Applied Clay Science 44 (2009) 265–268

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Polyoxyalkyleneamine as shale inhibitor in water-based drilling fluids

Yuanzhi Qu a,⁎, Xiaoqing Lai a,b, Laifang Zou a, Yi'nao Su a
a
Research Institute of PetroChina Drilling Engineering Technology, Beijing 100097, China
b
College of Petroleum Engineering, Yangtze University, Jingzhou, Hubei 434023, China

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

Article history: According to the conventional evaluation methods of drilling fluids, the inhibitive property of polyoxyalk-
Received 12 October 2008 yleneamine (POAM), which was prepared in the laboratory, to sodium montmorillonite (Na-MMT) was
Received in revised form 4 March 2009 investigated, and the shale cuttings recovery ratio and the rheological properties of drilling fluids were
Accepted 7 March 2009
measured before and after adding POAM in several water-based drilling fluids. The results showed that POAM
Available online 21 March 2009
was completely water-soluble, exhibited the superior performance to inhibit the hydration of Na-MMT and
Keywords:
reduced the swelling or hydration of shale cuttings effectively. In addition, the determination of the biological
Rheology toxicity and compatibility of POAM indicated that POAM was low toxic and compatible with other common
Polyoxyalkykeneamine (POAM) drilling fluid additives.
Shale inhibitor © 2009 Elsevier B.V. All rights reserved.
Water-based drilling fluids

1. Introduction
Water-based drilling fluids may cause swelling of the clay minerals
in shale formations that can create major problems for the drilling
operations. According to statistics (Dzialowski et al., 1993), shales
account for about 75% of the drilled sections in oil and gas wells, and
cause approximately 90% of the wellbore instability-related problems
during drilling operations. When water-sensitive shales are exposed
to the conventional water-based drilling fluids, shales have an
immediate tendency to take up water from the drilling fluid.
Depending on the chemical characteristics of the shale, this can result
in a rapid swelling or dispersion of the shale. Consequently, typical
problems such as bit-balling, disintegration of cuttings, borehole
wash-out, high torque and drag, and stuck pipe are often encountered
as a result of water adsorption by water-sensitive shales (Steiger and
Leung, 1992; van Oort et al., 1994). During the drilling practice in shale
formations, various chemicals have been used to reduce clay mineral
or shale swelling in water-based drilling fluids. Among the chemicals,
salts such as potassium chloride, sodium chloride and divalent brines
are the earliest and most widely used for inhibition of water-sensitive
shales. The inhibitive method relies on the use of high concentration
of salts. These salts somehow retard the hydration and swelling of
water-sensitive shales through a variety of mechanism. However,
these salts in large quantities adversely affect the environment. These
salts also flocculate the clay minerals resulting in both high fluid losses
and an almost complete loss of thixotropy. Further, increasing salinity
often decreases the functional characteristics of drilling fluid
additives. In the field application, polymer/KCl drilling fluids became
⁎ Corresponding author. Tel./fax: +86 10 62098361.
E-mail address: yuanzhiqu@petrochina.com.cn (Y. Qu).
popular (Clark et al., 1976; Twynam et al., 1994). A variety of polymers
in combination with KCl were evaluated to achieve a higher level of
shale inhibition as compared to KCl alone. However, surface swelling
due to insufficient shale inhibition and high viscosity of polymers
offered little partial success in providing the satisfactory results.
Since drilling operations impact the surrounding environment, the
drilling fluid additives should have low toxicity levels and should be
easy to handle and to use to minimize the dangers of environmental
pollution and harm to operators. It is desirable that additives work
both onshore and offshore. As an excellent inhibitive agent, it should
control the swelling of the clay minerals and drilled formations
without adversely affecting the desired performance of other
additives and the rheological properties of drilling fluids. In this
paper, we evaluated the toxicity, inhibitive property and compatibility
of polyoxyalkyleneamine as a shale inhibitive agent in water-based
drilling fluids.
2. Experimental
2.1. Materials and reagents
Encapsulating agent (UltraCap) and low viscous polyanionic
cellulose (PAC-LV) were supplied by M-I SWACO in America. Modified
starch, xanthan gum (XC), cationic inhibitor (CSW-1), carboxymethyl
starch (CMS), viscosifier (80A51), filtration control agent (CMJ-2) and
borehole-stabilizing agent (JYW-1) were all available in domestic
market. Sodium-montmorillonite (Na-MMT) was made in Huai'an in
Hebei in China. Polyoxyalkyleneamine (POAM) was synthesized
according to the references (Rasshofer, 1985; Gbard, 1985; Larkin
and Renken, 1988).

0169-1317/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2009.03.003
266 Y. Qu et al. / Applied Clay Science 44 (2009) 265–268

Table 1
Dial readings of all samples at different rpm after adding Na-MMT (hot rolling for 16 h at 70 °C).

