Copyright 2006, Society of Petroleum Engineers

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Abstract
Water based drill-in fluids usually contain starch and
xanthan polymers and sized calcium carbonate particles,
which help in developing an effective filter cake during
drilling process to control fluid loss. Proper removal of
the drill-in fluid filter cake from the pay zone is essential
to maximize productivity. The latest technique for filter
cake clean-up is the application of acid and enzymes in a
single stage. The prime advantage of this technique is
the uniform placement of acid through precursor in long
horizontal wells. Other benefits include: cost and time
saving by avoiding multistage treatment and reduced risk
of tools corrosion, which is associated with mineral
acids.
A detailed study was conducted to evaluate the
efficiency of acid-precursor-enzyme system to be used in
multi-lateral, maximum reservoir contact wells. The
evaluation was performed by using samples of polymer
based drill-in fluids and dry bulk of sized calcium
carbonate in terms of return permeability determination,
change in particle size distribution, and weight loss.
Results indicated that the generated acid mainly
targeted fine particles of calcium carbonate present in
drill-in fluids and dry bulk. This paper presents results
of lab investigations and merits (or demerits) of single
stage treatments.

Introduction
The acid-precursor-enzyme system (APES) is a wellbore
cleaning chemical. It is composed of ingredients
including enzymes and acid-precursor and designed to
act in two ways: to degrade the polymer present in the
filter cake by enzymatic action and to dissolve calcium
carbonate by acid generated in-situ. The basis of the
process is that an acid precursor compound is mixed in
brine, where the acid is generated over a period of time
and reacts with calcium carbonate, while substrate
specific enzymes simultaneously act on polymers like
starch and xanthan. The enzyme-based process of
generating acid in-situ and filter cake removal in a single
stage has been studied.
1-3
The present investigation is an
attempt to examine the merits and limitations of APES in
maximum reservoir contact (MRC) wells.
In the recent years, with the shift from vertical and
horizontal wells to MRC well types, the longer
horizontal hole section have become more challenging to
clean-up as access to the pay zone with coiled tubing is
becoming more expensive and in some cases difficult.
Hence a filter cake clean-up system was required to clean
the pay zone by using drill string immediate after
drilling. DIFs with reasonable properties and favorable
particle size distribution (PSD) were designed to meet
the challenging task of MRC drilling. MRC wells have
proved their success as a productivity enhancement and
economical option for field development in Saudi
Arabian fields.
4

The objective of the study was to determine the
efficiency of the APES in terms of permeability
improvement as a synergic effect of polymer degradation
by enzymes and calcium carbonate dissolution through
acid generation.

Experimental Procedures
In this study, DIFs with varying quantities of polymers
and calcium carbonate were used. The calcium
carbonate (dry) used in the preparation of DIF was also
used separately to study its solubility in the generated
acid by acid-precursor. Tests were conducted at
simulated reservoir conditions (210
o
F temperature and
500 psi pore pressure) by developing the filter cake on
the face of the core by circulating the DIF under dynamic
and static conditions and treating calcium carbonate
separately at ambient and high pressure (500 psi).
The APES

solution was prepared afresh in 7 wt% KCl
brine for each test. The solubility tests of calcium
carbonate were performed in two ways: in wide mouth
bottles of one liter capacity at ambient pressure and in
250 ml stainless steel accumulators at 500 psi static
pressure. In both cases, enough time was given, 6-48
hours, at 210
o
F for the reaction to take place. The
solubility was determined in terms of weight loss and
change in particle size distribution (PSD). The effect of
SPE 99799
Evaluation of Acid Precursor-Enzyme System for Filter-Cake Removal by a
Single-Stage Treatment
M.A. Siddiqui, SPE, H.A. Al-Anazi, SPE, A.A. Al-Ansari, SPE, M.A. Bataweel, SPE, and D.E. Hembling, SPE,
Saudi Aramco

2 SPE 99799
generated acid on PSD of DIF was studied by mixing
150 mL of acid-precursor solution with 50 gm of DIF in
a one liter glass bottle at 210
o
F.
The damage induced by drilling fluids was
evaluated using a prototype dynamic mudflow loop. The
flow loop was built to allow whole drilling fluid (as
opposed to filtrate) to be circulated against the core
face.
5-7
The test requires fluid flow and displacement in
two directions, designated as production and
treatment. The permeability was determined relative
to the production direction by injecting oil at various
flow rates and calculated using Darcys law for linear
flow. After mud circulation, the filtrate displacement
valve was closed and a cleanup fluid was circulated
through the system to remove mud from the mixing
chamber and from the core face. Crude oil was injected
in the direction opposite to the drilling mud filter cake.
The use of whole mud system allows the assessment of
the potential for solids invasion, and evaluation of the
degree of permeability damage caused by drilling fluids.

