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Methane (CH4) wettability of clay coated quartz at reservoir conditions Bin Pan, Franca Jones, Zhaoqin Huang, Yongfei Yang, Yajun Li, Seyed Hossein Hejazi, and Stefan Iglauer Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b03536 • Publication Date (Web): 17 Jan 2019 Downloaded from http://pubs.acs.org on January 20, 2019
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Energy & Fuels
Methane (CH4) wettability of clay coated quartz at reservoir conditions
1 2
Bin Pana, Franca Jonesb, Zhaoqin Huangc, Yongfei Yangc, Yajun Lid, Seyed Hossein Hejazia,
3
Stefan Iglauere
4
aDepartment
5
T2N 1N4,
[email protected];
[email protected] 6
bDepartment
7
Australia, PO Box U1987,
[email protected] 8
cSchool
9
Changjiang West Road, Qingdao, China, 266580,
[email protected];
of Chemical and Petroleum Engineering, University of Calgary, Calgary, Canada,
of Chemistry, Nanochemistry Research Institute, Curtin University, Perth WA 6845,
of Petroleum Engineering, China University of Petroleum (East China), No. 66,
10
[email protected] 11
dKey
12
(East China)), Ministry of Education, Qingdao, 266580, P.R. China,
[email protected] 13
eSchool
14
[email protected] Laboratory of Unconventional Oil & Gas Development (China University of Petroleum
of Engineering, Edith Cowan University, 270 Joondalup Drive, Joondalup, Australia,
15 16
*corresponding
17
[email protected])
authors (
[email protected];
[email protected];
[email protected];
18 19
Abstract
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Methane (CH4) wettability of shale is a key parameter which determines pore and reservoir-scale
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fluid distributions, CH4 reserves estimation, and ultimate recovery efficiency from shale gas
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reservoirs. Clay minerals usually fill the pore spaces or are adsorbed on the surface of shale rock,
23
thus influencing CH4 wettability. However, a systematic investigation of the influence of clay on
24
CH4 shale-wettability is lacking. Herein, we investigated the role of clay, pressure, temperature,
25
and salinity on CH4 wettability of clay coated quartz (i.e. a well-defined model system for
26
shales). Results indicated that the advancing and receding water contact angles for clean,
27
kaolinite coated and montmorillonite coated quartz increased with pressure. However, the effect
28
of temperature on wettability is complex, thus the advancing water contact angle for clean quartz
29
increased with temperature while an opposite trend was found for clay coated quartz. At low
30
temperature (i.e. 300 K), clay coating de-wetted the quartz surface, while at elevated temperature
31
(i.e. 323 K), clay coating increased the hydrophilicity of the quartz surface. Furthermore,
32
kaolinite clay particles demonstrated a stronger influence on quartz wettability than
33
montmorillonite particles, both, at high and low temperatures. In addition, higher NaCl salinity
34
led to higher advancing water contact angles for the aforementioned three solid surfaces. The
35
effect of salinity on CH4 wettability is thus intensified in the presence of clays. These insights
36
will thus improve the accuracy of CH4 reserve estimates and aid methane recovery schemes.
37 38
Key Words: Wettability; advancing and receding contact angles; elevated pressures and
39
temperatures; kaolinite; montmorillonite; shale gas recovery; shale gas reserves estimation.
40 41
1.
Introduction
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Shale reserves play an important role in meeting the global demands for energy. The significant
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development in gas production from such shale gas reservoirs is due to advances in horizontal
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drilling and hydraulic fracturing technology 1-6. Although in commercial production, there are
45
challenges in evaluating the characteristics of these hydrocarbon reservoirs due to the complexity
46
of gas storage and transport processes in the micro- and nano-scale pore geometries 7,8. In this
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context, wettability, characterized by the brine contact angles of CH4-brine-shale rock (𝜃) is a
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key parameter that determines CH4 reserves and production efficiency 9-13. In particular, CH4
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reserves, CH4 distribution, and free gas flow in the shale pores are strongly affected by the
50
capillary pressure (𝑃𝐶) which is a function of contact angle12,14-22. For example, for a circular
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capillary tube, based on the Young-Laplace Equation:
52
𝑃𝑐 =
2𝛾𝑐𝑜𝑠𝜃 𝑟
Equation 1
53
Where 𝛾 is the interfacial tension between CH4 and brine and 𝑟 is the average pore radius. When
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𝜃 < 90°, the shale rock has a stronger affinity to brine than CH4 and 𝑃𝑐 could be a driving force
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for CH4 recovery as water would imbibe more easily; while if 𝜃 > 90°, the shale rock is more
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CH4-wet than water-wet and 𝑃𝑐 would tend to resist water imbibition.