Concentration Fresh Water 2% KCl Solution 2% CSW Solution 2% POAM Solution

of Na-MMT,% ϕ600 ϕ300 ϕ3 G10' ϕ600 ϕ300 ϕ3 G10' ϕ600 ϕ300 ϕ3 G10' ϕ600 ϕ300 ϕ3 G10'
2.5 2.5 1.4 0 0 2 1 0 0 2 1 0 0 1 1 0 0
5.0 18 13.5 5 13 2.5 1.5 0 0 2.5 1.5 0 0 1.5 1 0 0
7.5 43.5 34.5 20 46 3 2 0 0 4 2.5 0 0 2 1 0 0
10.0 104.5 86.5 54 77 5 3 2 2 4 3 0.5 0.5 2.5 1.5 0 0
12.5 – – – – 12 9.5 5 4 6 4 1 0.5 3 2 0 0
15.0 – – – – 24 20 12 20 10 7 3.5 4 3 2 0 0
17.5 – – – – 59 54 36 42 25 20 8 11 3.5 3 0 1
20.0 – – – – 138 130 65 86 40 32 11 14 4 3.5 0 0
22.5 – – – – – – – – 82 68 30 32 5 4 1 1
25.0 – – – – – – – – 236 220 106 144 6 5 2 2
27.5 – – – – – – – – – – – – 10 7 4 5

– Indicates that the reading is greater than 300, no further readings were taken.

2.2. Rheological determination
The rheological properties of the fluid samples in this study were
measured using a model ZNN-D6 viscometer. The properties included
apparent viscosity, plastic viscosity, yield point and gel strength. The
apparent viscosity, plastic viscosity and yield point were calculated
from 300 and 600 rpm readings using following formulas from API
Recommended Practice of Standard procedure for field testing drilling
fluids (Recommended Practice, 1988):
cuttings (6-10 mesh) in 300 mL different drilling muds for 16 h at
100 °C. Before hot rolling, all muds were adjusted to about pH 9. After
hot rolling, the remaining cuttings were screened using a 40 mesh
screen and washed with 10 wt.% KCl solution, dried and then weighted
to obtain the percentage recovered of the cuttings in the different mud
systems.
2.4. Biological toxicity and compatibility test

Apparent viscosity (AV) = ϕ600/2 (cP)
Plastic viscosity (PV) = ϕ600 − ϕ300 (cP)
Yield point (YP) = ϕ600 − AV (N/m2).
2.3. Na-MMT and cuttings dispersion test
The inhibitive agents in the mud systems should be sufficient to
reduce the hydration and swelling of clay minerals in the shale
cuttings. By a trial and error method of testing the combination of
fresh water (or drilling fluids) and clay in the shale cuttings, the
approximate amount of POAM present in the experimental systems
was determinated and the concentration of POAM was about 2 wt.% of
the systems. To demonstrate the inhibitive property of POAM, the
experiments were designed to determine the maximum amount of
Na-MMT that can be inhibited by 2 wt.% POAM solution over several
days. All samples were adjusted to about pH 9 and treated with a
2.5 wt.% portion of Na-MMT at a medium rate of shear. After stirring
for 30 min, the samples were hot rolled in a roller oven for 16 h at
70 °C. When the samples were cooled, their rheologies were recorded.
All samples were treated again with Na-MMT as previously described.
This procedure was carried out for each sample until they were too
thick to measure.
Before cuttings dispersion tests, the crystalline components of the
cuttings were carried out by using Rigaku TTR-III X-ray diffractometer.
Cuttings dispersion tests were performed by hot rolling 30 g shale
The biological toxicity of the shale inhibition agent was measured
by the Mysid shrimp test. A detail account of the procedure for
measuring toxicity of drilling fluids is described in the reference (Duke
et al., 1984).
The compatibility test was carried out by measuring the change of
rheological properties and filtrate loss of several mud systems before
and after adding the shale inhibitive agent. Filtrate loss of drilling
fluids was determinated by a filter press. The filtrate loss of the mud
systems was measured in milliliters under 690 kPa of pressure
through a special filter paper for 30 min.
3. Results and discussion
3.1. Effect of POAM on Na-MMT dispersion
Rheological properties were measured for the different systems
after adding Na-MMT (Table 1). The plots of apparent viscosity (AV),
plastic viscosity (PV) and yield point (YP) of the samples versus Na-
MMT concentration were shown in Fig. 1–3 respectively. MMT in fresh
water easily absorbed water and swelled greatly (Fig. 4). As a result,
the viscosity of the system significantly increased, and the system was
too thick to measure the rheological readings after adding 12.5 wt.%
Na-MMT in fresh water. However, the other three systems exhibited
the inhibitive property at different degree (Table 2).

Fig. 1. Variation of apparent viscosity with Na-MMT concentration. Fig. 2. Variation of plastic viscosity with Na-MMT concentration.
 Y. Qu et al. / Applied Clay Science 44 (2009) 265–268 267

Table 2
Summary of the crystalline minerals for the shale cuttings.

Minerals Content,%
Quartz 32.9
Albite 16.7
Calcite 16.2
Clinochlore and Illite 34.2
Total 100.0

Table 3
Recovery rate (%) of the shale cuttings in the different mud systems.

