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Investigation of Some Copolymers Based On Acrylic Salts As Circulation Loss Control Agents
Investigation of Some Copolymers Based On Acrylic Salts As Circulation Loss Control Agents
a
Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
b
Faculty of Science, Banha University, Egypt
KEYWORDS Abstract In this work, six copolymers were prepared from sodium and potassium acrylate. Both
Sodium acrylate; salts individually were copolymerized with acrylamide, methacrylic acid and acrylic acid at different
Potassium acrylate; ratios. The monomer reactivity ratios for copolymerization reactions of both of acrylate salts with
Permeability plugging tester; acrylamide, methacrylic acid and acrylic acid, in solution with azobisisobutyronitrile (AIBN) as an
Spurt loss; initiator, were estimated by atomic adsorption analyser. The chemical structure was confirmed by
Rheological properties atomic adsorption spectroscopy and FT-IR spectroscopy.
The prepared copolymers were investigated as loss circulation control materials by measuring dif-
ferent filtration parameters such as; spurt loss, fluid loss and permeability plugging tester value
according to the American Petroleum Institute (API) standard. From the obtained data, it was
found that the 0.6% from the poly[PA-co-AM](0.4:0.6) exhibited the best results of the filtration
parameters among the other copolymers. At the same time all the studied copolymers enhanced
the rheological properties of the drilling mud. These results were discussed on the light of the swell-
ing capacity of the copolymers.
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Lost circulation problems may be encountered at any depth In this paper, six sodium and potassium acrylate copoly-
when the total pressure exerted against the formation exceeds mers should be prepared and investigated as lost circulation
the formation breakdown pressure [8–9]. control materials depending on their swelling properties and
Many products and techniques have been used to attempt its monomer reactivity ratios. The chemical composition of
to restore circulation while drilling [10]. The problem is nor- these copolymers may be used to discuss the obtained results.
mally addressed through the application of conventional lost
circulation materials (LCMs), such as calcium carbonate, 2. Experimental
mica, and salt pills.
Recently, treatments based on chemically activated cross- 2.1. Materials
linked pills have shown their effectiveness to plug large frac-
tures under downhole conditions of pressure [11,12]. These
Acrylic acid, methacrylic acid, acrylamide and sodium hydrox-
pills are activated by time and when set; they produce a sub-
ide were purchased from (Aldrich), potassium hydroxide,
stance described as rubbery, spongy and ductile that shows a
methanol, acetone, dimethyl formamide (DMF), and diethyl
good sealing effect that does not let drilling fluid to enter loss
ether were purchased from (Fluka), 2,20 -azobisisobutyronitrile
zones [13]. In spite of this property, it can easily be removed by
(AIBN) was purchased from Biolar company. All chemicals
acid treatment, therefore this material types will not damage
were used as received.
the formations [14].
Main advantages of this crosslinked polymer system are
2.2. Synthesis
firstly, no risk of bit nozzle plugging, and secondly, the ability
of penetrating into wide range of fracture widths [15].
2.2.1. Preparation of sodium and potassium acrylate salts
The main disadvantage of the crosslinked pills lies in the
placement of the fluid because of the crosslinking reactions ini- To a cold solution (0–5 C) of 7.2 g (0.1 mol) of acrylic acid
tiated on the surface. Therefore, a premature gelation can oc- (AA) in (30 ml) methanol was added 4 g (0.1 mol) of sodium
cur far before to penetrate the loss zones [16,17]. hydroxide (NaOH) or (KOH) in (20 ml) methanol drop by
Table 1 Filtration parameters for local water-based mud using different ceramic disks at different pressures.
Conc. Gm V7.5 min [ml] V30 min [ml] PPT value [ml] Spurt loss [ml] Static filtration [ml/min1/2]
100 300 100 300 100 300 100 300 100 300
At 10 micron ceramic disks
6.4% 80 130 100 160 200 320 120 200 14.6 21.9
drop, with stirring [18]. After stirring for 1 h at room temper- vacuum individually. The sodium and potassium acrylates
ature, the reaction mixture was poured into excess acetone and have the shape of a white solid. They were washed, dried
the precipitated sodium or potassium acrylate salts were re- and weighted. The yield of sodium acrylate was 70%, where
moved by filtration and the filtrate was evaporated to dry in potassium acrylate was 75% [19].
O R1
R1 R2
DMF, Solvent
CH2 CH CH2 C
OM + AIBN, Initiator
F2
MOOC F1 R2
70 oC
Acrylate Salts
Monomers
R1 = H, R2 = COOH ---> Acrylic acid (AA) Copolymer
R1 = Ch3, R2 = COOH ---> Methacrylic acid (MA)
R1 = H, R2 = CONH2 ---> Acrylamide (AM)
M = Potassium (K)
or
Sodium (Na)
Figure 2 Represents FTIR Spectrum for (a) PAcAM and (b) SAcMA.
