Role of fluid density on quartz wettability

Accepted Manuscript Role of fluid density on quartz wettability Bin Pan, Yajun Li, Liujuan Xie, Xiaopu Wang, Qingkun He, Yanchao Li, Seyed Hossein Hejazi, Stefan Iglauer PII:

S0920-4105(18)30843-X

DOI:

10.1016/j.petrol.2018.09.088

Reference:

PETROL 5351

To appear in:

Journal of Petroleum Science and Engineering

Received Date: 20 June 2018 Revised Date:

16 September 2018

Accepted Date: 27 September 2018

Please cite this article as: Pan, B., Li, Y., Xie, L., Wang, X., He, Q., Li, Y., Hejazi, S.H., Iglauer, S., Role of fluid density on quartz wettability, Journal of Petroleum Science and Engineering (2018), doi: https:// doi.org/10.1016/j.petrol.2018.09.088. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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CH₄ C₂H₆ C₃H₈ C₈H₁₈ C₁₀H₂₂ CO₂ N₂ He Ar Linear (Trend line)

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Role of fluid density on quartz wettability

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Bin Pana, Yajun Lib, Liujuan Xiec, Xiaopu Wangd, Qingkun Hee, Yanchao Lif, Seyed

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Hossein Hejazia, Stefan Iglauerg

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a

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Petroleum

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[email protected]

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b

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66, Changjiang West Road, Qingdao, China, 266580, [email protected]

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c

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Subsurface Fluidics and Porous Media Laboratory, Department of Chemical and University

of

Calgary,

Calgary,

T2N

1N4,

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Engineering,

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School of Petroleum Engineering, China University of Petroleum (East China), No.

Qingdao Institute of Marine Geology, China Geologic Survey, Qingdao, China,

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266071, [email protected]

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d

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of Petroleum (East China), Qingdao, China, 266555, [email protected]

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e

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University of Science and Technology, No. 579, Qianwangang Road, Qingdao, China,

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266590, [email protected]

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f

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610051, [email protected]

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g

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Australia, [email protected]

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National Engineering Equipment Testing and Detection Technology, China University

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Experiment Center of College of Materials Science and Engineering, Shandong

Downhole Service Company, Chuanqing Drilling Company, CNPC, Chengdu, China,

School of Engineering, Edith Cowan University, 270 Joondalup Drive, Joondalup,

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*

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[email protected]; [email protected] )

corresponding authors ([email protected]; [email protected];

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Abstract

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Hydrocarbon

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hydrocarbon-water-mineral wettability. However, wettability is a complex parameter

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and experimental measurements are still open to large uncertainty. We thus

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demonstrate here that quartz wettability correlates with the density of the non-aqueous

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fluid, e.g. oil, CO2, N2, etc. – which can be in liquid, gaseous or supercritical form.

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This insight significantly simplifies wettability assessments, thus enhancing

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fundamental understanding of wettability and the related fluid dynamics in

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siliciclastic hydrocarbon reservoirs. Furthermore, this observed correlation may

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promote hydrocarbon recovery and reserves prediction in siliciclastic reservoirs.

and

reserves

estimation

largely depend

upon

the

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recovery

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Keywords

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Quartz Wettability; Non-aqueous density; Hydrocarbon recovery.

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1.

Introduction

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Rock surface wettability - characterized by the rock-fluid-fluid contact angle ( ) -

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plays a key role in subsurface fluid dynamics and statics

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(Iglauer, 2017; Sahimi, 2011; Zhao et al. 2016). For example, pore-scale fluid

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distributions are strongly affected by θ (e.g. Al-Menhali et al. 2016; Chaudhary et al.

ACCEPTED MANUSCRIPT 2013; Iglauer et al. 2012a; Zhou et al. 2012, 2013, 2014), which again strongly affects

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how fluids flow and distribute at hectometer (reservoir)-scale (Al-Khdheeawi et al.

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2017; Bear, 1988; Blunt, 2017). θ is thus a prime parameter in terms of fluid-rock

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interactions and it determines geological or engineering fluids distributions and

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migrations, e.g. hydrocarbon reserves, efficiency of hydrocarbon recovery (Morrow

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and Mason, 2001; Zhou et al. 2000), CO2 geo-storage capacities (Iglauer et al. 2015b;

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Iglauer, 2017; Liang et al. 2017) and contaminant clean-up from soil (Karakasi and

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Moutsatsou, 2010).