5-7
Concentrations of the generated acid and the acid left
(unspent) after reaction with calcium carbonate were
determined by titrating against standard sodium
hydroxide solution (1.0 N) in each case. PSDs of the
calcium carbonate and DIFs were determined before and
after tests.

Calcium Carbonate and DIF Used
Calcium carbonate particles received from rig for tests
were of two grades; fine and medium, classified on the
basis of their particle size distribution (PSD). In this
paper, the calcium carbonate will be regarded as neat
calcium carbonate before treatment with in-situ acid.
The median particle size of neat fine and medium
particles were 10.8 m and 136.8 m, respectively. The
mineralogical composition of neat calcium carbonate
was determined by XRD analysis and was found to
contain 60 and 20 wt.% calcite in fine and medium
particles, respectively, while the quantity of dolomite
represented 40 wt.% in fine and 78 wt.% in medium
particles. In this study, three sets of drill-in fluids in two
loadings of calcium carbonate of fine and medium were
used (Table 1).
General pattern of PSD for neat calcium carbonate,
fine and medium are given in Table 2. Composition of
the APES solution used in this study is given in Table 3.

Results
A common observation during tests was that the acid-
precursor has generated an organic acid in various
concentrations in separate tests conducted over a period
of 6-48 hours at 210
o
F. The acid generated by 5 and 10
wt.% acid-precursor at ambient oxygen was found to be
nearly 3 vol.%. In oxygenated brine, 10 wt.% acid-
precursor generated nearly 6 vol.% of acid, while 5 wt.%
acid-precursor generated the same, 3 vol.%. The volume
of acid generated was same at ambient and pressurized
conditions (500 psi). Complete acid generation took
place at 24 hours soaking at 210
o
F.
The solubility of calcium carbonate in the generated
acid was different at different conditions. To determine
solubility of calcium carbonate, acid-precursor alone was
used. The quantity of calcium carbonate dissolved by
the generated acid is given in Table 4. The solubility of
neat fine and medium calcium carbonate in 5 wt.% acid-
precursor at ambient pressure was 36.5 and 26.7 wt.%,
respectively, while in 10 wt.% acid-precursor it was 66
and 37 wt.% for fine and medium, respectively.
The solubility was also examined by determining
PSD. A comparison of PSD for fine and medium
calcium carbonate before and after treatment is given in
Figure 1. It is obvious from the plot that the main target
of the generated acid is smaller particles up to 12 m.
Due to this preferential dissolution of finest particles, a
general shift in PSD of the fine calcium carbonate
occurred towards larger size. The finest particles reacted
with acid and disappeared leaving behind partially
reacted bigger particles. The ratio of decrease in volume
of particles after reaction with the generated acid is
shown in Figure 2.
In case of medium calcium carbonate, the particle size
decreased after reaction with acid. The decrease in size
is attributed to the partial digestion or partial solubility of
bigger particles. These medium particles reacted with
acid and get reduced in size, which is contrary to fine
particles, which disappeared due to complete dissolution.
The medium calcium carbonate after reaction with
generated acid produced smaller particles. The ratio of
increase in the volume of smaller particles is shown in
Figure 3.
The solubility of calcium carbonate particles was also
detemined at 500 psi pressure. The solubility of fine and
medium was found to be 24 and 2.5 wt.%, respectively.
The PSD of calcium carbonate after treatment with
generated acid at 500 psi is given in Figure 4. The low
solubility is attributed to the accumulation of products,
mainly carbon dioxide. It is obvious from the figure that
in case of fine particles the median particle size increased
to 18.7 m from the original 10.8 m, while in case of
medium calcium carbonate, a decrease in particle size
was observed; the median particle size was found to be
78 m (neat 136.8 m). The decrease in particle size at
high pressure is relatively less compared to the decrease
after dissolution at ambient pressure.
The results of solubility of calcium carbonate
indicated that the generated acid dissolved calcite more
readily than dolomite. As such the solubility of dolomite
is much less in weak acid. The XRD analysis of the
calcium carbonate left after dissolution in the generated
acid indicated 82 and 90 wt.% dolomite in fine and
medium, respectively.
The generation of acid in various brines like KCl,
NaCl, and CaCl
2
was determined at ambient oxygen.
The effect of cationic species on acid generation was not
observed as the quantity of acid generated was same in
all brines (3 vol.%). The effect of brine salinity on acid
generation was studied using 2, 5, and 7 wt.% KCl brine.
The volume of acid generated in these three brines was
found to be the same.
SPE 99799 3
Products obtained in acid generation and solubility
tests were identified by ferric chloride test as sodium and
calcium acetates.