484 A.M. Alsabagh et al.
Table 3 Monomer reactivity ratios for copolymerization of SA or PA with AM, MA and AA.
Poly[M1-co-M2] Fineman–Ross method Kelen–Tudos method r1r2
r1 r2 r1 r2 a
Poly[SA-co-AM] 0.7 ± 0.205 1.7 ± 0.15 0.8 ± 0.13 1.7 ± 0.16 0.70 1.2
Poly[SA-co-MA] 0.9 ± 0.04 0.3 ± 0.25 1.1 ± 0.07 0.3 ± 0.35 0.22 0.31
Poly[SA-co-AA] 0.6 ± 0.135 0.4 ± 0.105 0.7 ± 0.15 0.4 ± 0.05 0.26 0.24
Poly[PA-co-AM] 0.7 ± 0.19 1.4 ± 0.167 0.8 ± 0.185 1.6 ± 0.181 0.66 1.3
Poly[PA-co-MA] 0.7 ± 0.39 0.2 ± 0.01 0.7 ± 0.175 0.3 ± 0.14 0.27 0.21
Poly[PA-co-AA] 0.5 ± 0.125 0.4 ± 0.122 0.7 ± 0.08 0.5 ± 0.161 0.33 0.35
Figure 3 Fineman-Ross plots for copolymerizations of SA with: (d) AM, (e) MA and (f) AA and copolymerizations of PA with: (a) AM,
(b) MA and (c) AA.
485
2.2.2. Preparation of sodium and potassium copolymers commenced by adding AIBN (1 mol%). The tubes were
(copolymerization reactions) capped and thermostated at 70 C for 1–3 h, depending on
The sodium and potassium acrylates were copolymerized with the co-monomer pairs and composition. All copolymers were
acrylic acid, methacrylic acid, and acrylamide at different mole obtained by precipitation from diethyl ether and were collected
fractions as shown in Table 2. by decantation, then dried and weighted [18].
The copolymers were obtained by the solution polymeriza-
tion method in the presence of azobisisobutyronitrile (AIBN) 2.3. Preparation of water-based drilling fluids
as a free radical initiator. Thus the pre-determined amounts
of the comonomers (100 mol) were placed in glass tubes, and The base component of the water-based mud was prepared by
then was added dimethyl formamide. Polymerization was adding 350 ml of fresh water into a laboratory barrel then
Figure 4 Kelen- for copolymerizations of SA with: (d) AM, (e) MA and (f) AA and copolymerizations of PA with: (a) AM, (b) MA and
(c) AA.
486 A.M. Alsabagh et al.
22.5 g of bentonite was poured into the fresh water and they
[ml] PPT value [ml] Spurt loss [ml] Static filtration Rate [ml/min1/2]
were mixed by using a high-speed mixer for 20 min [19]. At
the end of the mixing, the different investigated polymers were
added in different concentrations. When high permeable for-
2.5
2.4
2.0
4.6
3.9
3.6
mations, with mean pore throat of 10 micron, are drilled with
300
this local mud, a seepage loss occurs. The results are shown in
Table 1.
2.4
2.3
1.5
3.9
3.7
2.9
100
The polymer samples were tested for swelling. The polymer
samples were ground to fine powders. 0.5 g of the sample
35.2
27.8
16.4
37.2
33.8
22.4
300
was then placed in a beaker containing a pre-determined vol-
ume of deionized water. The water sorption was allowed to oc-
31.2
23.6
15.8
37.2
29.6
21.8
cur for at least half an hour at room temperature to reach
100
equilibrium. The swollen polymer was filtered and weighed.
The water uptake, SW (g/g), was determined [20,21]:
48.8
28.4
62.8
42.4
300
41
55
SW ¼ mW =m0 ð1Þ
Filtration parameters for potassium acrylate based copolymers using 10 micron ceramic disks at different pressures.
where mw is the mass of swollen gel (g), and m0 is the mass of
58.8
50.4
38.2
100 300 100
the dry polymer (g).
