SPE 86484

Acid Fracturing With Encapsulated Citric Acid

Gerardo Burgos, Shell Venezuela S.A., George Birch, SPE, Shell Venezuela S.A., Marten Buijse, SPE, Shell International
Exploration and Production BV
Copyright 2004, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Symposium and Exhibition
on Formation Damage Control held in Lafayette, Louisiana, U.S.A., 1820 February 2004.
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Abstract
The paper evaluates the design considerations and execution
results of the first commercial field trial of a novel acid
fracturing technique, using encapsulated citric acid as the
etching agent. The treatment was executed in the Maraca tight
carbonate oil reservoir (16,000 ft, 270F) under Lake
Maracaibo, Venezuela. The main driver for this trial with an
alternative acid was to obtain a significant increase in etched
fracture length, over the current standard acid formulation for
this reservoir of acetic and formic acid. The encapsulated
citric acid is solid at temperatures up to 180F and coated with
vegetable oil to avoid dissolution in the carrier fluid. The job
was designed for a target etched half-length in excess of 300
ft. The job was an operational success, placing 30,000 lbs of
the solid acid in the formation. Post-treatment results,
however, did not show any improvement in production from
the test well. The paper also reviews several of the
possibilities for the failure of the treatment and the limitations
of the technology as an effective acid for fracturing carbonate
formations.
Introduction
The Cogollo reservoir is a tough carbonate play under Lake
Maracaibo in Venezuela. It consists of three formations: the
Maraca, Lisure and Apon, which together have a total
thickness of some 1,000 ft. The main producer out of the three
is the porous Maraca formation. It is also the shallowest of the
three (15,500-16,000 ft), having 20-30 ft of net pay and about
100 ft of gross height. The oil reservoir (28-30 API) is mainly
composed of calcite (over 90%) and the reservoir temperature
varies between 260 and 280 F.
Current development strategy for the reservoir focuses on
the development of the Maraca formation, targeting high
porosity areas with vertical wells completed with a cased and

cemented liner and stimulated during initial completion

through acid fracturing. Acid fracturing has been a successful
method to increase well productivity and make the
development of the Maraca reservoir economical.
As a result of the low to moderate permeability of most
wells in this area (2-25 mD), the main challenge in an acid
fracture treatment is maximizing etched fracture length to
maximize productivity. At this permeability level, fracture
conductivity plays a smaller role in productivity, as acidetched fractures in competent rocks tend to be extremely
conductive. A successful campaign of twelve acid fractured
wells was completed using a gelled organic acid blend of 13%
acetic and 9% formic acid. Organic acids were selected as a
result of their natural retardation, easier corrosion inhibition1
and better compatibility with formation fluids. Conventional
HCl systems were discarded because of their high tendency to
form heavy sludge upon contact with the reservoir fluid2. Even
though the campaign was very successful (field production
was effectively doubled in two years), computer simulations
indicated effective half-lengths of only 40-50 ft, suggesting
there was potential for a more retarded system to significantly
enhance productivity.
Encapsulated citric acid (ECA) was envisioned as a viable
alternative in the quest for longer fractures. This acid is coated
in a vegetable oil that keeps it from dissolving in water-based
fluids until the capsules start melting at around 180 F. The
job design aimed at obtaining fracture half-lengths in excess of
300 ft by placing the citric acid in a way similar to a
conventional propped fracture treatment.
Candidate Well Selection
The well selected for the trial was a typical oil well in the area
with an average permeability of 8 mD completed in the
Maraca interval only, with a net pay of 20 ft. Previously, the
well had been successfully acid fractured with 13% acetic and
9% formic acid, but after 2 years of production the
productivity index in the well had declined 33%, attributed to
a significant loss in fracture conductivity.
Job Design and Execution
The job design focused in obtaining an effective etched length
in the order of 250-300 ft by placing the solid acid in the
fracture in a similar way to a propped fracture. Given the
relatively high formation temperature, one of the main
challenges consisted in cooling down the fracture face below

