1. Introduction
Current estimates indicate that carbonate reservoirs contain over half of the crude oil, which remains after primary production and secondary recovery. Improved Oil Recovery (IOR) methods aim to increase the total volume of oil extractable from a reservoir. The most important mechanism of incremental oil recovery is counter-current spontaneous imbibition of brine into the rock, driven by the capillary pressure gradient,
, between the oil-saturated, low-permeability carbonate matrix [
1] (high
) and waterflooded rock fractures or permeable macropore systems (low
).
The dynamics of spontaneous water imbibition into porous media saturated with immiscible fluids follows from the displacement mechanisms in both fluids [
2,
3]. Analyzing imbibition dynamics can shed light on the pore-level processes that govern fluid displacement and help identify the most efficient IOR methods during laboratory screening. In the laboratory, the Amott method is commonly used for studying the spontaneous imbibition of brine into oil-saturated rock samples [
4]. This method uses an oil-saturated core plug inserted into a brine-filled glass jar and connected to a graduated glass burette used to measure the volumetric oil production history. The sufficiently wetting aqueous phase imbibes spontaneously into the porous rock displacing the non-wetting oil phase. Although some concerns exist [
5], the Amott test is believed to approximate closely reservoir conditions during waterflooding, relying on capillarity (but not imposed pressure gradient) and wettability to govern the spontaneous imbibition of brine into core plugs saturated with oil.
The Amott test was designed to evaluate
ultimate oil recovery [
4]. The original protocol does not focus on the
dynamics of oil recovery and introduces several artifacts that hinder the analysis and modeling of oil production dynamics. First, when oil is produced from a core, oil droplets at the water-wet external core surface must be “inflated” into the outer continuous aqueous phase. The droplet-inflation process introduces resistance to water imbibition, because a capillary pressure inflation threshold has to be overcome. Fernø et al. [
6,
7] described this effect and named it a capillary back-pressure. Curvature of oil droplets decreases monotonically during their growth in the surrounding brine, and the capillary back-pressure resistance has a uniformly decreasing effect. Indeed, past the initial resistance, the external drop inflation rate is rapid.
Second, the inflated drops can now only be detached by snap-off at the external surface, assisted by buoyancy. This process involves imbibition of the wetting phase and snap-off of emerging oil near the throat of the pores that expel the drops. The rate of this process is controlled by the local imbibition rate of the aqueous phase around that pre-droplet. This core behavior in an experiment is well captured in
Figure 5a, see the Results and Discussion section below. However, after the drop snaps off from the oil phase inside the rock, it can still linger on the outer rock surface because of contact-line pinning, external surface contamination, and wettability. Moreover, large drops can be fed from and therefore held by many pores.
All of these effects delay drop detachment and lead to experimental artifacts, especially in small cores, such as step-wise recovery histories, and/or delay of production onset. These artifacts have been reported in the literature. However, their occurrence and description is not systematic because of the large number of variables among published experiments. Below we discuss a few examples.
Oil droplets are usually dislodged from the external rock surface by manually shaking the Amott jar before each measurement [
8,
9] or by a Teflon rod [
10,
11]. Although intermittent manual shaking is effective in removing oil droplets, it does not eliminate recovery discontinuity and sometimes even amplifies it. To improve accuracy of data recording in spontaneous imbibition experiments, various modifications have been proposed. For example, earlier studies used rock samples suspended in brine with a thread attached to a balance, which registered rock weight changes [
11,
12]. However, this method still required manual removal of oil droplets using a Teflon rod. Another study investigated quasi-spontaneous imbibition of brine using a centrifuge operating at a slow rotational speed. A high-resolution camera was used to record the volumetrical oil production [
13]. However, centrifuge cups obstruct production from the core sides, significantly slowing the recovery process. Additionally, estimates of oil production based on time-lapse images may cause errors and lead to a reduction of cumulative oil production over time (Figure 13 in [
13]). None of the existing Amott-cell procedures allows for a
systematic, continuous and timely removal of the oil drops attached to the core.
Delay of initial production has been discussed in the literature, but the exact mechanism(s) are still not fully understood. For core plugs saturated with crude oil, some studies link the initial delay or the induction time to the rock wettability state [
14,
15]. Other studies note finite induction times for cylindrical water-wet cores with limited outer surface areas,
e.g. with only one or two open flat faces, and that induction time is uncommon in setups where all core surfaces are open [
6,
7]. To the best of our knowledge, no prior studies discussed delay in production onset in cylindrical cores with large exposed external surface area and finite initial water saturation.