29.4 31.4
25.2 27.5
19.1 21.2
2.5. Permeability plugging test (PPT test)
Poly[PA-co-AM](0.3:0.7)
Poly[PA-co-AA](0.4:0.6)
30 min
Lost circulation materials were evaluated by using a fann per-
[ml] V
meability plugging apparatus [19,22]. The laboratory studies
17.2
11.2
22.2
16.2
discussed here were carried out using the ceramic disks with
21
25
100 300
min
mean pore throat diameter of 10 micron as a filter medium
at differential pressures 100 and 300 psi. The filtration param-
[ml] PPT value [ml] Spurt Loss [ml] Static filtration [ml/min1/2] V7.5
19
15
10
24
20
15
eters can be made from the data collected at 7.5 and 30 min
intervals according to the following formulas [19]:
PPT ¼ 2 V30 min ð2Þ
1.7
1.6
1.4
2.8
2.8
2.6
300
SL ¼ 2 ðV7:5 min ðV30 min V7:5 min Þ ð3Þ
7.2
2.7
2.5
where, PPT is the permeability plugging tester value(ml); V30
100
33.2
29.8
18.4
the SFR is the static filtration rate (ml/min1/2).
300
32
12
33.2
25.6
17.8
100
54.8
34.4
300
40
20
47
50.8
42.4
30.2
8.4 10
Poly[PA-co-MA](0.4:0.6)
V30 min
22
8
[ml] min
100
16
12
21
17
12
where, gpl. is the plastic viscosity (cP), R600 is the dial read-
ing at 600 r/min, R300 is the dial reading at 300 r/min, sB is the
0.1
0.3
0.6
0.1
0.3
0.6
yield point (lb/100 ft2), and gapp. is the apparent viscosity (cP).
487
Figure 5 Illustrates concentration versus filtration parameters for potassium acrylate based copolymers at 100 psi (a) filtrate volume, (b)
PPT, (c) Spurt Loss.
2.6.2. Power law model atomic absorption spectroscopy confirmed the chemical struc-
n
ture of the prepared copolymers.
s ¼ kc ð8Þ For the industrial preparation of any copolymers, the
knowledge of reactivity ratio is very essential. The reactivity
Logs ¼ log k þ n log c ð9Þ
ratios of Na-A or K-A with AM, MA and AA were evaluated
where k, and n are consistency and flow index, respectively, s is from the monomer feed ratios and the copolymer composition.
the shear stress, and c is the shear rate. Table 2 illustrates the analytical data for copolymerization
reactions of Na-A or K-A with AM, MA and AA. From the
3. Results and discussion values of feed and copolymer composition, the monomer reac-
tivity ratios (r1 and r2) for each system were evaluated using
Fineman–Ross [27] and Kelen–Tudos [28] methods as given
The synthesis root of the six copolymers is shown in Fig. 1.
in Table 3. Figs. 3 and 4 show the Fineman-Ross and Ke-
Their chemical structures were justified by FTIR and atomic
len–Tudos plots respectively for all studied systems. The values
absorption.
of r1 and r2 obtained by Fineman–Ross and Kelen–Tudos
The FT-IR spectra for the poly[PA-co-AM] and poly[SA-co-
methods are almost identical. The r1r2 values for poly[SA-co-
MA] copolymers are shown in Fig. 2(a, b). The two stretching
MA], poly[SA-co-AA], poly[PA-co-MA] and poly[PA-co-AA]
bonds of (N–H) appeared at 3376 and 3170 cm1. The stretch-
(0.31, 0.24, 0.21 and 0.35, respectively) indicates that the
ing of amide (NHC‚O) was observed at 1639 cm1. The peak
copolymer should have a random distribution of the monomer
at 1422 cm1 is the stretching bond of C–N and 969 cm1 is an-
units, while for the poly[SA-co-AM] and poly[PA-co-AM] sys-
other peak related to the amide group. The peak at 1203 cm1
tems, the r1r2 values (1.2 and 1.3), respectively, illustrate a low
pointed to (C–O) stretching peak of (–COOK) (Fig. 2a).
tendency of monomers to be alternated, and the copolymer
In Fig. 2b for poly[SA-co-MA], a wide band corresponding
should be composed mainly of small sequences of monomeric
to stretching vibrations of the hydroxyl group appeared at
units of the same type.
3430 cm1. The characteristic absorption bands at the wave
number 1642 cm1 pointed to deformation vibrations of (C–
3.1. Filtration parameters for the studied copolymers
OH) meanwhile the two bands at 1447 and 1363 cm1 typically
donated the salts of carboxylic acids. The band corresponding
to stretching vibrations of (C–O) and deformation vibrations From filtration parameters Tables 4 and 5, it can be deduced
of (C–O–H) group appeared at the wave number 1199 cm1. that the filtration parameters are enhanced by increasing the
Table 2 shows the percentage of the sodium and potassium concentration of copolymers and by increasing the molar ratio
content in the prepared copolymers. Both the FT-IR and the of acrylates monomer in the studied copolymers.