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It is thus of key importance to know exact θ values to be able to accurately predict

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subsurface multi-phase flow and statics, so that geological processes can be better

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understood and engineering operations can be optimized. However, available data is

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disordered (e.g. θ varies between 0-180° for CO2 and hydrocarbons (Iglauer, 2017;

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Pan et al. 2018)) as the underlying phenomena are complex (Adamson and Gast, 1997;

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Butt and Kappl, 2006). It is thus highly desirable to simplify the data structures so that

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θ can be easily predicted and implemented in geological assessments and pore- and

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reservoir-scale simulators (e.g. Al-Khdheeawi et al. 2017; Hilpert and Miller, 2001;

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Van Dijke et al. 2006). To achieve this, Al-Yaseri et al. (2016) proposed that the brine

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contact angles of CO2, N2, He, Ar and SF6 on a quartz surface correlate with gas

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density. Remarkably this is independent of the gas type, although brine composition,

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mineral surface chemistry and temperature still influence θ (Al-Yaseri et al. 2016;

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Iglauer, 2017). However, it is unclear whether a similar relation also holds for

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hydrocarbons, despite their vital economic importance (Cooper, 2003).

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Note that hydrocarbon densities ( ) can vary significantly in the subsurface (Ashcroft

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and Isa, 1997; Batzle and Wang, 1992; Saryazdi et al. 2013), ranging from low values

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for volatile gas (methane density at 5 MPa and 323 K is 31.66 kg/m3 (Setzmann and

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Wagner, 1991)) to high values for heavy oil (e.g. 911 kg/m3 has been measured for an

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Ontario heavy oil (Yang and Gu, 2006)). We thus demonstrate here that quartz

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wettability also scales with hydrocarbon density.

2.

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Synthetic formation brine (SFB) was used as the aqueous phase during the contact

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angle measurement. The electrical conductivity of SFB was 219 mS/cm, measured

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with a Zetasizer Nano instrument (Malvern, UK). All other detailed information about

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SFB were listed in Table 1.

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Experimental Methodology

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All the salts had a purity of ≥ 99 mol% and were supplied from Sigma-Aldrich.

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Methane (CH4), Ethane (C2H6), Propane (C3H8), n-Octane (C8H18) and n-Decane

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(C10H22) were the hydrocarbons tested (purchased from Dalian Date Gas Co., Ltd,

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China, purities of all hydrocarbons were ≥ 99.9 mol%).

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An alpha-quartz single crystal (Supplied by Dade Quartz Co., Ltd, China) was chosen

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as a solid substrate as quartz is an abundant mineral in the subsurface and main

ACCEPTED MANUSCRIPT component of sandstone formations (Blatt and Schultz, 1976; Chiquet et al. 2007).

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The surface roughness of the quartz sample was quantified via a Bruker Multi mode 8

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Atomic Force Microscope; a root-mean-square (RMS) roughness of 2.77 nm was

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measured, which is very smooth (Cho et al. 2007).

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Advancing (

) and receding ( ) brine contact angles on the quartz substrate were

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then measured by a Krüss DSA 100 instrument, Figure 1a, using the titled plate

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method (Lander et al. 1993) as described in detail previously (Pan et al. 2018).

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Firstly, the pre-cleaned quartz substrate was placed into the measurement chamber;

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subsequently, the measurement chamber was achieved to pre-set pressure and

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temperature. Then a drop of SFB brine droplet (6-7 uL, without saturated by

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non-aqueous fluids) was introduced into the measurement chamber through the upper

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needle and then dispensed onto the titled quartz surface.

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simultaneously just before the droplet moved, Figure 1b.

and

were measured

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Note that

corresponds to hydrocarbon recovery by waterflooding and capillary

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trapping in CO2 geo-sequestration, while

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distribution and structural CO2 trapping beneath a caprock (Iglauer et al. 2015a,b;

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Swanson, 1980). To avoid bias caused by cross-contaminations, all flow lines in the

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apparatus were cleaned thoroughly before measuring a new type of hydrocarbon by

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first injecting acetone (purity = 99 mol% from Sigma-Aldrich), followed by the

is related to initial hydrocarbon/water

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injection of hot DI water (323K) to remove all acetone. Finally SFB and hydrocarbon

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were flushed through the flow lines.

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Prior to each experiment, the quartz substrate was also cleaned with acetone and

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subsequently immersed into piranha solution (3 parts of 98 wt% H2SO4 and 1 part of

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aqueous 30 wt% H2O2) for 30 mins to remove any residual contaminants from the

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surface (Iglauer et al. 2014; Love et al. 2005). The clean sample was covered with

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aluminum foil and dried at 353 K for 8 hours in a clean oven. The standard deviations

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for the

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measurements were ± 3° based on replicate measurements.

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3.

Results and Discussion

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3.1. Effect of pressure and fluid density on contact angles

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increased with pressure (Figure 2a,b), consistent with literature data for CO2 (e.g.

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Arif et al. 2016; Broseta et al. 2012; Chiquet et al. 2007; Iglauer et al. 2012b; Liang,

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2017) and N2, Ar, He, SF6 (Al-Yaseri et al. 2016).

