SPE 106361

Laboratory Technique for Screening Asphaltene Inhibitors for Kuwaiti

Reservoirs
G.P. Oskui, M. Salman, E.F. Gholoum, A. Rashed, Petroleum Production Dept. Petroleum Research and
Studies Center (PRSC) of Kuwait Institute for Scientific Research (KISR), and
B.S. Al Matar, M. Al- Bahar, K. Kahali, Kuwait Oil Company (KOC), Kuwait

This paper was prepared for presentation at the 2006 SPE Technical Symposium Mansoori (1989) Kokal ( 1995), Jamaluddin, Nighswander,
of Saudi Arabia Section held in Dhahran, Saudi Arabia, 21-23 May 2006. Joshi (2001), , Mansoori, Jiang Kawanka ( 1996), Karan,
This paper was selected for presentation by the Technical Symposium Program
Committee following review of information contained in full manuscript submitted Hammami, Flannery, Satnkiewics (2003) Dandekar,
by the author(s). Contents of the paper, as presented, have not been reviewed by Andersen, Simon, Stenby(2004), Novosad and Costain
the Society of Petroleum Engineers and are subject to correction by the author(s).
The material, as presented, does not necessarily reflect any position of the Society (1990), Fourest (1995).
of Petroleum Engineers, its officers, or members.

Copyright 2006 Society of Petroleum Engineers

The nature and behavior of asphaltenes in crude oils are
complicated. Asphaltenes are complex organic materials that
Keywords: Asphaltene, Inhibitor, Kuwait, Marrat reservoir are thought to be arranged in stacked, multi-ring structures.
They consist primarily of carbon, hydrogen, and a minor
ABSTRACT proportion of heteroelements such as oxygen, sulfur and
Currently Kuwait Oil Company (KOC) is facing asphaltene nitrogen (Pfeiffer,Sual, 1940). Asphaltenes are defined as
deposition problems in the wellbore of some of the Marrat the polar, polyaromatic and high molecular weight
Jurassic reservoirs in West Kuwait (WK) and South East hydrocarbon fraction of crude oil that are generally
Kuwait (SEK). This has caused a reduction in production characterized as insoluble in paraffins such as n-Heptane or
and shutting of some of the wells and a severe detrimental in n-pentane but soluble in aromatics. They are believed to
effect on the economics of oil recovery. This paper describes exist either dissolved in oil or as a finely dispersed colloidal
the results of the laboratory studies on the characterization suspension in oil stabilized by resins adsorbed on their
and phase behavior studies of three different crude oil surface (Speight, 1980). Resins and maltenes (structures that
samples from Marrat reservoirs, and the screening of a are comparable with asphaltenes but with much lower
number of commercially available inhibitors, which were molecular weight) are responsible for keeping the asphaltene
proposed as a remedy and prevention of asphaltene particles in dispersion. The asphaltene molecules are
deposition for this reservoir. surrounded by the polar heads of the resins and maltenes,
while the non-polar alkyl ends interact with the oil phase.
Initially the samples were characterized for their chemical Therefore, crude samples with a high ratio of resins to
and physical properties. Then the phase diagram (P-T) and asphaltenes are less subject to asphaltene deposition than
Asphaltene Deposition Envelope (ADE) for bottom-hole crudes with large amounts of non-polar saturates, which are
samples were established by measuring the saturation and more prone to exhibit asphaltene-precipitation problems
Asphaltene Onset Pressures (AOP) at different temperatures (Bouts, Wiersma and Muljs, 1995). At normal reservoir
from reservoir to surface conditions by using the laser conditions, the asphaltenes, resins, maltenes, and oil phase
technique Solid Detection System (SDS). Asphaltene Flock are in thermodynamic equilibrium. This equilibrium can be
Point (AFP) analyses were then performed by the titration disturbed by a number of factors: pressure reductions,
technique using Stock Tank Oil (STO) samples and n- change in temperature, change in crude oil chemical
Heptane as the asphaltene precipitant. The effects of composition, addition of miscible gases and liquids to the oil
different concentrations of each inhibitor on different as applied in various EOR techniques, and during acid
reservoir fluids were investigated in the laboratory, using the simulation, Anderson, and Stenby (1996), Gawrys
AFP technique. The most efficient inhibitor with the Spiecher, Matthew and Kilatrick ( 2003), Hammami et.
optimized concentrations for each reservoir fluid was Al(1998 ), Hirschberg et. al. ( 1984).
established for economical evaluation purposes. Based on
these studies, a selected inhibitor is now being used for a The upset of the colloidal system may result in irreversible
pilot field study. flocculation of asphaltenes. The precipitation of flocculated
asphaltenes can severely reduce the permeability of the
INTRODUCTION reservoir, cause formation damage and can also plug-up the
wellbore and tubing. This phenomenon is largely ascribed to
Asphaltene precipitation and deposition from oil reservoir the different extents of compressibility of the light ends and
fluids during production is a serious problem as it can cause the heavy components (resins and asphaltenes) of the under-
plugging of reservoir formation, wellbore, tubing and saturated crude. In fact, the relative volume fraction of the
production facilities. Asphaltene precipitation during light ends within the liquid phase increases as the pressure of
primary depletion of highly under saturated reservoirs due to the under-saturated reservoir fluid approaches its bubble
the changes in pressure, temperature and compositions or point. Similarly, adding a low molar mass hydrocarbon
during application of any of the improved oil recovery (IOR) (precipitant) to a crude oil causes asphaltene depeptization.
processes was described by many authors Leontaraitis,