Return Permeability Tests
To determine the effects of APES on return permeability
of the core, three tests were performed on reservoir cores
using three DIFs of various formulations (Table 1).
Return permeability tests were conducted using dynamic
mud loop system. Test temperature was 210
o
F, while
pore and confining pressures were 500 and 1,000 psi,
respectively. At first, the base permeability of the core
was established then the DIF was circulated across the
face of the core for 30 minutes in dynamic mode and for
16 hrs at static condition at an overbalance pressure of
200 psi. The fluid loss as a function of time was
measured during dynamic circulation. After the
completion of static exposure the filter cake was washed
with KCl brine of equivalent density, following which
the return permeability was determined. Then, the filter
cake was treated with APES solution and left to soak for
48 hours.
In the first test, KCl based DIF of the composition
given in Table 1 was used. The base permeability of the
core to formation brine was 303 mD. The return
permeability of the core was found to be 10%, which was
increased to 72% after treatment with APES (Figure 5).
The second test was conducted with a DIF containing
an optimized loading of fine and medium calcium
carbonate (Table 1). The leakoff during 30 minutes of
circulation was 6 mL. The low leakoff indicates good
bridging ability of the DIF. The return permeability was
found to be 73%. The increase in return permeability
after treatment with APES was marginal in this case, 3%
only (Fig. 5).
In the third test, a DIF with a relatively low loading of
calcium carbonate was used (Table 1). The base
permeability of this core was 124 mD, which reduced to
10% after DIF circulation. The fluid loss during the
circulation of DIF was 20 mL. High fluid loss and low
return permeability exhibit the incapability of the DIF to
create effective bridging. The return permeability after
treatment with APES was found to be 45% (Fig. 5).

Discussion
The reaction between calcium carbonate and organic acid
can be represented by a single-consolidated equation:

CaCO
3
+2R-COOH Ca (OOC-R)
2
+H
2
O + CO
2
.....(1)

R= H or CH
3

The equilibrium constant for any reaction is written as:

K
eq
= [Products]/[Reactants] ...(2)

The equilibrium equation for the reaction between
organic acid and calcium carbonate according to
equation 1 will be:

K
eq
= [Ca(OOC-R)
2
] [CO
2
]/ [CaCO
3
] [RCOOH]
2
(3)

As the activity of solids is always taken as unity, hence
the equation 3 will become;

K
eq
= [Ca(OOC-R)
2
] [CO
2
]/ [RCOOH]
2
.. (4)

The equilibrium shows that the rate of the reaction
depends on the activity of hydrogen ions.

Rate [H
+
]
n
(5)

The availability of hydrogen ions depends on the
dissociation capacity of an acid. The dissociation
capacity, which is called ionization or dissociation
constant, is very low for acetic acid, nearly 1.76x10
-5

mol/liter at 77
o
F. The pK
a
of acetic acid is 4.74, which
means acetic acid dissociates to its maximum extent at
this point, consequently reaction will attain equilibrium.
In other words due to high pK
a
value, the acetic acid
does not be consumed 100% in reactions.
Particle size of the calcium carbonate
(bridging/weighting material) in DIFs is a critical factor
in controlling fluid loss and particle invasion. To
examine the effect of APES

on bridging material and
polymer, the DIF (Table 1) was treated with APES
solution (Table 3). The median particle size (D
50
) of the
DIF increased after the treatment from 37 to 54 m
(Figure 6). It appears from the figure that the generated
acid has removed most of the fine particles. This can be
seen clearly from the shift in lower portion of the graph.
As a result, a shift towards larger particle size occurred.
This shows that the fine particles are targeted by the
generated acid.
The pH of the solution after reaction was high in case
of fine and relatively lower in case of medium (Table 4).
The differences in acid strengths and pH values of the
solutions after reaction show the amount of acid
consumed by each type of calcium carbonate particles;
more consumption of acid by fine particles, while little
less consumption by medium particles. This justifies the
solubility order of calcium carbonate particles in acid:
fine>medium.
The comparison between the PSD plots of fine
calcium carbonate before and after treatment shows that
the fine particles were attacked heavily by the generated
acid. For example, the particles lying in the range of
particle size up to 8 m were dissolved preferentially and
their volume was lowered from 41% to 13.68%. The
sudden decrease in the volume of these finest particles
raised the percentage of relatively bigger particles. This
is obvious from the increase in median particle size from
10.8 m before treatment to 25.7 m after treatment (Fig.
1). The ratio of decrease in volume of calcium carbonate
particles due to solubility in acid seems to be a function
of their particle size. The high decrease in volume of
calcium carbonate particles is more pronounced up to
particle size of 12 m (Fig. 2).
In case of the reaction of medium particles with the
generated acid, larger particles were reduced to smaller
particles and the PSD plot shifted towards smaller size
(Fig. 1). A close examination of the graph reveals that
4 SPE 99799
after reaction with the generated acid, smaller-sized
particles were produced by medium particles. This trend
is shown clearly in Figure 3.
The solubility of fine and medium calcium carbonate
at 500 psi pressure was found to be 24 and 2.5 wt.%,
respectively. The minimum quantity of medium
particles dissolved is the smallest particles (below 10
m) present. Figure 1

