amount of
favorable components in the system. Consequently, the
The physical and chemical properties of asphaltenes are asphaltenes are likely to be unstable. However, the SARA
different from those of neutral resins. The reported molecular analysis has several disadvantages that become apparent when it
weight of asphaltene varies considerably depending on the is used for purposes beyond its original intent. For example,
method and conditions of measurement. A major concern in dead oil lacks the gaseous components that are dissolved in live
reporting asphaltene molecular weight is the oils, and so the results are not representative of how the oil
association/aggregation of asphaltenes which can exist at the would act under reservoir conditions. In addition, laboratory
conditions of the method of measurement. Vapor pressure methods may vary greatly, and the solubility of asphaltenes
WAX
Wax, sometimes called ″Paraffin,″is defined as saturated
hydrocarbons with between 18 and 34 carbon atoms in a chain
of complex mixtures of high molecular weight alkanes ranging
between 360 and 500. Waxes are organic deposits caused by
changing wellbore conditions that upset the chemical
equilibrium so that various materials in the crude oil precipitate
out of the solution. It is of a crystalline structure and can be soft
with a high proportion of trapped oil such as Vaseline, or can
form hard deposits such as candle wax. Paraffins usually exist
in waxy crudes and create production problems and formation
damage. To eliminate these problems, the deposited paraffin
must be removed. Crude wax or paraffin deposits consist of tiny
crystals that tend to agglomerate and form granular wax
FIGURE 8: DESIGNATION AND CLASSIFICATION OF particles about the size of table salt grains. Deposited paraffin
NATURAL ASPHALT ACCORDING TO ABRAHAM [1] may also contain crude oil, sand, silt, corrosion products, scale,
and often water [15]. ASTM or API methods can be used for
Asphalt is classified into three fractions: conventional wax determination in crude oils. Both methods
- Neutral resins: insoluble in Alkalies and acids and involve cooling the oil to a specific temperature, precipitating
completely miscible with crude oil. the waxes, collecting, and weighing them. This normally results
- Asphaltenes: insoluble in light gasoline and petroleum in compounds containing an average of 22 or more carbon
ether. atoms being precipitated.
- Carboids (free carbons): found at high temperatures, Often iron sulfide and heavy wax are misidentified as
completely insoluble in benzene. asphaltenes, where asphaltenes are often found mixed with wax
or oil. One way to differentiate between them is by a melting
Note that both asphaltene and neutral resins are completely
test and a weak acid solubility test. Asphaltene solubility can be
soluble in benzene, chloroform, and carbon disulfide.
determined by conducting a series of titration experiments on
tank oil [27]. To understand the behavior of waxy crude, we
need to know the cloud point, pour point, wax content, and
RESINS
yield stress of the particular crude. When the temperature drops
On the other hand, resins are polycyclic molecules that
too low for wax to remain dissolved in the crude, it precipitates
exist in the oil in true solution and tend to adsorb easily in
out of the solution and deposits itself on pipeline walls, or
common adsorbents (i.e. clay and silica gel) and have a
inside facilities. The temperature at which the wax crystals can
molecular weight ranging between 250 to 1000 [14]. Other
first be detected is called the cloud point. The cloud point is
references reported that the molecular weights of resins range
also sometimes referred to as the wax appearance temperature
from 1100 to 2800 [27]. The resin fractions constitute the main
(WAT). When the operating temperature in a pipeline system
non-hydrocarbon part of residues with high contents of
drops below the cloud point, wax crystals will begin to form
heteroatoms [32]. Under normal conditions, asphaltenes are
and deposit. As the temperature drops further, more wax will
held in suspension by resins. Changes in the crude composition
come out of the solution until the crude in the pipeline
or pressure and temperature can alter their association with the
effectively gels up. The temperature at which this occurs is the
resins [3]. Resins play an important role in stabilizing and
pour point. When the crude in the pipeline gels up, a certain
peptizing of asphaltene molecules and help reducing the
force, yield stress, is required to shear the waxy crude and
flocculation and precipitation of the molecules out of the
restart the flow. Crude is generally considered to have a high
solution
wax content when there is more than about 10% wax, and a low
wax content when there is less than about 4%. Some examples
of low wax content crude are shown in Table 2.
Although the wax content of all these crude is 4%, there are
considerable differences in the pour point. As shown in Table 2,
we notice that the Malaysian Labuan crude would gel up at 90
o
C, whereas the Saudi Arabian Light crude would gel only if the
temperature drops below -36 oC. Table 3 summarizes the
behavior of waxy crude that have relatively high pour points. FIGURE 9: SEVERITY OF WAX DEPOSITION
(HTTP://OMRPUBLIC.IEA.ORG)
TABLE 3: HIGH WAX CONTENT CRUDE OILS Designers and operators of the pipeline need to thoroughly
ACCORDING TO IPIMS [15] evaluate the above factors when waxy crude is found in their
system. When deciding how to manage the production and
transportation of waxy crude, it is important to consider both
capital and operating cost over the whole life cycle of the field
for different options.
