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Fossil Fuels
Novel Insights into the Pore-scale Mechanism of Low Salinity
Water Injection and the Improvements on Oil Recovery
Mohammad Fattahi Mehraban, Seyed Amir Farzaneh, Mehran Sohrabi, and Adam Sisson
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.0c01599 • Publication Date (Web): 14 Sep 2020
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Page 1 of 55 Energy & Fuels
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1 Novel Insights into the Pore-scale Mechanism of
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2 Low Salinity Water Injection and the Improvements
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3 on Oil Recovery
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4 Mohammad Fattahi Mehraban*, Seyed Amir Farzaneh, Mehran Sohrabi, Adam Sisson
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24 5 Centre for Enhanced Oil Recovery and CO2 Solution, Heriot-Watt University, Edinburgh, UK
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27 6 Keywords: Low Salinity Water Injection, Low Salinity Water Effect, Wettability Alteration,
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7 Oil Swelling, Zeta potential, Spectroscopy, Water Microdispersion.
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33 8 Abstract
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37 9 The long-held industry view that the Low Salinity Effect (LSE) depends mainly on rock-fluid
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40 10 interactions has led to failures and successes that can be explained by fluid-fluid interactions.
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42 11 Therefore, elevating our knowledge about the microscopic interactions occurring in the
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44 12 crude oil/brine/rock system appear to be of paramount importance. This paper chooses to
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47 13 outline various analytical tools in combination with a microfluidic instrument (Micromodel)
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49 14 to identify these interactions at simulated reservoir conditions for the first time
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51 15 (temperature and pressure of 50= and 2000 psi). In this study, six crude oil samples have
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54 16 undergone testing for microdispersion quantification and surface charge evaluation.
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56 17 Microdispersion is a term referring to the spontaneous formation of water clusters (in
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Energy & Fuels Page 2 of 55
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3 18 micrometre sizes) within the crude oil during Low Salinity Water Injection (LSWI), which
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6 19 will be elaborated in this study. Despite all samples showing the same trend regarding the
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8 20 negative surface charges, they showed an entirely different propensity towards formation of
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21 water microdispersion. The analysis of the oil/water interface by Fourier-Transform
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13 22 Infrared spectroscopy (FT-IR), led to the understanding that conjugated acidic compounds
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15 23 within the crude oil are the main compounds for creation of water microdispersions. The
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24 Micromodel results revealed the predominant role of microdispersions in oil swelling and
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20 25 wettability alteration in a porous media leading to an increase in the microscopic sweeping
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22 26 efficiency thus leading to improved oil recovery. Also highlighted, is the pivotal importance
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27 of water microdispersion as a screening method for oil reservoirs before waterflooding
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27 28 operation.
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31 29 1 Introduction
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33 30 Low salinity water injection (LSWI) has gained attention over the past ten years being
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36 31 recognised as a cost-effective Enhanced Oil Recovery (EOR) method 1. There is a consensus
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38 32 about LSWI for sandstone reservoirs in which reduction of salinity to less than 5000 ppm
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40 33 leads to a low salinity water effect (LSE) 1-5. In contrast, several reports are showing the
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43 34 negligible influence of LSWI in carbonate reservoirs, meaning this EOR method is only
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45 35 effective in sandstone reservoirs (usually with a high clay content 2, 6). Early studies have
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36 attributed the role of clay minerals during LSWI, through which clay swelling and
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50 37 incremental pressure drop was introduced as the main mechanism 7-13. Wickramathilaka et
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52 38 al. 14 suggested that the incremental oil recovery by low salinity brine might be affected by
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39 total clay content and clay type. Austad et al. 15 argued that oil recovery by low salinity water
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3 40 is more controlled by clay minerals with a higher cation exchange capacity (CEC) in the order
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41 of Kaolinite > Chlorite > illite > smectite 15-18. Furthermore, it was claimed through
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8 42 coreflooding in a clay-rich Berea sandstone core that the negative response of LSWI can be
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43 attributed to presence of chlorite minerals 19. The discussions around the possible impact of
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13 44 clay minerals on LSE were becoming more ambiguous when researchers published a
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15 45 correlation on incremental oil recovery versus kaolinite content 20, 21. Following the line of
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46 research about the promising role of Kaolinite during waterflooding, a pore-scale study and
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20 47 an Atomic Force Microscopy (AFM) study also argued the positive impact of kaolinites on
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22 48 wettability state of sandstones during waterflooding 22, 23. It was argued that the addition of
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49 Kaolinite in pure quartz sand packs substantially affect the oil recovery during LSWI, which
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50 was ascribed to the characteristics of clay minerals coating the quartz surface 22.
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29 51 Considerable coverage of quartz surface by kaolinites was suggested to affect the surface
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52 properties such influencing the crude oil-solid (quartz and a combination of quartz and
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34 53 Kaolinite) interactions toward less oil-wet or more water-wet state. The studies conducted
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36 54 by Sanyal et al. 24, 25 showed that not only the clay type (Kaolinite and montmorillonite) but
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55 also the polar components of crude oil (asphaltenes with different polycyclic aromatic rings)
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41 56 and the presence of the ions in injection water would affect the performance of LSWI.
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43 57 However, the improvement in oil recovery has been illustrated not only for rocks containing
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46 58 other clay minerals (i.e., chlorite, illite, and muscovite) 26 but also for sandstone rocks free of
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48 59 clay minerals 27-30.
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50 60 With the incremental oil recovery in sandstone rocks being attributed to clay minerals, no
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53 61 possible implementation for the method had been considered for carbonate reservoirs. In
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55 62 2010 Yousef et al. 31 first reported additional oil recovery due to low salinity water injection
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3 63 in carbonates. This was reported at a time that many researchers could not see an application
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64 for low salinity water injection in carbonate formations 6, 32, 33. They asserted that the
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8 65 injection of seawater led to an improvement in oil recovery and highlighted the role of
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66 potential determining ions (PDIs) in wettability alteration to more favorable conditions
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13 67 resulting in additional oil recovery 34-38. Austad et al. 39 tried to justify the observations in
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15 68 Yousef's experiments by highlighting the role of sulphate ions. They claim that the
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69 mechanism of improved oil recovery observed by Yousef was the dissolution of anhydrite
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20 70 that led to the in-situ generation of SO42- ions. Romanuka et al. 40 reported additional oil
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22 71 recovery for diluted brines during spontaneous imbibition on limestone cores with zero oil
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72 recovery for free-NaCl seawater. Contrary to previous reports, Zahid et al. reported
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27 73 additional oil recovery for diluted seawater injection in carbonate rocks, which were free
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29 74 from dolomite and anhydrite minerals.
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75 All of the discrepancies around the main mechanism of LSWI and the influential
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34 76 parameters involving in LSE led to a new mechanism named electrical double layer
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36 77 expansion 41. Mahani et al. 42 argued that decreasing salinity of injection water causes more
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78 negative surface charges at the oil/brine and rock/brine interfaces leading to wettability
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41 79 alteration through electrical double layer theory. One year later, in 2017, they exhibited
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43 80 experimental results showing lower surface charges at both rock/brine and oil/brine
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46 81 interfaces when temperature increased 43. It was shown that the surface charges at either of
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48 82 interfaces tend to approach the point of zero charges, leading to electrical double layer
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50 83 contraction, which was not in line with published literature.
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53 84 Up until 2013, all the suggested mechanisms for LSWI were case dependent, with some
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55 85 working with specific rock types and certain conditions such as initial wettability, pH, initial
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3 86 salinity, and so on, while others did not work even under similar conditions. The possible
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6 87 role of crude oil and fluid-fluid interactions during LSWI in carbonate and sandstone
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8 88 reservoirs had been underestimated until microdispersion formation was introduced as the
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89 main responsible mechanism of LSWI 44. The microdispersion theory could support the extra
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13 90 oil recovery during LSWI regardless of rock type, which was a remarkable discovery for the
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15 91 oil and gas industry 45, 46. It was shown that microdispersions were water clusters
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92 surrounded with oil surface-active materials leading to wettability alteration through the
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93 detachment of surface-active materials from the rock surface 47-49, this work was also
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22 94 supported by other researchers 50, 51. Several studies have been published in the literature
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95 reporting the formation of water microdispersion as the main mechanism of LSWI
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96 irrespective of different terminologies 45, 52-65. Other mechanisms were also introduced to
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29 97 attribute the additional oil recovery during LSWI to the fluid-fluid interaction, such as
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98 interracial viscoelasticity variations 66 and osmotic effects 67. Alvarado et al. 68 suggested that
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34 99 either increasing the sulfate content or decreasing the salinity of injection water would lead
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36 100 to incremental oil recovery through increasing the interfacial viscoelasticity. Although all the
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101 efforts have been given recently to study the fluid-fluid based-mechanisms, the actual
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41 102 functional compounds of crude oil toward LSW has not distinguished. Subramanian et al. 69
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43 103 argued based on emulsion stability tests that the stability of water-in-oil emulsions is
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46 104 predominantly controlled by the acid-base interactions between acidic and basic moieties of
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48 105 asphaltenes and resin molecules. It is also the purpose of this study to investigate the
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50 106 functional compounds of crude oil, mainly responsible for water microdispersion and LSE.
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53 107 Furthermore, we aim to demonstrate the actual mechanism of LSWI in porous media by
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55 108 performing several Micromodel experiments. Micromodel experiments have been given
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3 109 tremendous attention since they can provide direct evidence of phenomena taking place
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6 110 between different phases at a porous medium 44, 52, 56, 67, 70. They have been used to provide
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8 111 valuable information about the flow of emulsion in porous media 71-73, heavy oil recovery 74-
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112 CO2 injection 77, 78, carbonated water injection 79, 80, water alternate gas injection (WAG)
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113 81, and low salinity water 44, 47, 52, 82, 83.
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15 114 In this study, we will use different crude oil samples with different tendencies toward LSE
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115 and microdispersion formation to confirm the main responsible mechanism of LSWI. The
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20 116 formation of microdispersion will be investigated through different experimental
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22 117 approaches such as FT-IR spectroscopy, surface charge evaluations, and Micromodel
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118 experiments. Additional scope of this study is to recognise the key chemical compounds
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27 119 within crude oil participating in the LSE and microdispersion. This is the first time that such
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29 120 a comprehensive experiment has been designed to investigate the fundamental mechanisms
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121 of LSWI. To achieve the objectives, six crude oil samples with different physicochemical
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34 122 properties were analysed to quantify the amount of microdispersion and evaluate the
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36 123 surface charges at the oil/water interface.