shows that some particles among
medium fall in the category of fines and range between
2-3%.
It is clear from Figure 4 that the majority of fine
particles have reacted with the generated acid at 500 psi.
For example, volumes of the fine particles of 1.5 m size
decreased from 13.35% to 5.72% and 12 m size
decreased from 53% to 34%. The particle size has
decreased from 136.8 to 78 m. In case of medium
calcium carbonate particles, apart from dissolution of
very fine particles, partial digestion of other bigger
particles also took place. Due to this partial digestion,
the size of all the medium particles decreased. The
median particle size for fines increased from 10.8 m to
18.7 m (Fig. 4). The increase in meadien particle size is
less than the increase in case of solubility at ambient
pressure (Fig. 1).
The lesser dissolution of CaCO
3
under pressurized
conditions may be due to accumulation of products in the
reaction cell, which brings the reaction to standstill in a
short time. The other reason may be that the amount of
acid generated at high pressure may be less. This
assumption is ruled out as the acid generated by 5 wt.%
acid-precursor at ambient and 500 psi was the same, 3
vol.% (Table 5). The first assumption looks more
appropriate as the reaction between acetic acid and
calcium carbonate completes to the extent of 50%.
8
It is
also a fact that the K
a
values for weak acids are usually
low, which shows their incomplete dissociation.
The generation of acid by acid-precursor was
determined in various ways. The acid-precursor in 7
wt.% KCl brine was heated for 6 to 48 hours at 210
o
F in
different tests. The acid generated by 5 wt.% acid-
precursor was found to be nearly 3 vol.% on heating for
24 - 48 hours. The acid generation started after 6 hours
of heating and was found to be around 1 vol.% in both 5
and 10 wt.% concentration of acid-precursor (Tables 5
and 6). Acid generated by 5 wt.% acid-precursor on 20
and 12 hours of heating was 2.8 and 2.3 vol.%,
respectively (Table 5).
The acid generated by 10 wt.% acid-precursor during
24-48 hours heating was nearly 3 vol.% (Table 6). This
is similar to the volume of acid generated by 5 wt.%
acid-precursor (Table 5). The concentration of acid
expected was more as the increased quantity of precursor
was used in this case. The reason of generating less
quantity of acid by 10 wt.% acid-precursor is that the
reaction might have attained equilibrium at the stage
where 3 vol.% of acid is generated. In this situation,
unless products are removed from the cell or consumed
by other species, the amount of acid does not increase.
This reason looks justified as the quantity of calcium
carbonate dissolved by 10 wt.% acid-precursor solution
was higher (66 wt.%) than the quantity of calcium
carbonate dissolved by 5 wt.% acid-precursor solution
(36 wt.%), in equal volumes (Table 4). Since the acid
generated was consumed by calcium carbonate, it created
space for the new acid to generate.
Based on the above observations, a test for acid
generation was performed in one gallon bottle to provide
more oxygen to reacting material compared to that of one
liter bottle. In this case, 200 ml of 10 wt.% acid-
precursor in 7 wt.% KCl brine was placed (similar to the
previous tests). The strength of acid generated after 24
hours was found to be 4.4 vol.% (Table 6). The obvious
reason of increased quantity of acid is the increased
volume of air (oxygen).
During the acid generation tests, it was observed that a
vacuum is being created in the reaction bottles. This
phenomenon associated with the increased volume of
acid generated in one gallon bottle led us to perform the
acid generation test in an oxygen-rich atmosphere.
The acid precursor, 10 wt.%, mixed in 7 wt.% KCl
brine, was placed in one liter bottle and pure oxygen was
flown into it for five minutes to replace the air. The
bottle was closed quickly and kept in the oven at 210
o
F
for 24 hours. The acid strength was found to be nearly
5.6 vol.%. This value is higher than the value obtained
in other similar tests (Table 6). The vacuum was
generated again. The creation of vacuum explains that
the maximum generation of acid will take place under
pressurized oxygen supply.
This was mentioned earlier that acid was generated in
equal volumes at high and ambient pressures. This was
mainly due to the limited availability of oxygen to the
precursor. This informs that availability of oxygen in
excess is a requirement for maximum acid to be
generated by APES. The ambient oxygen is just enough
to generate acid from 5 wt.% acid-precursor. The
solubility of medium calcium carbonate in oxygen-rich
atmosphere in 10 wt.% acid-precursor solution was
found to be nearly 48 wt.%, while in ambient oxygen it
was nearly 37wt.% (Table 4).