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Organic rich shales are mainly composed of consolidated clay sized particles with a high organic
58
content, a complex chemical composition filled or covered with clay 23-25, which complicates
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contact angle analysis. For example, clay crystal size is much smaller than the usual sessile
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droplet, which prevents standard wettability measurements 26-28. Previous literatures reported that
61
kaolinite and montmorillonite crystal sizes are smaller than 2 𝜇𝑚 29,30, while the usual sessile
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droplet size is around 2000 𝜇𝑚 31,32. To avoid the challenge to measure the contact angle of clay
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using the sessile method, Borysenko et al. 2009 used liquid-liquid extraction method to validate 3 ACS Paragon Plus Environment
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montmorillonite as a hydrophilic surface and kaolinite as a hydrophobic surface 28. However,
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liquid-liquid extraction method could not report the specific contact angle value 33. Schmatz et al.
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2015 reported a more water-wet nature of kaolinite based on cryo SEM results 34. However, cryo
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SEM method is destructive 35. Ballah et al. 2016 measured the wettability of clay coating on
68
glass slide using sessile method and all the contact angles measured in their work were smaller
69
than 40º (i.e. a strong water-wet surface) 36. However, all their measurements were conducted at
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ambient conditions, which could not represent the real wettability of clay at reservoir conditions
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as pressure and temperature could also influence wettability significantly 37,38. A recent study
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compacted clay powders into solid substrates and measured the brine contact angles of the
73
CO2/N2/oil-brine-clay systems at reservoir conditions 39. They concluded that montmorillonite is
74
oil-wet, while kaolinite and illite are water-wet at typical reservoir conditions 39. However, they
75
did not measure clay wettability in the system of CH4-brine-clay system, which is related to shale
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gas production 9-13. Molecular dynamic simulations, which overcome these limitations, predicted
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that Na-/Ca- montmorillonite becomes more hydrophobic when exposed to CO2 at reservoir
78
conditions 40. Šolc et al. 2011 calculated the contact angle of water-air-kaolinite was 105º using
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molecular dynamic simulation 41. Thus, the inconsistency between experimental and simulated
80
results is clear and clay wettability is still open to large uncertainty. However, how clay
81
influences the wettability of organic rich shales at reservoir conditions has not been explored.
82 83
In the present study, we thus investigate the CH4 wettability of clay coated quartz at reservoir
84
conditions. Note that we use the words clay and clay minerals interchangeably in this work. To
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isolate the role of shale constituents, we use quartz, one of the most primary components of shale
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42-47,
coated with clay particles, instead of real rock samples. Thus, we can elucidate the role of 4 ACS Paragon Plus Environment
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clay types on the wettability without perturbations from other chemical components in shale.
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Furthermore, the effects of pressure, temperature and salinity on CH4 wettability are also
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presented.
90 91
2.