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SPE-KSA 2006 G.P. Oskui, M Salman, E.F. Gholoum, A Rashed, B. Al Matar, M Al- Bahar, K Kahali

Bouts et al. (1995). Alkafeef (2001), Asomaning (2003), development plan for reservoir pressure maintenance with
Carnahan et.al. (1999), Gharfeh, Asomaning and Blumer water injection.
(2004), Thomas, Bennion, Hunter (1992), Wiehe and Torris
(2003). Recently, modern mercury-free PVT laboratories with
asphaltene and phase behavior measurement facilities and
Asphaltene Problems in Kuwait analytical capabilities have been established in Petroleum
Research and Studies Center (PRSC) in Kuwait Institute for
In Kuwait the problem of asphaltene precipitation has been Science Research (KISR). Some Asphaltene phase behavior
experienced and studied in North, West, East and South properties and fluid characterization such as density,
fields in KOC by De Bore, Leerkooyer and Bergan (1992), molecular weight, metal analysis, elemental analysis, GC
Kabir, Jamaluddin (1999), Alkafeef (2001),Gholoum, Oskui, compositional analysis, and SARA analysis asphaltene
Salman (2003, 2004). The major problems are in the properties studies for Kuwaiti oil sample were reported by
Jurassic production wells located in producing areas such as Gholoum, Oskui, Salman (2003, 2004).
West Kuwait (WK) and South East Kuwait (SEK) -Marrat.-
Figure 1. In this paper, the results of fluid characterization and phase
behavior measurements for asphaltene deposition envelope
(ADE) are presented. The method developed for screening
47E 48E commercially available inhibitors to prevent asphaltene
30N N RATQA / ZUBAIR
30N precipitation in the laboratory before making a strategic plan
RAUDHATAIN for a field trial is described.
SABIRIYAH

IRAQ BAHRAH
INSTRUMENTATION
Arabian Gulf
KUWAIT MEDINA

KHASHMAN
The Solid Detection System (SDS) is used to measure the
DHARIF PVT properties and Asphaltene onset point (AOP). The
GREATER BURGAN
ABDULIYAH system has been described (Gholoum, Oskui, Salman 2003,
MINAGISH
29N 29N Hammami et al., 1998-2000).

A schematic of the PVT/SDS system is illustrated in Figure

SAUDI ARABIA UMM GUDAIR
Neutral Zone 2. It consists of a mercury-free, fully visual, PVT cell
equipped with automated pump, sample/solvent injection
OIL FIELD WAFRA
cylinder and Back Pressure Regulator (BPR). Fiber optics
0 10 20
mi.
light transmission probes (source and detector) mounted
47E 48E
across the PVT cell to measure the onset of organic solids
precipitation (due to temperature, pressure, and
compositional changes) concurrently with fluid volumetric
Fig 1: Map of Kuwait and locations of Reservoirs data (PVT) during AOP and titration tests.

In the WK-Marrat reservoir, 50% of the wells have a

historical record of asphaltene clean-outs. These wells
contribute around 7% of the total oil production from WK. PRESS LASER
URE
The reservoir pressure for this reservoir is around 9500 psig GAUG
which is considerably above the AOP (estimated between
PVT TEMPER
4000 psig). Therefore, there is no likelihood of asphaltenes Cell ATURE
deposition in the reservoir in the near future. However,
SOLV

during production, as the pressure of the produced fluid

ENT

inside the tubing goes below the AOP, asphaltenes start to

flocculate (Kabir et. at. 1999). The asphaltenes gradually
V
SAM

deposit in the tubing, reducing its diameter and in the E

process, cause production rates to drop and eventually the N
well completely ceases to flow. Once this has occurred, the
tubing in the well must be cleaned out to restore the well to
production. The cleaning process takes around 1 month and
during this period the wells are completely shut off
(production loss of around 50,000 Bbl/day).

In South and East Kuwait, in the Marrat Reservoir, the initial

reservoir pressure is around 9600 psig and the present
reservoir pressure is around 8400 psig and AOP ranges from Fig. 2: Schematic diagram for SDS/PVT system
5700 psig to 6700 psig. Further reduction in reservoir
pressure below the AOP could cause asphaltene deposition EXPERIMENTAL PROCEDURE
in the reservoir itself. For this reason, all the wells in the Three oil samples from different WK and SEK reservoirs
Marrat reservoir have been closed since 1998 to avoid a were selected from different wells using the single-phase
further drop in the reservoir pressure, which had already down-hole sampler. These samples were used for complete
dropped near to AOP. Recently, KOC has decided to PVT and phase behavior characterization and measurements
produce the wells but only after a comprehensive of asphaltene onset pressures (AOP) at four different
21-23 May 2006, Dhahran
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SPE-KSA 2006 G.P. Oskui, M Salman, B. S Al Matar*, E.F. Gholoum, A Rashed

temperatures from down-hole conditions to surface analysis and the molecular weight, in order to estimate the
conditions. The data will be used for simulation studies to degree of carbonization.
develop the complete phase behavior and asphaltene
deposition envelope (ADE). Asphaltene Onset Pressure (AOP) Experiment Procedure

