Applied Clay Science 67–68 (2012) 36–43

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Applied Clay Science

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Research paper

Poly (oxypropylene)-amidoamine modified bentonite as potential shale inhibitor in

water-based drilling fluids
Hanyi Zhong, Zhengsong Qiu ⁎, Weian Huang, Jie Cao
School of Petroleum Engineering, China University of Petroleum, Qingdao 266555, China

a r t i c l e i n f o a b s t r a c t

Article history: A series of poly(oxypropylene)-amidoamine (POAA) compounds as potential shale inhibitors were synthe-
Received 9 January 2012 sized by condensation of low molar mass polyoxypropylene diamine POP230 with diacids. The synthesized
Received in revised form 7 June 2012 polymer was characterized by Fourier transform infrared spectroscopy (FT-IR) and mass spectrum (MS) anal-
Accepted 7 June 2012
ysis. The interaction between the POAA compounds and purified bentonite was investigated via FT-IR, X-ray
Available online 30 August 2012
diffraction (XRD), electrophoretic mobility (EM) measurement, thermogravimetric analysis (TGA), water ad-
Keywords:
sorption test, and scanning electron microscopy (SEM). The POAA compounds were intercalated by the
Water-based drilling fluid montmorillonite (Mt) with monolayer orientation. The protonated ammonium ions neutralized the nega-
Clay hydration tively charged sites and decreased the electrophoretic mobility. Hydrogen bonds were formed between
Polyamidoamine amide and siloxane groups. The intercalation reduced the water content of the Mt and rendered the clay min-
Inhibition evaluation eral surface more hydrophobic. The inhibitive properties of the modified Mt were evaluated by inhibition and
Bentonite cuttings hot-rolling dispersion tests. The POAA-Mt exhibited superior shale hydration and dispersion inhibi-
Montmorillonite tion capacity compared to conventional inhibitors.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction et al., 2010; Stamatakis et al., 1995; Van Oort, 2003; Zhang et al., 2000).
Nevertheless, these approaches were not completely successful in
In drilling engineering, swelling and dispersion of shales and cut- inhibiting the hydration of highly water sensitive clays and had various
tings led to various problems such as hole collapse, tight hole, stuck limitations (Young and Ramses, 2006). Among these methods, potassi-
pipe, poor hole cleaning, hole enlargement, plastic flow, fracturing, um chloride was the earliest and most widely used agent. When com-
lost circulation, and well control. In addition, the dispersed clay might bined with other additives such as partially hydrolyzed polyacrylamide
aggregate on the surface of bit or drilling tools, leading to bit balling (PHPA) (Steiger, 1981), polyglycol (Brady et al., 1998) and silicates
and penetration rate reduction (Bol, 1986; Lu, 1985; Sheu and (Guo et al., 2006), effective inhibition would be obtained by synergetic
Perricone, 1988). Most of the drilling problems that increased the dril- effects. Because of the high concentration required to obtain the satisfac-
ling costs were related to the wellbore stability (Lal, 1999). Shale inhibi- tory levels of inhibition, alternative cations that promised to be as effec-
tion was the most important factor in preventing hole problems when tive as potassium ions were needed. This became the starting point for
drilling in shale formations (Løklingholm, 2002). Oil-based drilling the evaluation of ammonium and amine-based compounds for shale in-
fluids were used to drill water-sensitive formations because of inherent hibition (Guerrero et al., 2006). Nitrogen derivatives, the simplest is am-
advantages such as excellent inhibition, high temperature stability, and monium chloride, were used as shale inhibitors for many years. The
outstanding lubricity (Rojas et al., 2006). However, the expensive costs history of amine compounds and their properties were reviewed
and adverse effects on environment limited their wide use (Morton et (Patel, 2009; Patel et al., 2007; Schlemmer et al., 2003). A recent advance
al., 2005). With the increasingly stringent environmental demands, was the introduction of water-based drilling fluids containing low molar
the search for an environmentally friendly water-based drilling fluid mass polyetheramine compounds (Aldea et al., 2005; Patel et al., 2001a,
to prevent hydration and swelling of clay minerals and to exhibit inhib- b; Qu et al., 2009). The ability of polyetheramine to reduce the swelling
itive characteristic similar to oil-based drilling fluids became more de- tendencies of shales was studied (Patel et al., 2007; Wang et al., 2011;
manding (Bruton and Mclaurine, 1993; Rosa et al., 2005). Zhong et al., 2011). Based on this inhibitor, a high performance water-
Over the past decades, a wide variety of approaches were proposed, based drilling fluid was designed and applied around the world with
like relatively high concentrations of inorganic salts, organic salts and great success, which represented a significant step-change improvement
many kinds of polymeric additives (Caenn and Chillingar, 1996; Souza over earlier attempts to develop a water-based drilling fluid performing
like an oil-based drilling fluid (Guerrero et al., 2006; Patel et al., 2002;
Young and Stamatakis, 2006).
⁎ Corresponding author. Tel.: + 86 532 86981705; fax: + 86 532 86981936. With the development of computer technologies, computer simu-
E-mail address: zhong3h3c@sina.com (Z. Qiu). lation became a useful tool to understand the underlying principles