Effect of Generated Acid on Carbonate Rock
A solid piece of carbonate core was placed in a 5 wt.%
solution of acid-precursor and heated for more than 48
hours at 210
o
F. The loss of weight was found to be
41.26%. The strength of the remaining acid was 0.15
vol.%, while the pH of the solution was 5.39. This
shows that the generated acid has reacted efficiently with
the carbonate content of the rock.
The treated carbonate rock was analyzed by an
Environmental Scanning Electron Microscope (ESEM).
The analysis revealed that the generated acid has
dissolved the fine particles (1 to 5m) of the rock, which
were mainly calcite, while the dolomite remained
unreacted (Photo 1).
The particles separated from the core due to the action
of acid on it were also analyzed by ESEM, which were
found to be 100% dolomite grains (Photo 2).
The acid-precursor was injected into a carbonate core
at 500 psi pore pressure and left to soak for 48 hours. An
SPE 99799 5
improvement in the permeability was expected due to
reaction between carbonate and generated acid, but no
improvement in permeability was observed, which
explains the non action of acid. The non reactivity of
acid was mainly due to pressurized conditions.
A comparison of the PSDs of DIFs with high and low
loading of fine calcium carbonate particles before and
after treatment with acid-precursor is shown in Figures 6
to 8.
The DIF used in the first return permeability test
contained large quantity of fine calcium carbonate (18
ppb). This is a common observation that DIFs with high
loading of fine calcium carbonate do not give good
return permeability. Solids from the drill-in fluids can
invade the formation and result into fines plugging.
7,9

The reduction in permeability in this case to the extent of
90% indicates the invasion of fine calcium carbonate into
the core. The filter cake was treated with APES

solution.
The return permeability of the core increased from 10%
to 72% (Fig. 5). The increase in permeability after
treatment seems to be due to the dissolution of fine
particles. It was observed that the generated acid
dissolves majority of fine particles (Fig. 1). On this
basis, it is concluded that the APES is useful where DIFs
with heavy loadings of fines are used. Similar increase
in permeability could be obtained by simple acid wash
with brine of pH 2-3. In other cases where the loadings
of fine calcium carbonate was relatively low,
permeability loss was not very high, hence the effect of
APES

was insignificant, as was seen in Test 2.
In the second retrun permeability test, the quantity
of calcium carbonate in the DIF was optimized (8 ppb
fine and 15 ppb medium), hence the initial return
permeability of the core was high (73%). This indicates
an effective bridging by the DIF, which could minimize
invasion of fines and filtrate to the core. Treatment of
the residual filter cake in this case did not result into high
improvement in permeability (Fig. 5).
The DIF used in the third return permeability test
contained low quantity of calcium carbonate, 15 ppb
only (Table 1). The filter cake was treated with APES
solution. The net increase in the core permeability after
treatment was found to be 36%. Usually, it has been
observed in the lab tests that the increase in permeability
of the reservoir rock ranges to the limit of 20% by
enzymatic treatment.
7,10
This should be noted that all
polymer molecules do not undergo 100% degradation by
enzymes.
11
Depending on the nature of the core, size of
the pore throat, composition of DIF, concentration of
mud solids, and application of the chemical, the
effectiveness of the treatment varies. The improved
permeability in this case indicates a synergic effect of
enzymes and the generated acid by this treatment. The
increase in permeability in this test is very limited.
A visual observation of the residual filter cake on the
core indicated that the fine and medium particles of
calcium carbonate were still present (Photo 3). XRD
analysis of the residual filter cake revealed the presence
of calcite as a major component. The calcium carbonate
particles in the filter cake that were not dissolved by acid
may be contributing to the permeability loss. Acids are
capable of dissolving calcium carbonate, but in practice
calcium carbonate particles in DIFs are coated with
polymer residue due to which their removal becomes
non-uniform.
11,12
Enzymes used for treatments do not
destroy all polymer molecules.
11
The high content of
calcite in the residual filter cake shows that most of the
calcium carbonate particles may had been covered by
polymer layers, which resulted into poor contact with the
acid. Due to this reason improper dissolution of calcium
carbonate took place.
The function of enzymes at a pH range of 2-3 is not
pronounced due to their least activity. The activity of
enzymes varies with pH.
13
Enzymes have highest
activity at pH 5, while at pH 3 its activity was found to
be 60% only.
14
In the present study, the acid generated
in-situ creates a pH in the range of 2-3, which is more
suitable for reaction with calcium carbonate but not
highly favorable for the action of enzymes. Unless the
acid is consumed by the reaction with calcium carbonate,
pH of the solution does not rise. Therefore, enzymes can
not exhibit their efficiency at the beginning. This is the
reason that in this test the filter cake remains almost
intact after soaking for 48 hours (Photo 3).
This result again confirms that this chemical is more
useful in cases where DIFs with high loadings of fine
calcium carbonate are employed for drilling. The
dissolution of calcium carbonate was found to be less at
high pressure (200-500psi). Due to the accumulation of
products, the reaction between organic acid and
carbonate completes only to 50%.
8
At downhole
conditions, weak acids do not spend 100%.
15
When the
pH value of the reacting solution lies in the range of 4-6,
the weak acid does not dissociate further.
15