Surface samples were also collected from each well for Identification of asphaltene precipitation conditions for a
chemical analysis and characterization studies and for given crude is the commencing step in the quest towards an
Asphaltene Flock Point (AFP) analysis to screen different engineering solution to the depositional problem. Asphaltene
inhibitors with different concentrations. Onset Pressure (AOP), the pressure at which asphaltene
starts flocculating at a particular temperature, is an important
The overall test procedures used for each were as follows: parameter for understanding the asphaltene deposition
characteristics of crude. Various laboratory techniques are
1. Complete compositional and PVT analysis with AOP available for determining AOP. These methods are basically
measurements at different temperatures. isothermal depressurization processes under controlled
conditions for live oil. It is important that single-phase
2. Characterization of the crude oil samples for elemental
Downhole samples be used for any PVT and asphaltene
SARA analysis, density and molecular weight.
studies and the samples should be restored to reservoir
3. Asphaltene Flock Point (AFP) analysis by titration for conditions in the lab first.
blank crude oil (untreated).

4. AFP analysis by titration for crude samples with The reservoir fluid was tested for its propensity to precipitate
different inhibitors of known concentrations. asphaltenes during isothermal pressure depletion at
reservoir, wellhead, and wellbore temperatures followed by
5. Selection of the most efficient inhibitor with the the standard Constant Composition Expansion (CCE)
optimized concentrations for each well. experiment to measure the bubble point pressure. Asphaltene
Onset Pressure (AOP) and bubble point pressure (Psat) were
Samples Used measured using SDS (Solid Detection System) by laser
spectroscopy. A pressure depletion test was performed
Three Single-Phase Bottom-hole (BHS) and Stock-Tank oil isothermally at reservoir temperature from 9500 psig by
(STO) samples from SEK, WK reservoirs (with code names 50psig (pressure step) and mixed vigorously continuously
MG-K1, MG-K2, AB-K3) were used in this study. BHS till equilibrium conditions were achieved. At each
were used for PVT, AOP studies to characterize ADE. STO equilibrium condition, the final pressure, temperature, laser
samples were used for oil characterization and performing transmission, volume and time were recorded automatically
asphaltene flocculation point (AFP) studies with three through a data acquisition system. This process is repeated
inhibitors (namely A, B, C) for screening studies. continuously till the final set pressure (500psig) was
reached.
Sample Restoration
After completion of the above test the sample in the cell was
The Bottom Hole Samples (BHS) are restored at reservoir re-pressurized to 9500psig and mixed vigorously for a 12hrs
temperature and pressure and agitated vigorously for some period and the AOP test was repeated as per above
time. Our experience showed that restoration time should be technique. This test was repeated again to check for the
at least ten days, before starting any asphaltene studies reversibility of the asphaltene onset processes after
(Gholoum, Oskui, Salman 2003). asphaltene flocculation in the PVT cell. If the power of
transmitted light (PTL) increases and returns to its original
base line value, this is a possible indicator that the
Crude Oil Characterization precipitation may be reversible

SARA (Saturated Aromatic and Resin and Asphaltene)

analysis was performed using two different techniques. These Inhibitor Screening Technique
techniques were described in our previous paper (Gholoum, The Inhibitor screening tests were performed by
Oskui, Salman 2003). SARA analysis was performed on the determination of the onset of asphaltene flocculation point
dead oil sample. For this purpose the sample was distilled to (AFP) by adding n-Heptane and using solid Detection
260°F and the light fraction (< 260° F) was analyzed using System (SDS) with Near Infra Red (NIR).
super critical chromatography (ASTM 5186 91) to obtain the
distribution of saturates and aromatics. The heavy fraction (> A sample is heated to a fixed temperature first and allowed
260° F) was used for SARA analysis. to come to equilibrium. An asphaltene precipitant (n
Heptane ) is then titrated into the solution at a constant rate
and the power of Light Transmittance (PLT) of the NIR-
Laser is monitored. In the initial stage of titration, due to the
decrease in density of the solution resulting from addition of
Elemental Analysis for Crude Oils and Inhibitors the precipitant, the transmittance power of the laser
increases. When the asphaltene begins to flocculate, the laser
transmittance will decrease, resulting in an inflection in a
The elemental analysis was performed using LECO plot of transmittance, PLT vs. volume added of precipitant
Elemental Analyzer, (D5291 method). For this purpose a (n Heptane). The point of inflection, expressed as an index
known amount of Asphaltene was used to measure the of the Asphaltene flocculation Point (AFP), corresponds to
amounts of Sulphur, Nitrogen, Carbon and Hydrogen. The the point of asphaltene precipitation and provides a relative
number of atoms of each element and the ratio of carbon to measure of how stable the asphaltenes in oil are. The higher
hydrogen atom (C/H) is determined from the elemental the AFP indexes, the more stable the asphaltenes are.