0169-1317/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2012.06.002
 H. Zhong et al. / Applied Clay Science 67–68 (2012) 36–43 37

Scheme 1. Preparation of POAA by condensation of POP230 and diacids.

behind clay swelling and determine the interaction between inhibi- (abbreviated as POP230) with the general formula H2NCH(CH3)CH2
tors and clay minerals. Furthermore, the combination of computer sim- [OCH2(CH3)CH]2.6NH2 was purchased from Huntsman Chemical Co.
ulation and experimental studies provided an effective way to design
novel high performance inhibitors with favorable molecular structures 2.2. Synthesis of the POAA compounds
(Anderson et al., 2010a; Bains et al., 2001; Greenwell et al., 2005;
Ratcliffe et al., 2009). After analyzing the properties and summarizing The reactions were carried out in a 500 mL four-neck flask equipped
the inhibitive actions of various inhibitors with the combination of com- with a stirrer and condenser. The flask was immersed into a thermostat
puter simulation and experimental results, sets of “rule-based” design oil bath. Nitrogen gas was purged into the flask to remove oxygen.
criteria for clay swelling inhibitors were developed (Anderson et al., POP230 (230 g, 1 mol) and adipic acid (73 g, 0.5 mol) were added
2010b; Suter et al., 2011). Therefore, in this study, we tried to synthesize while stirring. The mixture was heated to 140–150 °C for 4 h. During
poly(oxypropylene)-amidoamine (POAA) modified bentonites as po- the process, water was removed under the nitrogen atmosphere through
tential shale inhibitors. a water separator. The reaction product is abbreviated as POP230-AA.
With a similar procedure, a series of POP230-amidoamines were pre-
2. Experimental pared from the reaction of POP230 and succinic acid or ethane diacid
(abbreviated as POP230-SA and POP230-EA). The FT-IR spectra were
2.1. Materials recorded by a NEXUS FT-IR spectrometer (Thermo Nicolet Corporation),
scanning from 4000 to 400 cm− 1, with 4 cm− 1 resolution in transmis-
Sodium bentonite was obtained from Xiazijie Bentonite Company, sion. The molar mass distribution of the POP230-amidoamine was esti-
China, and was purified before use. The bentonite was dispersed in de- mated by using 7200 Q-TOF GC/MS mass spectrometer (Agilent, USA).
ionized water for 24 h to make an 80 g/L dispersions. The dispersions The solution surface tension was measured at 25 °C with the DCAT21
were centrifuged at 8000 r/min for 30 min, and the upper part of the surface/interface tensiometer (Beijing Eastern-Dataphy Instruments
dispersions was recovered. The purified bentonite sample was dried at Co., Ltd).
105 °C for 24 h and sieved by 200 mesh sieve. The cation exchange ca-
pacity was determined to be 1.05 mmol/g by ammonium acetate 2.3. Modified bentonite
method. A drilling fluid bentonite was supplied by Weifang Huawei
Bentonite Group Co., Ltd, China, following the API standard. Adipic Purified Na-bentonite (8 g) was dispersed in 1 L of deionized water
acid, succinic acid, ethane diacid, potassium chloride, potassium for- for 24 h, and POAA compounds with concentrations of 0.2, 0.5, 1.0, 2.0,
mate and sodium formate were purchased from Sinopharm Chemical 3.0, 5.0%(m/v) were added. After stirring for 30 min, the dispersions
Reagent Co., Ltd, China, in analytical purity. Ultrahib, a commercial poly- were allowed to stand for 24 h. The dispersions were centrifuged and
amine shale inhibitors, was provided by M-I SWACO in America. (2, 3- washed thoroughly with deionized water for several times. One part
Epoxypropyl) trimethylammonium chloride (NW-1) was supplied by of the sediment was used for XRD measurement. The other part was
Shandong Juxin Checmical Co., Ltd, China. Polyoxypropylene diamine dried in a vacuum oven at 80 °C and ground to powder. Samples were