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To further explore the relationship between the brine contact angle and the density of

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the non-aqueous liquid, we recalled and compared the pressure-density relation of the

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non-aqueous fluids investigated, Figure 3. For instance, when pressure increased from

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0.1 MPa to 20 MPa (at 323 K), the densities of CH4 and C2H6 increased from 0.6

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kg/m3 and 1.1 kg/m3 to 135.7 kg/m3 and 386.1 kg/m3, respectively. Hence,

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CH4 and C2H6 increased from 0° and 3° to 38° and 60°, while the corresponding

for

ACCEPTED MANUSCRIPT increased from 0° and 2° to 33° and 49°, a significant increase and a clear shift in

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wettability away from completely water-wet to partially wetting. While CH4 and C2H6

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always remained gaseous at all tested pressures, C3H8 liquified at pressures above 2

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MPa (at 323 K), and C8H10 and C10H22 always existed in liquid form. Thus, the

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densities of liquid C3H8, C8H10 and C10H22 only increased very slightly while the

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corresponding brine contact angles of the liquid hydrocarbons also only slightly

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increased. For example, when pressure increased from 10 MPa to 20 MPa,

SC

for C3H8 increased by 3° and 1° respectively;

and

and

for C8H10 increased by

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3° and 2°;

140

previous reports where no apparent pressure effect on the brine contact angle of liquid

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hydrocarbons on quartz (Rajayi and Kantzas, 2011; Wang and Gupta, 1995), mica

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(Hansen et al. 2000) or calcite (Hansen et al. 2000) was measured. However,

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Al-Yaseri et al. (2016) reported a clear influence of pressure on the rock wettability in

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case of gaseous or supercritical fluids. We conclude that for any pressure changes at

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high pressure, significant changes in wettability are only expected for gases or

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supercritical fluids, but not for liquids.

for C10H22 increased by 3° and 2°. This is consistent with

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and

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Thus θ increased with increasing ρ (i.e. the non-aqueous phase density) for all fluids

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tested (Figure 4), and remarkably independent of the specific fluid, consistent with

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Al-Yaseri et al. (2016). Importantly, this correlation now includes hydrocarbons (CH4,

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C2H6, C3H8, C8H10 and C10H22), which are of key economic importance.

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Mechanistically, this wettability dependence on non-aqueous fluid density can be

ACCEPTED MANUSCRIPT attributed to an increase in intermolecular interactions between the non-aqueous fluid

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and the quartz surface at higher pressure, essentially caused by increased molecular

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density (Chen et al. 2015; Iglauer et al. 2012b; Liang et al. 2017), and a related drop

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in non-aqueous fluid-quartz interfacial tension (Arif et al. 2016).

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It is noteworthy that at 0.1 MPa and 323 K,

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respectively, while

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literature reports, where

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hydrocarbons on clean quartz at 0.1 MPa and 298 K (MacCaffery and Mungan, 1970;

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Xie and Morrow, 1998). The significant discrepancy was probably caused by the

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variation of temperature (Iglauer, 2017), brine composition (Haagh et al. 2017) and

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measurement method (MacCaffery and Mungan, 1970; Wan et al. 2014). In our work,

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we

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quartz-octane/decane-brine. Before the brine droplet was injected, the quartz was

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contacted with decane/octane for 10 mins to guarantee that decane/octane temperature

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had reached to 323 K. When the brine droplet was subsequently injected and fell

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down onto the quartz surface, a layer of decane/octane film already existed on the

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quartz surface (Gee et al. 1989), and the presence of n-alkane films on the quartz

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surface strongly decreased its surface hydration (Staszczuk, 1984), which rendered the

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surface more hydrophobic so that the contact angle approached 60°.

for C8H18 were 61° and 53°,

for C10H22 were 64° and 58°, inconsistent with were measured as 0° ~ 15° for the pure liquid

the

sessile

method

to

measure

the

contact

angle

of

dry

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used

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and

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and

and

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Subsequently we determined the equilibrium brine contact angle (

) from the

ACCEPTED MANUSCRIPT versus ρ

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receding and advancing contact angle data (Tadmor, 2004) and plotted cos

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in Figure 5. Clearly, cos

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0.9427), irrelevant of the type of non-aqueous phase. Note, however, that it is

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expected that brine composition, mineral surface chemistry and temperature still

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influence θ (Al-Yaseri et al. 2016; Iglauer, 2017).

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= -0.0007 ρ + 0.9446

(1)

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cos

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correlated linearly with ρ (see below equation (1), R2 =

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This relation indicates that the brine contact angle is naturally and directly related to

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the non-aqueous phase density. In order for interpretation the underlying mechanism

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on the relation between cos

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approximation (Al-Yaseri et al. 2016; Dietrich and Napiórkowski, 1991; Merath,

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2008)

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(

=

∆

−1

(2)

is the density difference between liquid brine film (

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where ∆

EP

cos

189 190

and ρ, we used below equation, sharp-kink

); I is the van der Waals potential integral, I = −

) and hydrocarbon

∞

∫ V ( z )dz . This equation implied

zmin

maintained constant with change in ∆ , which led to a linear correlation between and ∆

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cos

(Please see supporting information in Al-Yaseri et al. (2016)).