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SPE-KSA 2006 G.P. Oskui, M Salman, E.F. Gholoum, A Rashed, B. Al Matar, M Al- Bahar, K Kahali

PRESENTATION AND DISCUSSION OF THE Table 2: Reservoir Fluid Analysis for Samples MG-K1
EXPERIMENTAL RESULTS and MG-K2

Oil Characterization test Well No MG-K1 MG-K2

The Asphaltene content for the three crude samples were Compositions Mole % Mass % Mole% Mass%
measured using the standard method IP143. Densities of the
liquid mixtures were measured with a digital densio-meter Nitrogen 0.56 0.18 0.01 0
model DMA 48 calibrated with deionized water and air.
Molecular weights were also measured by API standard Carbon Dioxide 0.81 0.41 0.99 0.52
method (D2503) 15-16. The results are shown in Table 1. Hydrogen Sulfide 0 0 0 0

Table 1: Physical properties measured for STO samples. Methane 41.87 7.82 43.09 8.24

Test Required MG-K1 MG-K2 AB-K3 Ethane 10.7 3.74 10.72 3.84

Propane 7.3 3.74 7.08 3.72

Asphaltene
1.23 0.85 2.11
Content (wt %) I - Butane 0.86 0.58 0.88 0.61

Density N - Butane 3.4 2.3 3.22 2.23

0.8303 0.8227 0.8475
(g/cc) @ 25 © I - Pentane 1.13 0.95 1.05 0.91

N - Pentane 1.96 1.64 1.72 1.48

Molecular Wt
212 221 230 pseudo C6H14 2.46 2.41 2.18 2.19
( g/mole )
pseudo C7H16 2.54 2.84 2.33 2.67

pseudo C8H18 2.96 3.68 3.07 3.91

pseudo C9H20 2.74 3.86 2.86 4.12

Compositional Analysis pseudo C10H22 2.42 3.77 2.5 3.99

Compositional analyses, performed by gas chromatography, pseudo C11H24 2.04 3.49 2.09 3.66
for samples MG-K1 and MG-K2 are shown in Table 2.
pseudo C12H26 1.69 3.16 1.72 3.31
SARA Analysis pseudo C13H28 1.46 2.98 1.49 3.11

Table 3 shows the normalized weight percentage of the total pseudo C14H30 1.22 2.69 1.24 2.8
Saturates, Aromatics, Resins & Asphaltene based on the original
crude weight for all samples. From the SARA data, the pseudo C15H32 1.12 2.69 1.14 2.8
asphaltene/resin ratio and the colloidal instability Index (CII) of pseudo C16H34 0.95 2.46 0.97 2.57
these samples were calculated. CII is the ratio of the sum of
saturates and asphaltene fractions to the sum of the aromatic and pseudo C17H36 0.8 2.22 0.82 2.31
resin fractions, where:
pseudo C18H38 0.75 2.18 0.75 2.23
CII= (Saturate% +Asphaltene %) / (Aromatic %+ Resin %) pseudo C19H40 0.71 2.18 0.72 2.26
CII < 0.7 oils are stable pseudo C20H42 0.62 1.98 0.62 2.04

CII 0.7-0.9 oils are moderately stable pseudo C21H44 0.56 1.89 0.57 1.97

CII > 0.9 oils are very unstable. pseudo C22H46 0.49 1.71 0.5 1.8

pseudo C23H48 0.45 1.63 0.44 1.65

As seen in Table 3 all the oils are unstable and have
asphaltene precipitation problems. pseudo C24H50 0.42 1.59 0.41 1.59

Elemental Analysis for Crude Oils and Inhibitors pseudo C25H52 0.35 1.39 0.36 1.44

pseudo C26H54 0.34 1.39 0.34 1.4

The elemental analysis results for the STO samples are
shown in Table 4. The elemental analyses with this method pseudo C27H56 0.32 1.35 0.33 1.42
are generally accurate to ± 2%.
pseudo C28H58 0.29 1.26 0.31 1.36

pseudo C29H60 0.29 1.28 0.29 1.34

C30+ 3.43 22.57 3.19 20.52

Total 100 100 100 100

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SPE-KSA 2006 G.P. Oskui, M Salman, B. S Al Matar*, E.F. Gholoum, A Rashed

Table 3: SARA Analysis results for crude oil samples

Power(uW) AOP@240F=6200 psig, Re Pressurization
Fraction Name MG-K1 MG-K2 AB-K3
7.00E-05

6.00E-05
Saturates 63.88 63.79 60.49
5.00E-05
Aromatics 32.23 31.67 33.84
4.00E-05
AOP @ 204F=6210psig- de-pressurization
Resins 2.50 2.61 3.23 3.00E-05

2.00E-05
Asphaltene 1.23 0.89 2.11
1.00E-05
Pressure(psig)
Resins/Asph. 2.0 2.93 1.53 0.00E+00
2000 3000 4000 5000 6000 7000 8000 9000 10000
CII 1.87 1.89 1.69
Fig 3: Asphaltene reversibility test reservoir
Temperature, 240F
Power(W)

Table 4: Elemental Analysis for crude oil Samples and 0.00007 AOP @ 240F=6200psig

Inhibitors
0.00006

Element C H N S H/C
0.00005
AOP @ 237 F= 6300
MG-K1 wt % 86 12 0.06 0.87 1.77 0.00004 i

0.00003
MG-K2 Wt% 86 12 0.04 0.82 1.77
0.00002
AB-K3 Wt% 85 11 0.08 1.20 1.68
0.00001
Inhibitor A Wt% 86 9. 0.63 0.17 1.37
Pressure(psig)
0
Inhibitor B Wt% 87 10 0.01 0.08 1.46 2000 3000 4000 5000 6000 7000 8000 9000 10000

Inhibitor C Wt% 86 10 0.02 0.1 1.48

Fig. 4: AOP tests for a typical oil at different
temperatures.