D D
3370
3290

2980

1500
1390
3430
1300

798
3240

1620
1370
1510

814
3620
1640

C
2880
2970

916
1110

C
1540
2970

1380

798
3430
3240

1640
3280

1560

3620

841
2880
2970

1370
1700

1110

916

B
B
3270

1500
1450

2970

798
1370

1380
3430

1630
3250
2970
2870

1550
1640

841
1110

3620

916

A
A
3290

1590
3370

1460
1370
2960
2870

1110

1630

798
3430
3620

916

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
-1 -1
Wavenumber(cm ) Wavenumber(cm )

Fig. 1. FT-IR spectra of POAA and polyoxypropylene diamine. (A) POP230; (B) POP230-AA; Fig. 2. FT-IR of (A) purified Na-bentonite; (B) bentonite modified with POP230-AA;
(C) POP230-SA; (D) POP230-EA. (C) bentonite modified with POP230-SA; (D) bentonite modified with POP230-EA.
38 H. Zhong et al. / Applied Clay Science 67–68 (2012) 36–43

-1.6
(a)
-1.8
POP230-AA
2θ =6.153 POP230-SA

Electrophoretic mobility(10 m /Vs)

F POP230-EA
d001=1.46 nm -2.0

2
2θ =6.202

-8
-2.2
E
d001=1.46 nm
-2.4
2 θ =6.053
D
d001=1.44 nm -2.6

2 θ =6.035 -2.8
C
d001=1.43 nm
-3.0

2θ =6.399 -3.2
B d001=1.38 nm
-3.4
0 10 20 30 40 50

A 2θ =8.855 d001=1.21 nm
Concentration of polymer(g/L)

Fig. 4. Electrophoretic mobility of modified bentonites in aqueous dispersions.

2 4 6 8 10 12 14 16
o
2Theta ( )
(b) mixed with KBr and pressed into pellets for FT-IR analysis. The basal
spacing of the modified Mt was determined by X-ray diffraction (XRD,
2 θ =6.392 X-ray powder diffractometer, X'pert PRO MPD diffractometer CuK
F
d 001=1.40 nm alpha 45 kV, 50 mA). Thermal gravimetric analysis (TGA) was per-
2 θ =6.346 formed with the WCT-2D (Beijing Optical Instrument Factory) ther-
E mal analyzer at a scan rate of 20 °C/min under nitrogen flow. The
d 001=1.39 nm
Hitachi S-4800 field-emission scanning electron microscope (SEM)
was used to study morphological features of the powdered samples.
2 θ =6.356
D The electrophoretic mobility (EM) measurement was reported pre-
d 001=1.39 nm
viously (Zhong et al., 2011). For the water adsorption test, 1 g of
modified bentonite was placed in a sealed glass desiccator with
2 θ =6.314
C water in the bottom. The amount of water adsorbed was calculated
d 001=1.38 nm
from the mass changes (Montes-H et al., 2003).