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124 Furthermore, the crude oil samples were studied by FT-IR spectroscopy method to gain an
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41 125 insight into the compositional changes within the oil/water interface and recognise the most
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43 126 effective compounds concerning the LSE and water microdispersion formation. Detecting
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46 127 the main responsible compounds of crude oil toward water microdispersion can lead to a
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48 128 better screening process for crude oil reservoirs for utilization of LSWI. Finally, Micromodel
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50 129 experiments were conducted at elevated pressure and temperature (temperature of 50=
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53 130 and pressure of 2000 psi) in order to directly observe the mechanism of LSWI in the porous
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55 131 media under varied initial wettability conditions (i.e., water- and oil-wet wettability states).
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132 2 Materials and Methods
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7 133 2.1 Fluids
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9 134 High salinity water (HSW) and low salinity water (LSW) solutions were prepared by
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135 mixing the appropriate amount of pure salts [BioXtra grade salts, I 99.5 (AT), supplied by
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14 136 Sigma-Aldrich chemicals Co. Inc] with Deionized Water (DW) [molecular biology reagent
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16 137 grade with a conductivity of approximately 0.05KS/cm, supplied by Sigma-Aldrich chemicals
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138 Co. Inc]. All brines were vacuumed to remove any dissolved air before use in the various
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21 139 experiments. The composition of brines is shown in Table 1.
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25 141 Table 1. The ionic concentration of brines.
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HSW SW SW25d SW100d/LSW
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Salts
30 (ppm) (ppm) (ppm)
(ppm)
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33 NaCl 141314 28400 1136 284.05
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36 KCl 628 800 32 8
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MgCl2 2854 13729 549 137
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41 CaCl2 40286 1828 73 18
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44 Na2SO4 2586 4490 179 44
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47 NaHCO3 2014 100 4 1
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50 pH 6.65 6.88 7.12 7.43
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TDS* (ppm) 189689 49347 2000 493.53
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Ionic
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5 Strength** 3.674 0.83 0.033 0.008
6 (mole/Litre)
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*Total Dissolved Solids
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**Ionic strength is defined as
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N
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L=
2 OQ R
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P P
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16 Where QP is the concentration of ionic species i in mol/L and QP is its charge.
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18 142
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143 Table 2 demonstrates the physicochemical properties of crude oil samples used in this
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24 144 study, such as Total Acid Number (TAN), Total Base Number (TBN), and SARA analysis. The
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26 145 IP-143 standard protocol measured the asphaltene content. The Total Acid Number (TAN)
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146 and Total Base Number (TBN) were also measured according to potentiometric titration
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31 147 based on ASTM D664 and ASTM 2896, respectively. The crude oil samples were centrifuged
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33 148 before the experiments to remove any possible dissolved solid and emulsion.
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149 Table 2. Physicochemical properties of crude oil samples.
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39 TAN TBN
40 Saturated Aromatics Resins Asphalten
Crude ID
41 (%wt) (%wt) (%wt) e (%wt) (mg (mg
42 KOH/g) KOH/g)
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44 Crude F 76.06 21.13 2.49 0.32 0.11 2.98
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46 Crude U9 33.64 46.76 16.93 2.67 0.30 0.55
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48 Crude C 58.75 30.18 9.87 1.20 0.19 0.11
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50 Crude U1 36.72 41.00 20.45 1.83 0.22 0.68
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Crude U5 68.94 18.63 10.87 1.56 0.20 0.20
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Crude B 43.80 25.86 29.94 0.40 0.35 4.90
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3 150
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7 151 2.2 Quantifying amount of microdispersions
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9 152 Six different crude oil samples were selected (as shown in Table 2) to investigate the
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11 153 formation of water-in-oil microdispersion. To determine the amount of microdispersion
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14 154 formed, a sample from the oil/water interface was taken and analysed by Karl Fischer
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16 155 Titrator (KFT) [Titrator Compact C20SX, Mettler, Toledo]. The schematic summary of crude
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18 156 oil/water contact procedure is shown in Figure 1 in which oil and brines are contacted for a
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21 157 period of time in a funnel. The aqueous phase was slowly depleted from the bottom, ensuring
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23 158 not to physically disturb the oil/water interface, before the oil/water interface sample
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159 (containing WMD) is taken (Figure 1-c). It should be stated that the amount of
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28 160 microdispersions is reported in the water microdispersion ratio (a dimensionless
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30 161 parameter), which is the water content of the sample at the interface after contacting process
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162 (in ppm) divided by the intrinsic water content of the original crude oil (in ppm). The error
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35 163 of these measurements was around ± 50 ppm, which was calculated according to the
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37 164 standard deviation of three measurements for each sample. Additionally, the interfacial
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165 crude oils (the crude oil samples from the oil/water interface) were investigated through
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42 166 FT-IR spectroscopy and will hereon be described as the contacted sample.
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3 181 brines). The electrophoretic mobility is then deployed in Smoluchowski approximation of
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6 182 Henry's equation to calculate the zeta potential.
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8 183 The crude oil samples were centrifuged and filtered to break any emulsion and remove any
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184 dispersed solid before the measurements. 2 cm3 of crude oil was emulsified in 20 cm3 of
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13 185 brine using an ultrasonic probe mixer. Right after sonication, the volume ratio of 1:10 was
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15 186 used to mix 5 cm3 of prepared emulsion in 50 cm3 of parent brine. The mixture was
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187 homogenized by a magnetic mixer for 1 hour and followed by acid/base titration using NaOH
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20 188 (1 M) and HCl (0.1 M) to adjust the solution pH, constantly being homogenised with a magnet
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22 189 mixer. Zeta potential measurement of quartz particles [ I 99.995% trace metals basis,
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190 Sigma-Aldrich], the procedure followed: A weight percent of 5 % was selected to disperse 5
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27 191 gr of rock particles in 100 gr of the brine solution. The Sonication probe was used to make
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29 192 dispersed suspension of rock particles in the brines. Immediately after sonication, the
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193 homogenization was carried out with a magnetic mixer, while pH adjustment was performed
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34 194 using NaOH (1 M) and HCl (0.1 M) solutions. The pure quartz particles were used in this
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36 195 study to replicate the surface charges of micromodel in the presence of brines with different
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196 salinities.
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41 197 It should be stated that the zeta potential results are reported at a neutral pH of 7 for
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43 198 different salinities. Each reported zeta potential is an average value of five measurements
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46 199 with 13-100 runes per measurement. The measurement error was about ± 3 mV, which had
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48 200 been calculated according to the standard deviation of those five measurements.
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51 201 2.4 FT-IR Spectroscopy
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53 202 The FT-IR spectroscopy for the interfacial crude oil samples was implemented using a
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56 203 Jasco IR spectrometer [FT-IR 4600 instrument]. The interfacial crude oil sample was placed
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3 204 on a single-reflection glass window of the FTIR spectrometer, with 18 scans captured for
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6 205 each crude oil. The IR spectrum was taken for each interfacial crude oil sample in the
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8 206 wavenumber range 4500-650 cm-1. Moreover, the background spectrum, which was used for
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207 calibration, was performed with air as a baseline. Noteworthy to say is that the glass window
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13 208 was cleaned before and after each measurement with toluene and methanol [reagent grade,
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15 209 Sigma-Aldrich Chemical Co. Inc] successively and dried with pressurized dry nitrogen gas.
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210 Furthermore, the Jasco software was deployed to analyse the IR spectra of samples.
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211 2.5 Micromodel Experiments
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23 212 The schematic diagram of the Micromodel device is demonstrated in Figure 2, with the
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25 213 physical characteristics of the Micromodel provided in Table 3 outlining porosity,
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214 permeability, and dimensions. Figure 2-b displays the graphical design of Micromodel's
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30 215 holder in which five different ports connect the Micromodel with the injection fluids in the
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32 216 fluids' oven. The port number 1 is only connected to the Micromodel-holder and transfers
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217 the hydraulic overburden fluid into the cell to exert overburden pressure on the Micromodel.
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37 218 The other ports are connected to the Micromodel inlet and outlet through a bypass line.
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39 219 There is a double-action bypass configuration within the system that can conduct the
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220 injection fluids either through the top or through the bottom of the Micromodel. In this study,
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44 221 crude oil and cleaning fluids (i.e., toluene, methanol, and distilled water) were injected from
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46 222 the top, while LSW and HSW solutions were injected from the bottom of the Micromodel. The
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49 223 Micromodel can handle the maximum pore pressure of 5000 psi at 50 = with an overburden
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51 224 pressure of 5500 psi. All experiments were conducted at an elevated temperature of 50 =
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53 225 and pressure of 2,000 psi, while the overburden pressure was kept constant at 2,500 psi. The
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56 226 Micromodel rig contains two separate ovens, one which is used for heating the injection
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3 227 fluids the other holding the micromodel at the test temperature. A temperature control unit
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6 228 (TCU) adjusts and monitors the temperature within the ovens throughout the experiments.
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8 229 A camera with high magnification ability is equipped to capture images through the side-
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230 glass provided on the Micromodel-holder cell (Figure 2-b, number 6). Facilitating the high-
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13 231 quality and bright image capturing, a light source illuminates the Micromodel through the
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15 232 side glass. The dual-cylinder Quizix pumps (SP-5200, Chandler Engineering) were used for
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233 controlling the fluids injections and retractions. The QUARTZDYNE pressure transducers
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20 234 (Quartzdyne Inc, U.S.A) (+/- 0.005 MPa) were mounted on the pump-sides and fluid-sides
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22 235 of each cell including the Micromodel cell to read and control the pressure inside the system.
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236 Platinum Resistance thermometers (PRT) (+/- 0.1 K) were designed within the temperature
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27 237 control unit to control the temperature inside the ovens.
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4 Pore Etch
Length Width Porosity Permeability
5 Volume Depth
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0.7
5 cm 0.01 mL 40 K 0.61 10 D
9 cm
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11 241
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14 242 All experiments were started with a cleaning process consisting of a sequential injection
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243 of toluene and methanol through the bypass lines and the micromodel. Distilled water was
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19 244 injected after methanol to avoid any salt precipitation before high salinity water (HSW)
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21 245 injection. HSW injection was carried out for the establishment of connate water saturation.