Asphaltene on Set Pressure (AOP) data Figure 4 shows the AOP tests for a sample at different
temperatures.
Figure 3 shows typical AOP tests for a BHS at reservoir Table 5 summarizes the measured saturation pressure, AOP
temperature of 240°F. As shown in this figure, the PTL of the MG-K1, MGK2 and AB-K3 samples at different
signal increases linearly as the pressure decreases (from temperatures.
8000 to 2500 psig). This is due to the decrease in the fluid
density with decreasing pressure within this range. The point Table 5: Saturation pressures and AOP data measured
of departure of the PTL curve from the linear behavior (the for each samples
maximum PTL value) is interpreted as the onset of
asphaltene precipitation (6200psig). The observed break in Reservoir Fluid Temp. Onset Pressure Sat. Pressure
the curve is the net effect of two competing processes.

The effect of fluid density decreases with decreasing Well No °F AOP, psig Psat , psig
pressure causing an increase in PTL, and the simultaneous MG- K1 240 6200 3100
increase in size and amount of precipitated asphaltenes tends 237 6300 3073
to decrease the PTL reading.
198 7500 2921
Figure 3 also shows an example of the re-pressurization test 159 9300 2767
for a reservoir fluid at reservoir temperature 240°F. As MG-K2 235 5800 3100
shown in this figure, the PTL signal is returned to the initial
baseline value registered before the de-pressurization test. 231 5890 3158
The measured AOP was found to be 6210psig, indicating 194 7000 2913
that the asphaltene onset process for this sample at this 159 8300 2830
condition is reversible and repeatable (within ±10psig).
156 8450 2797
AB-K3 252 3000 1741
207 3900 1615
180 4650 1568
159 5500 1500

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SPE-KSA 2006 G.P. Oskui, M Salman, E.F. Gholoum, A Rashed, B. Al Matar, M Al- Bahar, K Kahali

Figure 5 illustrates the P-T phase envelope and asphaltene

deposition envelope (ADE) for MG-K1, MG-K2 samples . Table 6: A typical Example of output data for Titration test
As shown in this figure, as the temperature decreases, the Time Tem Vol. Pressure Power Vol norm
AOP increases, and the bubble point increases. p

(min) (°F) (cc) (psi) (W) ratio Power

(u)

0 72.8 0 2988 7.99E-10 0.00E+00 1.00E+00

10000 0.51 72.7 0.5 3038 9.68E-10 2.38E-02 1.21E+00

9000
8000
1.01 72.6 1 3086 1.88E-09 4.76E-02 2.36E+00
Pre s s ure ,ps ia

7000
MG -K2, AOP
6000
5000 MG-K2, Psat 1.51 72.6 1.5 3123 4.62E-09 7.14E-02 5.79E+00
4000 MG-K1, AOP
3000 MGK1,Psat 2.01 72.7 2 3150 8.48E-09 9.52E-02 1.06E+01
2000
1000
0 2.51 72.7 2.5 3165 1.12E-08 1.19E-01 1.41E+01
150 170 190 210 230 250
Temperature,Deg, F 3.01 72.8 3 3170 1.28E-08 1.43E-01 1.60E+01

3.51 72.5 3.5 3191 1.41E-08 1.67E-01 1.77E+01

Fig 5: Saturation phase envelope and Asphaltene Phase 4.01 72.8 4 3189 1.60E-08 1.90E-01 2.00E+01
Deposition Envelope (ADE) for Magwa (SEK) samples
5.51 72.8 5.5 3186 2.18E-08 2.62E-01 2.72E+01

6000 …. … … … … … …
5000
Pressure,psia

4000

3000 50

1.12
2000 45
Blank-run1

40
Blank-run 2
1000
35

0 30
Norm power

150 170 190 210 230 250 25

AB-K3 AOP 20

Temperature,Deg, F AB-K3 -Psat 15

10

Fig 6: Saturation phase envelope and (ADE) for Abdali 5

(WK ) samples for AB-K3 0

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9

Vol. Ratio (cc of solvent/ cc of oil)

Figure 6 shows the same diagram for (SEK) sample AB-

K3. Figure 7: Flock Point Test for MG-K-1, Blank
sample
Flock Point Analysis (FPA)-Titration Tests