The equilibrium of the reaction between acid and
carbonate is related to the concentration of carbon
dioxide (products). As the carbonic acid tends to
dissociate into carbon dioxide and water due to energy
and entropy factors, it is necessary to maintain a constant
pressure during soaking period to accommodate the
liberating carbon dioxide gas. This will enable the
reaction between carbonate and acetic acid to drive to
full extent, according to Le Chateliers principle. Since
the pK
a
value of acetic acid is 4.75, the dissolution of
calcium carbonate does not proceed further once the
solution attains pH equal to pK
a
. This is the reason that
the pH value of the solution after reaction with fine and
medium calcium carbonate is around 4.75 at ambient and
pressurized conditions (Table 4).
On the basis of this study, it is concluded that the
single stage treatment in removing filter cake is safe and
economical. It provides operational freedom in the field
with minimum to zero health and environment problems.
The treatment fluid does not pose any serious threat of
tools corrosion or early spending of acid. The advantage
of using in-situ generating acid seems to be more in
deeper wells (>10,000 feet) where it can be placed
uniformly all over the treatment zone. In deep gas wells,
use of mineral acid or acidic brine needs extra care and
equipments coupled with other types of chemicals.
6 SPE 99799
The limitation of the system is that the effectiveness of
the treatment was not pronounced in removing polymer
due to high acidic environment at the early stage.
Dissolution of calcium carbonate that is present in the
filter cake to the maximum extent was hindered due to
incomplete degradation of polymer chains.
For shallow oil wells, fine calcium carbonate particles
can be easily removed by acidic brine wash with a pH of
2-3 that requires few hours, following which enzymes
can be placed into the well for a similar soaking period.

Conclusions
1. The acid-precursor, 5 and 10 wt.%, generated
acetic acid (3 vol.%) at ambient oxygen, while
nearly 6 vol.% acid was generated by 10 wt.%
precursor in oxygenated brine at 210
o
F.

2. Complete acid generation took place in 24 hours
soaking time at 210
o
F. Extended soaking time
did not increase the volume of generated acid.
3. The strength of acid generated is independent of
the nature of brine, salinity, and pressure.
4. The generated acid dissolved fine particles of
calcium carbonate more readily than medium.
5. The acid precursor is more useful in the DIFs
with high loadings of fine calcium carbonate.
6. The dissolution of calcium carbonate in the
generated acid is more at low pressure.
7. Acid generation is temperature dependent;
hence it will minimize placement and tools
corrosion problems, which are associated with
mineral acids.

Acknowledgements
Authors gratefully acknowledge Saudi Aramco for
granting permission to present and publish this paper.
Authors are thankful to core analysis team of Petrophysic
Unit for determining core properties. Personnel from
DF&CU are acknowledged for facilitating DIFs and PSD
analyses. Thanks go to Spectroscopy and Elemental
Analysis Unit for ESEM and XRD analyses.

Acronyms
DIF = Drill-in fluid
ESEM = Environmental scan electron microscope
N = Normality
PSD = Particle size distribution
ppb = Pound per barrel

References

1. Almond, S. W., Harris, R. E., and Penny, G. S.:
Utilization of Biologically Generated Acid for
Drilling Fluid Damage Removal and Uniform Acid
Placement Across Long Formation Intervals, paper
SPE 30123 presented at the 1995 SPE European
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2. Harris, R.E. and Mckay, I.D.: New Applications for
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50621 presented at the 1998 SPE European
Petroleum Conference held in The Hague, the
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3. Harris, R.E., McKay, I.D., Mbala, M.J., and Schaaf,
R.P.: Stimulation of a producing Horizontal Well
Using Enzymes that Generate Acid In-Situ- Case
History, paper SPE 68911 presented at the 2001SPE
European Formation Damage Conference held in The
Hague, the Netherlands, May 21-22.

