SPE-178034-MS

Investigation of Acid-Induced Emulsion and Asphaltene Precipitation in Low

Permeability Carbonate Reservoirs
Tariq AlMubarak, Mohammed AlKhaldi, Saudi Aramco, Majed AlMubarak, KAUST, Majid Rafie, Hussain Al-Ibrahim,
Nooreddeen AlBokhari, Saudi Aramco

Copyright 2015, Society of Petroleum Engineers  

 
This paper was prepared for presentation at the SPE Saudi Arabia Section Annual Technical Symposium and Exhibition held in Al-Khobar, Saudi Arabia, 21-23 April
2015.  
 
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s).
Contents of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not
necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this
paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than
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Abstract
The increasing demand for energy has extended the development horizon towards relatively tighter formations all over the
world. In Saudi Arabia, hydrochloric and organic acids have been extensively used to enhance well productivity or injectivity
in low permeability formations. However, the use of these acids was associated with severe formation damage, which is
attributed to acid/oil emulsions and/or asphaltene precipitation in some of the low permeability carbonate reservoirs.
Consequently, a detailed study on different factors that influence the acid/oil emulsion and asphaltene precipitation mechanism
was carried out for these reservoirs. Several compatibility studies were conducted using representative crude samples and
different acid systems such as HCl and formic acid. The experiments were conducted at various temperatures up to 240ºF
using HP/HT aging cell for both live and spent acid samples, where some of the experiments included anti-sludge, iron control
and demulsifier chemical additives. In addition, another set of experiments was performed in the presence of ferric ions (Fe3+).
The total iron concentration in these experiments varied between 0-1,000 ppm.
The results obtained from this study have revealed that the acid systems were not compatible with several representative oil
field samples. The amount of asphaltene precipitation and the stability of formed emulsions increased significantly in the
presence of ferric ions. Several wells have already been acidized and damaged prior to initiating this study. This paper
discusses different tests conducted to identify, quantify and treat acid-oil emulsions/asphaltene precipitation in tight carbonate
reservoirs. It also provides details of a special solvent treatment fluid recommended to revive dead wells which were damaged
by acid-induced emulsion and asphaltene precipitation.

Introduction
LF Formation is the deepest of the upper Jurassic limestone reservoirs in field F. Underlying two other carbonate
reservoirs, LF has been appraised as a relatively lower-quality formation with Reservoir Quality Index (RQI) ~0.13, Flow
Zone Indicator (FZI) ~0.73 and a net to gross ratio of ~0.62. This reservoir can also be described as being heterogeneous and
clay rich limestone/dolomite with permeability in the range of 1 – 15 mD, and porosity ranging between 5 – 20%. LF is
expected to be more challenging than common reservoirs due to its low kh, high H2S content~ 7% and crude quality. The wells
in this reservoir are drilled as horizontal multilateral wells and completed as open-hole completions. Several wells have been
acidized based on adjacent field recipes and have resulted in complete loss of production. After that, LF oil has been tested and
found to have the tendency to precipitate asphaltene. The calculated colloidal instability index (CII) for LF oil was found to be
above 0.9, indicating that LF oil is unstable and tends to precipitate asphaltenes (De Boer, R. B, et al., 1995). In addition LF
formation was drilled with oil-based drill-in mud (OBM), which created an oil-based mudcake that acted as an impermeable
barrier on the formation face. Hydrochloric and organic acids have been extensively used in acid stimulation treatments and
acid wash to enhance well productivity or injectivity. However, one main potential problem associated with these acids is the
incompatibility issues with the reservoir's oil. This incompatibility causes precipitation of asphaltene particles, thus forming
thick sludge, which can plug the formation, resulting in severe formation damage (Moore et al. 1965, Houchin 1990, Barker
2007).
SPE-178034-MS 2

Emulsion and asphaltene precipitation

Asphaltenes are negatively charged particles, composed mainly of condensed aromatic ring structures containing oxygen,
sulfur and nitrogen atoms. Asphaltenes exist in heavy crude oil as dispersed colloidal particles, which are stabilized by
adsorbed resin (maltene) particles. Both asphaltenes and resins form stabilized micelles in heavy crude oil (Moore et al.
1965). These stabilized micelles are disrupted by acid contact, resulting in asphaltene precipitation by two main mechanisms:
dissolution of resins, and neutralization of asphaltenes. Following dissolution of resins and neutralization of asphaltenes by
proton ions (H+), colloidal asphaltene particles form large aggregates which precipitate out of heavy crude oils and deposit at
the formation pore throats. The precipitation plugs the formation and causes severe damage (Strassner 1968). The degree of
acid-induced sludge is affected by several factors. Two main factors that can increase the degree of asphaltene precipitation
are the type/strength of the acid and the presence of contaminants such as iron. Generally, asphaltene precipitation is relatively
higher when heavy oil contacts high strength HCl acid. Compared to live HCl, organic and spent HCl acids have less potential
of causing sludge in asphaltic crudes. Presence of ferric ions can aggravate the asphaltene precipitation. It will result in
flocculation of asphaltene particles following their coordination with different functional groups present in heavy oil such as
phenolic hydroxyl (Houchin 1990, Barker 2007). Acid-oil sludge can be reduced or prevented by minimizing the oil contact
with acid. One way to achieve this is by using a pre-flush ahead of main acid stage, acting as a barrier between heavy oil and
injected acid. This pre-flush fluid contains mainly mutual solvent such as ethylene glycol monobutyl ether (EGMBE).
Another cost-effective method is to add surfactants to the injected acid. The surfactant additive will act as an anti-sludging
agent and prevent asphaltene precipitation (Copple 1975, Strassner 1968).
Another potential problem associated with acid/oil interactions is the formation of emulsions. Generally, the formation of
emulsions in oil is due to the presence of polar compounds (resins), heterocyclic compounds such as acids, bases, phenolics,
asphaltenes, and high molecular weight complex compounds, which act like a surfactant. They trap (1-20 µm) droplets of
water in the oil phase. On the other hand, volatile aromatic compounds, mono-aromatics and polycyclic aromatics, in crude
oils, such as benzene and ethylbenzene, dissolve asphaltenes and resins. Therefore, crude oils containing higher quantities of
these volatile compounds have lower tendency to form emulsions when they come in contact with water (Bobra, 1990, 1991,
1992; Fingas et al., 1993).