The Flock Point Analysis (FPA) tests were performed to Flock Point Test for MG-K1-(with Inhibitors)
measure the Asphaltene onset point (as volume ratio of
solvent added/crude oil, precipitant injected volume / sample
volume, cc/cc) using SDS (Solid Detection System) by laser After establishing the base line for the blank sample, the
spectroscopy. A typical example output data for this sample was mixed well with the inhibitor with a known
measurement is shown in Table 6. concentration, and then titrated with n-Heptane. An attempt
was made at this stage to investigate the optimized
Flock point tests for MG-K1 i.e. blank crude (untreated i.e. concentration for comparison purposes. For this purpose,
no inhibitor added ), were conducted using n-Heptane as the three solutions with three different concentrations were
precipitant solvent to establish the base line for comparison. tested individually for each inhibitor (0.1%, 0.5%, and 5%).
Figure 7 illustrates a plot of the normalized laser Figures 8, 9, and 10 show the comparison of the flock point
transmission versus the volume ratio (precipitant injected tests results for each inhibitor at different concentrations for
volume / sample volume, cc/cc). As shown in this, the flock the MG-K1 sample.
point for this sample was indicated at 1.12 as volume ratio.
Figure 8 shows that inhibitor A, at concentration of 0.10%
shows a flock point at 1.29cc/cc, that is 15% shifting from
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SPE-KSA 2006 G.P. Oskui, M Salman, B. S Al Matar*, E.F. Gholoum, A Rashed

the blank sample, whereas inhibitors B and C with the same

45
concentration, have flock points of 1.30, 1.14cc/cc,
respectively i.e. shifting the AFP of the MG-K1 sample by 40 FlockPoint(A)=3.0
16% and 2%, towards the right direction of the blank
sample. This indicates that at 0.1 % concentration, inhibitor 35
B with the highest shift percent is the most efficient inhibitor
for asphaltene flocculation for this oil sample 30

25

norm p
45
20
Onset for Blank= 1.12
40

Onset for A= 1.3 15

35
InhibitorA
Onset for B= 1.28
30 Onset for C= 1.14 10 Blank
norm power

25 InhibitorB
inhibitor A
Inhibitor B 5 InhibitorC
20 Inhibitor C
Blank with C7

15 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
10

5
vol.ratio
0
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5

vol. ratio

Figure 8: Flock Point Test for MG-K-1 with Figure 10: Flock Point Test for MG-K1 with different
different inhibitors at 0.1 % concentration. inhibitors at 5 % concentration

45
Onset forBlank=1.12 Flock Point Test for AB-K3
40 Onset forA=1.38
inhibitorA.0.5%

. Blank Onset forB=1.9

Flock point tests for AB-K3, blank crude, were conducted
35 InhibitorB(0.5%)
Onset forC=1.75
InhibitorC(0.5) As shown in Figure 11, the flock point for the blank sample
30
was 1.28 cc/cc. Inhibitor A, at concentration of 0.50% shows
25 a flock point 1.83cc/cc, that is 43% shifting from the blank
nor

sample, whereas inhibitors B and C with the same

20
concentration, showed flock points of 1.60, 1.42cc/cc,
15 respectively i.e. shifting the AFP by 25% and 11%, to the
10
right direction. This indicates that at 0.5 % concentration,
inhibitor A is the most efficient inhibitor for asphaltene
5
flocculation for this oil sample. For concentration of 5%,
0 there was no flocculation (NF) for all the inhibitors showing
0 0.5 1 1.5 2 2.5 3
vol. ratio
that at this concentration, all of these inhibitors work
efficiently.

Figure 9: Flock Point Test for MG-K-1 with different

inhibitors at 0.5 % concentration. 4.50E+01

Blank1

Figure 9 shows the same diagram for concentration of 0.5% 4.00E+01

Blank=1.28
InhibitorA(0.5%)

for each inhibitor for MG-K1. As seen in this diagram, 3.50E+01 InhibitorA=1.83
InhibitorB(0.5%)

InhibitorC(0.5%)
inhibitor A at concentration of 0.5% shows a flock point InhibitorB=1.6
(1.38cc/cc), that is 23% shifting towards the right of the 3.00E+01
InhibitorC=1.42
blank, ,whereas inhibitors B and C have the flock points
Norm. P

2.50E+01
(1.90, 1.75), with 70% and 56%, respectively shifting from
the blank, at this concentration. Again indicating that at 2.00E+01

concentration of 0.5%, inhibitor B with the highest shift

percent is the most efficient inhibitor for this sample. 1.50E+01

1.00E+01
Figure 10 shows that at a higher concentration of (5%)
inhibitor A has a flock point at 3.0cc/cc i.e. almost 168%, 5.00E+00

whereas with other inhibitors, B and C, no asphaltene

0.00E+00
flocculation (NF ) was observed due to the strong inhibition 0 0.5 1 1.5 2 2.5 3 3.5 4

effect of these inhibitors at 5% concentration. VolumeRatio, cc/cc

From the above screening tests (Fig 7 ,8 & 9), it can be

concluded that inhibitor B at all concentrations of 0.1%,
0.5%, 5% showed the highest shift percent and therefore Figure 11: Flock Point Test for AB-K3 with
has the most efficient inhibition effect for fluid sample from different inhibitors at 0.5 % concentration.
well No. MG-K1. Inhibitor C shows an inhibition effect From the above tests (Fig 11), it can be concluded that
only at the high concentration of 5%. inhibitor A at all concentrations of 0.1%, 0.5%, 5% showed

21-23 May 2006, Dhahran – Saudi Arabia 7 of 9

SPE-KSA 2006 G.P. Oskui, M Salman, E.F. Gholoum, A Rashed, B. Al Matar, M Al- Bahar, K Kahali

the highest shift percent and therefore has the most efficient A simple inhibitor screening technique was designed and
inhibition effect for fluid sample from well No. AB-K3. used in the laboratory by titration technique to measure
Inhibitors B and C show an inhibition effect only at the high Asphaltene flocculation point (AFP) using Stock tank oil
concentration of 5%. samples (STO).