4. Nughamish, F.N., Faraj, O.A., Al-Afaleg, N.I. and
Al-Otaibi, U.F.: First Lateral-Flow-Controlled
Maximum Reservoir Contact (MRC) Well in Saudi
Arabia: Drilling & Completion: Challenges &
Achievments: case Study, paper SPE 87959
presented at the 2004 IADC/SPE Asia Pacific
Drilling Technology Conference and Exhibition held
in Kula Lumpur, Malaysia, 13-15 September.

5. Lynn, J.D.: and Nasr-El-Din, H.A.: Formation
Damage Associated With Water-Based Drilling
Fluids and Emulsified Acid Study, paper SPE 54718
presented at the 1999 SPE European formation
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Netherlands, 31 May 1 June.

6. Lynn, J.D.: Evaluation of Drilling Fluids Damage
Using a Closed Loop Dynamic Slurry Circulation
System, paper SPE 29833 presented at the 1995 SPE
Middle East Oil Show, held in Manama, Bahrain
March 11-14.

7. Siddiqui, M.A and Nasr-El-Din, H.A.: Evaluation of
Special Enzymes as a Means to Remove Formation
Damage Induced by Drill-in Fluids in Horizontal Gas
Wells in Tight Reservoirs, paper SPE 81455
presented at the 2003 SPE 13th Middle East Oil
Show & Conference held in Manama, Bahrain, April
5-8.

8. Huang, T., McElfresh, P.M., and Gabrysch, A.D.:
Carbonate Matrix Acidizing Fluids at High
Temperatures: Acetic Acid, Chelating Agents or
Long-Chained Carboxylic Acids?, paper SPE 82268
presented at the 2003 SPE European Formation
Damage Conference held in The Hague, The
Netherlands, May 13-14.

9. Moghadasi, J., Jamialahmadi, M., Muller-Steinhagen,
H., Sharif, A. and Izadpanah, M.R.: Formation
Damage in Iranian Oil Fields, paper SPE 73781
presented at the 2002 SPE International Symposium
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10. Al-Otaibi, M.B., Nasr-El-Din, H.A., and Siddiqui,
M.A.: Chemical Treatments to Enhance Productivity
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SPE 99799 7
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Table 1. Composition of DIF used in tests.




Table 2. Particle sizes of neat calcium carbonate.
















Table 3. Composition of APES solution used in
this study.















Test # 1 Test # 2 Test # 3
Ingredient Quantity Quantity Quantity
Water, bbl 0.96 0.96 0.95
Defoamer, gpb 0.01 0.01 0.01
XC-polymer, ppb 2.0 2.0 1.5
PAC-R, ppb 0.5 0.5 0.75
Dextrid, ppb 8.0 8.0 4.0
KCl, ppb 14.0 14.0 8.7
Lime, ppb 0.15 0.15 0.25
CaCO
3
fine, ppb 18.0 8.0 5.0
CaCO
3
medium,
ppb
5.0 15.0 10.0
D
50
of DIF, m 37.58 58.14 34.88
Material D
50,
m, D
90,
m
Fine CaCO
3
10.8 31.5
Medium CaCO
3
136.8 276.4
Ingredient Quantity
7 wt% KCl Brine, vol.% 89.9
Acid-precursor, wt.% 5.0
Surfactant, vol.% 0.1
Catalyst, wt.% 1.5
Enzymes for Starch, vol.% 0.5
Enzymes for Xanthan, vol.% 1.0
8 SPE 99799



Table 4. Solubility of calcium carbonate in acid-precursor solution at 210
o
F.



















a
at ambient oxygen and ambient pressure.

b
in oxygenated brine at ambient pressure.


Table 5. Concentration of acid generated by 5 wt.% acid-precursor in 7 wt.% KCl brine at 210
o
F.
























a
with catalyst.

b
in oxygenated brine at ambient pressure.
c
at 500 psi pressure at 210
o
F.
d
percent of generated acid calculated relative to 1% acetic acid.