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246 Injection of HSW is pivotal because it establishes the initial conditions in the micromodel and
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26 247 also the base wettability of the micromodel after aging, which is dependent on the salinity of
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28 248 connate water 84, 85. Having ensured that the micromodel is fully saturated with HSW and the
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249 ionic equilibrium is met, the injection rate was decreased, and the micromodel was left to
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33 250 soak for one day. Crude oil was then injected into the micromodel with a low flow rate of
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35 251 0.01 cm3/hr (1 ft/day in our system), this was to avoid any phase agitation and emulsion
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38 252 formation in the porous media. When the initial conditions, including desired initial oil in
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40 253 place and initial water saturation, were established, HSW was injected at 0.01 cm3/hr into
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42 254 the micromodel as a secondary injection mode. HSW injection continued until no extra oil
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45 255 was recovered from the micromodel, then the injection was switched over low salinity water
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47 256 (LSW), where the injection rate remained at 0.01 cm3/hr.
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49 257 Stearic acid [grade I, I543 S (capillary GC)] was used to change the initial wettability of
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52 258 the Micromodel 86 as it was mixed with decane [anhydrous, I55SJ with the ratio of 0.1 wt%.
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54 259 After establishing initial water with HSW, the stearic acid solution was injected into the
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1
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3 260 micromodel with a flow rate of 0.01 cm3/hr. The Micromodel was aged in the stearic acid
4
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6 261 solution for one day. During this period, stearic acid monomers adsorbed onto the pore
7
8 262 surfaces through cation bridging mechanism with the cations such as Ca2+, Mg2+, and Na+ 87.
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263 Crude oil was then injected with the flow rate of 0.1 cm3/hr to sweep out the stearic acid
11
12
13 264 solution. Ensuring that the stearic acid solution was entirely removed from the porous
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15 265 media, the injection rate was decreased to 0.01 cm3/hr, and the Micromodel was aged with
16
17
266 crude oil for three days. Figure S.f. 1 (see Supporting Document) shows that the initial
18
19
20 267 wettability state of the Micromodel after introducing injection brine is strongly oil-wet.
21
22
23 268 3 Results and Discussions
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25
26
27
269 3.1 Water Content of Crude Oils
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29 270 After contacting the crude oil samples with HSW and LSW aqueous solutions, the oil
30
31 271 samples from the oil/water interface were analysed with the KFT method. Figure 3 shows
32
33
34
272 the water microdispersion ratio of interfacial crude oil samples after contacting brines,
35
36 273 which shows the water content of crude oils is more significant for LSW contact tests
37
38 274 compared to HSW. The crude oil samples react differently with the contrasting brines and
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40
41
275 exhibit different propensities toward LSW and HSW in terms of water microdispersion
42
43 276 formation. It can be observed that crude-U9 retains the most substantial amount of water at
44
45 277 the oil/LSW interface, while crude-F shows the weakest response to water microdispersion
46
47
48 278 formation. According to an in-house protocol, the crude oil samples are divided into two
49
50 279 different categories of positive and negative crude oils. The different potencies of crude oil
51
52 280 samples toward the formation of water microdispersion roots in the physicochemical
53
54
55 281 properties such as asphaltene and acidic contents 44, 45, 47, 62. It should be noted that water
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1
2
3 282 microdispersions cannot occur outside the interface area. This is a pure fluid-fluid
4
5
6 283 interaction taking place at the oil/water interface and its intensity decreases by the distance
7
8 284 from the interface. Although the microdispersion phase can span over a relatively longer
9
10
285 distances from the interface as well. Furthermore, the accuracy of this in-house protocol has
11
12
13 286 been validated several times to be accurately in line with LSE in the literature 45-47, 49, 60, 88-90.
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15
16
90
17
77.83
18 80 LSW HSW
19
Water Microdispersion Ratio
20 70
21
60
22 49.27
23 50
24 38.83
25 40
26 29.55
30
27
28 20
29
5.85 6.01
30 10 3.65 2.03 0.97 2.62 2.54 2.85
31
0
32
33 287 Crude-C Crude-F Crude-U9 Crude-U1 Crude-U5 Crude-B
34
35 288 Figure 3. Water microdispersion ratio of the crude oil samples toward the low, and the high
36
37 289 salinity brines.
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39
40
41
290 3.2 Surface Charges of Crude Oils
42
43 291 Surface charges of crude oil samples along with surface charges of pure quartz minerals in
44
45 292 HSW, Seawater (SW), and different dilutions of SW were measured at a neutral pH of 7 and
46
47
48
293 reported in Figure 4. The surface charges of pure quartz minerals, as the only component
49
50 294 constituting the micromodel, were measured to show the electrostatic forces at the
51
52 295 micromodel surface in the presence of brines with different salinities. As shown in Figure 4,
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296 surface charges of crude oil samples at lower salinities show a stronger negative response
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17
1
2
3 297 meaning that the oil/brine interface is exceptionally saturated with negatively charged
4
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6 298 species such as carboxylic acids with low pKa (i.e., compounds with RCOO- functional group
7
8 299 with pKa < 6.0 91). Due to the hydrophilicity degree of carboxylic acids in crude oil, they tend
9
10
300 to diffuse into the interface (through deprotonation) and partition into the water phase at
11
12
13 301 the pH values higher than their pKa. This result indicates the higher tendency of acidic
14
15 302 materials, such as carboxylic acids, toward the oil/brine interface during LSWI. In higher
16
17
303 salinities of SW and FW, the negative surface charges tend to decrease and get closer to the
18
19
20 304 point of zero charges. Also, the stronger negative response in surface charges of crude oil
21
22 305 samples in LSW solutions is in line with the measured microdispersion ratios, as shown in
23
24
306 Figure 3. Accumulation of negatively charged compounds and water microdispersion at the
25
26
27 307 oil/water interface in low salinity brines reveals the vital importance of acidic compounds
28
29 308 in LSWI and microdispersion formation. Organic acidic compounds can potentially act like
30
31
32
309 natural surfactants in which they form micelles in concentrations beyond the Critical Micelle
33
34 310 Concentration (CMC) 64. The formation of micelles or reverse micelles strongly depends on
35
36 311 the properties of surface-active materials such as polarity and chain length 92. Therefore,
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38
39
312 when the concentration of acidic materials at the oil/brine interface increases, there is the
40
41 313 formation of reverse micelle-shaped structures with water molecules, known as
42
43 314 microdispersion.
44
45
46 315 Surface charges of pure quartz minerals at low and high salinity brines (DW and FW) are -
47
48 316 31.2 and -1.5 mV, respectively. Based on the electrical double layer theory 41, 42, 93, the thin
49
50 317 brine film covering the rock surface would be adequately stable and thick in lower salinities
51
52
53 318 which would lead to water-wet wettability state (electrostatic repulsion between oil/brine
54
55 319 and rock/brine interfaces with strong negative surface charges). In contrast, the electrical
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18
1
2
3 320 double layer would collapse, and wettability shifts toward oil-wet at higher salinities of SW
4
5
6 321 and FW (electrostatic attraction between oil/brine and rock brine interfaces with positive
7
8 322 and negative surface charges). Forthwith, the wettability state of quartz particles would be
9
10
323 oil-wet, and it would turn towards a more water-wet state during LSWI, and further oil
11
12
13 324 recovery would be expected for all crude oil samples, which will be shown that does not
14
15 325 happen all the times 27, 32, 94-98.
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17
18 10
19 Crude-C Crude-F Crude-U9 Crude-U1
0 Crude-U5 Crude-B Quartz
20
21 -10
Zeta Potential (mV) at pH of 7.0
22
-20
23
24 -30
25
-40
26
27 -50
28
29 -60
30 -70
31
32 -80
33 -90
34
35 -100
36 326 DW SW100d SW25d SW HSW
37
38 327 Figure 4. The zeta potentials of the crude oil samples and pure quartz particles within
39
40 328 different brines.
41
42
43
44 329 3.3 Composition Changes through FT-IR Spectroscopy
45
46 330 The interfacial crude oil samples were also studied with IR spectroscopy to distinguish the
47
48 331 compositional changes occurring at the interface. Grasping the most abundant molecules at
49
50
51 332 the oil/brine interface (responsible for LSE and microdispersions) can help gain better
52
53 333 insight into the underlying mechanism of LSWI and provides an opportunity to control and
54
55 334 design this EOR method effectively. Figure 5 illustrates the IR spectra of interfacial crude oil-
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57
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19
1
2
3 335 C (i.e., the crude oil samples from oil/LSW and oil/HSW interfaces) in which several vital
4
5
6 336 regions at different wavenumbers can be analysed. Each vibration band can be attributed to
7
8 337 a corresponding molecular bond. Usually, hydrocarbons exhibit two sharp bands at 2916
9
10
338 and 2850 cm-1, each of which stands for asymmetric and symmetric stretching vibrations of
11
12
13 339 sp3 carbons in methyl groups 99. Besides, two more distinct vibration bands exist at 1455
14
15 340 and 1375 cm-1 representing the sp2 carbons of the methylene groups. There are two other
16
17
341 types of vibration bands with lower intensities at 1614 cm-1 and between 900-650 cm-1,
18
19
20 342 which belong to C=C and out-of-plane bending vibrations of C-H bonds of aromatic rings,
21
22 343 respectively. Vibrations at the wavenumber of 1680 cm-1 indicate the presence of C=O bonds
23
24
344 (C=O bonds stem from the functional group of COOH most likely stand for carboxylic acids
25
26
27 345 within the crude oil phase 100, 101). Moreover, the broad peak between 4000-3100 cm-1 is the
28
29 346 most fundamental vibration band standing for polar O-H bonds of either water molecules or
30
31
32
347 acidic materials (i.e., with COOH functional group). The broad peaks for both interfacial
33
34 348 crude oils can be pertaining to microdispersions at the oil/brine interface.