Table 5 summarizes Asphaltene flocculation point analysis AFP analysis was performed on four STO oil samples with
(AFP) for samples MG-K1, MG-K2 and AB-K3 for different three different commercially available inhibitors (A,B,C )
inhibitors at different concentrations. for screening purposes.

The AFP analysis indicated that, for Magwa samples MG-

Table 5: Summary for the Inhibitor Screening Analyses K1 and MG-K2, all the inhibitors showed some effect of
Inhibito Flocculation Shift delaying the flocculation point. However, inhibitor B has the
Well Recommended most efficient effect on flocculation at concentrations of
r [%]
0.1% (1000ppm ) and higher.
Conc. Inhibitor Inhibitor
No. For WK sample (AB-K3 ), AFP analysis indicated that all
(%) A B C the inhibitors show an effective delaying of the asphaltene
flocculation point. However, inhibitor A performed slightly
0 0 0 0 better at lower concentrations.

0.10 15 26 2 It is recommended that flow studies such as core flooding

tests in the laboratory should be performed to investigate the
MG-K1 B effect of the interaction of rock-inhibitors using reservoir
0.50 23 70 56
core samples before any economical evaluation and field
16 trial studies.
5.00 NF NF
8
ACKNOWLEDGMENTS
0 0 0 0
The authors are grateful to Kuwait Oil Company (KOC) and
0.10 38 44 40 Kuwait Institute for Scientific Research (KISR) management
MG-K2 B for their financial support during this study.
1.00 60 81 58

19
5.00 NF 154 REFERENCES
9
Alkafeef, A.F.: “An Investigation of The Stability of
0 0 0 0
Colloidal Asphaltene in Petroleum Reservoirs”, SPE
0.50 43 25 11 paper No. 65018, presented at the SPE International
AB-K3 A Symposium on oilfield Chemistry in Houston, Texas,
N. 13-16 Feb.,2001
5.00 N.F N.F
F Anderson, S.I. and Stenby E. H: “Thermodynamics of
Asphaltene Precipitation and Dissolution Investigation
of Temperature and Solvent Effects”. Fuel Science
Technology Int. J. , 1996, 14 (1&2), pages 231-287,.
CONCLUSIONS Asomaning, S. : “Test Methods for Determinig Asphaltene
Stability in Crude Oils”. Petroleum Science and
An attempt was made to review the challenges within KOC Technology Journal, Vol. 21, Nos 3&4 PP 581-590,
regarding asphaltene deposition problems for Kuwaiti (WK, 2003.
SEK) reservoirs.
Bouts, M.N., Wiersma, R.J., and Muljs, H.M.: “An
As a vital requirement for any asphaltene studies, three Evaluation of New Asphaltene Inhibitors: Laboratory
single-phase bottom-hole samples (BHS) were obtained Study and Field-Testing,” SPE paper No. 28991,
successfully from these reservoirs. presented at the SPE International Symposium on
Oilfield Chemistry in San Antonio, TX, Feb. 14-17,
SARA and elemental analyses for all oil samples were 1995.
performed. The colloidal instability indices (CII) were found
to be in the range 1.7-1.9, indicating the unstable nature of Carnahan, N. J., Salager, R. Antone, and A. Davila,
these oil samples causing asphaltene flocculation. “Properties of Resins Extracted from Boscan Crude Oil
and Their Effect on Stability of Asphaltenes in Boscan
Laboratory studies were performed such as oil and Hamaca Crude oils”, Energy Fuels, 1999, V 13,
characterization, PVT, phase behavior diagram, and AOP page 309.
measurement at different temperatures to define the Dandekar, Abhijit Y., Andersen. Simon I. and Stenby. Erling
Asphaltene Deposition Envelope (ADE). H.”Solid Organic Deposition during Gas Injection
Studies” Petroleum Science and Technology Journal,
Re-pressurization experiments showed evidence of Vol. 22, Nos 7&8 PP 1209-1229, 2004.
reversibility of asphaltene precipitation.