2 θ =6.480
B d 001=1.36 nm
2.4. Inhibitive properties

A 2 θ =8.855 Volumes of 400 mL of tap water containing 12 g of inhibitor were

d 001=1.21 nm
reacted with 5%(m/v) drilling fluid bentonite and stirred for 30 min
2 4 6 8 10 12 14 16 every day. After hot rolling at 70 °C for 16 h, the rheological properties
o
2Theta ( ) were measured daily before amounts of 20 g drilling fluid bentonite
(c) were added. These daily additions of drilling fluid bentonite and hot
rolling were carried out until the sample became too viscous to be mea-
2 θ =6.421 sured. The rheological properties of the dispersions were measured
F d 001=1.38nm using a model ZNN-D6 viscometer. The apparent viscosity, plastic vis-
cosity and yield point were calculated from 300 and 600 rpm readings
2 θ =6.427 using the API recommended practice of standard procedure for field
E d 001=1.38nm
testing drilling fluids (Recommended Practice, 1988):
2 θ =6.460 Apparent viscosity (AV) = φ600/2 (mPa·s)
D d 001=1.38nm
Plastic viscosity (PV) = φ600−φ300 (mPa·s)
2 θ =6.460 Yield point (YP) = (φ300 − PV)/2 (N/m 2)
C d 001=1.37nm For the cuttings hot-rolling dispersion test, 50 g of the shale cuttings
(6–10 mesh) obtained from Sha Hejie formation in Shengli oilfield were
2 θ =6.448
added to 350 mL formulated solutions in a sealed cell. The cell was hot
B d 001=1.37nm rolled at 77 °C for 16 h. Then, the cuttings were screened through a 40
mesh sized sieve and washed with 10 mass% KCl solution. The collected
cuttings were dried in a vacuum oven at 105 °C for 4 h. The amounts of
A 2 θ =8.855 d 001=1.21nm recovered cuttings were determined (Khodja et al., 2010; Patel, 2009).
2 4 6 8 10 12 14 16
o
2Theta ( )
Fig. 3. X-ray diffraction patterns of bentonite-POAA at various polymer concentrations
(%(m/v)) with dry sample. (a) POP230-AA: (A) 0; (B) 0.2; (C) 0.5; (D) 1.0; (E) 2.0;
(F) 3.0;(b) POP230-SA: (A) 0; (B) 0.2; (C) 0.5; (D) 1.0; (E) 2.0; (F) 3.0;(c) POP230-
EA: (A) 0; (B) 0.2; (C) 0.5; (D) 1.0; (E) 2.0; (F) 3.0.
 H. Zhong et al. / Applied Clay Science 67–68 (2012) 36–43 39

100 75
POP230-AA
70 POP230-SA
95 D
POP230-EA
C
B 65

Surface tension(mN/m)
90
Mass loss (%)

A 60
85
55
80
50

75
45

70
40

65 35
0 200 400 600 800 -4 -3 -2 -1 0 1
o
Temperature( C) lgc(g/L)

Fig. 5. TGA curves of bentonites at POAA concentrations of 0.5%(m/v). (A) purified Na- Fig. 7. Surface tension curves of POAA solutions.
bentonite; (B) bentonite modified with POP230-AA; (C) bentonite modified with
POP230-SA; (D) bentonite modified with POP230-EA.
3.2. Interaction of POAA compounds with Mt