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Equation 2 is appropriate for analyzing contact angles variation with density changes

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caused by pressure and/or temperature changes, although this equation was derived

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for one component system. Re-writing equation 2 gained,

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cos

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+

−1

(3)

Clearly, equation 3 demonstrated that the cosine of equilibrium brine contact angle

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has a linear relationship with the density of non-aqueous phase. Such a relation

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significantly simplifies contact angle prediction, and we suggest here that this relation

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is implemented in siliciclastic reservoir (hectometer)-scale simulators so that

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hydrocarbon recovery, reserve estimate and CO2 geo-sequestration predictions can be

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optimized. This correlation also effectively avoids the uncertainty and complexity

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arising from direct contact angle measurements, because the density of different

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non-aqueous fluids is readily available in the literature (e.g. Friend et al. 1991; Huber

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et al. 2004; Setzmann and Wagner, 1991; Span and Wagner, 2003; Younglove and Ely,

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1987).

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4.

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In order for accurately hydrocarbon recovery prediction and reserves estimation in the

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subsurface, it is of key importance to know precise θ values (Bear, 1988). However,

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available data is scarce as the experimental measurement is challenging and the

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underlying phenomena are complex (Adamson and Gast, 1997; Butt and Kappl, 2006).

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It is thus highly desirable to simplify the data acquisition so that θ can be easily

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implemented in multi-scale simulations (e.g. Al-Khdheeawi et al. 2017; Hilpert and

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Miller, 2001) and hydrocarbon migration and operations (Iglauer et al. 2015b; Iglauer,

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2017; Morrow and Mason, 2001; Liang et al. 2017).

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Conclusions and Implications

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ACCEPTED MANUSCRIPT Thus, it was shown here that cos

for a specific temperature, mineral surface and

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brine composition correlated linearly with hydrocarbon and generally the

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non-aqueous fluid density ρ, consistent with literature data available for CO2, N2, He,

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Ar and SF6, (Al-Yaseri et al. 2016; Iglauer, 2017). This is a significant simplification

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of a complex parameter, which may improve interpretation of reserve estimates and

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hydrocarbon recovery in siliciclastic reservoir.

Acknowledgements

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The authors wish to acknowledge financial assistance from the National Science and

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Technology Major Project (2016ZX05023-001; 2017ZX05049-006), the Fundamental

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Research Funds for the Central Universities (18CX02104A), the Natural Science

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Foundation of China (41602143; 51774310; 51509260) and the Chinese Scholarship

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Council. The authors also acknowledge support from the University of Calgary

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Beijing Research Site, a research initiative associated with the University of Calgary

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Global Research Initiative in Sustainable Low Carbon Unconventional Resources, and

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the Kerui Group.

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References

238 239

Adamson, A.W. and Gast, A.P., 1997. Physical Chemistry of Surfaces (6th ed.), Wiley,

240

New York.

ACCEPTED MANUSCRIPT 241 242

Al-Khdheeawi, E.A., Vaille, S., Barifcani, A., Sarmadivaleh, M., Iglauer, S., 2017. Effect of reservoir wettability and heterogeneity on CO2-plume migration and

244

trapping capacity. Int. J. Greenhouse Gas Control. 58, 142-158.

245

https://doi.org/10.1016/j.ijggc.2017.01.012.

RI PT

243

246

Al-Menhali, A.S., Menke, H.P., Blunt, M.J., Krevor, S.C., 2016. Pore scale

248

observations of trapped CO2 in mixed-wet carbonate rock: Applications to storage in

249

oil

250

https://pubs.acs.org/doi/pdf/10.1021/acs.est.6b03111.

fields.

Environ.

Sci.

251

M AN U

SC

247

Technol.

50

(18),

10282–10290.

Al-Yaseri, A.Z., Roshan, H., Lebedev, M., Barrifcani, A., Iglauer, S., 2016.

253

Dependence of quartz wettability on fluid density. Geophys. Res. Lett.

254

3771-3776. https://doi.org/10.1002/2016GL068278.

TE D

252

EP

255

43,

Arif, M., Barrifcani, A., Iglauer, S., 2016. Solid/CO2 and solid/water interfacial

257

tensions as a function of pressure, temperature, salinity and mineral type: Implications

258

for CO2-wettability and CO2 geo-storage. Int. J. Greenhouse Gas Control. 53, 263-273.

259

https://doi.org/10.1016/j.ijggc.2016.08.020.

AC C

256

260 261

Ashcroft, S.J., and Isa, M.B., 1997. Effect of dissolved gases on the densities of

262

hydrocarbons.

J.

Chem.

Eng.

Data.

42

(6),

1244-1248.

ACCEPTED MANUSCRIPT 263

https://pubs.acs.org/doi/pdf/10.1021/je9701588.