35
36 349 Figure 5 demonstrates a higher intensity of O-H bonds between 4000-3000 cm-1 at the
37
38
39
350 oil/LSW interface compared to the oil/HSW interface revealing the higher amount of formed
40
41 351 microdispersion. The higher amount of microdispersion at the oil/LSW interface is in good
42
43 352 agreement with water content measurements in Figure 3. The interesting point about the IR
44
45
46 353 spectra of interfacial crude oil samples is the intensity of C=O bonds at 1680 cm-1. It can be
47
48 354 observed that the higher intensity of O-H bonds coincides with the greater abundance of C=O
49
50 355 bonds at the interface of crude oil and LSW. This was also performed for the other interfacial
51
52
53 356 crude oil samples mentioned throughout this paper and, as such, can be found in the
54
55 357 Supporting Document figure S.f. 2 to S.f. 6. Accordingly, it can be observed for the other crude
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369 3.4 Visual Evidence about the Mechanism of LSWI
5
6 370 Micromodel experiments for different crude oil samples with different propensities in
7
8 371 forming microdispersion were conducted at an elevated temperature of 50= and elevated
9
10
11 372 pressure of 2000 psi. Due to the intrinsic water-wet characteristic of glass micromodels,
12
13 373 investigating wettability alteration can be extremely demanding. It is of paramount
14
15 374 importance to have a porous media with varied initial wettability conditions in which the
16
17
18 375 impact of low salinity water on the oil/brine interactions and other pertinent phenomena be
19
20 376 possible. Therefore, two initial wettability states of water-wet and oil-wet were established
21
22 377 in the micromodel by using different crude oil samples and different aging procedures. In the
23
24
25 378 following, the results for water-wet and oil-wet Micromodel experiments and the impact of
26
27 379 LSWI on the wettability state of porous media will be elaborated.
28
29 380 LSE in a Water-Wet Porous Media
30
31
32
381 In this section, the Micromodel results for a tertiary LSW injection performed with samples
33
34
35 382 of crude-C, crude-F, crude-B, crude-U9, and crude U1 are presented when the initial
36
37 383 wettability is water-wet. It should be mentioned that crude-C, crude-U9, and crude-U1
38
39
40
384 reacted positively toward LSWI, whereas crude-F and crude-B responded negatively.
41
42 385 Figure 6 represents the Micromodel full-length pictures during aging, HSW injection, and
43
44 386 tertiary LSW injection for crude-C, which was a potent crude oil to form microdispersions
45
46
47
387 (microdispersion ratio = 38.83). It can be seen in Figure 6-a that after aging, most pores are
48
49 388 saturated with crude oil, and initial water saturation is relatively low. After HSW injection, a
50
51 389 large portion of crude oil is produced, and residual oil saturation is low. It should be stated
52
53 vK
54 390 that the displacement stability is controlled by capillary number (which is defined as [\ = ]
55
56
57
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59
22
1
2
3 391 in which v is the velocity of displacing fluid, K is the viscosity of displacing fluid, and ] is the
4
5
6 392 interfacial tension between displacing and displaced fluids which is 21.5 mN/m) and
7
8 _`
393 mobility ratio (which is defined as ^ = _a , in which _` and _a is the viscosity of water and
9
10
11 394 oil, respectively). For HSW injection, capillary number is small ([\ = 1.26 × 10 c6) and
12
13
14 395 mobility ratio is far less than 1 (M= 0.2916 ) denoting the dominant capillary fingering flow
15
102.
16 396 pattern across the model Therefore, the residual crude oil ganglia are trapped by
17
18 397 capillary forces inside the pores (i.e., in the middle of the pores due to wettability state) and
19
20
21 398 snap-off mechanism 103. When crude oil phase distribution reached the residual saturation
22
23 399 level, the injection was switched to tertiary LSW. It can be seen in Figure 6-c that a
24
25 400 considerable amount of residual oil is produced and formation of microdispersion, which
26
27
28 401 appears as black-color-particle shapes within the crude oil phase during LSW flooding.
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1
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3 410 move from water-wet to a more water-wet state. It seems that the capillary disequilibrium
4
5
6 411 conditions during HSW injection become more stable through LSW injection as capillary
7
8 412 pressure increases. Therefore, oil droplets tend to have the lowest possible surface area with
9
10
413 the surrounding water. Accordingly, the crude oil ganglion is peeled off the glass
11
12
13 414 micromodel, possessing minimum local energy 104, therefore become more symmetrical in
14
15 415 shape. This process takes place due to wettability alteration at the solid surface by the
16
17
416 formation of microdispersions, which can be identified visually by the colour of crude oil
18
19
20 417 during LSW injection. The red rectangular at the top right side of Figure 7 represents the
21
22 418 area in which LSW recovers the residual oil clusters through the formation of water
23
24
419 microdispersion. The red arrows pinpoint the microdispersion in black colour within the
25
26
27 420 crude oil phase. Hence, the formation of water microdispersion within the crude oil phase
28
29 421 has led to the crude oil detachment from the surface and then form a more continuous oil
30
31
32
422 phase (an oil bank). It is evident in Figure 7 (red rectangle and arrows) that the continuous
33
34 423 oil phase subsequently produced by LSW. Furthermore, the impact of microdispersion
35
36 424 formation on the residual oil phase recovery is shown by blue circles, and blue arrows
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38
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425 indicate the locations of them.
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1
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3 465 The other crude oil forming high levels of microdispersion (microdispersion ratio =
4
5
6 466 77.83), which was studied through Micromodel experiments, is crude-U9. The magnified
7
8 467 image sequence obtained during tertiary LSW injection is demonstrated in Figure 10. The
9
10
468 consecutive colour changes of the crude oil phase from light brown to dark black can be
11
12
13 469 recognised during LSW injection, indicating the formation of water microdispersion. The
14
15 470 creation of microdispersion occurs shortly after starting LSW injection and reproduces in
16
17
471 the oil phase after 8 hours (Figure 10-c), a consequence of which the oil phase swells
18
19
20 472 considerably. Further demonstrations have been carried out by colouring continuous water
21
22 473 fronts in some pores to disclose the effect of microdispersion formation. The light blue
23
24
474 colours in Figure 10-a (show by point 1 in the figure) highlights two LSW clusters in two
25
26
27 475 different pores. As it is evident, the crude oil films in Figure 10-a interact with LSW clusters
28
29 476 resulting in the progressive formation of microdispersions over time (Figure 10-f), which
30
31
32
477 can be observed by the change in the colour of crude oils.
33
34 478 Consequently, the crude oil films swell and change into strongly repellent oil droplets that
35
36 479 block the pores. Crude oil films are relatively stable during HSW injection and hold a large
37
38
39
480 specific surface area; hence they possess small local energy 104. Given the LSW injection and
40
41 481 microdispersion formation, the oil films are no longer stable and tend to retain the minimum
42
43 482 surface area and local energy. Subsequently, due to local energy disequilibrium, spread oil
44
45
46 483 films become more spherical (i.e., more stable structure with minimum local energy) when
47
48 484 HSW injection is substituted with LSW injection.
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3 508 Figure 11. Two magnified sections of Micromodel experiment with crude-F and crude-B at
4
5
6 509 the end of HSW and LSW waterfloodings. The water microdispersion phenomenon does not
7
8 510 take place for these crude oils; hence there is no LSE.
9
10
11 511
12
13
14 512 LSE in an Oil-Wet Porous Media
15
16
17
18
513 From the second series of micromodel experiments, examining the effect of different saline
19
20 514 solutions on the performance of waterflood in an oil-wet porous media, it was found that
21
22 515 injection of the low saline aqueous solution had a significant impact on the wettability state.
23
24
25
516 In the following, it will be shown that the formation of microdispersion contributes to
26
27 517 wettability alteration and oil swelling in porous media, elevating the microscopic sweeping
28
29 518 efficiency. Figure Sf. 7 (see Supporting Information) demonstrates the secondary HSW
30
31
32 519 injection into the hydrophobic magnified section of Micromodel over time for crude oil U5
33
34 520 (microdispersion ratio is 49.27). As shown, the first front of HSW drainage enters a
35
36 521 Micromodel section at 60 seconds, and three other different moving fronts are invading the
37
38
39 522 section by 180 seconds (Figure Sf. 7-c). A close inspection of magnified images shows the
40
41 523 different mechanism of residual oil saturation than the water-wet Micromodel experiments
42
43 524 (Figure 6). Most residual oil after 36 seconds (Figure Sf. 7-f) are those that are left on the
44
45
46 525 pore walls and inside the dead-end pores due to the strong tendency of porous media toward
47
48 526 crude oil (negative capillary forces).
49
50 527 The magnified images of different sections of the Micromodel during secondary HSW
51
52
53 528 injection and tertiary LSW injection are illustrated in Figure 12. It can be seen in Figure 12-
54
55 529 that the oil/brine curvatures changed considerably as the average contact angle during LSW
56
57
58
59
32
1
2
3 530 injection is estimated to be 70°. In contrast, it is 125° during HSW injection (Figure 12-b).
4
5
6 531 This is evident in the figures that wettability alterations take place due to the formation of
7
8 532 microdispersion (i.e., they can be seen in black colour within the crude oil phases in light
9
10
533 brown colour). Red arrows indicate other examples of wettability alteration due to
11
12
13 534 microdispersion formation. It is demonstrated in Figure 12-c and Figure 12-d that injection
14
15 535 of LSW leads to the formation of microdispersion and wettability alteration subsequently as
16
17
536 contact angle shifts from 120° into 55°. Moreover, the oil swelling effects as a consequence
18
19
20 537 of microdispersion formation are depicted by green circles. The wettability alteration and oil
21
22 538 swelling effects due to microdispersions are shown in Figure 12-e and Figure 12-f (also see
23
24
25
539 Figure Sf. 7, Supporting Information).
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1
2
3 544 The formation of microdispersion was directly shown to be the main reason behind
4
5
6 545 wettability alteration due to LSW injection in a porous media containing crude oil. However,
7
8 546 the impacts of microdispersions on the wettability state of the micromodel network were
9
10
547 more pronounced in the hydrophobic system (initial wettability state was oil-wet). It was
11
12
13 548 shown through FT-IR spectroscopy, and zeta potential measurements that negatively
14
15 549 charged polar compounds within the crude oil phase are mainly responsible for
16
17
550 microdispersion formation. These polar species have been widely recognised as the main
18
19
20 551 agents in wettability alteration of oil reservoirs 101, 105-107. When LSW is introduced into the
21
22 552 porous media, the polar components of crude oil have a preference to interact with water
23
24
553 molecules rather than the rock surface (as suggested by zeta potential data, Figure 4). These
25
26
27 554 surface-active materials are adsorbed into the oil/LSW interface and form microdispersions,
28
29 555 which leads to wettability alteration and oil swelling. As a result, the swelled oil ganglia
30
31
32
556 restrict the injection water flow and change it toward unswept regions. Additionally, oil
33
34 557 swelling increases the hydraulic discontinuity in injection water flow, and consequently, the
35
36 558 pressure drop across the model would increase, and the microscopic sweeping efficiency
37
38
39
559 improves.