Calcium Carbonate Acid-
precursor,
wt.%
solubility,
wt.%
pH
Fine
a
5 36.42 5.08
Medium
a
5 26.73 4.85
Fine
a
10 66.0 5.83
Medium
a
10 36.97 5.50
Fine, at 500 psi 5 24.0 5.29
Medium, at 500 psi 5 2.5 4.71
Medium
b
10 47.84 NM
Conditions Concentration, vol.% pH
48 hrs soaking
a
2.607 3.63
48 hrs soaking 2.84 2.90
24 hrs

soaking 2.85 2.92
20 hrs

soaking 2.82 -
12 hrs soaking 2.29 2.94
6 hrs

soaking 1.035 2.95
12 hrs soaking
b
2.29 2.95
6 hrs soaking
b
1.11 2.99
With fine CaCO
3
, 48 hrs soaking 0.575 5.08
With medium CaCO
3
, 48 hrs soaking 0.4414 4.85
48 hrs

soaking
c
2.85 2.93
With fine CaCO
3
,

48 hrs soaking
c
0.263 5.29
With medium CaCO
3
, 48 hrs soaking
c
0.52 4.71
1% acetic acid solution (standard)
d
1.0 2.99
SPE 99799 9

Table 6. Concentration and pH of the acid generated by 10 wt.% acid-precursor in 7 wt.% KCl brine at 210
o
F.
























0
20
40
60
80
100
1 10 100 1000 10000
Particle Size, m
C
u
m
u
l
a
t
i
v
e

V
o
l
u
m
e
,

%
Neat Fine, D50 =10.8m
Treated Fine, D50 =25.7m
Neat Medium, D50 =136.8m
Treated Medium, D50 =70m

Figure 1. PSD of neat fine and medium calcium carbonate before and after treatment with APES.

Conditions Acid, % pH
6 hrs soaking 1.024 3.01
24 hrs soaking 2.84 2.78
48 hrs soaking 2.85 2.76
24 hrs soaking in 1 L bottle in oxygen-rich brine 5.608 2.60
24 hrs soaking in 1 gallon bottle 4.416 2.69
36 hrs soaking with medium CaCO
3
in oxygen-rich brine for 36
hours
0.7733 4.92
10 SPE 99799
0
2
4
6
8
10
0 10 20 30 40 50
Particle Size, m
V
o
l
u
m
e

D
e
c
r
e
a
s
e
R
a
t
i
o

Figure 2. Ratio of decrease in volume of fine calcium carbonate after treatment with generated acid.

0
25
50
75
100
125
0 10 20 30 40 50
Particle Size, m
V
o
l
u
m
e

I
n
c
r
e
a
s
e

R
a
t
i
o

Figure 3. Ratio of increase in volume of medium calcium carbonate after treatment with generated acid.
0
20
40
60
80
100
1 10 100 1000 10000
Particle Size, m
C
u
m
u
l
a
t
i
v
e

V
o
l
u
m
e
,

%
Neat fine, D50 =10.8m
Treated fine, D50 =18.7m
Neat medium, D50 =136.8m
Treated medium, D 50 =78m

Figure 4. Comparison of PSD of fine and medium calcium carbonate after treatment
with acid-precursor under pressurized conditions.
SPE 99799 11
0
20
40
60
80
1 2 3
Test Numbers
R
e
t
u
r
n

P
e
r
m
e
a
b
i
l
i
t
y
,

%
After KCl wash
After APES
10% 10%
72%
73%
76%
45%

Figure 5. Comparison of permeability of cores before and after APES treatment.

0
20
40
60
80
100
1 10 100 1000 10000
Particle Size, m

C
u
m
u
l
a
t
i
v
e

V
o
l
u
m
e
,

%
Fresh DIF, D50 =37 m
Treated DIF, D50 =54 m

Figure 6. Comparison of the PSD of DIF after treatment with APES.

0
20
40
60
80
100
1 10 100 1000 10000
Particle Size, m
C
u
m
u
l
a
t
i
v
e

V
o
l
u
m
e
,

%
Fresh DIF, D50 =58.14 m
Treated DIF, D50 =72.44

Figure 7. Comparison of the PSD of DIFs with low loading of fine calcium carbonate,

before and

after treatment with acid-precursor.

12 SPE 99799
0
20
40
60
80
100
1 10 100 1000 10000
Particle Size, m
C
u
m
u
l
a
t
i
v
e

V
o
l
u
m
e
,

%
Fresh DIF, D50 =34.88 m
Treated DIF, D50 =66.02 m

Figure 8. Comparison of the PSD of DIFs with low loading of calcium carbonate,

before and

after treatment with acid-precursor.









Photo 1: Back scattered electron (BSE) image of the treated core showing etched dolomite grains.
Fine grained calcite are not present, Magnification 76X.













SPE 99799 13




Photo 2: BSE image of particles collected on filter paper after the treatment of the core.
100 m dolomite grains, absence of fine grained calcite, Magnification 100X.

























Photo 3. Filter cake remained on the core face after treatment with APES.




Vugs filled
with fines
Partially
removed filter
cake