Summary Kerogen is often considered to be fully hydrocarbon–wet in reservoir characterization. However, wettability of kerogen is not well–understood and quantified. Thermal maturation induces changes in the chemical structure of kerogen and alters its oxygen (O) and hydrogen (H) content. This process affects the surface properties of kerogen and can influence its wettability. Assumptions made regarding the wettability of kerogen affect the interpretation of borehole geophysical measurements such as electromagnetic measurements. Therefore, it is important to quantify the wettability of kerogen as a function of its thermal maturity. The objectives of this research are to experimentally quantify the wettability of kerogen at different thermal–maturity levels and to quantify the influence of chemical composition of kerogen on its wettability. To achieve these objectives, kerogen was first isolated from organic–rich mudrock samples from two different formations at different thermal–maturity levels. The extracted kerogen samples were then synthetically matured. Variations in the composition and chemical–bonding state of carbon (C) present in kerogen at different levels of natural and synthetic thermal maturity were determined using X–ray photoelectron spectroscopy (XPS). The sessile drop method was used to measure the contact angle to quantify the wettability of kerogen. We then investigated the effects of thermal maturity and chemical composition/bonding of kerogen on its wettability. Kerogen samples from two organic–rich mudrock formations (Formations A and B) were tested, and it was demonstrated experimentally that the wettability of kerogen varies with thermal maturity. Kerogen from Formation A at low thermal maturity formed a 44° air/water–contact angle and 110° air/oil–contact angle. However, at higher thermal maturities (heat treated at 650°C), the air/water–contact angle increased to 122°, and the oil droplet completely spreads on the kerogen sample. The results suggest that kerogen is oleophilic and hydrophobic at high thermal maturity and hydrophilic at low thermal maturity. The air/water–contact angles in kerogen samples were also recorded after the removal of bitumen generated during synthetic maturation of kerogen using chloroform. The air/water–contact angle was shown to increase from 44 to 90° and from 111 to 125° with an increase in thermal maturity in Formations A and B, respectively, in the absence of bitumen. Thus, kerogen becomes hydrophobic with increasing thermal maturity in both the presence and absence of bitumen. The outcomes of this study can potentially improve the formation evaluation of organic–rich mudrocks, in addition to improving our understanding of fluid–flow mechanisms in unconventional reservoirs.

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Summary The wettability of organic-rich mudrocks has a significant effect on multiphase-fluid flow and hydrocarbon recovery. This important rock property has still not been well-quantified in organic-rich mudrocks. Kerogen constitutes a significant fraction of mudrocks and can considerably affect their wettability. Recent publications suggested that kerogen wettability is affected by the thermal maturity of rocks and can influence the wettability of mudrocks. In this paper, we experimentally quantify the influence of geochemistry and thermal maturity of kerogen on the wettability of organic-rich mudrocks, and the influence of thermal maturity and chemical bonding on the wettability of kerogen. The wettability of organic-rich-mudrock samples at different experimental thermal-maturity levels was measured using the sessile-drop method, and also qualitatively estimated using a Flotation test and spontaneous-imbibition experiments on crushed-organic-rich-mudrock samples. The concentration of minerals in the mudrock samples was quantified using X-ray diffraction (XRD) at different experimental maturity levels. We then isolated kerogen samples from an organic-rich-mudrock formation and experimentally matured them. The variation in the chemical-bonding state of carbon present in kerogen at different levels of natural and experimental thermal maturity was determined using X-ray-photoelectron-spectroscopy (XPS) measurements. Finally, the wettability of pure-kerogen samples at different thermal-maturity levels was quantified using the sessile-drop method and the effect of aromatic carbon content on the wettability of the kerogen samples was determined. The sessile-drop test performed on the organic-rich-mudrock-rock samples showed a 5° increase in contact angle with a 96% decrease in the hydrogen index (HI). The Flotation test showed that the oil-wet fraction of the mudrock samples increases by 81% as the heat-treatment temperature increases from nonheated to 650°C. The water-imbibition measurements in crushed-mudrock samples suggest that the volume of water imbibed was higher by 22 cm3 at lower thermal maturity [i.e., HI of 328 mg hydrocarbon/g organic carbon (mg HC/g OC)] compared with mudrock samples at higher thermal maturity (i.e., HI of 10 mg HC/g OC). Results indicate that the thermal maturity of kerogen could potentially affect the wettability of mudrocks and that the mudrock has higher water wettability at lower thermal maturity of kerogen. The experimental results also demonstrated that the wettability of kerogen changes from waterwet to hydrocarbon-wet with an increase in the aromatic carbon content. The contact angle of the water droplet on the kerogen samples from Formation A increased by 78° when the aromatic carbon concentration increased by 19%. The results contribute to a better understanding of the effects of kerogen wettability and thermal maturity on the wettability of organic-rich mudrocks. The outcomes can also have potential future contributions in understanding flow mechanisms in organic-rich mudrocks as well as in developing reliable rockphysics models for the interpretation of borehole geophysical measurements [e.g., electromagnetic and nuclear-magnetic-resonance (NMR) measurements] in organic-rich mudrocks.

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