40
41 560 Herein, the remaining oil saturation in the micromodel porous media during the
42
43 561 experiments was calculated by image analysis and shown in Figure 13. It can be observed
44
45
46 562 that the performance of LSWI is in proportion to the propensities of crude oil samples to
47
48 563 form water microdispersion. For the crude oil samples with weak potencies toward
49
50 564 microdispersion formation, the change in remaining oil saturation is not considerable,
51
52
53 565 revealing the negligible LSE in terms of additional oil recovery during tertiary LSWI. On the
54
55 566 opposite side, tertiary LSWI leads to an additional oil recovery, which was shown to stem
56
57
58
59
35
1
2
3 567 from wettability alteration and oil swelling phenomena due to microdispersion formation
4
5
6 568 within the crude oil phase.
7
8
End of Secondary HSWI End of Tertiary LSWI
9
10 60
11
Remaining Oil Saturation (%)
48.2
12 50
13 42.2 41.7
14 40 36.5 35.9 35.9
34.5 33.6
15 32.8
30.1
16 28.5
26.8
30
17 22.6
18 18.2
20
19
20
21 10
22
23 0
24 Crude-C Crude-F Crude-U9 Crude-U1 Crude-U5 Crude-B Crude-U1
25 (Oil-Wet)
26 Crude Oil ID
27 569
28
29 570 Figure 13. Remaining Oil Saturation at the end of secondary and tertiary HSW and LSW,
30
31 571 respectively. The performances of crude oil samples are in line with their propensities
32
33
34 572 toward microdispersion formation, as crude-F and crude-B responded negatively toward
35
36 573 LSWI in terms of microdispersion formation.
37
38
39 574 This study showed the paramount importance of fluid-fluid interactions (formation of
40
41
575 microdispersion) through Micromodel experiments composing of single-component
42
43
44 576 materials (quartz). Although the possible role of rock-fluid interactions was investigated
45
46 577 through changing the initial wettability, further evaluations are required to fully discover the
47
48
578 effect of rock minerals on the performance of microdispersion formation in terms of
49
50
51 579 wettability alteration during LSWI. Functionalising the Micromodel experiments with clay
52
53 580 minerals can also be a decent suggestion for future investigation to further evaluate the multi
54
55
56
581 ion exchange20 and fine migration 12 hypotheses during LSWI.
57
58
59
36
1
2
3
4
582 4 Conclusion
5
6 583 In this study, a number of analytical tools were combined, for the first time, with a direct
7
8 584 visual technique to evaluate the mechanism of LSWI under conditions that closely replicate
9
10
11 585 reservoir conditions. It was revealed that despite the same magnitude of surface charges of
12
13 586 crude oil samples, they showed different potentials to respond positively to LSWI in terms
14
15
587 of microdispersion formation. Further analysis of the oil/water interface through FT-IR
16
17
18 588 spectroscopy showed that conjugated acidic compounds are mainly responsible for the
19
20 589 creation of microdispersions. These conjugated acidic compounds could be either carboxylic
21
22
590 acids or acidic asphaltene molecules within the crude oil phase. The micromodel
23
24
25 591 experiments provided some direct visual evidence that the formation of microdispersion
26
27 592 during LSWI results in wettability alteration toward a more water-wet state.
28
29
30
593 Furthermore, the oil swelling phenomenon takes place extensively across the porous
31
32 594 media; consequently, the injection water phase is diverted into unswept areas to sweep the
33
34 595 residual oil saturation. Another aftereffect of oil swelling was shown to be the increase in
35
36
37
596 hydraulic discontinuity of the injection water phase would lead to an incremental pressure
38
39 597 drop across the model. Accordingly, the formation of microdispersion, by conjugated acidic
40
41 598 compounds within the crude oil, during LSWI leads to improving the microscopic sweep
42
43
44 599 efficiency in a porous media. The findings also provide valuable information about the
45
46 600 criteria require consideration before any waterflooding operations and a reminder of the
47
48 601 paramount importance of a reliable screening method of oil reservoirs for LSWI.
49
50
51 602
52
53 603 Supporting Information
54
55
56
57
58
59
37
1
2
3 604 A magnified picture of Micromodel after using stearic acid solution [0.1 wt%] to change
4
5
6 605 the initial wettability (Figure S.f. 1); FT-IR spectra of interfacial crude oil B samples (Figure
7
8 606 S.f. 2); FT-IR spectra of interfacial crude oil SF samples (Figure S.f. 3); FT-IR spectra of
9
10
607 interfacial crude oil U1 samples (Figure S.f. 4); FT-IR spectra of interfacial crude oil U5
11
12
13 608 samples (Figure S.f. 5); FT-IR spectra of interfacial crude oil U9 samples (Figure S.f. 6);
14
15 609 Magnified image sequence of Micromodel experiment with crude-U5 (Figure S.f. 7);
16
17
610 Magnified image sequence of Micromodel experiment with crude-U5 during tertiary LSWI
18
19
20 611 (Figure S.f. 8).
21
22
23 612 Author Information
24
25
26
613 Corresponding Author
27
28
29
30 614 E-mail: mf68@hw.ac.uk
31
32
33 615 ORCID
34
35
36 616 Mohammad Fattahi Mehraban: 0000-0001-7857-6171
37
38
39
40
617 Present Address
41
42 618 Riccarton, Heriot-Watt University, Institute of GeoEnergy Engineering, Edinburgh, United
43
44 619 Kingdom, EH14 4AS.
45
46
47
620 Notes
48
49 621 The authors declare no competing financial interest.
50
51
52
622 Acknowledgments
53
54
55
56
57
58
59
38
1
2
3 623 This work was performed as a part of the Low Salinity Water Injection joint industry
4
5
6 624 project (JIP) in the Centre for Enhanced Oil Recovery (EOR) and CO2 Solutions at Heriot-Watt
7
8 625 University, Edinburgh, Scotland, UK. The project is equally funded by ADNOC, BP, the UK Oil
9
10
626 and Gas Authority, Total E&P, Wintershall Dea GmbH, Woodside Energy, and ConocoPhillips
11
12
13 627 which is gratefully acknowledged.
14
15
16 628 Funding Sources
17
18 629 This study is equally funded by ADNOC, BP, the UK Oil and Gas Authority, Total E&P,
19
20
21 630 Wintershall Dea GmbH, Woodside Energy, and ConocoPhillips.
22
23 631
24
25
26
632 References
27
28
633 1. Morrow, N.; Buckley, J., Improved oil recovery by low-salinity waterflooding. Journal
29
30 634 of Petroleum Technology 2011, 63, (05), 106-112.
31
32
33 635 2. Lager, A.; Webb, K. J.; Collins, I. R.; Richmond, D. M. In LoSal enhanced oil recovery:
34
35 636 Evidence of enhanced oil recovery at the reservoir scale, SPE symposium on improved oil
36
37
38 637 recovery, 2008; Society of Petroleum Engineers: 2008.
39
40
41 638 3. McGuire, P.; Chatham, J.; Paskvan, F.; Sommer, D.; Carini, F. In Low salinity oil
42
43 639 recovery: An exciting new EOR opportunity for Alaska's North Slope, SPE western regional
44
45
46 640 meeting, 2005; Society of Petroleum Engineers: 2005.
47
48
49 641 4. Nasralla, R. A.; Bataweel, M. A.; Nasr-El-Din, H. A. In Investigation of wettability
50
51 642 alteration by low salinity water, Offshore Europe, 2011; Society of Petroleum Engineers:
52
53
643 2011.
54
55
56
57
58
59
39
1
2
3 644 5. Seccombe, J.; Lager, A.; Jerauld, G.; Jhaveri, B.; Buikema, T.; Bassler, S.; Denis, J.; Webb,
4
5
6 645 K.; Cockin, A.; Fueg, E. In Demonstration of low-salinity EOR at interwell scale, Endicott field,
7
8 646 Alaska, SPE improved oil recovery symposium, 2010; Society of Petroleum Engineers: 2010.
9
10
11 647 6. Fathi, S. J.; Austad, T.; Strand, S., “Smart water” as a wettability modifier in chalk: the
12
13
14 648 effect of salinity and ionic composition. Energy & fuels 2010, 24, (4), 2514-2519.
15
16
17 649 7. Baptist, O. C.; Sweeney, S., The effect of clays on the permeability of reservoir sands to
18
19 650 waters of different saline contents. Clays and Clay Minerals 1954, 3, (1), 505-515.
20
21
22 651 8. Martin, J. C. In The effects of clay on the displacement of heavy oil by water,
23
24
25 652 Venezuelan annual meeting, 1959; Society of Petroleum Engineers: 1959.
26
27
28 653 9. Bernard, G. G. In Effect of floodwater salinity on recovery of oil from cores containing
29
30 654 clays, SPE California Regional Meeting, 1967; Society of Petroleum Engineers: 1967.
31
32
33 655 10. Hughes, R. V.; Pfister, R. J., Advantages of brines in secondary recovery of petroleum
34
35
36 656 by water-flooding. Transactions of the AIME 1947, 170, (01), 187-201.
37
38
39 657 11. Reiter, P. K. A water-sensitive sandstone flood using low salinity water. University of
40
41 658 Oklahoma, 1961.
42
43
44 659 12. Tang, G.-Q.; Morrow, N. R., Influence of brine composition and fines migration on
45
46
47 660 crude oil/brine/rock interactions and oil recovery. Journal of Petroleum Science and
48
49 661 Engineering 1999, 24, (2-4), 99-111.
50
51
52
53
54
55
56
57
58
59
40
1
2
3 662 13. Morrow, N. R.; Tang, G.-q.; Valat, M.; Xie, X., Prospects of improved oil recovery related
4
5
6 663 to wettability and brine composition. Journal of Petroleum science and Engineering 1998,
7
8 664 20, (3-4), 267-276.