Drill-in fluids and mudcake removal

Drill-in fluids (DIF) are commonly used in drilling the pay-zone of many horizontal/multilateral wells. DIF systems are
typically designed by incorporating xanthan gum, starch or polyanionic cellulose with bridging agents such as calcium
carbonate. Compared to regular mud systems, such DIF systems are relatively clean and cause less formation damage to the
target zone. They are designed to form a thin impermeable mudcake, on the borehole wall in permeable formations as a result
of filtration into the rock pores. The formed mudcake will seal the wellbore and prevent both the fluid filtrate and drilling
solids from invading and damaging the pay zone. Once drilling activities are completed, effective mudcake removal is
essential to restore the well productivity or injectivity and to reduce DIF associated skin factors. Both mechanical and
chemical means have been used in the field to cleanup DIF mudcake. Chemical means include acids, oxidizers, chelating
agents, enzymes or a combination of these chemicals. Achieving uniform mudcake removal across long horizontal section
with open-hole completion using rapid reacting chemicals such as HCl is a challenging task (Mason, S.D. et al. 2001). These
approaches are used to dissolve the calcium carbonate bridging materials in the mudcake, Although the use of harsh
chemicals such as HCl is widespread, there are many concerns and limitations associated with their use, especially in high
temperature formations. Strong acids have high corrosion rates which are difficult to inhibit at high temperatures (Crowe et
al. 1990). In addition, their high reaction rates with calcium carbonate result in the degradation of mudcake at the point of acid
introduction. This promotes a rapid and localized reaction which results in un-even removal of the mudcake, leaving the rest
of formation untreated.
The main objectives of this study are to: 1) evaluate several systems for the removal of OBM mudcake; 2) explore the
compatibility of LF reservoir oil with HCl acid; and 3) design an effective non-damaging acid recipe to stimulate the acid
sensitive formation.

Procedure and Experimental Work

Materials
Representative heavy oil samples from LF reservoir were used to conduct all acid-oil sludge experiments. Solutions of 20
wt% HCl acid were prepared using analytical grade 37 wt% HCl and distilled water with a resistivity greater than 18Ω.cm at
room temperature. The anti-sludge, iron control and demulsifier additives were supplied by a service company and were used
as received for the sludge/emulsion tests. Pre-flush, surfactants and micro-emulsion chemical were used as received for the
mudcake removal tests. The surfactants were supplied by a second service company, while the micro-emulsion chemical
system was supplied by a third service company. The micro-emulsion system contains solvents, surfactants and acetic acid,
Table 1. Paraffin dissolver, tar dissolver, surfactant and diesel were supplied by a fourth service company and were used for
sludge/emulsion removal tests. The conventional asphaltene/sludge removal treatment recipe is shown in Table 2.

X-Ray Diffraction
X-Ray Diffraction (XRD) was performed on core samples to gain knowledge about the mineralogy of the reservoir rock.
SPE-178034-MS 3

The samples were crushed to fine powder using a mill. The clay size fractions of the sample were separated and air dried on a
glass slide. The air dried glass slide was glycolated in a desiccator containing ethylene glycol at 140°F in the oven. The
identification of the crystalline phases was analyzed. Subsequent semi-quantification of XRD data was done using the Rietveld
Refinement method. The clay-size material (<2 microns equivalent spherical diameter) was separated from the larger size
particles by sedimentation techniques.

Environmental Scanning Electron Microscope (ESEM)

Micro-structural characterizations, in terms of porosity, pore size, presence of clay and foreign materials in the pores are
important in understanding the behavior of reservoirs. In addition, such investigations help in selecting the right acidizing
treatment for the formation in order to increase productivity.
In this test the Environmental Scanning Electron Microscope (ESEM) analytical techniques with integrated ultra-thin window
energy dispersive X-ray detector were utilized to perform comprehensive microstructural characterizations of the core samples
in this reservoir.
The ESEM/EDS data are required in order to identify the minerals in the core, any materials blocking the pore space, type of
cementing materials and also the elemental compositions of the core plug samples. In addition, ESEM could indicate any clay
settlement close to the pore throats, which would potentially block the fluid flow pathways.
The primary goal in this test was to identify the main components of the reservoir core samples and to correlate them with the
XRD results in order to have a better understanding of the acid/rock in this reservoir.

Coreflood
Core flood apparatus was designed and built to simulate fluid flow in porous media in the reservoir. Positive displacement
pump equipped with a programmable controller was used to deliver fluids at constant flow rates at variable speeds up to 200
cm3/min and pressures up to 10,000 psi. The pump was connected to two accumulators to deliver brine or chemical solutions.
Accumulators with floating pistons rated up to 3,000 psi and 250 ºF were used to store and deliver fluids. A set of valves were
used to control the injected fluid into the core sample. The core-holder can accommodate a core plug with diameter of 1.5
inches and a length up to 3 inches. Pressure transducers were used to measure the pressure drop across the core. A back
pressure regulator was used to control the flowing pressure downstream of the core. A second back pressure regulator was also
used to control the confining pressures on the core plug. A convection oven was used to provide temperature controlled
environment. A data acquisition system was used to collect data from the pressure transducers. Below are the procedures used
to prepare the core for the core flooding experiments:

1. Core samples were dried overnight in a 212 °F oven

2. Core samples were saturated with formation brine in a vacuum, then centrifuged to initial water saturation
3. Core samples were loaded into the core holder and confining pressure was applied
4. 6% KCl brine was injected in the core to establish ~ 100% water saturation
5. Base permeability to water were measured using flow rate (1 cm3/min)
6. Distilled water was then pumped to test the sensitivity of clay swelling and migration ( 2 and 4 cm3/min)

Formation water/mixing water compatibility

The high pressure/high temperature (HPHT) aging cell was used to investigate the mixing water/formation water scaling
tendency. The experiments were performed at a temperature of 240°F. The pressure was maintained at 500 psi using nitrogen
gas. The duration of the water compatibility test was 24 hours. The mixing water/formation water ratios are (10/90, 25/75,
40/60, 50/50, 75/25, 90/10). In addition to the lab experiments, a scale simulation was run to predict the scaling tendency of
the two water types. The simulation included water compositions and reservoir properties.

SARA analysis
The four SARA-fractions are saturates (iso- and cyclo-paraffins), aromatics (contain one or more aromatic rings), resins
(polar substituent, miscible with heptanes or pentane), and asphaltenes (polar substituent, insoluble in an excess of heptanes or
pentane). It’s a method for characterizing heavy oil based on fractionation, where a heavy oil sample is separated into smaller
quantities or fractions, with each fraction having a different composition. Fractionation is based on the solubility of
hydrocarbon components in various solvents used in this test. Each fraction consists of a solubility class containing a range of
different molecular-weight species. Gravity-driven chromatographic separation (adsorption chromatography) was used to
determine the fractions of the reservoir's oil (Fan, 2002).
Gravity-driven chromatographic separation is conducted as follow:
1. Prepare crude oil sample
2. Use n-hexane to separate the asphaltenes
3. Use 2 columns to separate the rest
a. An attapulgite clay-packed column adsorbs the resins
b. A column packed with activated silica gel separates the aromatics from the saturate fraction
SPE-178034-MS 4

4. Use a 1:1 mixture of toluene and acetone to recover the resin fraction from the clay packing
5. Recover aromatics by Soxhlet extraction of the silica gel in hot toluene
6. Calculate the amount of the lost volatile components during the process by calculating weight difference

Oil/acid compatibility
The high pressure/high temperature (HPHT) aging cell was used to investigate the sludging tendency of LF oil after
contacting live and spent 20 wt% HCl acids. The experiments were performed at temperatures ranging from 140 to 240°F.
The pressure was maintained at 500 psi using nitrogen gas. Another set of experiments were conducted using the anti-sludge,
iron control and demulsifier additives. The duration of each acid-oil sludge test varied between 2 to 24 hours. The acid/oil
ratio was kept constant for all conducted tests at mixing volume ratios of 1:1. Each oil sample was filtered using 100 µm mesh
size, before and after sludging test. For spent acid sludging experiments, HCl acid solution was neutralized with calcium
carbonate until pH reached 3. Another set of sludging experiments were conducted in the presence of ferric ions (Fe3+). The
total iron concentration in the experiments varied between 0-1,000 ppm. Moreover, several tests were conducted to determine
the effect of H2S on the sludge/asphaltene formation and stability. The H2S tests were conducted using a closed system loop.
H2S was generated by reacting iron sulfide (FeS) with 10 wt% HCl in an erlenmeyer flask, the generated H2S gas was then
diverted to second flask containing live 20 wt% HCl acid and LF oil at a 1:1 ratio with iron concentrations ranging from 0-
1000 ppm. After exposing the solution to H2S gas, the H2S was then diverted to a third flask containing Cadmium Sulfate
(CdSO4) where H2S was scavenged completely into Cadmium Sulfide (CdS). The setup is shown in Figure 1. The H2S
experiments lasted 2-4 hours and the acid/oil was then filtered through 100µm mesh size to determine the severity of the
sludge/asphaltene.

Removal of LF acid-induced sludge

The effectiveness of different mixtures of paraffin dissolver, tar dissolver, surfactant and diesel to remove LF acid-induced
sludging material was explored. The sludge/asphaltene removal experiments were performed at a temperature of 140°F and
atmospheric pressure. The ratio of dissolver/sludging material was kept at 10:1 (mL:g). The duration of all conducted sludging
removal experiments was 4 hours.

Mudcake removal
The mudcake removal experiments were performed using high pressure-high temperature filter press cell (HPHT). Nearly
200 mL representative sample of oil-based DIF, used during LF drilling operations, was introduced into the fluid loss cell.
Using 3 µm ceramic disks as a medium, filtration process was initiated by applying a differential pressure of 300 psi. This
filtration process was continued at 240°F until the fluid loss reached a constant volume, indicating that the mud filter cake was
built on top of the ceramic disk. The mud filter cake was then soaked in the treatment for 4 hours under 240°F and 300 psi.
The weight of the formed mudcake was measured before and after it was soaked in clean-out treatment acid. The recorded
values were used to calculate the loss percent in the cake weight due to its interaction with the clean-out treatment acid.

