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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
SPE 86484
Fluid
Type
15750
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
5.0
2.00
10.0
7.2
0.00
0.0
Depth (ft)
15900
15950
16000
16050
16.00
16100
16150
High
16500
100
21000
25500
30000
100
119
200
138
157
176
195
300
214
400
233
252
271
290
500
Length (ft)
691 ft
294 ft
0.08 in.
64 ft
2
0.38 lb/ft
120
32
30
100
28
26
24
22
80
20
18
60
16
14
12
40
10
8
6
20
4
2
0
6.00
10.00
14.00
18.00
37.00
40.00
62.00
86.00
88.00
100.0
124.0
BSW (%)
Low
16250
12000
kppm CaCO3
Permeability
16200
pKa = 3.1
pKa = 4.8
pKa = 6.4
(1)
(2)
(3)
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
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.
SPE 86484
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.
References
10% Citric
1.5
1
0
100
200
300
400
500
Time, minutes