9
10
11 665 14. Wickramathilaka, S.; Howard, J.; Morrow, N.; Buckley, J. In An experimental study of
12
13
14 666 low salinity waterflooding and spontaneous imbibition, IOR 2011-16th European
15
16 667 Symposium on Improved Oil Recovery, 2011; European Association of Geoscientists &
17
18 668 Engineers: 2011; pp cp-230-00051.
19
20
21
669 15. Austad, T.; RezaeiDoust, A.; Puntervold, T. In Chemical mechanism of low salinity
22
23
24 670 water flooding in sandstone reservoirs, SPE improved oil recovery symposium, 2010;
25
26 671 Society of Petroleum Engineers: 2010.
27
28
29 672 16. Jackson, M.; Vinogradov, J.; Hamon, G.; Chamerois, M., Evidence, mechanisms and
30
31
32 673 improved understanding of controlled salinity waterflooding part 1: Sandstones. Fuel 2016,
33
34 674 185, 772-793.
35
36
37 675 17. Carroll, D., Ion exchange in clays and other minerals. Geological Society of America
38
39
40
676 Bulletin 1959, 70, (6), 749-779.
41
42
43 677 18. Law, S.; McDonald, A.; Fellows, S.; Reed, J.; Sutcliffe, P. In Influence of clay content and
44
45 678 type on oil recovery under low salinity waterflooding in North Sea reservoirs, SPE Offshore
46
47 679 Europe Conference and Exhibition, 2015; Society of Petroleum Engineers: 2015.
48
49
50
51 680 19. Zhang, Y.; Morrow, N. R. In Comparison of secondary and tertiary recovery with
52
53 681 change in injection brine composition for crude-oil/sandstone combinations, SPE/DOE
54
55 682 symposium on improved oil recovery, 2006; Society of Petroleum Engineers: 2006.
56
57
58
59
41
1
2
3 683 20. Lager, A.; Webb, K.; Black, C. In Impact of brine chemistry on oil recovery, IOR 2007-
4
5
6 684 14th European Symposium on Improved Oil Recovery, 2007; European Association of
7
8 685 Geoscientists & Engineers: 2007; pp cp-24-00020.
9
10
11 686 21. Seccombe, J. C.; Lager, A.; Webb, K. J.; Jerauld, G.; Fueg, E. In Improving wateflood
12
13
14 687 recovery: LoSalTM EOR field evaluation, SPE symposium on improved oil recovery, 2008;
15
16 688 Society of Petroleum Engineers: 2008.
17
18
19 689 22. Lebedeva, E. V.; Fogden, A., Micro-CT and wettability analysis of oil recovery from
20
21
690 sand packs and the effect of waterflood salinity and kaolinite. Energy & Fuels 2011, 25, (12),
22
23
24 691 5683-5694.
25
26
27 692 23. Hassenkam, T.; Mitchell, A. C.; Pedersen, C. S.; Skovbjerg, L.; Bovet, N.; Stipp, S. L. S.,
28
29 693 The low salinity effect observed on sandstone model surfaces. Colloids and Surfaces A:
30
31
32 694 Physicochemical and Engineering Aspects 2012, 403, 79-86.
33
34
35 695 24. Sanyal, S.; Bhui, U. K.; Kumar, S. S.; Balaga, D., Designing injection water for enhancing
36
37 696 oil recovery from kaolinite laden hydrocarbon reservoirs: a spectroscopic approach for
38
39
40
697 understanding molecular level interaction during saline water flooding. Energy & Fuels
41
42 698 2017, 31, (11), 11627-11639.
43
44
45 699 25. Sanyal, S.; Bhui, U. K.; Balaga, D.; Kumar, S. S., Interaction study of montmorillonite-
46
47 700 crude oil-brine: Molecular-level implications on enhanced oil recovery during low saline
48
49
50 701 water flooding from hydrocarbon reservoirs. Fuel 2019, 254, 115725.
51
52
53 702 26. Cissokho, M.; Bertin, H.; Boussour, S.; Cordier, P.; Hamon, G., Low salinity oil recovery
54
55 703 on clayey sandstone: Experimental study. Petrophysics 2010, 51, (05).
56
57
58
59
42
1
2
3 704 27. Pu, H.; Xie, X.; Yin, P.; Morrow, N. R. In Low-salinity waterflooding and mineral
4
5
6 705 dissolution, SPE annual technical conference and exhibition, 2010; Society of Petroleum
7
8 706 Engineers: 2010.
9
10
11 707 28. Lebedeva, E.; Senden, T.; Knackstedt, M.; Morrow, N. In Improved Oil Recovery from
12
13
14 708 Tensleep Sandstone–Studies of Brine-Rock Interactions by Micro-CT and AFM, IOR 2009-
15
16 709 15th European Symposium on Improved Oil Recovery, 2009; European Association of
17
18 710 Geoscientists & Engineers: 2009; pp cp-124-00062.
19
20
21
711 29. Pu, H.; Xie, X.; Yin, P.; Morrow, N. R. In Application of coalbed methane water to oil
22
23
24 712 recovery from Tensleep Sandstone by low salinity waterflooding, SPE Symposium on
25
26 713 Improved Oil Recovery, 2008; Society of Petroleum Engineers: 2008.
27
28
29 714 30. Hassenkam, T.; Pedersen, C. S.; Dalby, K.; Austad, T.; Stipp, S. L. S., Pore scale
30
31
32 715 observation of low salinity effects on outcrop and oil reservoir sandstone. Colloids and
33
34 716 Surfaces A: Physicochemical and Engineering Aspects 2011, 390, (1-3), 179-188.
35
36
37 717 31. Yousef, A. A.; Al-Saleh, S.; Al-Kaabi, A. U.; Al-Jawfi, M. S. In Laboratory investigation of
38
39
40
718 novel oil recovery method for carbonate reservoirs, Canadian Unconventional Resources
41
42 719 and International Petroleum Conference, 2010; Society of Petroleum Engineers: 2010.
43
44
45 720 32. Zahid, A.; Shapiro, A. A.; Skauge, A. In Experimental studies of low salinity water
46
47 721 flooding carbonate: A new promising approach, SPE EOR Conference at Oil and Gas West
48
49
50 722 Asia, 2012; Society of Petroleum Engineers: 2012.
51
52
53
54
55
56
57
58
59
43
1
2
3 723 33. Austad, T.; Shariatpanahi, S.; Strand, S.; Black, C.; Webb, K., Conditions for a low-
4
5
6 724 salinity enhanced oil recovery (EOR) effect in carbonate oil reservoirs. Energy & fuels 2012,
7
8 725 26, (1), 569-575.
9
10
11 726 34. Hognesen, E. J.; Strand, S.; Austad, T. In Waterflooding of preferential oil-wet
12
13
14 727 carbonates: Oil recovery related to reservoir temperature and brine composition, SPE
15
16 728 Europec/EAGE Annual Conference, 2005; Society of Petroleum Engineers: 2005.
17
18
19 729 35. Strand, S.; Høgnesen, E. J.; Austad, T., Wettability alteration of carbonates—Effects of
20
21
730 potential determining ions (Ca2+ and l8 and temperature. Colloids and Surfaces A:
22
23
24 731 Physicochemical and Engineering Aspects 2006, 275, (1-3), 1-10.
25
26
27 732 36. Zhang, P.; Tweheyo, M. T.; Austad, T., Wettability alteration and improved oil recovery
28
29 733 by spontaneous imbibition of seawater into chalk: Impact of the potential determining ions
30
31
32 734 Ca 2+, Mg 2+, and SO 4 l3 Colloids and Surfaces A: Physicochemical and Engineering
33
34 735 Aspects 2007, 301, (1), 199-208.
35
36
37 736 37. Strand, S.; Standnes, D.; Austad, T., New wettability test for chalk based on
38
39
40
737 chromatographic separation of El and l3 Journal of Petroleum Science and
41
42 738 Engineering 2006, 52, (1-4), 187-197.
43
44
45 739 38. Pierre, A.; Lamarche, J.; Mercier, R.; Foissy, A.; Persello, J., Calcium as potential
46
47 740 determining ion in aqueous calcite suspensions. JOURNAL OF DISPERSION SCIENCE
48
49
50 741 ANDTECHNOLOGY 1990, 11, (6), 611-635.
51
52
53
54
55
56
57
58
59
44
1
2
3 742 39. Austad, T.; Shariatpanahi, S.; Strand, S.; Black, C.; Webb, K., Conditions for a low-
4
5
6 743 salinity enhanced oil recovery (EOR) effect in carbonate oil reservoirs. Energy & fuels 2011,
7
8 744 26, (1), 569-575.
9
10
11 745 40. Romanuka, J.; Hofman, J.; Ligthelm, D. J.; Suijkerbuijk, B.; Marcelis, F.; Oedai, S.;
12
13
14 746 Brussee, N.; van der Linde, H.; Aksulu, H.; Austad, T. In Low salinity EOR in carbonates, SPE
15
16 747 Improved Oil Recovery Symposium, 2012; Society of Petroleum Engineers: 2012.
17
18
19 748 41. Ligthelm, D. J.; Gronsveld, J.; Hofman, J.; Brussee, N.; Marcelis, F.; van der Linde, H. In
20
21
749 Novel Waterflooding Strategy By Manipulation Of Injection Brine Composition,
22
23
24 750 EUROPEC/EAGE conference and exhibition, 2009; Society of Petroleum Engineers: 2009.
25
26
27 751 42. Mahani, H.; Keya, A. L.; Berg, S.; Bartels, W.-B.; Nasralla, R.; Rossen, W. R., Insights into
28
29 752 the mechanism of wettability alteration by low-salinity flooding (LSF) in carbonates. Energy
30
31
32 753 & Fuels 2015, 29, (3), 1352-1367.
33
34
35 754 43. Mahani, H.; Menezes, R.; Berg, S.; Fadili, A.; Nasralla, R.; Voskov, D.; Joekar-Niasar, V.,
36
37 755 Insights into the impact of temperature on the wettability alteration by low salinity in
38
39
40
756 carbonate rocks. Energy & Fuels 2017, 31, (8), 7839-7853.
41
42
43 757 44. Emadi, A.; Sohrabi, M. In Visual investigation of oil recovery by lowsalinity water
44
45 758 injection: Formation of water micro-dispersions and wettabilityalteration, SPE annual
46
47 759 technical conference and exhibition, 2013; Society of Petroleum Engineers: 2013.