Results and Discussion

Mineralogical and rock analysis
XRD analysis is necessary to screen the rock from any possibility of acid sensitive clays such as excess amounts of chlorite
or illite. The XRD results showed that the samples consisted of carbonate minerals (calcite and ankerite) with minor quantities
of clay minerals (kaolinite, I-S and illite), and sand (quartz) in some of the samples. Table 3 gives the chemical compounds of
many of the common minerals in the oil industry. Table 4 shows the bulk mineralogical composition of several core plugs
from this reservoir. The data indicated that calcite was the most dominant mineral in the samples with wt% ranges between 70
to 98%. The Second dominant mineral is dolomite with 1 – 16 wt%. Clay minerals including total clays of mixed layers illite-
smectite, illite and kaolinite were also detected in the same samples, and reached up to 14 wt% in the extreme case. On the
other hand, some core samples did not have any clay in them.
Figure 2 contains the environmental scanning electron microscope ESEM images confirming the presence of CaCO3 mainly
in the reservoir core sample. In addition, Figure 2 shows that the pore throats are clay free in the reservoir core sample.
Multiple solubility tests were conducted following the XRD analysis to confirm the abundant presence of CaCO3, Figure 3.

Clay swelling and migration

Core flood tests were run several times to test the sensitivity of clay swelling and migration. The core flood graphs are
shown in Figure 4. The core was first flooded with a temporary salt clay stabilizer to determine a base permeability, the core
was then flooded with distilled water at 2 cm3/min and 4 cm3/min for 90 pore volumes at each rate. The pressure drop was
measured between the inlet and the outlet of the core sample. The pressure drop showed no change while pumping distilled
water at 2 cm3/min. Furthermore, the rate was increased to 4 cm3/min, where the pressure drop did not show any significant
spikes or changes. This indicated that the clays in the core samples didn’t have major swelling or migrating effects that would
hinder the flow of hydrocarbons.
SPE-178034-MS 5

Scale analysis
Scale formation in the reservoir rock could block the pores and hydrocarbon pathways, which hinders the flow of
hydrocarbons to the wellbore. Mixing water was used to mix the acid system which was then used in the stimulation jobs. In
addition, formation water will be encountered while pumping, which makes it very critical to test both water compositions for
scaling compatibility. The mixing water and formation water were analyzed and shown in Table 5.
Simulation runs were performed to determine the critical mixing ratios at which scale could occur. The results are shown in
Figure 5. The simulation indicated that we have minor scales precipitating, but the amount of scale precipitating was below
the threshold of scale quantities that would hinder the flow of hydrocarbons to the wellbore. To confirm this, seven samples
were tested for compatibility in the lab at different ratios of mixing water/formation water (10/90, 25/75, 40/60, 50/50, 75/25,
90/10). The samples were prepared and kept in a convection oven for 24 hours under reservoir temperature. The compatibility
results indicated no precipitation/scale issues between the mixing water/formation water as shown in Figure 6.

SARA analysis
SARA analysis was conducted on the crude oil to determine the amount of saturates, aromatics, resins and asphaltene in the
oil. Several coefficients can be calculated to determine if the oil is problematic in terms of asphaltene/sludge precipitation. One
of the most common misconceptions in diagnosing asphaltene problems is calculating the resin to asphaltene ratio and basing
the decision solely on this. This method is not very accurate because there are many other factors contributing to the stability
of asphaltenes in the crude oil other than resin content. One coefficient was found to be very helpful in taking many
components of the oil into consideration prior to determining the stability of asphaltene. This coefficient is the Colloidal
Instability Index (CII) shown in Equation 1.

(𝑺𝒂𝒕𝒖𝒓𝒂𝒕𝒆𝒔!𝑨𝒔𝒑𝒉𝒂𝒍𝒕𝒆𝒏𝒆)
𝑪𝑰𝑰 = (𝑹𝒆𝒔𝒊𝒏𝒔!𝑨𝒓𝒐𝒎𝒂𝒕𝒊𝒄𝒔)
........................................................................................................................................1

High resin and aromatic content help keep the asphaltene stabilized in the oil, preventing it from precipitating out and
hindering the flow. On the other hand, high saturates content destabilize the asphaltene. CII > 0.9 indicates that the asphaltenes
are unstable. when 0.7 < CII < 0.9 indicates that we have a potential asphaltene problem. CII < 0.7 indicates that the
asphaltenes are stable in the oil (A. Yen, 2001). The CII calculated for LF oil is 1.6, which indicates problematic oil in terms
of sludge/asphaltene precipitation. The SARA analysis results and CII index calculation are shown in Table 6.

Oil/acid compatibility
Several compatibility experiments were performed to assess the LF oil tendency of forming sludge/emulsion due to mixing
with live and spent 20 wt% HCl. The experiments were conducted using 1:1 acid/oil mixing ratio, at 240°F and 500 psi for 24
hours. Using 100 µm mesh size, it was observed that heavy sludge/asphaltene occurred when LF oil was in contact with both
live and spent 20 wt% HCl, Figure 7. Compared to live HCl acid, the amount of sludge material was more in spent HCl. For
example, nearly 6 and 8.5 g of sludge material precipitated out of 100 mL of LF oil when it was mixed with 100 mL of live
and spent 20 wt% HCl, respectively, Figure 8.
Another set of LF oil/acid compatibility experiments was performed in the presence of ferric ions (Fe3+) at 240°F and for 24
hours. Figure 8 depicts the amount of sludge/asphaltene of LF oil after it was mixed with live and spent 20 wt% HCl as a
function of Fe3+ concentration. The amount of sludge/asphaltene in LF oil/acid mixture clearly increased in the presence of
iron. For example, in the 100/100 mL LF oil/live 20 wt% HCl, the amount of sludging material increased from 6 to 8 g when
the ferric ions concentration was increased from zero to 1,000 ppm. Similarly, the amount of sludge in LF oil/spent 20 wt%
HCl increased from 8.5 to 12.5 g when iron concentration was increased from zero to 1,000 ppm. In addition to
sludge/asphaltene precipitation, it was found that LF oil formed stable emulsion when it was mixed with 20 wt% HCl. The
stability of this emulsion mainly depended on acid solution pH, presence of ferric ions, and time.
Figures 9 and 10 show the percentage of separated acid from LF oil and acid emulsion as a function of time and ferric ions
concentration for both live and spent 20 wt% HCl at 140°F and 24 hours. The maximum percentage of separated acid for both
live and spent 20 wt% HCl reached only 40% of present acid amount in LF oil and HCl emulsion. However, compared to live
20 wt% HCl, the LF oil formed more stable emulsion with spent 20 wt% HCl. The maximum percentage of separated acid
was reached after nearly one hour in spent 20 wt% HCl/LF oil emulsion compared to only 10 minutes in live 20 wt% HCl
emulsion with LF oil. In addition to acid solution pH value, it was found that the presence of ferric ions stabilized the LF
oil/acid emulsion.
The presence of ferric ions up to 1,000 ppm had no effect on the emulsion stability of LF oil/spent 20 wt% HCl, Figure 10.
For example, the separation percentage of present spent 20 wt% HCl in LF oil/acid emulsion, after nearly one hour, remained
constant when the ferric ions amount increased from zero to 1,000 ppm. In contrast, presence of ferric ions had significant
impact on the stability of LF oil emulsion with live 20 wt% HCl. The percentage of separated acid phase from LF oil/acid
emulsion dropped from 40% to zero when ferric ions concentration increased from zero to 500 ppm, Figure 9.
Several H2S experiment results indicated that H2S and iron combination stabilized the sludge and asphaltene further more.
Figure 11 shows the result of filtering the acid and oil after exposing it to 1000 ppm iron and low concentrations of H2S for 4
SPE-178034-MS 6