Experimental Methodology
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To remove any residual contaminants from the quartz surface 48,49, all alpha - quartz substrates
93
(Supplied by Dade Quartz Co., Ltd, China, with RMS surface roughness of less than 1 nm
94
measured with an JPK NanoWizard 4 Atomic Force Microscope (AFM), SI-Figure 1a) were
95
carefully cleaned following a standard procedure. First, the substrates were washed by acetone
96
and subsequently soaked in piranha solution (3 parts of 98 wt% H2SO4 and 1 part of aqueous 30
97
wt% H2O2 for 30 mins at 300 K; H2SO4 and H2O2 were purchased from Sinopharm Chemical
98
Reagent Co., Ltd.). Afterwards, the immersed substrates were covered with aluminum foil and
99
dried in a clean oven for 8 hours at 353 K. A concentration of 2 wt% kaolinite or
100
montmorillonite suspension was prepared respectively through adding kaolinite or
101
montmorillonite powders into 1.5 wt% NaCl brine (kaolinite, montmorillonite, and sodium
102
chloride were obtained from Sigma-Aldrich; NaCl purity was 99 mol%). Note that the
103
chemical formula of kaolinite is Al2O7Si2 · 2H2O and the montmorillonite is K 10 catalyst,
104
MgNaAl5(Si4O10)3(OH)6. A relatively high NaCl salinity was used here to impede clay
105
accumulation/swelling and promote clay adsorption onto quartz surface 50,51. The total salinities
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of clay suspensions in DI water and in 1.5 wt% NaCl brine were measured using Starter3100M
107
at room temperature, See SI-Table 1 in supporting information. It was found that the total
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salinity of clay suspensions is extremely low, showing no apparent difference with the salinity of
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pure DI water. A concern may be that such high Na+ concentration would exchange with in-situ 5 ACS Paragon Plus Environment
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divalent cations from clay minerals. However, as we shown in SI-Table 1 and 2, the ions salinity
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from in-situ clay were extremely low and the wettabilities for Na+ and Mg2+ were very similar.
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Thus, it was assumed that the ions exchange would not influence wettability in this work. The
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particle size distributions (PSD) of the kaolinite and montmorillonite were measured thrice via a
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Zetasizer Nano instrument (Malvern, UK). The average particle sizes for kaolinite and
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montmorillonite were 1050 nm and 900 nm respectively. The total organic content (TOC) for
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kaolinite and montmorillonite were 335 mg/kg and 3093 mg/kg, respectively, measured by an
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Elab-TOC instrument.
118 119
The kaolinite and montmorillonite suspensions were stirred for 2 hours at 323 K. Afterwards, the
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clean quartz substrates were aged in the 2 wt% kaolinite or montmorillonite suspensions for 6 hrs
121
and then the aged substrates were covered with clean aluminium foil and dried for 6 hrs. The
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total 12 hrs duration would assure a stable coating 50. The morphological properties of clean and
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coated substrates were characterized using AFM (Note that RMS roughness of clean and
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kaolinite coated quartz were measured by JPK NanoWizard 4 Atomic Force Microscope, while
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RMS of montmorillonite quartz was measured via Bruker Multi mode 8 Atomic Force
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Microscope, please see SI-Figure 1 in the supporting information) and SEM measurements (by
127
Philips XL 30 SEM), Figures 1. The RMS roughness values for clean, kaolinite coated and
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montmorillonite coated quartz were 483.7 pm, 629.8 nm and 863 nm, respectively. However, at
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this scale, the effect of roughness on contact angle is insignificant 52. Based on the analysis of
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SEM images using MATLAB, the average kaolinite and montmorillonite coverages were
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37.48% and 39.02%, respectively, please see SI-Figure 2 in the supporting information.
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Furthermore, the SEM images demonstrated a more compact coating on the montmorillonite 6 ACS Paragon Plus Environment
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coated surface. The advancing (𝜃𝑎) and receding (𝜃𝑟) brine contact angles of CH4-brine-
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clean/clay coated quartz systems were then measured by a Krüss DSA 100 instrument using the
135
tilted plate method 53 as described previously in detail 23. All the contact angle measurements
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were finished within the initial 30 s. We did not observe the contact angle for a long time in this
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work, because the droplet could destabilise and displace the clay coating after long time contact.
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However, a future work would investigate long-term clay wettability using a recent developed
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LbL coating method 54. Furthermore, we did not consider the influence from CH4-brine
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dissolution because of a very low dissolution capacity between brine and CH4 55. Note that in
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shale gas extraction, 𝜃𝑎 corresponds to CH4 recovery, while 𝜃𝑟 is related to initial CH4/water
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distribution 56.