264

Batzle, M., and Wang, Z.J., 1992. Seismic properties of pore fluids. Geophysics. 57

266

(11), 1396-1408. https://doi.org/10.1190/1.1443207.

RI PT

265

267 268

Bear, J., 1988. Dynamics of fluids in porous media, Dover, New York, America.

SC

269

Blatt, H., and Schultz, D. J., 1976. Size distribution of quartz in mudrocks.

271

Sedimentology. 23 (6), 857–866. https://doi.org/10.1111/j.1365-3091.1976.tb00113.x.

M AN U

270

272

Blunt, M.J., 2017. Multiphase flow in permeable media: A pore-scale perspective,

274

Cambridge University Press, Cambridge, United Kingdom.

TE D

273

275 276

Broseta, D., Tonnet, N., Shah, V., 2012. Are rocks still water-wet in the presence of

277

dense

278

https://doi.org/10.1111/j.1468-8123.2012.00369.x.

H2S?.

EP

or

Geofluids.

12

(4),

280–94.

AC C

279

CO2

280

Butt, H.J., and Kappl, G.K., 2006. Physics and Chemistry of Interfaces, Wiley,

281

Weinheim, Germany.

282 283

Chaudhary, K., Cardenas, M.B., Wolfe, W.W., Maisano, J.A., Ketcham, R.A., and

284

Bennett, P., 2013. Pore-scale trapping of supercritical CO2 and the role of grain

ACCEPTED MANUSCRIPT 285

wettability

and

shape.

Geophys.

286

https://doi.org/10.1002/grl.50658.

Res.

Lett.

40

(15),

3878-3882,

287

Chen, C., Wan, J.M., Li, W.Z., Song, Y.C., 2015. Water contact angles on quartz

289

surfaces under supercritical CO2 sequestration conditions: Experimental and

290

molecular dynamics simulation studies. Int. J. Greenhouse Gas Control. 42, 655–665.

291

https://doi.org/10.1016/j.ijggc.2015.09.019.

SC

RI PT

288

M AN U

292 293

Chiquet, P., Broseta, D., Thibeau, S., 2007. Wettability alteration of caprock minerals

294

by

295

https://doi.org/10.1111/j.1468-8123.2007.00168.x.

carbon

dioxide.

7,

112–122.

TE D

296

Geofluids.

297

Cho, N.J., Amour, J.N.D., Stalgren, J., Knoll, W., Kanazawa, K., Frank, C.W., 2007.

298

Quartz resonator signatures under Newtonian liquid loading for initial instrument

299

check.

300

https://doi.org/10.1016/j.jcis.2007.06.020.

Interface

Sci.

EP

Colloid

AC C

301

J.

315

(1),

248-254.

302

Cooper, J.C.B., 2003. Price elasticity of demand for crude oil: estimates for 23

303

countries.

304

https://doi.org/10.1111/1468-0076.00121.

OPEC

Energy

Review.

27

(1),

1-8,

2003.

305 306

Dietrich, S., and Napiórkowski, M., 1991. Analytic results for wetting transitions in

ACCEPTED MANUSCRIPT 307

the

presence

of

van

der

Waals

tails,

Physical

Review

308

https://journals.aps.org/pra/abstract/10.1103/PhysRevA.43.1861.

A.

43

(4),

309

Friend, D.G., Ingham, H., Ely, J.F., 1991. Thermophysical properties of ethane. J.

311

Phys. Chem. Ref. Data. 20 (2), 2, 275-347. https://doi.org/10.1063/1.555881.

RI PT

310

312

Gee, M.L., Healy, T.W., White, L.R., 1989. Ellipsometric studies of alkane adsorption

314

on

315

https://doi.org/10.1016/0021-9797(89)90140-9.

J.

Colloid

Interface

Sci.

131

(1),

18-23.

M AN U

quartz.

SC

313

316

Haagh, M.E.J., Siretanu, I., Duits, M.H.G., Mugele, F., 2017. Salinity-dependent

318

contact angle alteration in oil/brine/silicate systems: the critical role of divalent

319

cations. Langmuir. 33, 3349-3357. http://doi,org/10.1021/acs.langmuir.6b04470.

TE D

317

320

Hansen, G., Hamouda, A.A., Denoyel, R., 2000. The effect of pressure on contact

322

angles and wettability in the mica/water/n-decane system and the calcite+stearic

323

acid/water/n-decane

324

https://doi.org/10.1016/S0927-7757(99)00498-7.

system.

Colloids

Surf.,

A.

172

(1-3),

7-16.

AC C

325

EP

321

326

Hilpert, M., and Miller, C.T., 2001. Pore-morphology-based simulation of drainage in

327

totally

328

https://doi.org/10.1016/S0309-1708(00)00056-7.

329

wetting

porou

media.

Adv.

Water

Res.

24

(3-4),

243-255.