hours. The majority of the fluid was unable to pass through the 100µm mesh size, which indicated that the sludge became
more severe due to H2S and iron effect on the sludge/asphaltene.
It is evident from the above results that LF oil forms sludging material and stable emulsion when it is in contact with 20 wt%
HCl acid, especially in the presence of ferric ions. Therefore, demulsifier, anti-sludge and iron control acid additives were
used. Citric acid (iron control agent) was used at 20 lb/gal to chelate nearly 2,500 ppm of ferric ions. The concentration of
both demulsifier and anti-sludge agents was varied until no sludge/emulsion occurred when 20 wt% HCl was mixed with LF
oil. Figure 12 and 13 shows that adding demulsifier agent at 5 gpt, anti-sludge agent at 5 gpt and iron control agent at 20
lb/gal was effective to prevent sludge/emulsion formation when LF oil was mixed with 20 wt% HCl at 1:1 and 140°F.

Asphaltene/sludge removal
As mentioned, several LF wells were previously stimulated with HCl acid excluding demulsifier and anti-sludge additives.
The wells ceased to flow after the stimulation treatments. Results indicated the high possibility that the stimulated wells were
damaged with sludge/emulsion due to the incompatibility of HCl acid and LF oil. Therefore, several solvent formulations
were tested to find the effective sludge/emulsion treatment recipe. Initially, neat paraffin dissolver solvent was used to
dissolve sludge/asphaltene laboratory samples formed after mixing LF oil with live 20 wt% HCl. This solvent was not
effective as it only dissolved 20% of sludging material after 4 hours at 1:10 solid:liquid ratio and 140°F, Figure 14.
Therefore, the effectiveness of several recipes of two solvents (paraffin and tar dissolver), surfactant and diesel was
investigated in terms of removal efficiency and cost effectiveness, Figure 15, 16 and Table 7. It was found that
solvents/surfactant/diesel at volume percentage of 30/2/68, respectively, is the most economical and effective recipe to remove
the acid-induced sludge of LF oil. It removed more than 90% of LF sludge after soaking time of 4 hours at 240°F, Figure 15
and 17.

Mudcake removal treatment

The DIF mud recipe used to drill the pay zone is shown in Table 8. To effectively remove the generated oil-based
mudcake, different removal recipes were investigated, Table 9. Two recipes, 1 and 2, consisted of two-stage treatment: mutual
solvent/surfactant and acetic acid. The first stage utilizes surfactant to alter the wettability of the mudcake to water-wet to and
enables the second stage, acetic acid to easily dissolve the mudcake bridging material, CaCO3 particles.
Initially, an oil-based mudcake, weighing 9 g, was soaked for 4 hours at 240°F in 200 mL of mutual solvent and surfactant 1
solution at 10 vol% and 3 gpt, respectively. Then, the mudcake was soaked in 200 mL of 10 wt% acetic acid solution for 4
hours at 240°F. It was observed that the stage-1 treatment had no effect on the mudcake, while the acetic acid removed only
27% of the mudcake, Figure 18. Similarly, recipe 2 supplied by the same service company was not effective in dissolving the
LF oil-based mudcake. After soaking for 4 hours at 240°F in 200 mL of mutual solvent and surfactant 2 at 10 vol%, there was
no weight loss in oil-based mudcake. This was followed with 10 wt% acetic acid treatment for 4 hours. However, acetic acid
was also not effective, indicating that the calcium carbonate particles in the mudcake were still covered with oil, Figure 19.
After testing the different possible two-stage treatments, a single stage oil-based mudcake removal was investigated. Micro-
emulsion system, supplied by a service company, is a system that consists of an organic dissolver, micro emulsion surfactant
and acetic acid, Table 9. It was found that the Micro-emulsion treatment was capable of dissolving the organic layer and
treating the CaCO3 weighting material with acid all in one stage. It removed nearly 95% of LF oil-based mudcake after 4
hours soaking time at 240ºF when 200 mL of this system was used to dissolve 9 g oil-based mudcake, Figure 20.