21-23 May 2006, Dhahran

8 of 9
SPE-KSA 2006 G.P. Oskui, M Salman, B. S Al Matar*, E.F. Gholoum, A Rashed

De Bore, R.B.,Leerlooyer,K.,Mij, B.V., and Van Marrat Reservoir” This paper presentation at the 1999
Bergan,A.R,.D.: " Screening of Crude Oils for Asphalte SPE No. paper 53155, presented at the SPE Middle
Percipitation: Theory, Practice and the Selection of East Oil Show Conference in Bahrain 20-3 Feb 1999.
Inhibitors", SPE paper No. 24987, presented at
European Petroleum Conference held in Cannee, Karan, K. Hammami, A. Flannery, M., and Stankiewicz,
France, 16-18 November 1992. B.A. : “Evaluation of Asphaltene Instability and a
Chemical Control During Production of Live Oils”
Firoozabadi, A., “Thermodynamics of Hydrocarbon Petroleum Science and Technology Journal, Vol. 21,
Reservoirs”, McGraw-Hill, Chapter 5, New York City Nos 3&4, PP. 629-645, 2003.
1999.
Kokal, S.L. and S.G. Sayegh, “Asphaltenes: the Cholesrtol
Fourest, J.M., “Study of Asphaltenes Precipitation from of Petroleum,” SPE paper 29787, presented at the SPE
Hamaca Crude Oil”, Technical Report of FIRP-ELF Middle East Oil Show in Bahrain, March 11-14, 1995.
Aquitan Project, University of the Andes: Merida,
Venezuela, 1995. Leontaritis, K.J. and G.A. Mansoori,: “Asphaltene
Flocculation during Oil Production and Processing: A
Gawrys, Keith L., Spiecker, P.Matthew, and Kilpatrick, Thermodynamic-Colloidal Model”, SPE Paper 16258
Peter K. “The Role of Asphaltene Solubility and Presented at the SPE International Symposium on
Chemical Composition on Asphaltene Aggregation” Oilfield Chemistry, San Antonio, TX, February 4-6,
Petroleum Science and Technology Journal, Vol. 21, 1989.
Nos 3&4 PP 461-489, 2003.
Mansoori, G.A., T.S. Jiang, and S Kawanaka, : “Asphaltene
Gharfeh, S., Yen, A. Asomaning, S., and Blumer, D. Deposition and its role in Petroleum Production and
“Asphaltene Flocculation Onset Determinations for Processing”, The Arabian Journal for Science and
Heavy Crude Oil and Its Implications” Petroleum Engineering, Volume 13, No 1.
Science and Technology Journal, Vol. 22, Nos 7&8 PP
1055-1075, 2004. Novosad, Z. and Costain, T.G.: “Experimental and Modeling
Studies of Asphaltene Equilibria for a Reservoir under
Gholoum, E.F, Oskui, G.P., and Salman, M: "Investigation CO2 Injection,” SPE paper 20530, presented at the SPE
of Asphaltene Onset Conditions for Kuwaiti Annual Technical Conference and Exhibition, New
Reservoirs,” SPE paper 81571, presented at the SPE Orieans, Sept. 23-26, 1990.
13th Middle East Oil Show Conference in Bahrain 5-8
April 2003. Pfeiffer, J.P., and Sual, R.N., 1940 “Asphaltic Bitumen as a
Colloid System”, Journal of Physical. Chemistry, V 44,
Gholoum, E.F., and Oskui, G.P. "Investigation of p.139.
Asphaltene precipitation Process for Kuwaiti
Reservoir," Petroleum Science and Technology Journal, Speight, J.G.1980 “The chemistry and Technology of
Vol. 22, Nos 7&8 PP 1165-1185, 2004. Petroleum”, Marcel Dekker Inc., New York City 192.

Hammami, A., H. Phelps, and T.M Little: “Asphaltene Srivastava, R.K., S.S. Huang, and. Dyer S.B:
Precipitation from Live Oils: An Experimental “Quantification of Asphaltene Flocculation During
Investigation of the Onset Conditions and Reversibility Miscible CO2 Flooding in Weyburn Reservoir,” paper
” , Energy Fuels 2000, V 14, p 14-18. no.28, presented at the Fifth Petroleum Conference of
the South Saskatchewan Section, The Petroleum
Hammami, A., Kevin A, Freworn and John A.: “Asphaltenic Society of CIM, held with CANMET in Regina,
Crude Oil Characterization: An Experimental October 18-20, 1993.
Investigation of the Effect of Resins on the Stability of
Asphaltenes” Petroleum Science and Technology Thomas, F.B., Bennion, D.B., Bennion, D.W. and Hunter,
Journal, Vol. 16, Nos 3&4 PP 227-249, 1998. B.E.: ”Experimental and Theaoretical Studies of Solids
Precipitation from Reservoir Fluid”, J. Canadian
Hammami, A., Raines, M.A. : ”Paraffin Depostion From Petroleum Technology. January 1992, Volume 31,
Crude Oils: Comparison of Laboratory Results With No.1.
Field Data” SPE Journal, Vol. $, No. 1, March 1999.
Wiehe, Irwin A. and Jermansen, Torris G. “Design of
Hirschberg, A. et al.: “Influence of Temperature and Synthetic Dispersants for Asphaltenes”. Petroleum
Pressure on Asphaltene Flocculation”, SPEJ June 1984, Science and Technology Journal, Vol. 21, Nos 3&4 PP
p.283-293. 527-536, 2003.
Jamaluddin, A.K.M., Nighswander, J., Joshi, N., Calder, D.,
and Ross, B. “Asphaltenes Characterization: A Key to
Deepwater Developments” This paper presentation at
the 2001 SPE No. paper 77936 presented at the SPE
conference and exhibition held in Melbourne,
Australia, 8-10 Oct. 2002
Jamaluddin, A.K.M., Nighswander, J., and Joshi, N. “A
Systematic Approach in Deepwater Flow Assurance
Fluid Characterization” This paper presentation at the
2001 SPE No. paper 71546 presented at the SPE annual
Technical conference and exhibition held in New
Orleans, Louisiana, 30 Sept.- 3 Oct, 2001.
Kabir, C.S., Jamaluddin, A.K.M.: “Asphaltene
Characterrization and Mitigation in South Kuwaite’s

21-23 May 2006, Dhahran – Saudi Arabia 9 of 9