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144 145
(a)
146
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(b)
149 150
(c)
151 152
(d)
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(e)
154 155
Figure 1. SEM images of clean (a), kaolinite coated (b,c) and montmorillonite coated (d,e)
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quartz used in the experiments. The light color is clay particle and the dark color is quartz
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substrate.
158 159
3.
Results and Discussion
160
3.1
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The effects of pressure and temperature on the brine contact angles were measured for the
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various substrates at multiple pressures (0.1 MPa to 20 MPa) and temperatures (300 K and 323
163
K), Figure 2.
Effect of pressure and temperature on contact angles
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Energy & Fuels
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Clean, 300 K
Advancing contact angle [º]
45
Clean, 323 K
40
Kaolinite coated, 300 K
35
Kaolinite coated, 323 K Montmorillonite coated, 300 K
30
Montmorillonite coated, 323 K
25 20 15 10 5 0 0
5
10 P [MPa]
164
15
20
(a)
165
50 Receding contact angle [º]
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
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Clean, 300 K
40
Clean, 323 K
35
Kaolinite coated, 300 K Kaolinite coated, 323 K
30
Montmorillonite coated, 300 K
25
Montmorillonite coated, 323 K
20 15 10 5 0 0
166
5
10 P [MPa]
15
20
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(b)
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Figure 2. Effect of pressure and temperature on the (a) advancing and (b) receding brine contact
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angles of clean/kaolinite coated/montmorillonite coated quartz-CH4-brine systems. (Note that the
170
aqueous phase is 1.5 wt% NaCl brine).
171 172
Both, 𝜃𝑎 and 𝜃𝑟 for all substrates clearly increased with pressure, consistent with literature data
173
measured for several different gases on various substrates 23,38, 43,52,57,58,59. For example, at 300
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K, when pressure increased from 0.1 MPa to 20 MPa, 𝜃𝑎 for clean, kaolinite and montmorillonite
175
coated quartz increased by 30º, 29º and 21º, respectively, while 𝜃𝑟 for the above three surfaces
176
increased by 22º, 25º and 15º, respectively.
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Noteworthy was the effect of temperature on the wettability. 𝜃𝑎 for clean quartz increased with
178
temperature, consistent with literature data reported for quartz 52, hydrophilic dolomite 31 and
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shale 37, while 𝜃𝑎 for clay coated quartz decreased with temperature, consistent with literature
180
data reported for mica 58,59, hydrophobic dolomite 31 and 3 wt% TOC shale 23. Specifically, at 15
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MPa, when temperature increased from 300 K to 323 K, 𝜃𝑎 changes for clean, kaolinite coated
182
and montmorillonite coated quartz were 9º, -13º and -8º respectively; at 20 MPa, for the same
183
temperature increase, 𝜃𝑎 changes for above three surfaces were 5º, -24º and -6º, respectively.
184
Physically, the influence of pressure on wettability can be attributed to the higher non-aqueous
185
phase density 38,57, the consequently stronger intermolecular interactions between CH4 and the
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solid surface due to the increased molecular density 23,57,60-63, and the corresponding decrease in
187
the interfacial tension between the solid surface and CH4 64. The underlying mechanism of the
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temperature influence on wettability can be explained by the sharp-kink approximation 31,37,
189
equation 2 below.
190
𝑐𝑜𝑠𝜃 = ―1 +
∆𝝆𝑰 𝜸𝒍𝒈
Equation 2
191
Where ∆𝜌 is the approximate density difference between the adsorbed brine film and CH4; 𝛾𝑙𝑔 is
192
the interfacial tension between brine and CH4; and I is the van der Waals potential integral.
193
Clearly, both 𝛾𝑙𝑔 and ∆𝜌 increased with temperature 58,65. However, the relative increase in ∆𝜌
194
with temperature was more significant than that of 𝛾𝑙𝑔 31,37, which reduces the contact angle; the
195
van der Waals potential decreases with temperature 66, which increases the contact angle. Thus,
196
in both scenarios, a increase or decrease with temperature is possible. For clean quartz, the
197
temperature-driven influence on van der Waals interaction was more effective, resulting in a
198
contact angle increase with temperature 31. For clay coated quartz, this van der Waals interaction
199
might be relatively weak, thus the contact angle decreased with temperature.