Test No. Formulations of drilling fluid systems Total

Fig. 3. Variation of yield point with Na-MMT concentration. recovered
1# 11.5% Sodium formate + 1.3% Modified starch + 0.6%XC 67.0%
Compared with fresh water, 2 wt.% KCl solution and 2 wt.% CSW 2# 11.5% Sodium formate + 1.3% Modified starch + 0.6%XC + 89.0%
2%POAM
solution, the 2 wt.% POAM solution exhibited the superior perfor-
3# 5%KCl + 0.5%UltraCap + 1%PAC-Lv + 0.5%XC (1.20 g/cm3 72.3%
mance to inhibit the hydration and swelling of Na-MMT. Despite KCl weighed with barite)
can reduce the swelling and hydration of most clay minerals, 4# 5%KCl + 0.5%UltraCap + 1%PAC-Lv + 0.5%XC + 2%POAM 90.3%
especially smectite, it is only moderately effective for illite and may (1.20 g/cm3 weighed with barite)
actually increase swelling of kaolins (van Oort, 1997; Santarelli and 5# 5%KCl + 2%CSW-1 + 3%CMS + 0.2%80A51 + 0.3%XC + 59.3%
2%CMJ-2 + 1%JYW-1
Carminati, 1995). As a kind of low molecular mass polyamines, the 6# 5%KCl + 2%CSW-1 + 3%CMS + 0.2%80A51 + 0.3%XC + 65.7%
reaction of POAM with clay minerals can involve several mechanisms 2%CMJ-2 + 1%JYW-1 + 2%POAM
including hydrogen bonding, dipole interactions and ion exchange
Note: Continuous phase of all drilling fluid systems was fresh water.
(Theng, 1974; Sithole and Guy, 1985). The molecules of POAM were
adsorbed on the surfaces of clay minerals and compete with water
molecules for reactive sites, which could serve to reduce clay mineral cuttings had a high clay mineral content, POAM exhibited a good
swelling. Low molecular mass amines can also be intercalated. inhibiting property and reduced the swelling or hydration of shale
cuttings effectively.

3.2. Effect of POAM on shale cuttings dispersion

Experimental cuttings were obtained from the shale formation of
Chang-301 well depth of 1550 m in Yumen Oilfield. The samples were
composed mainly of clay minerals, feldspar and quartz. The shale
cuttings studied had a high clay fraction. Generally, shales with a high
clay content should easily absorb water molecules and swell greatly.
Shale cuttings were a clay-rich waste stream generated by the
drilling process and could become unstable by the mechanisms
similar to the hydration and swelling of clay minerals. The results of
the shale cuttings dispersion tests (Table 3) indicated that the
recovery rate of the shale cuttings increased after adding 2 wt.%
POAM in three different mud systems. Especially for the former two
mud systems, the recovery rate of the shale cuttings increased from
67.0% to 89.0% and from 72.3% to 90.3%, respectively. Since the shale
3.3. Biological toxicity and compatibility of POAM
According to the reference (Duke et al., 1984), the biological
toxicity of POAM was measured by the Mysid shrimp test and the LC50
of POAM was much greater than 30000 ppm. Generally, an LC50 value
of greater than 30000 had been considered as environmental
compatibility. As a shale inhibitive agent in water-based drilling
fluids, POAM exhibited low toxicity and could be used both onshore
and offshore.
The results of the compatibility test were shown in Table 4. POAM
had no influence on the rheological properties and filtrate loss of the
mud systems before and after adding the shale inhibitive agent. This
indicated that POAM did not change the performance of other
additives and the rheological properties of drilling fluids. Thus,

Fig. 4. X-ray diffractograms of the shale cuttings of Chang-301 well depth of 1550 m in Yumen Oilfield. Note: Q = Quartz, A = Albite, C = Calcite; Cl = Clinochlore, I = Illite.
268 Y. Qu et al. / Applied Clay Science 44 (2009) 265–268

Table 4 References
Effect of POAM on rheological properties of water-based drilling fluids.
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No. of test ϕ600 ϕ300 ϕ3 G10' API FL AV PV YP chloride mud for drilling water-sensitive shales. J. Petrol. Technol. 28, 719–727.
1# 68 52 16 7 8.4 34 16 18 Duke, T.W., Parrish, P.R., Montgomery, R.M., 1984. Acute toxicity of eight laboratory
2# 65 50 15 6.5 9.2 32.5 15 17.5 prepared generic drilling fluids to mysids (mysidopsis). EPA-600/3-84-067.
3# 76 57 11 5 6 38 19 19 Dzialowski, A., Hale, A., Mahajan, S., 1993. Lubricity and wear of shale: effects of drilling
fluids and mechanical parameters. SPE/IADC Drilling Conference. SPE, Amsterdam,
4# 62 50 9 3.5 6.4 31 12 19
p. 25730.. February.
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Acknowledgements

We would like to thank the financial support from PetroChina Fund

under No. 2008A-2303 for this work.