488 A.M. Alsabagh et al.
[ml] PPT value [ml] Spurt loss [ml] Static filtration rate [ml/min1/2]
it was found that the poly[PA-co-AM](0.4:0.6) exhibited better
results among poly[PA-co-AM](0.3:0.7) and poly[PA-co-
MA](0.4:0.6). The worst results were obtained by poly[PA-co-
2.7
2.4
2.4
4.5
4.3
4.0
AA](0.4:0.6) as shown in Fig. 5. The filtration loss was: 8.4,
300
12.1, 15.1 and 19.1 ml, respectively for the four copolymers.
By changing the pressure from 100 to 300 psi, the poly[PA-
co-AM](0.4:0.6)exhibited the best performance in the all filtra-
tion parameters such as; filtrate volume after 30 min; PPT va-
2.3
2.1
4.2
3.9
3.5
1.6
100 lue; spurt loss and static filtration at 0.6% concentration.
By investigation the data in Table 5, for sodium acrylate
based copolymers, the poly[SA-co-AM](0.4:0.6) shows the best
43.8
48.8
36.8
25.2
300
32
20
results among poly[SA-co-AM](0.3:0.6) and poly[SA-co-
MA](0.4:0.6). The bad results were obtained by poly[SA-co-
39.6
28.2
44.4
33.2
22.4
17.4
73.6
60.8
48.4
33.6
300
co-AM](0.4:0.6).
At concentration 0.6% with using 10 micron ceramic disk
26.2 29.3 52.4
19.9 22.8 39.8
67.6
54.8
41.6
13.3 16.8 26.6
and pressure 100 psi, the filtrate loss after 30 min (ml) was
100 300 100
Filtration parameters for sodium acrylate based copolymers using 10 micron ceramic disks at different pressures.
30.6
24.4
18.4
13.4
23
17
28
22
16
11
2.8
2.7
2.5
dium acrylate (ranging from 0.12 to 0.14 mm) and their filter
cakes also have stability and no bubbles. The obtained good
results by the poly[PA-co-AM](0.4:0.6)in the filtration parame-
ters may be due to the poly[PA-co-AM](0.4:0.6) that has the
2.2
1.8
1.4
2.5
2.2
1.8
100
47.4
35.4
23.8
31.8
100
38
16
43
21
shown in Sketch 1.
43.2
30.8
50.2
37.8
300
56
63
44.2
15.4 24
57
31
300 100 300 100
Poly[SA-co-MA](0.4:0.6)
12.4 12
V30
can plug the pores. This result may be due to the potassium
ion smaller than sodium ion so its mobility is faster than so-
[ml]
100
22
16
10
25
19
13
0.1
0.3
0.6
copolymers.
489
Figure 6 Illustrates concentration versus filtration parameters for sodium acrylate based copolymers at 100 psi (a) filtrate volume, (b)
PPT, (c) spurt loss.
Table 6 Rheological properties of water-based drilling fluid (M) and with 0.6% conc. of the studied copolymers.
Materials Bingham plastic parameters Power law parameters
Plastic Apparent Yield Gel strengths(0 min) Gel strength(10 min) Thixotropy Flow Consistency
viscosity viscosity point sB [lb/100 ft2] [lb/100 ft2] [lb/100 ft2] index [n] index
gpl [cP] gapp [cP] [lb/100 ft2] [lb.sn/100 ft2]
M 3 26.5 47 28 31 3 0.04 29.6
Poly[PA-co-AM](0.4:0.6) 10 70 52.4 79 84 5 0.1 62
Poly[PA-co-AM](0.3:0.7) 6 65 53.5 90 95 5 0.1 59
Poly[SA-co-AM](0.4:0.6) 5 60 50.2 87 91 4 0.08 57
Poly[SA-co-AM](0.3:0.7) 5 55 45 77 81 4 0.08 66
Poly[PA-co-MA](0.4:0.6) 4 50 42 62 66 4 0.06 69
Poly[SA-co-MA](0.4:0.6) 4 45 37.2 64 67 3 0.06 78
Poly[PA-co-AA](0.4:0.6) 3 42.5 37.4 65 67 2 0.07 81
Poly[SA-co-AA](0.4:0.6) 2 40 35.3 73 75 2 0.07 67
Figure 8 Shear rate versus shear stress for potassium acrylate based copolymers.
Figure 9 Shear rate versus shear stress for sodium acrylate based copolymers.
Figure 10 Relationship between effective viscosity (cP) versus shear rate (s1) for potassium acrylate based copolymers.
491
Figure 11 Relationship between effective viscosity (cP) versus shear rate (s1) for sodium acrylate based copolymers.
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[4] J. Adach, L. Bailey, Schlumberger, IADC/SPE 87224, 2004.
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[5] R. Aguilera, Naturally Fractured Reservoirs, second ed.,
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[14] R. Kharrat, Petroleum University of Technology, Ahwaz, Iran,
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