3.2.1. FT-IR analysis

3. Results and discussion
The FT-IR spectrum of Na-Mt showed absorption band at 3430 cm− 1
and 1630 cm− 1, corresponding to the O―H stretching and bending
3.1. Synthesis and characterization of POAA compounds
band of water. 916 cm- 1 is the characteristic bending vibration of
Al―OH. For the bentonite-polymer system, the vibrations of the methyl
The condensation of POP230 and diacid in a molar ratio of 2:1 is
groups were found around 2980 and 2970 cm− 1 as well as that of the vi-
shown in Scheme 1. The FT-IR spectrum of POP230 showed absorption
bration bands of C―H groups at about 1380 cm− 1 (Fig. 2).
bands at 1590 cm − 1 corresponding to the N―H bending vibration of
In comparison with the FT-IR spectrum of POAA and POP230-AA, the
the amine group (Fig. 1). In the case of POP230-AA, the absorption of pri-
characteristic bands of amide I and amide II at 1640 cm− 1 and
mary amine N―H stretching modes was at 3270 cm− 1. The new band at
1550 cm− 1 were shifted to 1630 cm− 1 and 1500 cm− 1. This suggested
1640 cm− 1 indicated the C O stretching vibration. The band at
hydrogen bonds between the amide groups and siloxane groups. For
1550 cm− 1 corresponded to the N―H bending vibration. 1640 cm− 1
POP230-SA and POP230-EA, the absorption bands of amide I and amide
and 1550 cm− 1 were the characteristic absorption bands of amide I
II at 1700, 1560 cm− 1 and 1640, 1510 cm− 1 were shifted to 1640,
and amide II (Schmidt et al., 2006). For POP230-SA and POP230-EA,
1540 cm− 1 and 1620, 1500 cm− 1 also indicating hydrogen bonds (Lin
the absorption band of amide I and amide II were observed at 1700,
et al., 2007).
1560 cm− 1 and 1640, 1510 cm− 1. The appearance of the amide I and
amide II bands demonstrated the formation of amide groups. The
3.2.2. XRD patterns
molar mass distributions of the three polyamideamines were 191–736,
The XRD patterns of the bentonite indicated a basal spacing of
191–661 and 113–621 with the average molar mass values of 508, 476
1.21 nm. In the case of POP230-AA at a concentration of 0.2%(m/v),
and 418.
the basal spacing increased to 1.38 nm. When the concentration was
0.5%(m/v), the basal spacing increased to 1.43 nm. At higher loadings,
the basal spacing changed only slightly with the increasing concentra-
tion, demonstrating that the polymer formed a monolayer arrangement
70 in the interlayer space. The monolayer orientation in the interlayer
space regardless of the polymer concentration was stabilized by strong
60
hydrogen bonds, which hindered further intercalation (Greenwell et al.,
2006). POP230-SA and POP230-EA exhibited the same tendency. How-
50
ever, POP230-AA enlarged the basal spacing to 1.46 nm because of the
Water adsorption (%)

40
higher molar mass (Fig. 3).

30 3.2.3. Electrophoretic mobility measurement

The electrophoretic mobility of the purified Na-bentonite was −3.2
20 (10− 8 m2/Vs). POP230-AA adsorption increased the electrophoretic
Na-bentonite mobility to −2.6 (10 − 8 m 2/Vs) at about 5 g/L polymer content
10
Na-bentonite-POP230-AA (Fig. 4). At higher polymer content, the electrophoretic mobility in-
Na-bentonite-POP230-SA creased towards less negative values.
0 Wang et al. (2010) assumed that the pKa values of POP230 were
Na-bentonite-POP230-EA
similar to those of 1,6-hexanediamine (pKa1 = 9.8, pKa2 = 10.9). The
-10
0 50 100 150 200 250 pKa values of the polymers would increase after the reaction with
the acids. At pH of 8–11 as in our case, a certain part of the molecules
Time(h)
would be protonated and interact with the surface charges by electro-
Fig. 6. Adsorbed water content as a function of the testing time at a POAA concentra- static forces. As a consequence of the polymer adsorption, the hydra-
tion of 0.5%(m/v). tion of the clay mineral and the degree of dispersion were reduced.
40 H. Zhong et al. / Applied Clay Science 67–68 (2012) 36–43

Fig. 8. SEM photographs of purified and modified bentonites (magnifications 50,000×; 5.0 kV) at a POAA concentration of 0.5%(m/v): (A) purified Na-bentonite; (B) bentonite mod-
ified with POP230-AA; (C) bentonite modified with POP230-SA; (D) bentonite modified with POP230-EA.

POP230-EA compensated the negative surface charges to a higher de- of the solution decreased to 38.8, 38.1, and 43.5 mN/m for POP230-
gree than the two other polymers. AA, POP230-SA and POP230-EA.

3.2.4. TGA 3.2.6. SEM observations

The mass loss steps observed up to 200 °C were attributed to the de- The purified bentonite showed dense particle aggregates which,
sorption of physically adsorbed water, second mass loss step the dehy- after polymer adsorption, changed into extended aggregates forming
dration of the hydrated exchangeable cations such as Na + and Ca2+. an open network with pores (Fig. 8). The extended aggregates im-
Between 200 and 500 °C, the organic compounds were decomposed proved the clay stabilization.
(Barick and Tripathy, 2010).
The thermal degradation of the modified bentonites differed signifi-
cantly from that of the purified bentonite between room temperature 2.1

and 200 °C (Fig. 5). All POAA polymers reduced the water content of POP230-AA POP230-SA
the modified bentonite. At 200 °C, the mass loss of pristine bentonite, 2.0 POP230-EA Ultrahib
KCl NW-1
POP230-AA, POP230-SA and POP230-EA bentonite was 12%, 9%, 7%,
1.9 NaCOOH KCOOH
and 5%. Thus, the adsorption of POAA reduced the water content of the
sample.
Basal spacing(nm)