ACCEPTED MANUSCRIPT 330

Huber, M.L., Laesecke, A., Xiang, H.W., 2004. Viscosity correlations for minor

331

constituent fluids in natural gas: n-octane, n-nonane and n-decane. Fluid Phase

332

Equilib. 224, 2, 263-270. https://doi.org/10.1016/j.fluid.2005.03.008.

RI PT

333 334

Iglauer, S., Fernø, M.A., Shearing, P., Blunt, M.J., 2012a. Comparison of residual oil

335

cluster size distribution, morphology and saturation in oil-wet and water-wet

336

sandstone.

337

https://doi.org/10.1016/j.jcis.2012.02.025.

Interface

Sci.

375

(1),

SC

Colloid

187-192.

M AN U

J.

338

Iglauer, S., Mathew, M.S., Bresme, F., 2012b. Molecular dynamics computations of

340

brine–CO2 interfacial tensions and brine–CO2–quartz contact angles and their effects

341

on structural and residual trapping mechanisms in carbon geo-sequestration. J. Colloid

342

Interface Sci. 386 (1), 15, 405-414. https://doi.org/10.1016/j.jcis.2012.06.052.

TE D

339

343

Iglauer, S., Salamah, A., Sarmadivaleh, M., Liu, K.Y., Phan, C., 2014. Contamination

345

of silica surfaces: Impact on water–CO2–quartz and glass contact angle measurements.

346

Int.

347

https://doi.org/10.1016/j.ijggc.2014.01.006.

AC C

348

EP

344

J.

Greenhouse

Gas

Control.

22,

325–328.

349

Iglauer, S., Al‐Yaseri, A.Z., Rezaee, R., M. Lebedev, 2015a. CO2 wettability of

350

caprocks: Implications for structural storage capacity and containment security.

351

Geophys. Res. Lett. 42 (21), 9279-9284. https://doi.org/10.1002/2015GL065787.

ACCEPTED MANUSCRIPT 352 353

Iglauer, S., Pentland, C.H., Busch, A., 2015b. CO2 wettability of seal and reservoir

354

rocks and the implications for carbon geo-sequestration. Water Resour. Res.

355

729–774. https://doi.org/10.1002/2014WR015553.

RI PT

51 (1),

356

Iglauer, S., 2017. CO2-water-rock wettability: Variability, influencing factors, and

358

implications for CO2 geostorage. Accounts of Chemical Research. 50 (5), 1134–1142.

359

https://pubs.acs.org/doi/abs/10.1021/acs.accounts.6b00602.

M AN U

SC

357

360

Karakasi, O.K., and Moutsatsou, A., 2010. Surface modification of high calcium fly

362

ash for its application in oil spill clean up. Fuel. 89 (12), 3966-3970.

363

https://doi.org/10.1016/j.fuel.2010.06.029.

TE D

361

364 365

Lander, L.M., Siewierski, L.M., Brittan, W.J., Vogler, E.A., 1993. A systematic

366

comparison

367

https://pubs.acs.org/doi/abs/10.1021/la00032a055.

angle

EP

contact

methods.

Langmuir.

9

(8),

2237-2239.

AC C

368

of

369

Liang, Y.F., Tsuji, S., Jia, J.H., Tsuji, T., Toshifumi Matsuoka, T., 2017. Modeling

370

CO2−water−mineral wettability and mineralization for carbon geosequestration.

371

Accounts

372

https://pubs.acs.org/doi/full/10.1021/acs.accounts.7b00049.

373

of

Chemical

Research.

50,

1530−1540.

ACCEPTED MANUSCRIPT 374

Love, J.C., Estroff, L.A., Kriebel, J.K. Nuzzo, R.G., Whitesides, G.M., 2005.

375

Self-assembled monolayers of thiolates on metals as a form of nanotechnology.

376

Chemical

377

https://pubs.acs.org/doi/abs/10.1021/cr0300789.

105

(4),

1103-1169.

RI PT

Reviews.

378

MacCaffery, F.G., and Mungan, N., 1970. Contact angle and interfacial tension

380

studies of some hydrocarbon-water-solid systems. Journal of Canadian Petroleum

381

Technology. https://doi.org/10.2118/70-03-04.

M AN U

SC

379

382 383

Merath, C., 2008. Microscopic calculation of line tensions. Ph.D. Thesis, Institute for

384

Theoretical and Applied Physics, University of Stuttgart, Stuttgart, Germany.

TE D

385 386

Morrow, N.R., and Mason, G., 2001. Recovery of oil by spontaneous imbibition.

387

Current

388

https://doi.org/10.1016/S1359-0294(01)00100-5.

in

Colloid

&

Interface

Science.

6

(4),

321-337.

389

AC C

EP

Opinion

390

Pan, B., Li, Y.J., Wang, H.Q., Jones, F., Iglauer, S., 2018. CO2 and CH4 wettabilities

391

of

392

https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.7b01147.

organic-rich

shale.