A development plan for managing a waxy crude field will be
different and probably more costly than a non-waxy crude field.
Hence, early prediction in terms of compositional simulators,
especially for wellbore vicinity is very important. There are
several models being developed that take into account wax
deposition in the wellbore. Waxy crude production can be
handled using the following options [15]:
- Using wax inhibitors, growth modifier, or dispersants
Wax formation in crude oil flowing in pipelines (Figure 9) can - Using a pour point reducer
be predicted by sampling and analyzing the crude based on the - Using dilution, in order to minimize wax content
following four properties: - Using sophisticated pipeline insulation techniques
- Cloud point: measured using the cold finger technique or - Using heating systems or steam tracing for the pipeline
cross polar microscopy
- Pour point: measured using differential scanning ASPHALTENE PROPERTIES
calorimetry (DSC) Production and processing operations of crude oil require
- Wax content: measured using solid phase analysis a thorough understanding of phase behavior. Pressure-volume-
- Carbon distribution: measured using high temperature gas temperature (PVT) properties play a crucial role throughout the
chromatography (HTGC) life of the reservoir. Reservoir fluid properties provide the main
input for any simulator used to predict asphaltene precipitation
It is important to use a representative sample of the crude for or describing the fluid properties as a function of pressure,
testing and to follow the correct experimental procedures in temperature, and composition. Consequently, accurate PVT
order to achieve the most accurate results. These results may be properties are required to get appropriate and representative
used as the base input parameters for a simulation model. Waxy simulation results. As mentioned earlier, the main factors
crude with high cloud points and pour points will need a special affecting asphaltene precipitation are pressure, temperature, and
design to take into account the operational challenges. composition. However, a good understanding of properties’
behavior is needed. These properties are density, solubility,
viscosity and molecular weight, which can be directly affected
by any changes in pressure, temperature, or composition. For
that purpose those four factors will be highlighted in detail in
the following sections.
1 1
1 1
x , (3)
M T A T A
1
A , (4)
SI
SOLUBILITY
Several attempts were made to model asphaltene solubility
FIGURE 12: SOLUBILITY PARAMETER OF
using experimental measurements of density which is then
ASPHALTENE AS A FUNCTION OF TEMPERATURE
correlated with molar mass. Asphaltene solubility in crude oil
FOR P = 100 BAR AS INDICATED BY YEN AND
has been the subject of several theoretical investigations.
CHILINGARIAN [32]
Hirschberg et al. [13] combined Hildebrand regular solution
theory with a Flory-Huggins theory to express asphaltene
solubility in crude oil as a function of molar volume and the The effect of pressure on the solubility parameter of
solubility parameter. Since asphaltenes are mixtures of asphaltene at T = 300 K is shown in Figure 13. The solid
molecules, the solubility can be determined using flash line represents a linear regression line through the data
calculation. With the large molecules size of asphaltenes, it is points. It indicates that the solubility parameter of
necessary to use the Flory-Huggins theory. The solubility asphaltene is not affected very much with the change in
parameter is defined as follows: pressure. However, as discussed earlier, Leontaritis and
Mansoori [19] suggested that at constant temperature, the
solubility parameter’s general trend is proportional to the
ΔU vap 1/2
il ( ) , (7) pressure depletion until the pressure reaches the bubble
vil point. Below the bubble point pressure, the solubility is
inversely proportional to the pressure trend as depicted in
Figure 14. Generally, pressure holds dissolved gases and
- Molecular diffusion
Molecular diffusion basically depends on monitoring the
FIGURE 13: SOLUBILITY PARAMETER OF diffusion of individual molecules using special measuring
ASPHALTENE AS A FUNCTION OF TEMPERATURE techniques (i.e., fluorescence techniques). The slower the
FOR T = 300 K AS INDICATED BY YEN AND diffusion, the larger the molecule size and vice versa. This type
CHILINGARIAN [32] of measurement is very helpful, because the estimated molecule
size is used to infer the molecule weight by a comparison with
model compounds [26]. Table 5 shows a summary of mass
spectrometry measurements with a short description for each
technique.
MOLECULAR WEIGHT
Asphaltenes’ molecular weight is difficult to measure since
it depends on three factors [30]:
- Nature and amount of solvent (can be controlled by using
specific types of solvents that prevent aggregation)
- Temperature
- Contact time
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