Field Quality Assurance/Quality Control

There are many factors one must consider to achieve a successful stimulation treatment. Planning the recipe and testing the
chemicals are important. However, having a clean and smooth operation application is the key to a successful treatment. To
achieve this, several procedures must be followed, known as the QA/QC procedures. Each stage or chemical has its own
procedure to check quality and performance. Operational QA/QC is divided to several parts and discussed below:

Recipe general guidelines

For matrix acidizing the total treatment acid volume should be 15 gpf (the regular HCl and the diversion acid). Pre-flush and
post flush are inert fluids used for formation conditioning. A spacer before the acid stage should be pumped to displace the
completion fluid away from wellbore. Pre-flush and post flush could be water based or diesel based depending on several
factors such as the reservoir pressure. In addition, mutual solvent and surfactant should be added to the pre-flush and post
flush. Pre-flush should be at least 1/3 of main treatment acid volume at 5 gpf and post flush volume should be able to displace
all acids away from the wellbore. Necessary chemical additives such as H2S scavenger, anti-sludge, demulsifiers, iron control,
corrosion inhibitor, surfactants, diversion fluids or foams should be evaluated on a well to well basis.

Chemical QA/QC
• HCl acid concentration, a titration test must be conducted to determine the acid wt%
• Emulsified acid, a conductivity test or a drop test in water must be completed
• Iron concentration should be less than 100 ppm, excess iron will initiate severe sludge or emulsion formation
SPE-178034-MS 7

• Sulfate should be less than 100 ppm, excess sulfate will form insoluble CaSO4 scale in spent acid
• All mixing and transporting tanks should be clean, flushed and corrosion free

Acid flowback
• To calculate pH and determine the optimum soaking time
• To analyze the reaction products and determine the effectiveness of the acid concentrations
• To analyze the cations including iron content to determine the proper loading of iron control
• To look for presence of emulsions. If the emulsion does not break, then test to see if higher concentrations of
demulsifier is required

The above guidelines/tests were conducted on the wells where new acid recipe and removal treatment were applied. Many
chemicals mixes were not up to standard and were asked to remix. Mixing water was often contaminated. In addition,
emulsified acid quality was a major issue due to low emulsifier concentration and cleanliness of the diesel tanks, Figure 21
and 22. The results were very successful due to the collaboration between the lab and field engineers. A power injector well
drilled in LF reservoir had an injectivity increase of around 500% after undergoing a stimulation treatment with the new recipe
Moreover, an oil producer achieved a PI increase of 200% after the new recipe adjustments and guidelines were applied, Table
10.

Conclusion
The compatibility of LF oil with hydrochloric acid (HCl) was extensively investigated at different conditions. It was
evaluated as a function of the pH value of acid solution, presence of iron and temperature. Several experiments and different
techniques were explored to prevent and treat the compatibility issues of HCl-induced emulsion/asphaltene. Additionally,
several removal systems for LF oil-based mudcake were evaluated. Based on this study, the following conclusions were
drawn:
• LF oil was found to be incompatible with both live and spent 20 wt% HCl. It formed stable emulsion and
asphaltene/sludge at 240ºF.
• The presence of iron aggravates the LF oil HCl-induced emulsion/asphaltene. The significant impact of iron presence
was observed in live 20 wt% HCl.
• The formed asphaltenes/sludge can be prevented by using anti-sludge, demulsifier and iron control agents at
concentration of 5 gpt, 5 gpt and 20 lb/gal, respectively.
• The formed asphaltene/sludge was found to be soluble in a mixture of solvents (Paraffin dissolver and tar dissolver),
surfactant and diesel. Nearly 90% of LF asphaltene/sludge was dissolved in 30% solvents, 2% surfactant and 68%
diesel after 4 hours at 240ºF.
• Micro-emulsion system was found to be effective in removing LF OBM mudcake. More than 95% of the mudcake was
dissolved after soaking for 4 hours at 240ºF.
• Field operation was successful and results in a water injector injectivity increase of 500%, and an oil producer PI
increase of 200%.
SPE-178034-MS 8

Acknowledgements
The authors would like to thank the management of Saudi Aramco for permission to publish this paper.

References
A. Yen, Y. R. Yin, and S. Asomaning, “Evaluating asphaltene inhibitors: laboratory tests and field studies,” in Proceedings of
the SPE International Symposium on Oilfield Chemistry, SPE 65376, pp. 613–619, Houston, Tex, USA, February
2001.

Barker, K. M., & Newberry, M. E. (2007, January 1). Inhibition and Removal of Low-pH Fluid-Induced Asphaltic Sludge
Fouling of Formations in Oil and Gas Wells. Society of Petroleum Engineers. doi:10.2118/102738-MS

Bobra, M. 1990. A Study of the Formation of Water-in-Oil Emulsions. Proc., 1990 Arctic and Marine Oil Spill Program
Technical Seminar, Edmonton, Canada.

De Boer, R. B., Leerlooyer, K., Eigner, M. R. P., & van Bergen, A. R. D. (1995, February 1). Screening of Crude Oils for
Asphalt Precipitation: Theory, Practice, and the Selection of Inhibitors. Society of Petroleum Engineers.
doi:10.2118/24987-PA

Fan, T., Wang, J., and Buckley, J. 2002. Evaluating Crude Oils by SARA Analysis. SPE

Fingas et al., 1993, Fingas, M., Fieldhouse, B., Bobra, M., Tennyson, E., 1993. The physics and chemistry of emulsions. In:
Proceedings of the Workshop on Emulsions, Marine Spill Response Corporation, Washington, DC, p. 7

Houchin, L. R., Dunlap, D. D., Arnold, B. D., & Domke, K. M. (1990, January 1). The Occurrence and Control of Acid-
Induced Asphaltene Sludge. Society of Petroleum Engineers. doi:10.2118/19410-MS

Mason, SD, et al.: “e-Methodology for Selection of Wellbore Cleanup Techniques in Open-Hole Horizontal Completions”
paper SPE 68957 presented at the SPE European Formation Damage Conference, The Hague, The Netherlands, 21-
22 May 2001