200 201
3.2
Effect of brine salinity on contact angles
202
All 𝜃𝑎 increased with salinity as depicted in Figure 3. Specifically, when NaCl salinity increased
203
from 1.5 wt% to 15 wt%, 𝜃𝑎 for clean, kaolinite coated and montmorillonite coated quartz
204
increased by 6º, 15º and 10º, respectively.
205
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50 45
Clean
40 Contact angle [°]
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Energy & Fuels
Kaolinite coated
35 Montmorillonite coated
30 25 20 15 10 5 0 2
4
8 10 Salinity [wt%]
206
14
207
Figure 3. The advancing brine contact angles of CH4-clean/kaolinite coated/ montmorillonite
208
coated quartz-brine systems at 10 MPa and 323 K.
209 210
This result is consistent with literature data for NaCl - oil - sandstone 67, NaCl - glass/kaolinite
211
coated glass - crude oil 68, NaCl - oil - kaolinite coated glass 69, NaCl - CO2 - mica 58,59,70; and
212
NaCl-CO2-quartz 38,62 systems. The effect of salinity on the advancing water contact angles can
213
be explained with the Derjaguin Landau Verwey Overbeek (DLVO) theory as discussed in our
214
previous work23. In order to shed more light on the underlying mechanism of salinity influence
215
on the contact angles, we also measured the corresponding zeta potentials (using a Zetasizer
216
Nano instrument, Malvern, UK) and pH values (using a RHA-SHKY pH Meter Model 8601
217
instrument), Table 1. Every zeta potential measurement was repeated 18 times, and every pH
218
measurement was repeated 3 times. 13 ACS Paragon Plus Environment
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Table 1. Zeta potential and pH data for various systems at two different temperatures in this
221
work.
300 323 300 323 300
Mean zeta potential [mV] -0.86 1.21 1.91 3.49 -14.7
300
-21.9
0.574
323
-12.6
0.872
323
-19.6
0.967
300 300 323 323 323 323
-7.51 -10.1 -3.04 -2.14 2.37 3.48
7.88 6.3 6.58 3.59 9.31 8.97
Temperature [K]
Samples 1.5 wt% NaCl 1.5 wt% NaCl 5 wt% NaCl 5 wt% NaCl 2 wt% Kaolinite + 1.5 wt% NaCl 2 wt% Montmorillonite + 1.5 wt% NaCl 2 wt% Kaolinite + 1.5 wt% NaCl 2 wt% Montmorillonite + 1.5 wt% NaCl 2 wt% Kaolinite + 5 wt% NaCl 2 wt% Montmorillonite + 5 wt% NaCl 2 wt% Kaolinite +5 wt% NaCl 2 wt% Montmorillonite +5 wt% NaCl 2 wt% Kaolinite +10 wt% NaCl 2 wt% Montmorillonite +10 wt% NaCl
Standard Mean Standard deviation pH deviation [mV] 1.01 6.45 0.786 4.94 6.25 0.03 6.65 0.436 6.25 0.58 4.74
0.23
5.61 3.48
0.02 0.01
222 223
Higher temperatures led to less negative zeta potentials; while the addition of kaolinite or
224
montmorillonite reduced the zeta potential. Furthermore, clay suspensions are not stable and
225
uniform solutions and this intrinsic property could cause a significant variation in the measured
226
properties 71.