Energy

&

Fuels.

32

(2),

1914-1922.

393 394

Rajayi, M., and Kantzas, A., 2011. Effect of temperature and pressure on contact

395

angle and interfacial tension of quartz/water/bitumen systems. Journal of Canadian

ACCEPTED MANUSCRIPT 396

Petroleum Technology.

https://doi.org/10.2118/2009-195.

397

Sahimi, M., 2011. Flow and transport in porous media and fractured rock: From

399

conventional methods to modern approaches, Wiley-Vch, Weinheim, Germany.

RI PT

398

400

Saryazdi, F., Motahhari, H., Schoeggl, F.F., Taylor, S.D., Yarranton, H.W., 2013.

402

Density of hydrocarbon mixtures and bitumen diluted with solvents and dissolved

403

gases.

404

https://pubs.acs.org/doi/abs/10.1021/ef400330j.

Fuels.

27

(7),

3666–3678.

M AN U

Energy

SC

401

405

Setzmann, U., and Wagner, W., 1991. A new equation of state and tables of

407

thermodynamic properties for methane covering the range from the melting line to

408

625 K at pressures up to 1000 MPa.

409

https://aip.scitation.org/doi/abs/10.1063/1.555898.

TE D

406

EP

410

J. Phys. Chem. Ref. Data. 20 (6), 6, 1061-1151.

Span, R., and Wagner, W., 2003. Equations of state for technical applications. II.

412

Results

413

https://link.springer.com/article/10.1023%2FA%3A1022310214958.

414

AC C

411

for

nonpolar

fluids.

Int.

J.

Thermophys.

24

(1),

41-109.

415

Staszczuk, P., 1984. Effect of n-alkanes and n-alcohols on quartz surface hydration.

416

Materials

417

https://doi.org/10.1016/0254-0584(84)90016-6.

Chemistry

and

Physics.

10

(5),

473-486.

ACCEPTED MANUSCRIPT 418 419

Swanson, B.F., 1980. Rationalizing the influence of crude oil wetting on reservoir

420

fluid flow with electrical resistivity behavior. https://doi.org/10.2118/7442-PA.

RI PT

421 422

Tadmor, R., 2004. Line energy and the relation between advancing, receding, and

423

Young

424

https://pubs.acs.org/doi/abs/10.1021/la049410h.

angles.

Langmuir.

(18),

7659–7664.

M AN U

425

20

SC

contact

426

Van Dijke, M.I.J., Sorbie, K.S., Sohrabi, M., Danesh, A., 2006. Simulation of WAG

427

floods in an oil-wet micromodel using a 2-D pore-scale network model. J. Pet. Sci.

428

Eng. 52 (1-4), 71-86. https://doi.org/10.1016/j.petrol.2006.03.014.

TE D

429

Wan, J.M., Kim, Y.M., Tokunaga, T.K., 2014. Contact angle measurement ambiguity

431

in supercritical CO2-water-mineral systems: Mica as an example. Int. J. Greenhouse

432

Gas Control. 31, 128-137. https://doi.org/10.1016/j.ijggc.2014.09.029.

EP

430

AC C

433 434

Wang, W., and Gupta, A., 1995. Investigation of the effect of temperature and

435

pressure

436

https://doi.org/10.2118/30544-MS.

on

wettability

using

modified

pendant

drop

method.

437 438

Xie, X.N., and Morrow, N.R., 1998. Wetting of quartz by oleic/aqueous liquids and

439

adsorption from crude oil. Colloids Surf., A. 138, 97-108.

ACCEPTED MANUSCRIPT 440

https://doi.org/10.1016/S0927-7757(98)00222-2.

441

Yang, C.D., and Gu, Y.A., 2006. A new method for measuring solvent diffusivity in

443

heavy oil by solvent diffusivity in heavy oil by dynamic pendant drop shape analysis

444

(DPDSA). SPE Journal. https://doi.org/10.2118/84202-PA.

445

RI PT

442

Younglove, B.A., and Ely, J.F., 1987. Thermophysical properties of fluids. II.

447

Methane, ethane, propane, isobutane and normal butane. J. Phys. Chem. Ref. Data. 16,

448

4, 577-798. https://doi.org/10.1063/1.555785.

449

M AN U

SC

446

450

Zhao, B.Z., MacMinn, C.W., Juanes, R., 2016. Wettability control on multiphase flow

451

in

452

https://doi.org/10.1073/pnas.1603387113.

microfluidics.

PNAS.

113

(37),

10251-10256.

TE D

453

patterned

Zhou, X.M., Morrow, N.R., Ma, S.X., 2000. Interrelationship of wettability, initial

455

water saturation, aging time and oil recovery by spontaneous imbibition and

456

waterflooding. SPE Journal. https://doi.org/10.2118/62507-PA.