Moore, E. W., Crowe, C. W., & Hendrickson, A. R. (1965, September 1). Formation, Effect and Prevention of Asphaltene
Sludges During Stimulation Treatments. Society of Petroleum Engineers. doi:10.2118/1163-PA

Strassner, J. E. (1968, March 1). Effect of pH on Interfacial Films and Stability of Crude Oil-Water Emulsions. Society of
Petroleum Engineers. doi:10.2118/1939-PA
SPE-178034-MS 9

TABLE  1–  MICROEMULSION  RECIPE  FOR  MUDCAKE  REMOVAL  

Component   Amount,  vol.%  
Fresh  Water   63  
Surfactant   21  
Solvent   5  
Acid  Corrosion  Control   1  
Acetic  Acid   10  
 

TABLE  2  –  TYPICAL  PARAFFIN  DISSOLVER/TAR  DISSOLVER    SLUDGE  TREATMENT  

Component   Amount,  vol.%  
Paraffin  Dissolver   30  
Tar  Dissolver   30  
Diesel   38  
Surfactant   2  
 
 
TABLE-­‐3  CHEMICAL  COMPOSITION  OF  MINERALS  
Calcite   Ankerite   Dolomite   Illite   Koalanite   Quartz   Pyrite  
CaCO3   Ca(Fe,Mg,Mn)(CO3)2   CaMg(CO3)2   (K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]   Al2Si2O5(OH)4   SiO4   FeS2  
 
 
TABLE-­‐4  XRD  RESULTS  
Grain  
Plug   Calcite   Ankerite   Illite  +  IS   Kaolinite   Quartz  
Density  
3
#   wt%   wt%   wt%   wt%   wt%   g/cm  
1   70   16   7   4   3   2.75  
2   80   12   4   2   2   2.75  
3   95   0.5   0   0   4.5   2.75  
4   91   9   0   0   0   2.75  
5   98   1   1   0   0   2.75  
 
 
 
TABLE-­‐5  COMPARISON  BETWEEN  MIXING  WATER  AND  FORMATION  WATER  
Parameter   Ca   Mg   Cl   Fe   K   Na   Sr   SO4  
Mixing  water   200   2   100   10   5   20   0   50  
Formation  water   37000   6700   122500   30   1000   34000   1400   480  
 
 
 
TABLE  6  –  SARA  ANALYSIS  
Saturates   Aromatics   Resins   Asphaltenes   CII  
60.3   30.4   8.1   1.2   1.6  
 
 
 
SPE-178034-MS 10

TABLE  7  –  DIFFERENT  RECIPES  USED  TO  DISSOLVE  OIL/ACID  SLUDGE  

Concentration,  vol.%  Paraffin  Dissolver/Tar  

Recipe   Dissolver/Surfactant/Diesel   Cost,  $/bbl  
1   30/30/2/38   1,055  
2   90/0/2/8   510  
3   30/10/2/58   483  
4   30/0/2/68   195  
 
TABLE  8  –  OIL-­‐BASED  MUD  (OBM)  USED  TO  DRILL  FORMATION  
Component   Initial  Fresh  Mud  Properties   Average  Properties  
Base  Oil,  bbl   0.76/0.60   Density,  pcf   58.0  -­‐  64.0  
Primary  Emulsifier,  gal   0.75-­‐1.00   Plastic  Viscosity,  cP   16.0  -­‐    20.0   <35  
2
Alkalinity  Source,  lbs   8.00   Yield  Point,  lb/100  ft   8.0  -­‐  11.1   18.0  -­‐  26.0  
Organophilic  Lignite,  lbs   6.00-­‐8.00   6  RPM  readings   6.0  -­‐  8.0   7.0  -­‐  9.0  
2
Fresh  water,  bbl   0.13/0.25   Gels,  10  sec,  lbs/100  ft   5.0  -­‐  7.0   10.0  -­‐  12.0  
2
Organophilic  Clay,  lbs   6.00-­‐8.00   Gels,  10  min,  lbs/100  ft   7.0  -­‐  10.0   13.0  -­‐  15.0  
Low  Shear  Rheology  
2
Modifier,  ppb   2.00-­‐3.00   Gels,  30  min,  lbs/100  ft   7.0  -­‐  10.0   16.0  -­‐  22.0  
Secondary  Emulsifier,  gal   1.50   FL  HPHT  250⁰F,  mL/30  min   4.0  -­‐  6.0   <4  
CaCl2  (78%),  lbs   25.00   Electrical  stability,  Volts   250   >600  
CaCO3  "fine",  lbs   8.00/15.00   Chlorides   195,000   190,000  -­‐  200,000  
CaCO3  "Medium",  lbs   7.00/15.00      
Wetting  Agent,  gal   1.00-­‐2.00                              
 
 
TABLE  9  –OIL-­‐BASED  MUDCAKE  REMOVAL  EFFICIENCY  
Recipe   Components   Removal  Efficiency,  wt.%  
Stage  1:  Mutual  Solvent  (10  vol%),  Surfactant  #1  (3  gpt)   0  
1  
Stage  2:  Acetic  Acid  (10  wt%)   27  
Stage  1:  Mutual  Solvent  (10  vol%),  Surfactant  #1  (10  vol%)   0  
2  
Stage  2:  Acetic  Acid  (10  wt%)   0  
Microemulsion  System:  
Fresh  Water   63%  
3   Surfactant   21%   >95  
Solvent   5%  
Acid  Corrosion  Control   1%  
 

TABLE  10  –  FIELD  TREATMENTS  AFTER  ADJUSTING  RECIPE  

PI/Injectivity  
Well   Type   Increase  
1   Injector   500%  
2   Producer   200%  
SPE-178034-MS 11