48
49
50
51 760 45. Sohrabi, M.; Mahzari, P.; Farzaneh, S. A.; Mills, J. R.; Tsolis, P.; Ireland, S., Novel insights
52
53 761 into mechanisms of oil recovery by use of low-salinity-water injection. SPE Journal 2017, 22,
54
55 762 (02), 407-416.
56
57
58
59
45
1
2
3 763 46. AlHammadi, M.; Mahzari, P.; Sohrabi, M., Fundamental investigation of underlying
4
5
6 764 mechanisms behind improved oil recovery by low salinity water injection in carbonate rocks.
7
8 765 Fuel 2018, 220, 345-357.
9
10
11 766 47. Mahzari, P.; Sohrabi, M.; Cooke, A. J.; Carnegie, A., Direct pore-scale visualization of
12
13
14 767 interactions between different crude oils and low salinity brine. Journal of Petroleum Science
15
16 768 and Engineering 2018, 166, 73-84.
17
18
19 769 48. Mahzari, P.; Sohrabi, M. In Crude oil/brine interactions and spontaneous formation of
20
21
770 micro-dispersions in low salinity water injection, SPE improved oil recovery symposium,
22
23
24 771 2014; Society of Petroleum Engineers: 2014.
25
26
27 772 49. Facanha, J. M.; Mahzari, P.; Sohrabi, M. In Direct observation of low-salinity water
28
29 773 effect: relationship between micro-dispersion formation and wettability alteration, SPE
30
31
32 774 Middle East Oil & Gas Show and Conference, 2017; Society of Petroleum Engineers: 2017.
33
34
35 775 50. Bartels, W.; Rücker, M.; Berg, S.; Mahani, H.; Georgiadis, A.; Brussee, N.; Coorn, A.; van
36
37 776 der Linde, H.; Fadili, A.; Hinz, C. In Micro-ct study of the impact of low salinity waterflooding
38
39
40
777 on the pore-scale fluid distribution during flow, International Symposium of the Society of
41
42 778 Core Analysts, Snowmass, CO, 2016; 2016; pp 1362-1373.
43
44
45 779 51. Bartels, W.-B.; Mahani, H.; Berg, S.; Menezes, R.; van der Hoeven, J.; Fadili, A. In Low
46
47 780 salinity flooding (LSF) in sandstones at pore scale: micro-model development and
48
49
50 781 investigation, SPE Annual Technical Conference and Exhibition, 2016; Society of Petroleum
51
52 782 Engineers: 2016.
53
54
55
56
57
58
59
46
1
2
3 783 52. Song, W.; Kovscek, A. R., Functionalization of micromodels with kaolinite for
4
5
6 784 investigation of low salinity oil-recovery processes. Lab on a Chip 2015, 15, (16), 3314-3325.
7
8
9 785 53. Wang, X.; Alvarado, V., Effects of aqueous-phase salinity on water-in-crude oil
10
11 786 emulsion stability. Journal of Dispersion Science and Technology 2012, 33, (2), 165-170.
12
13
14
787 54. Moradi, M.; Alvarado, V.; Huzurbazar, S., Effect of salinity on water-in-crude oil
15
16
17 788 emulsion: evaluation through drop-size distribution proxy. Energy & fuels 2011, 25, (1),
18
19 789 260-268.
20
21
22 790 55. Fredriksen, S.; Rognmo, A.; Sandengen, K.; Fernø, M., Wettability effects on osmosis as
23
24
25 791 an oil-mobilization mechanism during low-salinity waterflooding. Petrophysics 2017, 58,
26
27 792 (01), 28-35.
28
29
30 793 56. Bartels, W.-B.; Mahani, H.; Berg, S.; Menezes, R.; van der Hoeven, J. A.; Fadili, A., Oil
31
32
33
794 configuration under high-salinity and low-salinity conditions at pore scale: a parametric
34
35 795 investigation by use of a single-channel micromodel. Spe Journal 2017, 22, (05), 1,362-1,373.
36
37
38 796 57. Duboué, J.; Bourrel, M.; Dusautoir, T.; Santanach, E.; Klimenko, A.; Agenet, N.; Boupat-
39
40 797 Passade, N.; Lequeux, F. In Relevance of Water/oil Interfacial Structure to Low Salinity Oil
41
42
43 798 Recovery Process, IOR 2019–20th European Symposium on Improved Oil Recovery, 2019;
44
45 799 European Association of Geoscientists & Engineers: 2019; pp 1-17.
46
47
48 800 58. Du, Y.; Xu, K.; Mejia, L.; Zhu, P.; Balhoff, M. T., Microfluidic Investigation of Low-Salinity
49
50
51 801 Effects During Oil Recovery: A No-Clay and Time-Dependent Mechanism. SPE Journal 2019.
52
53
54
55
56
57
58
59
47
1
2
3 802 59. Mohammadi, M.; Mahani, H., Direct insights into the pore-scale mechanism of low-
4
5
6 803 salinity waterflooding in carbonates using a novel calcite microfluidic chip. Fuel 2020, 260,
7
8 804 116374.
9
10
11 805 60. Sohrabi, M.; Mahzari, P.; Farzaneh, S.; Mills, J.; Tsolis, P.; Ireland, S., Novel Insights into
12
13
14 806 Mechanisms of Oil Recovery by Low Salinity Water Injection, Paper SPE-172778 presented
15
16 807 at the SPE Middle East Oil & Gas Show and Conference, Manama, Bahrain, 8–11 March. DOI:
17
18 808 http://dx. doi. org/10.2118/172778-MS 2015.
19
20
21
809 61. Tetteh, J. T.; Barati, R., Crude-Oil/Brine Interaction as a Recovery Mechanism for Low-
22
23
24 810 Salinity Waterflooding of Carbonate Reservoirs. SPE Reservoir Evaluation & Engineering
25
26 811 2019, 22, (03), 877-896.
27
28
29 812 62. Song, J.; Rezaee, S.; Guo, W.; Hernandez, B.; Puerto, M.; Vargas, F. M.; Hirasaki, G. J.;
30
31
32 813 Biswal, S. L., Evaluating physicochemical properties of crude oil as indicators of low-salinity–
33
34 814 induced wettability alteration in carbonate minerals. Scientific Reports 2020, 10, (1), 1-16.
35
36
37 815 63. Spooner, S.; Rahnama, A.; Warnett, J. M.; Williams, M. A.; Li, Z.; Sridhar, S., Quantifying
38
39
40
816 the Pathway and Predicting Spontaneous Emulsification during Material Exchange in a Two
41
42 817 Phase Liquid System. Scientific reports 2017, 7, (1), 1-16.
43
44
45 818 64. Fathi, H.; Kelly, J. P.; Vasquez, V. R.; Graeve, O. A., Ionic concentration effects on reverse
46
47 819 micelle size and stability: implications for the synthesis of nanoparticles. Langmuir 2012, 28,
48
49
50 820 (25), 9267-9274.
51
52
53
54
55
56
57
58
59
48
1
2
3 821 65. Tagavifar, M.; Xu, K.; Jang, S. H.; Balhoff, M. T.; Pope, G. A., Spontaneous and flow-
4
5
6 822 driven interfacial phase change: dynamics of microemulsion formation at the pore scale.
7
8 823 Langmuir 2017, 33, (45), 13077-13086.
9
10
11 824 66. Alvarado, V.; Moradi Bidhendi, M.; Garcia-Olvera, G.; Morin, B.; Oakey, J. S. In
12
13
14 825 Interfacial visco-elasticity of crude oil-brine: An alternative EOR mechanism in smart
15
16 826 waterflooding, SPE improved oil recovery symposium, 2014; Society of Petroleum
17
18 827 Engineers: 2014.
19
20
21
828 67. Fredriksen, S. B.; Rognmo, A. U.; Fernø, M. A. In Pore-scale mechanisms during low
22
23
24 829 salinity waterflooding: water diffusion and osmosis for oil mobilization, SPE bergen one day
25
26 830 seminar, 2016; Society of Petroleum Engineers: 2016.
27
28
29 831 68. Garcia-Olvera, G.; Alvarado, V., Interfacial rheological insights of sulfate-enriched
30
31
32 832 smart-water at low and high-salinity in carbonates. Fuel 2017, 207, 402-412.
33
34
35 833 69. Subramanian, D.; May, N.; Firoozabadi, A., Functional molecules and the stability of
36
37 834 water-in-crude oil emulsions. Energy & Fuels 2017, 31, (9), 8967-8977.
38
39
40 835 70. Barnaji, M. J.; Pourafshary, P.; Rasaie, M. R., Visual investigation of the effects of clay
41
42
43 836 minerals on enhancement of oil recovery by low salinity water flooding. Fuel 2016, 184, 826-
44
45 837 835.
46
47
48 838 71. Ning, J.; Wei, B.; Mao, R.; Wang, Y.; Shang, J.; Sun, L., Pore-level observations of an
49
50
51 839 alkali-induced mild o/w emulsion flooding for economic enhanced oil recovery. Energy &
52
53 840 fuels 2018, 32, (10), 10595-10604.
54
55
56
57
58
59
49
1
2
3 841 72. Xu, K.; Liang, T.; Zhu, P.; Qi, P.; Lu, J.; Huh, C.; Balhoff, M., A 2.5-D glass micromodel for
4
5
6 842 investigation of multi-phase flow in porous media. Lab on a Chip 2017, 17, (4), 640-646.
7
8
9 843 73. Xu, K.; Agrawal, D.; Darugar, Q., Hydrophilic Nanoparticle-based enhanced oil
10
11 844 recovery: microfluidic investigations on mechanisms. Energy & fuels 2018, 32, (11), 11243-
12
13
14 845 11252.
15
16
17 846 74. Jamaloei, B. Y.; Babolmorad, R.; Kharrat, R., Visualization and analysis of viscous
18
19 847 fingering in alcohol-assisted surfactant waterflooding of heavy oil in a two-dimensional
20
21
848 sandstone micromodel. Fuel 2016, 184, 169-179.
22
23
24
25 849 75. Farzaneh, S.; Ghazanfari, M.; Kharrat, R.; Vossoughi, S., An experimental and
26
27 850 numerical investigation of solvent injection to heavy oil in fractured five-spot micromodels.