227
In addition, montmorillonite suspensions were more acidic than the corresponding kaolinite
228
suspensions; while a higher NaCl salinity led to a lower pH value for both, montmorillonite and
229
kaolinite, suspensions. Higher pH values lead to more negative zeta potentials 72, and thus lower
230
contact angles. However, it would not be explained why the contact angle for 2 wt% 14 ACS Paragon Plus Environment
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231
montmorillonite + 1.5 (or 5 wt%) wt% NaCl brine sample was smaller than that for 2 wt%
232
kaolinite + 1.5 (or 5 wt%) wt% NaCl brine sample at 300 K just based on pH. We hypothesize
233
that the surface microstructural evolution and (clay) hydration of the coated surface also played
234
an important role, causing the different wettability behavior for kaolinite and montmorillonite
235
coated surfaces, besides the solution property 60,73. Clearly, the contact angle strongly correlated
236
with the zeta potential, Table 2 and Figure 4.
237
Table 2. The used data for plotting Figure 4.
238
Solution Systems 2 wt% Montmorillonite + 1.5 wt% NaCl 2 wt% Kaolinite + 1.5 wt% NaCl 2 wt% Kaolinite +5 wt% NaCl 2 wt% Montmorillonite +5 wt% NaCl 2 wt% Kaolinite +10 wt% NaCl 2 wt% Montmorillonite +10 wt% NaCl
Zeta potnetial [mV]
Advancing contact angle [º]
-19.6
15
-12.6 -3.04 -2.14 2.37 3.48
15 22 23 24 26
239
Advancing contact angle [º]
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
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30 25 20 15 10 5 0 -20
-15
-10 -5 Zeta potential [mV]
0
5
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241
Figure 4. The relationship between advancing contact angle and the corresponding zeta potential
242
at 10 MPa, 323 K and various NaCl salinities.
243 244
At 323 K, higher salinity led to larger zeta potential, thus higher contact angles. The zeta
245
potential for kaolinite was smaller than that for montmorillonite at the same NaCl salinity (5
246
wt% and 10 wt%, respectively), thus the contact angle for kaolinite was smaller than
247
montmorillonite. However, note that the zeta potential was measured at ambient conditions,
248
while the contact angle was measured at high pressure, although a correlation has been proposed
249
previously 71.
250 251
In summary, the increasing salinity increases the ionic strength, which better screens the surface
252
charge 61. Thus, the surface potential approaches zero and in some circumstances, positive
253
values. As a result, surface polarity and water affinity decreases, hence, an increasing water
254
contact angle results.
255 256
3.3
Effect of clay on quartz wettability
257
Based on the results and discussion in sections 3.1 and 3.2, it is easy to conclude that the effect
258
of clay on quartz wettability is extremely complex. For example, the effect of clay coating on
259
quartz wettability was different at low and high temperatures, Figure 2. At low temperature (i.e.
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300 K), kaolinite or montmorillonite coating de-wetted the quartz, which could be attributed to
261
the lowered pH and intensified acidic properties, thus less negative zeta potential 72, and a larger
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contact angle 74; while at high temperature (i.e. 323 K), these coatings intensified quartz
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hydrophilicity.
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Furthermore, kaolinite always had a stronger influence on quartz wettability than
265
montmorillonite. For example, at 20 MPa and 300 K, 𝜃𝑎 for clean, kaolinite and montmorillonite
266
coated quartz were 30º, 47º and 34º, respectively, while at 20 MPa and 323 K, 𝜃𝑎 for above three
267
surfaces were 35º, 23º and 28º. The low temperature results (300 K) are consistent with literature
268
reports that a) kaolinite and montmorillonite clays were more oil-wet than quartz at 298 K and
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0.1 MPa 28, that b) quartz had a stronger water adsorption capacity than kaolinite at 298 K 75 and
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that c) brine contact angles of oil-water-sandstone systems increased with clay content on the
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sandstone surface at ambient condition (i.e. 0.1 MPa and 287 K) 67. Furthermore, the results for
272
the clay influence at 323 K are consistent with literature reports where kaolinite reduced water
273
repellency of silica sand at 323 K more efficiently than montmorillonite 76. Although a recent
274
study reported clay wettability for CO2/N2/oil-brine-clay systems at reservoir conditions39, we
275
did not find any literature related to clay influence on shale wettability at high temperature and
276
high pressure, noting that reservoir conditions (i.e. elevated pressure and temperature) are critical
277
for gas behaviour at the pore-scale 77, which is again vital for the evaluation of CH4 reserves and
278
recovery.