Acid Fracturing with Encapsulated Citric Acid

the melting point of the capsules (~180 F) to enable

placement of the acid in a solid form. The acid encapsulation
would be either dissolved after heating of the formation above
180 F or be crushed after fracture closure.
Significant thermal modeling of the treatment was carried
out to size a proper cool down stage ahead of the main pad.
The cool down stage required was estimated at 50,000 gal of
linear gel with a 50 lb/Mgal polymer load. The main pad stage
consisted of 40,000 gal of a high temperature crosslinked gel
with 50 lb/Mgal polymer load.
Stress Profile

SPE 86484

diffusive, 10,000 lbs diffusive release) into the formation at an

average rate of 16 bpm and a maximum pressure of 9000 psi
at surface. At the end of the job, the well was monitored and
opened up only after fracture closure to avoid flow back of the
encapsulated acid from the critical near well bore area. Table 1
shows the actual pump schedule and Table 2 shows the
fracture parameters predicted by simulation.
Treatment Schedule
Stage
#

Fluid
Type

Wellbore 50# Linear Gel

Fluid
1
50# Linear Gel

15750

Temperature of Slurry in Fracture (F)

15800

Clean Prop
Vol.
Conc
(kgal) (ppg)
7.4

Stage
Prop.
(klbs)

Slurry
Rate
(bpm)

Prop
Type

50.0

0.00

0.0

16.00

39.9

0.00

0.0

16.00

15.0

0.50

18.8

16.00 ECA 1
16.00 ECA 2

15850

2
3

50# Crosslinked
Gel
50# Linear Gel

50# Linear Gel

5.0

2.00

10.0

50# Linear Gel

7.2

0.00

0.0

Depth (ft)

15900

15950

16000

16050

16.00

16100

Table 1. Treatment Schedule

16150

High

16500

100

21000

Closure Stress (psi)

25500

30000

100

119

200

138

157

176

195

300

214

400

233

252

271

290

500

Length (ft)

Figure 1. End of Job Temperature Profile in the Fracture

The encapsulated acid was to be carried with a linear gel,

which would provide sufficient carrying capacity for the light
20-40 mesh encapsulated acid. One of the placement problems
to overcome was the availability of water inside the fracture
after all the acid was placed to enable the dissociation and
reaction of the citric acid. At the end of the placement, and
after fracture closure (when the coating would be crushed)
most of the carrying fluid would have leaked off into the
formation leaving almost dry acid in the fracture. The job was
then designed for the etching to occur upon flow back of the
well, when the frac fluids returned through the fracture into
the well bore, contacting the acid and allowing it to dissociate.
It was decided then to use two stages of encapsulated acid, the
first with 75% of the total acid with a non diffusive coating
(ECA1) and a second stage with an encapsulation such that it
allowed for diffusive release of the acid (ECA2) and etching
during placement to ensure that the fracture would have
sufficient conductivity during initial flow back to be the
preferred path for the frac fluids into the well bore, achieving
contact with the bulk of the acid inside the fracture.
The total amount of acid required was selected after
laboratory testing of the etching capabilities of the citric acid,
which showed that 0.35 lb/ft2 of acid in the fracture would
generate sufficient conductivity (10,000-30,000 mD*ft) for the
formation permeability of the test well.

Hydraulic Fracture Half Length

Etched Fracture Half Length
Average Etched Width
Fracture Height
Average Acid Concentration in Fracture

691 ft
294 ft
0.08 in.
64 ft
2
0.38 lb/ft

Table 2. Simulator Predicted Fracture Properties

Results
During initial flow back the well was sampled and the flow
back water was characterized to determine calcium hardness
as an indication of rock dissolution. The original BS&W for
the test well was below 1%. As seen in Figure 2, the relatively
high hardness (6,000-30,000 ppm) indicated that the acid had
removed significant reservoir rock (lake water used in frac
fluids has 20 ppm Ca++ as CaCO3). However, no increase in
production was observed from the test well, suggesting the
reservoir rock removed did not generate more fracture
conductivity.
34

120

32
30
100

28
26
24

Calcium Hardness (as CaCO3)

BS&W

22

80

20
18

60

16
14
12

40

10
8
6

20

4
2

Prior to the main treatment, a minifrac test was conducted

to calibrate the models for the fluids to be used in the test
well. The main job was pumped successfully afterwards,
placing 30,000 lbs of encapsulated citric acid (20,000 lbs non-