28
29 851 Petroleum science and technology 2010, 28, (15), 1567-1585.
30
31
32
33
852 76. Mehranfar, A.; Ghazanfari, M. H., Investigation of the microscopic displacement
34
35 853 mechanisms and macroscopic behavior of alkaline flooding at different wettability
36
37 854 conditions in shaly glass micromodels. Journal of Petroleum Science and Engineering 2014,
38
39
40
855 122, 595-615.
41
42
43 856 77. Seyyedi, M.; Sohrabi, M., Pore-scale study of fluids flow and fluid-fluid interactions
44
45 857 during near-miscible CO2 EOR and storage in oil reservoirs. ASEG Extended Abstracts 2019,
46
47 858 2019, (1), 1-5.
48
49
50
51 859 78. Song, Z.; Zhu, W.; Wang, X.; Guo, S., 2-D pore-scale experimental investigations of
52
53 860 asphaltene deposition and heavy oil recovery by CO2 flooding. Energy & fuels 2018, 32, (3),
54
55 861 3194-3201.
56
57
58
59
50
1
2
3 862 79. Mahzari, P.; Tsolis, P.; Sohrabi, M.; Enezi, S.; Yousef, A. A.; Eidan, A. A., Carbonated
4
5
6 863 water injection under reservoir conditions; in-situ WAG-type EOR. Fuel 2018, 217, 285-296.
7
8
9 864 80. Seyyedi, M.; Mahzari, P.; Sohrabi, M., A Fundamental Micro Scale Study of the Roles of
10
11 865 Associated Gas Content and Different Classes of Hydrocarbons on the Dominant Oil Recovery
12
13
14 866 Mechanism by CWI. Scientific reports 2019, 9, (1), 1-12.
15
16
17 867 81. Sohrabi, M.; Tehrani, D.; Danesh, A.; Henderson, G. D. In Visualisation of oil recovery
18
19 868 by water alternating gas (WAG) injection using high pressure micromodels-oil-wet & mixed-
20
21
869 wet systems, SPE Annual Technical Conference and Exhibition, 2001; Society of Petroleum
22
23
24 870 Engineers: 2001.
25
26
27 871 82. Amirian, T.; Haghighi, M.; Mostaghimi, P., Pore scale visualization of low salinity water
28
29 872 flooding as an enhanced oil recovery method. Energy & fuels 2017, 31, (12), 13133-13143.
30
31
32
33
873 83. Aziz, R.; Joekar-Niasar, V.; Martínez-Ferrer, P. J.; Godinez-Brizuela, O. E.;
34
35 874 Theodoropoulos, C.; Mahani, H., Novel insights into pore-scale dynamics of wettability
36
37 875 alteration during low salinity waterflooding. Scientific reports 2019, 9, (1), 1-13.
38
39
40 876 84. Shehata, A. M.; Nasr-El-Din, H. A., Laboratory investigations to determine the effect of
41
42
43 877 connate-water composition on low-salinity waterflooding in sandstone reservoirs. SPE
44
45 878 Reservoir Evaluation & Engineering 2017, 20, (01), 59-76.
46
47
48 879 85. Suijkerbuijk, B.; Hofman, J.; Ligthelm, D. J.; Romanuka, J.; Brussee, N.; van der Linde,
49
50
51 880 H.; Marcelis, F. In Fundamental investigations into wettability and low salinity flooding by
52
53 881 parameter isolation, SPE Improved Oil Recovery Symposium, 2012; Society of Petroleum
54
55 882 Engineers: 2012.
56
57
58
59
51
1
2
3 883 86. Sørgård, H. N.; Totland, C.; Nerdal, W.; Seland, J. G., Crude oil adsorbates on calcite and
4
5
6 884 quartz surfaces investigated by NMR spectroscopy. The Journal of Physical Chemistry C
7
8 885 2017, 121, (38), 20892-20899.
9
10
11 886 87. Kobayashi, K.; Liang, Y.; Murata, S.; Matsuoka, T.; Takahashi, S.; Amano, K.-i.; Nishi, N.;
12
13
14 887 Sakka, T., Stability evaluation of cation bridging on muscovite surface for improved
15
16 888 description of ion-specific wettability alteration. The Journal of Physical Chemistry C 2017,
17
18 889 121, (17), 9273-9281.
19
20
21
890 88. Masalmeh, S.; Al-Hammadi, M.; Farzaneh, A.; Sohrabi, M. In Low Salinity Water
22
23
24 891 Flooding in Carbonate: Screening, Laboratory Quantification and Field Implementation, Abu
25
26 892 Dhabi International Petroleum Exhibition & Conference, 2019; Society of Petroleum
27
28
29
893 Engineers: 2019.
30
31
32 894 89. Mahzari, P.; Sohrabi, M.; Facanha, J. M., The Decisive Role of Microdispersion
33
34 895 Formation in Improved Oil Recovery by Low-Salinity-Water Injection in Sandstone
35
36 896 Formations. SPE Journal 2019.
37
38
39
40
897 90. Farzaneh, S. A.; Carnegie, A.; Sohrabi, M.; Mills, J. R.; Facanha, J. M.; Sellers, B. In A case
41
42 898 study of oil recovery improvement by low salinity water injection, Abu Dhabi International
43
44 899 Petroleum Exhibition & Conference, 2017; Society of Petroleum Engineers: 2017.
45
46
47 900 91. Bertheussen, A.; Simon, S.; Sjöblom, J., Equilibrium partitioning of naphthenic acids
48
49
50 901 and bases and their consequences on interfacial properties. Colloids and Surfaces A:
51
52 902 Physicochemical and Engineering Aspects 2017, 529, 45-56.
53
54
55
56
57
58
59
52
1
2
3 903 92. Huang, C.; Cui, M.; Sun, Z.; Liu, F.; Helms, B. A.; Russell, T. P., Self-regulated
4
5
6 904 nanoparticle assembly at liquid/liquid interfaces: A route to adaptive structuring of liquids.
7
8 905 Langmuir 2017, 33, (32), 7994-8001.
9
10
11 906 93. Lee, S. Y.; Webb, K. J.; Collins, I.; Lager, A.; Clarke, S.; O'Sullivan, M.; Routh, A.; Wang, X.
12
13
14 907 In Low salinity oil recovery: increasing understanding of the underlying mechanisms, SPE
15
16 908 improved oil recovery symposium, 2010; Society of Petroleum Engineers: 2010.
17
18
19 909 94. Sharma, M. M.; Filoco, P., Effect of brine salinity and crude-oil properties on oil
20
21
910 recovery and residual saturations. Spe Journal 2000, 5, (03), 293-300.
22
23
24
25 911 95. Skrettingland, K.; Holt, T.; Tweheyo, M. T.; Skjevrak, I., Snorre Low-Salinity-Water
26
27 912 Injection--Coreflooding Experiments and Single-Well Field Pilot. SPE Reservoir Evaluation &
28
29 913 Engineering 2011, 14, (02), 182-192.
30
31
32
33
914 96. Winoto, W.; Loahardjo, N.; Xie, S. X.; Yin, P.; Morrow, N. R. In Secondary and tertiary
34
35 915 recovery of crude oil from outcrop and reservoir rocks by low salinity waterflooding, SPE
36
37 916 Improved Oil Recovery Symposium, 2012; Society of Petroleum Engineers: 2012.
38
39
40 917 97. Awolayo, A.; Sarma, H., Impact of multi-ion interactions on oil mobilization by smart
41
42
43 918 waterflooding in carbonate reservoirs. J. Pet. Environ. Biotechnol 2016, 7, 1-8.
44
45
46 919 98. Rivet, S.; Lake, L. W.; Pope, G. A. In A coreflood investigation of low-salinity enhanced
47
48 920 oil recovery, SPE annual technical conference and exhibition, 2010; Society of Petroleum
49
50
51 921 Engineers: 2010.
52
53
54 922 99. Kalsi, P., Spectroscopy of organic compounds. New Age International: 2007.
55
56
57
58
59
53
1
2
3 923 100. Andersen, S. I.; Chandra, M. S.; Chen, J.; Zeng, B. Y.; Zou, F.; Mapolelo, M.; Abdallah, W.;
4
5
6 924 Buiting, J. J., Detection and impact of carboxylic acids at the crude oil–water interface. Energy
7
8 925 & Fuels 2016, 30, (6), 4475-4485.
9
10
11 926 101. Tsiamis, A.; Taylor, S. E., Adsorption behavior of asphaltenes and resins on kaolinite.
12
13
14 927 Energy & Fuels 2017, 31, (10), 10576-10587.
15
16
17 928 102. McDougall, S. R.; Salino, P.; Sorbie, K. In The effect of interfacial tension upon gas-oil
18
19 929 relative permeability measurements: Interpretation using pore-scale models, SPE Annual
20
21
930 Technical Conference and Exhibition, 1997; Society of Petroleum Engineers: 1997.
22
23
24
25 931 103. Al-Khafaji, A.; Wilson, M.; Neville, A.; Wen, D., Pore-Scale Displacement Efficiency
26
27 932 during Different Salinity Water Flooding in Hydrophilic and Hydrophobic Microstructures.
28
29 933 Energy & Fuels 2019, 33, (5), 3859-3870.
30
31
32
33
934 104. Singh, K.; Menke, H.; Andrew, M.; Lin, Q.; Rau, C.; Blunt, M. J.; Bijeljic, B., Dynamics of
34
35 935 snap-off and pore-filling events during two-phase fluid flow in permeable media. Scientific
36
37 936 reports 2017, 7, (1), 1-13.
38
39
40 937 105. Hu, X.; Yutkin, M. P.; Hassan, S.; Wu, J.; Prausnitz, J. M.; Radke, C. J., Asphaltene
41
42
43 938 adsorption from toluene onto silica through thin water layers. Langmuir 2018, 35, (2), 428-
44
45 939 434.
46
47
48 940 106. Aslan, S.; Firoozabadi, A., Effect of water on deposition, aggregate size, and viscosity
49
50
51 941 of asphaltenes. Langmuir 2014, 30, (13), 3658-3664.
52
53
54 942 107. Langevin, D.; Argillier, J.-F., Interfacial behavior of asphaltenes. Advances in colloid
55
56 943 and interface science 2016, 233, 83-93.
57
58
59
54
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