1.8

3.2.5. Water adsorption tests 1.7

The time-dependent adsorption of all samples showed a consider-
able increase at the initial stage (Fig. 6). Compared with purified ben- 1.6
tonite, the amounts of adsorbed water of the modified bentonites
were much lower. After 238 h, the amount of water adsorbed by 1.5

POP230-AA, POP230-SA and POP230-EA bentonite was reduced by

about 29%, 27% and 21% compared to the purified bentonite. The reduced 1.4

affinity of the clay mineral surface to water had favorable impact on clay
stabilization (Wang et al., 2011). Because of different hydrophilicity/ 1.3
-1 0 1 2 3 4 5 6 7 8
hydrophobicity ratios of the three polymers, the affinity to water
Concentration of inhibitor(%m/v)
decreased in the order POP230-EA > POP230-SA > POP230-AA. This
was consistent with the results of surface tension measurements Fig. 9. X-ray diffraction patterns of bentonite (wet samples) in the presence of
(Fig. 7). With increasing concentrations of what, the surface tension inhibitors.
 H. Zhong et al. / Applied Clay Science 67–68 (2012) 36–43 41

Table 1
Rheometer readings of all samples after adding bentonite.

Bentonite Fresh water KCl Ultrahib PPO230-AA PPO230-SA PPO230-EA

(%m/v)
φ600 φ300 φ3 φ600 φ300 φ3 φ600 φ300 φ3 φ600 φ300 φ3 φ600 φ300 φ3 φ600 φ300 φ3

5 42 37 21 7 4 0.5 3 1.5 0 3.5 2 0 3.5 2 0 4 2.5 0

10 186 167 91 18 11 1 3 2 0 6 3.5 0.5 6 3.5 0.5 5 3 0
15 – – 176 30 21 10 7 4 0 12 8 2 9 5.5 1 7 4 0.5
20 59 48 24 20 14 3 25 20 10 28 22 13 9 5 0.5
25 162 145 90 67 62 38 271 258 84 171 160 52 13 7 0.5
30 – – 258 155 143 81 – – 237 – – 131 20 12 4
35 – – 224 29 18 9

– Indicates that the readings were > 300, no further readings were taken.