Figure 1- H2S generation setup used in testing the effect of H2S on sludge and asphaltene precipitation

Figure 2- ESEM analysis confirming the presence of CaCO3 mainly in the reservoir, and the pore throats being clay
free
SPE-178034-MS 12

Solubility  Core  #4  

100  

90  

80  

70  
Dissolved,  %  

60  

50  

40  

30  

20  

10  

0  
0   0.5   1   1.5   2   2.5   3   3.5   4   4.5   5   5.5  
Time,  Hours  

Figure 3- Solubility test result indicates high amount of CaCO3 in the reservoir core sample

Sample#314  
70

60

50
6%  KCl@  1  cm3/min  
DP,  psi  

40
Dis\lled  Water  @  4  cm3/min  
30

20 Dis\lled  Water@  2  cm3/min  

10

0
0 20 40 60 80 100 120 140 160 180
Pore  Volume    
Figure 4- Coreflood indicates no clay swelling and migrating damaging effects
SPE-178034-MS 13

Figure 5- Mixing water/Formation water simulation results indicate very minimal scale with no issues of hindering the
flow of hydrocarbons

Figure 6- Mixing water/Formation water compatibility tests at (10/90, 25/75, 40/60, 50/50, 60/40, 75/25, 90/10) ratios
respectively, indicating no scaling issues
SPE-178034-MS 14

Figure 7- LF oil asphaltenes/sludge precipitation after mixing with both live and spent 20 wt% HCl at 240ºF for 24
hours

14
20 wt% HCl
12 Live Acid
Weight of sludge/asphaltene, g

Spent Acid
10

0
0 100 500 1000
Ferric ions (Fe3+) concentration, ppm
Figure 8: Amount of LF oil sludge/asphaltene after mixing with live and spent 20 wt% HCl as a function of Fe3+
concentration at 240ºF for 24 hours.
SPE-178034-MS 15

100
Fe3+ concentration, ppm
90
Percentage of separated acid phase, %

Iron 0 ppm
80 Iron 100 ppm

70 Iron 500 ppm

Iron 1000 ppm
60

50

40

30

20

10

0
0 10 20 30 40 50 60 70 80 90 100

Time, minutes
Figure 9: Percentage of separated acid phase out of LF oil/live 20 wt% HCl emulsion at 1:1 mixing ratio and 140ºF

100

90 Fe3+ concentration, ppm

Percentage of separated acid phase, %

80 Iron 0 ppm
Iron 100 ppm
70
Iron 500 ppm
60 Iron 1000 ppm

50

40

30

20

10

0
0 10 20 30 40 50 60 70 80 90 100
Time, minutes

Figure 10: Percentage of separated acid phase out of LF oil/spent 20 wt% HCl emulsion at 1:1 mixing ratio and 140ºF
SPE-178034-MS 16

Figure 11- Oil was run through 100 µm mesh sieve then the acid/oil sludge mix that was generated in the presence of
H2S and 1000ppm iron was poured on the sieve, following that hot water was poured on the sieve; the remaining
material is thick sludge precipitation
SPE-178034-MS 17

Figure 12- Effect of adding different concentration of demulsifier agent to the acid/oil mix (0-15 gpt)

a b

Figure 13- HCl (20 wt%)/LF oil mixture at 1:1 ratio and 140ºF for 24 hours: (a) without additives, (b) with demulsifier,
anti-sludge and iron control agents

Figure 14- Paraffin dissolver treatment of LF oil sludging material at a ratio of 10:1 liquid:solid ratio at 140ºF for 4
SPE-178034-MS 18

hours

100

Paraffin dissolver/Tar dissolver/Surfactant/Diesel, vol%

30/0/2/68 30/10/2/58
Sludge solubility, %

90

80

70
140 Temperature, ⁰F 240
Figure 15: Solubility of LF oil/acid sludge in different solvent recipes at 1/10 solid/liquid ratio for 4 hours

a b c

Figure 16- Paraffin dissolver/tar dissolver/surfactant/diesel combination at a ratio of 10:1 at 140 ºF for 4 hours. a:
30/30/2/38, b:30/20/2/48, c: 30/10/2/58
SPE-178034-MS 19

1 g of LF oil acid- induced

sludge completely dissolved in
10 mL of solvent

Figure 17- Paraffin dissolver /Surfactant/Diesel of LF oil sludging material at a ratio of 10:1 liquid:solid ratio at 240ºF
for 4 hours

a b c
Figure 18- LF oil-based mudcake treated with recipe 1, (Mutual solvent/surfactant #1 followed by 10 wt% acetic acid),
at 240ºF for 4 hours, a: mudcake before treatment, b: after treatment with 10 vol% mutual solvent and 3 gpt
surfactant #1, and c: after treatment of 10 wt% acetic acid

a b c
Figure 19- LF oil-based mudcake treated with recipe 2, (Mutual solvent/surfactant #2 followed by 10 wt% acetic acid),
at 240ºF for 4 hours, a: mudcake before treatment, b: after treatment with mutual solvent and surfactant #2 at 10
SPE-178034-MS 20

vol%, and c: after treatment of 10 wt% acetic acid

.
a b
Figure 20- LF oil-based mudcake treated with recipe 3, (Microemulsion), at 240ºF for 4 hours, a: mudcake before
treatment, b: after treatment with microemulsion system

Figure 21- Shows the samples taken while mixing, a: The diesel and emulsifier portion of the emulsified acid, the
quality was monitored and remixed until the fluid was cleaner, b: First failed emulsified acid mix, c: Tests on site to
increase the emulsifier concentration, d: Emulsified acid passed drop test after adjustments and remixing
SPE-178034-MS 21

Figure 22-Mixing water was sampled in each stage and remixed when quality didn’t meet standards