0
6.00

10.00

14.00

18.00

37.00

40.00

62.00

Flowback time (hr)

Figure 2. Flow Back Samples Analysis

86.00

88.00

100.0

124.0

BSW (%)

Low

16250
12000

Slurry Temperature (F)

kppm CaCO3

Permeability

16200

Gerardo Burgos, George Birch, Marten Buijse

Several sources have been identified as possibilities to

explain the disappointing results, amongst them polymer
damage from the large amount of polymer used, poor
connectivity of the fracture with the well bore or poor
connection of the created etched channels between them, not
enough etched width, calcium citrate precipitation etc.
Of all the potential reasons that could explain the result,
two are specific for this sort of treatment and need to be
further evaluated. Firstly, when pumping an encapsulated acid,
the etching is not done during placement, as opposed to
conventional acid fracs, when all the etching is done during
the pumping of a reactive acid that etches the fracture face and
connects all the created channels on the fracture. In an
encapsulated acid frac if the solid acid pellets are not evenly
distributed on the fracture face, the acid can leave etched
patches on the fracture face with poor connectivity.
Secondly, the other main issue to be considered when using
citric acid as a main stimulation fluid is calcium citrate
precipitation. Significant lab testing was done upfront, that
suggested no precipitation would occur at downhole
conditions, but following the results of the trial, further testing
was carried out that suggested that precipitation is indeed
possible at downhole conditions.
Citric Acid Carbonate Chemistry
Citric acid is a triprotic organic acid, H3Citrate. Dissolved in
water, citric acid dissociates in three steps:
H3Citrate H+ + H2CitrateH2Citrate- H+ + HCitrate-2
HCitrate-2 H+ + Citrate-3

pKa = 3.1
pKa = 4.8
pKa = 6.4

(1)
(2)
(3)

The dissociation and the distribution of the ionic species

depends on the pKa values and on the pH of the solution. In
Figure 3 the ionic distribution is plotted as a function of pH.
When citric acid is dissolved in water, without any pH
adjustment, the pH is in the range 1.7-2.1, depending on the
strength. At this pH value >95% of the acid is in the neutral
form, H3Citrate, while <5% of the acid is dissociated in H+
and H2Citrate-. When citric acid spends on carbonate the pH
will increase and more acid will dissociate.
Like other weak acids, such as acetic or formic, the
spending of citric acid on carbonate is incomplete. The final
pH of the spent acid will be about 5 and is controlled by the
buffering of CO2 (actually H2CO3) that is generated during the
acid-carbonate dissolution reaction3. At this pH value the citric
dissociation is still incomplete (see Figure 3) and part of the
acid will not spend. For example, the dissolving power of 10%
citric is theoretically about 75 kg CaCO3 per m3 acid.
However, under downhole conditions, when most CO2 stays in
solution, the dissolving power is closer to 50 kg per m3 acid.
To put this number in perspective: the downhole dissolving
power of 15% HCl and 13/9% acetic/formic acid is 220 kg
CaCO3 and 130 kg per m3 acid respectively.

0.30
pH of spent acid

concentration (mol/l)

SPE 86484

0.25

H3 Citrate

0.20

H2 Citrate

Citrate

HCitrate

-3

-2

0.15
0.10
0.05
0.00
1

pH

Figure 3. Distribution of citric acid ions as function of pH for a

0.25 mol/l citric solution

Calcium-Citrate Precipitation
When citric acid spends on CaCO3 rock, the released Ca+2 ions
will form complexes with the various citric ions present in
solution: CaH2Citrate+, CaHCitrate, etc. One of these
complexes, Ca3Citrate2, is only poorly soluble and will
ultimately precipitate.
Available data in literature at 167F and ambient pressure
indicate that Ca3Citrate2 precipitation already starts at a pH of
about 2.5 or below4. For a 10% citric solution this means that
precipitation will occur after the dissolution of only 12 grams
of CaCO3 per liter acid. To analyze the Ca3Citrate2
precipitation under downhole conditions several tests were
performed in an autoclave at 250F and 1200 psi. Pieces of
limestone were put in the autoclave, after which it was heated
and pressurized. Pre-heated 10% citric acid was added under
pressure. The acid was continuously stirred during the test.
Fluid samples were taken periodically and analyzed. After 24
hours the test was stopped and the (partially) dissolved pieces
of carbonate were examined for the presence of precipitate.
Figure 4 is a plot of the pH development during acid
spending. From this plot it can be concluded that the citric
spending is relatively slow. The initial pH of the unspent acid
is 1.7. After 30 min of spending the pH has increased to a
value of only 2.2, while after 24 hours of spending the pH is
still only 2.7. So even after 24 hours, the first proton of citric
acid has not yet completely spent. In the same Figure 4, the
pH development of a similar test with 13/9% acetic/formic is
plotted. Compared to 10% citric, the initial pH of 13/9%
acetic/formic is the same, but it reacts much faster and the pH
increases much more rapidly during spending. After 30 min,
the pH has a value of 3.5, and after about 8 hours the final pH
of 4.2 is reached.