AC C

457

EP

454

458

Zhou, Y.F., Helland, J., Hatzignatiou, D.G., 2012. A dimensionless capillary pressure

459

function for imbibition derived from pore-scale modelling in mixed-wet-rock images.

460

SPE Journal. https://doi.org/10.2118/154129-PA.

461

ACCEPTED MANUSCRIPT 462

Zhou, Y.F., Helland, J., Hatzignatiou, D.G., 2013. Dynamic capillary pressure curves

463

from

464

https://doi.org/10.2118/154474-PA.

pore-scale

modelling

in

mixed-wet-rock

images.

SPE

Journal.

RI PT

465

Zhou, Y.F., Helland, J., Hatzignatiou, D.G., 2014. Pore-scale modelling of

467

waterflooding in mixed-wet-rock images: Effects of initial saturation and wettability.

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SPE Journal. https://doi.org/10.2118/154284-PA.

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EP

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Table 1. The detailed information about SFB.

Resources SigmaAldrich

1.075~1.085

0.01

M AN U TE D EP AC C

Brine density (kg/m3, 0.1 MPa and 25C)

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Concentration (wt%) 10 1 0.5 0.5

SC

Brine composition NaCl KCl CaCl2 MgCl2 DI water

Electrelectrical conductivity (mS/cm)

(b)

M AN U

(a)

SC

RI PT

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Figure 1. Schematic of the advancing and receding contact angle measurement, a) An image of

AC C

EP

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HPHT Kruss DSA 100; b) An image of the advancing and receding contact angle.

ACCEPTED MANUSCRIPT

80

RI PT

60 50 40

CH₄

30

SC

C₂H₆

20

C₃H₈ C₈H₁₈

10 0

0

5

M AN U

Advancing contact angle [°]

70

10 Pressure [MPa]

AC C

EP

TE D

(a)

15

C₁₀H₂₂

20

ACCEPTED MANUSCRIPT

70

RI PT

50 40

SC

30

CH₄ C₂H₆

20 10 0 5

10 Pressure [MPa]

TE D

0

M AN U

Receding contact angle [°]

60

15

C₃H₈ C₈H₁₈ C₁₀H₂₂

20

(b)

Figure 2. Effect of pressure on the (a) advancing and (b) receding brine contact angles of various

AC C

EP

hydrocarbons (on quartz at 323 K). Note color is used in print.

ACCEPTED MANUSCRIPT

800 700 CH₄

C₂H₆

500

C₃H₈

RI PT

Density [kg/m3]

600

C₈H₁₈

400

C₁₀H₂₂

300

He

200

0 5

10

15

M AN U

0

SC

N₂

100

Ar CO₂

20

Pressure [MPa]

Figure 3. Effect of pressure on the density of non-aqueous fluids. Note that the data for the nonaqueous fluid densities was taken from the literature (Al-Yaseri et al. 2016; Friend et al. 1991; Huber et al. 2004; Setzmann and Wagner, 1991; Span and Wagner, 2003; Younglove, and Ely,

AC C

EP

TE D

1987). Color is used in print.

ACCEPTED MANUSCRIPT

70

CH₄ 50

C₂H₆

RI PT

C₃H₈

40

C₈H₁₈

C₁₀H₂₂

30

He

20

N₂

SC

Advancing contact angle [°]

60

10 0 100

200

300

400 500 3 Density [kg/m ]

M AN U

0

600

Ar CO₂ 700

800

TE D

(a)

70

CH₄ C₂H₆ C₃H₈ C₈H₁₈ C₁₀H₂₂ He N₂ Ar CO₂

EP

50

40

AC C

Receding contact angle [°]

60

30 20 10 0

0

100

200

300

400

500

Density [kg/m3]

600

700

800

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(b) Figure 4. Effect of non-aqueous fluid density on the (a) advancing and (b) receding brine contact

AC C

EP

TE D

M AN U

SC

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angles (on quartz at 323 K). Note color is used in print.

ACCEPTED MANUSCRIPT

1 0.9 0.8

RI PT

0.6 0.5 0.4 0.3 0.2 0.1 0 0

100

200

SC

CH₄ C₂H₆ C₃H₈ C₈H₁₈ C₁₀H₂₂ CO₂ N₂ He Ar Linear (Trend line)

M AN U

cos𝜃e

0.7

300

400

500

600

700

800

Density [kg/m3]

AC C

EP

used in print.

TE D

Figure 5. Effect of the density of non-aqueous fluids on cos𝜃𝑒 (on quartz at 323 K). Note color is

ACCEPTED MANUSCRIPT

Highlights Quartz wettability correlates with non-aqueous fluid density, irrelevant of fluid type

•

Water-wetness decreases with increasing non-aqueous fluid density

•

The cosine of the equilibrium brine contact angle correlates linearly with the non-aqueous

AC C

EP

TE D

M AN U

SC

fluid density in the siliciclastic reservoir

RI PT

•