279 280
In addition, the effect of salinity on CH4 wettability was intensified in the presence of clays at 10
281
MPa and 323 K, Figure 3. Specifically, when the NaCl salinity increased from 1.5 wt% to 15
282
wt%, for clean quartz, 𝜃𝑎 increased by 6° from 25° to 31°; compared with this, salinity had a
283
stronger influence on 𝜃𝑎 for the kaolinite coated (e.g. 𝜃𝑎 increased by 10° from 15° to 25°) and
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montmorillonite coated surfaces (e.g. 𝜃𝑎 increased by 15° from 15° to 30°). Mechanistically, clay
285
particles have negatively charged surfaces at typical reservoir conditions 78, consistent with our
286
zeta potential results; the isoelectric points for quartz, kaolinite and montmorillonite are pH=3 52,
287
6 and 6.7 78. Montmorillonite has a greater number of structurally charged sites than kaolinite 79,
288
which results in a stronger attraction to positive charges (e.g. Na+). Thus, the surface potential
289
for Montmorillonite coated quartz approaches zero more quickly. Consequently, 𝜃𝑎 for
290
montmorillonite coated quartz increased more significantly than 𝜃𝑎 for both, kaolinite coated
291
quartz and clean quartz.
292 293
4.
Conclusions
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CH4-shale wettability is a key parameter for predicting CH4 reserves and distribution9-13.
295
However, due to the complexity of the shale structure and composition, CH4-shale wettability
296
evaluation is still open to uncertainties. Specifically, clay minerals, as one of the abundant
297
constituents of shale formations, significantly increase the complexity of CH4-shale wettability.
298
Furthermore, a systematic investigation of clay effects on CH4-shale wettability in a
299
representative system is still scarce. To elucidate how clay influences shale wettability, we used
300
a well-defined model (i.e. clay coated quartz) to investigate the role of clay, pressure,
301
temperature and salinity on the CH4 wettability. The following conclusions were reached:
302
1. The quartz substrates became more water-wet at high temperature (i.e. 323 K) when coated
303
by clays, while they became more CH4-wet at low temperatures (i.e. 300 K). Kaolinite had
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a stronger influence on quartz wettability than montmorillonite with respect to temperature
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variations. We did not find any previous reports to compare the influence of clay coating 18 ACS Paragon Plus Environment
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or adsorption on shale and quartz wettability at different temperatures, especially at
307
reservoir pressures.
308 309 310 311 312 313
2. Elevated pressures increased the hydrophobicity of all three tested surfaces (i.e. clean, kaolinite coated and montmorillonite coated quartz). 3. Elevated temperatures de-wetted the clean quartz, while, it increased the hydrophilicity of clay coated quartz. 4. High NaCl salinity reduced surface hydrophilicity. This salinity effect was intensified in the presence of clays.
314 315
Acknowledgements
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The authors wish to acknowledge financial assistance from the National Science and Technology
317
Major Project (2016ZX05023-001; 2016ZX05060-010; 2017ZX05009001), the Natural Science
318
Foundation of China (41602143; 51774310; 51509260; 51674280; 51711530131), Key Research
319
and Development Plan of Shandong Province (2018GSF116009), Applied Basic Research Projects
320
of Qingdao Innovation Plan (16-5-1-38-jch), the Fundamental Research Funds for the Central
321
Universities (18CX02104A; 18CX05029A; 17CX05003), the Chinese Scholarship Council, the
322
University of Calgary Global Research Initiative in Unconventional Hydrocarbon Resources-
323
Beijing Site, Kerui-MITACS Accelerate Research Fund Application Ref. IT09328, and Natural
324
Sciences and Engineering Research Council of Canada (NSERC).
325 326
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50 Brine advancing contact angle [º] of 1.5 wt% NaCl-CH4-solid
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Clean, 300 K
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Clean, 323 K
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Kaolinite coated, 300 K
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Kaolinite coated, 323 K Montmorillonite coated, 300 K
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Montmorillonite coated, 323 K
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