Acid Fracturing with Encapsulated Citric Acid

SPE 86484

models3 and pressure transient analysis data indicate that the

actual etched lengths obtained in the field with the
conventional organic acids are in the order of 150-250 ft.

4.5
pH after 24 hours: 4.2
4

13/9% Acetic/Formic

3.5

pH

Following the results from this trial, the well was acid
fractured with a formic/acetic acid blend, achieving a 30%
increase in productivity, showing that there was scope for
productivity improvement that could not be realized with the
encapsulated citric acid.

pH after 24 hours: 2.7

2.5

References

10% Citric

1. van Domelen, M.S., Jennings, A.R.: Alternate Acid Blends for

HPHT Applications, paper SPE 30419, presented at the
Offshore European Conference, Sep. 5-8, 1995, Aberdeen.

1.5

1
0

100

200

300

400

500

Time, minutes

Figure 4. Spending of 10% Citric and 13/9% Acetic/Formic on

Calcium Carbonate rock at 250F and 1200 psi

No precipitation occurred in the samples taken during the test,

also not after several hours. However, examination of the
limestone pieces after the test revealed a layer of white
Ca3Citrate2 precipitate on the surface. It is not surprising that a
precipitate will preferentially form at the limestone surface,
and not in the bulk solution. The acid-rock dissolution reaction
will create conditions at the surface that favor precipitation:
relatively high Ca+2 concentration and high pH.
The Ca3Citrate2 precipitation, coating the rock surface,
explains the slow reaction rate observed in the autoclave tests.
The precipitate forms an effective barrier and will slow down
and eventually completely stop the dissolution reaction.
Precipitation on the rock surface was also present after a test
that lasted only 15 min. The conclusion is that Ca3Citrate2 will
precipitate even when only a small fraction of the citric acid
has spent.
Conclusion
A commercial trial of acid fracturing using encapsulated citric
acid was carried out in the Maraca Limestone under Lake
Maracaibo, Venezuela. The job was operationally successful
in placing 30,000 lb of encapsulated acid inside a
hydraulically created fracture. However, the productivity of
the treated well was not affected after the job.
There are several explanations for the disappointing
results, but the available data stops short of identifying a
single source. From the field results is not clear if calciumcitrate precipitation contributed to the poor success of the
encapsulated acid treatment. However, in our opinion the
potential problems associated with precipitation in the
formation are serious enough to exclude citric acid as a
stimulation fluid for carbonate formations.
The case for the encapsulated citric acid trial was built
upon the belief that the acid fracs with organic acid were
achieving etched lengths in the order of 40-50 ft. Current

2. Rietjens, M., Nieuwpoort, M.: Acid-Sludge: How Small

Particles Can Make a Big Impact, SPE 54727, presented at the
SPE European Formation Damage, 31 May-1 June, 1999, The
Hague.
3. Buijse, M.A., de Boer, P., Breukel, B., Klos, M., Burgos, G.:
Organic Acids in Carbonate Acidizing, SPE 82211, presented
at the European Formation Damage Symposium, 13-14 may,
2003.
4. Al-Khaldi, M.H., Nasr-El-Din, H.A., Blauch, M.E., Funkhouser,
G.P.: New Findings on Damage Potential, Geochemical
Reaction
Mechanisms,
and
Production
Enhancement
Applications for Citric Acid, SPE 82218, presented at the
European Formation Damage Symposium, 13-14 may, 2003.