3.3. Inhibitive properties addition. The inhibition decreased as POP230-EA>Ultrahib>POP230-

SA>POP230-AA>KCl.
3.3.1. XRD analysis of wet samples
The basal spacing of Na-Mt increased from 1.21 nm to 2.02 nm after
thorough hydration (Fig. 9). In the presence of 0.2%(m/v) POP230-AA, 3.3.3. Cuttings hot-rolling dispersion tests
it decreased from 2.02 nm to 1.51 nm. At higher polymer concentrations, The inhibitive qualities of the POAA compounds were further evalu-
the basal spacing remained almost constant as a consequence of the ated by conventional hot-rolling dispersion tests with highly reactive
polymer monolayer adsorption. The intercalation of POAA prevented shales (Table 2). The cuttings recovery in fresh water was 14.2%, indi-
water molecules from entering the interlayer space and diminished the cating high hydration and dispersion. After adding 7% (m/v) KCl, the re-
water content of the systems, in agreement with the thermogravimetric covery was 44.5%. At 3% (m/v) Ultrahib addition the recovery was
analysis. 57.7%, but higher values were reached with the POAA compounds.
Ultrahib as a shale hydration inhibitor, reduced the basal spacing in a POP230-EA improved the cuttings recovery to the highest value, indi-
similar way. In comparison with other conventional clay swelling inhib- cating the best shale stability.
itors like KCl, sodium and potassium formate and NW-1, POP230-EA and
Ultrahib reduced the basal spacing to a minimum, indicating the best in- 3.3.4. Inhibition mechanism
hibition performance. Furthermore, the POAA compounds reduced the Scheme 2 depicted the chemical structure and action of POAA. Due
basal spacing of the hydrated samples with relatively low polymer con- to the monolayer arrangement of the polycations in the interlayer
centrations and were, therefore, superior to KCl and the formates, which space, the silicate layers were diminished the tendency to imbibe
generally required high concentrations to achieve ideal suppression. water from an aqueous environment. Furthermore, after reaching ad-
sorption saturation, the hydrophobic region of the polymer rendered
3.3.2. Bentonite inhibition the clay mineral surface relatively hydrophobic which further hin-
Measuring the rheological properties of cationic materials was one of dered the uptake of water.
the simplest tests for the evaluation of inhibitive properties (Stamatakis
et al., 1995). In fresh water without inhibitor, Na-Mt dispersed into colloi-
dal particles (Table 1), which increased the viscosity. When the bentonite 4. Conclusions
content reached 15%(m/v), the fresh water system became too viscous to
measure the yield point (Fig. 10). In the presence of inhibitors the yield According to the rules of designing successful shale inhibitors with
point changed sharply at different bentonite concentrations. Due to the respect to molecular structure, POAA compounds with low molar
lower rheological viscosity, POAA addition was more effective than KCl mass were synthesized by condensation of polyoxypropylene diamine
POP230 and diacids. The intercalated polymer adopted a monolayer ar-
rangement pulling the adjacent layers together. The interaction be-
tween the POAA compounds and the clay mineral mainly included
Fresh water electrostatic interaction, hydrogen bonding and van der Waals interac-
120
KCl tion, which caused a significant reduction of hydration and swelling.
Ultrahib POAA compounds exhibited superior inhibition compared to conven-
100 POP230-AA tional inhibitors. POP230-EA showed the best inhibitive properties.
POP230-SA The POAA compounds were alternatives to other state of the art inhib-
80 POP230-EA itors in water-based drilling fluids.
Yield point(Pa)

60

Table 2
40 Cuttings recovery of various inhibitor systems.

Inhibitor Recovery (%)

20
Fresh water 14.2
3 (% m/v) Ultrahib 57.7
0 7(% m/v) KCl 44.5
10 (% m/v) NaCOOH 27.1
0 5 10 15 20 25 30 35 40 10 (% m/v) KCOOH 54.3
Concentration of drilling fluid bentonite(%m/v) 0.5 (% m/v) NW-1 44.3
3 (% m/v) POP230-AA 62.6
3 (% m/v) POP230-SA 61.3
Fig. 10. Yield point as a function of the concentration of drilling fluid bentonite in the
3 (% m/v) POP230-EA 65.3
presence of inhibitors.
42 H. Zhong et al. / Applied Clay Science 67–68 (2012) 36–43

Scheme 2. Chemical structure of POAA.

Nomenclature Guerrero, X., Guerrero, M., Warren, B., 2006. Use of amine/PHPA system to drill high re-
active shales in the Orito field in Colombia. SPE Paper 104010, the First Internation-
API American Petroleum Institute al Oil Conference and Exhibition. Mexico, 31 August −2 September.
AV Apparent viscosity Guo, J.K., Yan, J.N., Fan, W.W., Zhang, H.J., 2006. Applications of strongly inhibitive
EM Electrophoretic mobility silicate-based drilling fluids in troublesome shale formations in Sudan. Journal of
Petroleum Science and Engineering 50, 195–203.
FT-IR Fourier transform infrared spectroscopy Khodja, M., Canselier, J.P., Bergaya, F., Fourar, K., Khodja, M., Cohaut, N., Benmounah, A.,
Mt Montmorillonite 2010. Shale problems and water-based drilling fluid optimisation in the Hassi
MS Mass spectrum Messaoud Algerian oil field. Applied Clay Science 49, 383–393.
Lal, M., 1999. Shale stability: drilling fluid interaction and shale strength. SPE Paper
Na-Mt Sodium montmorillonite
54356, SPE Latin American and Caribbean Petroleum Engineering Conference. Ven-
NW-1 (2, 3-Epoxypropyl) trimethylammonium chloride ezuela, 21–23 April.
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