Imbibition experiments are often conducted using core plugs that are fully saturated with oil (initially water-free). However, the dynamics of spontaneous imbibition changes fundamentally when initial water is present in the pore corners compared to situations with 100% initial oil saturation. For example, Akin et al. [
16] showed that in cores entirely filled with mineral oil, a uniform and piston-like sharp front of water is seen throughout spontaneous imbibition. In contrast, experiments with initial water demonstrate a uniform increase in water saturation throughout the core. This uniform saturation is attributed to the swelling of connate water that remains connected throughout the core. After initial water drainage by invading oil, some water always remains within the rock, maintaining capillary connectivity through pore corners and thin, sometimes molecularly thin, water films [
17,
18,
19,
20,
21,
22]. To mimic accurately the waterflooding of reservoir rocks, spontaneous imbibition experiments must always be conducted in the presence of initial (“connate”) water.
An additional complexity in the classic Amott experiment arises from the presence of various flow regimes. Brine typically imbibes into a cylindrical core plug from all directions. Regardless of the sample orientation, for many reasons, axial and radial imbibition rates are quite different in general, making modeling both of them rather difficult. This challenge has been extensively discussed in the literature [
12,
23,
24,
25]. To minimize the axial flow regime, many studies on spontaneous imbibition use core samples with sealed ends. However, these methods often involve permanent sealing, usually with epoxy resin [
26,
27] or polyester [
28,
29], which make these core samples unsuitable for repeated experiments.
We argue that the systematic, precise measurements of oil production dynamics can significantly enhance the understanding of spontaneous imbibition mechanisms. In our study, we modify the classic Amott experiment by incorporating continuous, automated shaking of the Amott cell, accompanied by frequent data recording. This modification minimizes the oil holdup effect and enables quantitative measurement of recovery histories. Additionally, we introduce a non-destructive sealing method that permits core reuse in subsequent experiments. This aspect is essential for conducting reproducibility studies and ensuring reliability of experimental outcomes. Finally, our method allows for conducting the imbibition experiments at elevated temperatures. To our knowledge, such a combination of experimental modifications has neither been documented in academic literature nor implemented commercially.
Pioneering studies by Richards [
30], Richards [
31], Muskat [
32], and Rapoport and Leas [
33] developed classical continuum models for spontaneous imbibition. They characterize this
essentially transient non-equilibrium process using
equilibrium capillary pressure curves and
steady state relative permeabilities. In other words, the classical continuum models assume that water and oil flows are locally distributed along their steady flow paths, and that capillary pressure and relative permeability are universal functions of local water saturation. This assumption results in an ability to estimate relative permeabilities from steady-state flow experiments [
34,
35,
36,
37]. However, spontaneous imbibition is essentially non-equilibrium multiphase flow. The fluid-fluid and fluid-solid interfaces are created and destroyed, continue to change shapes and surface areas, and the equilibrium Young-Laplace relation may no longer describe curvatures of the interfaces between immiscible fluids. Consequently, static capillary-pressure and relative-permeability functions no longer hold.
Barenblatt et al. [
38] introduced and compared a non-equilibrium model for capillary imbibition with the classical continuum mechanics model.
Figure 4 and
Figure 5 of Barenblatt et al. [
38] show that the continuum model does not capture recovery dynamics, which can only be modeled with a non-equilibrium approach. Moreover, the current equilibrium models of imbibition contain a large number of parameters that are rarely independently and precisely determined. Commonly, these parameters are adjusted to fit experimental data [
39,
40,
41]. Given the large number and uncertainty of the involved parameters, the agreement of equilibrium models of spontaneous imbibition with experimental data does not confer physical validity. Based on this analysis, we explore an alternative scaling approach to model the dynamics of spontaneous imbibition without contradicting the non-equilibrium essence of the process.
Silin and Patzek [
42] developed a non-equilibrium scaling formulation for counter-current spontaneous imbibition in large blocks of homogeneous isotropic rock without initial water saturation. As mentioned previously, presence of connate water is the key differentiator between the diametrically different flow regimes. Consequently, the non-equilibrium description proposed by Silin and Patzek [
42] cannot be applied for settings with initial water saturation.
In our study, we employ Generalized Extreme Value (GEV) statistics [
43] to model non-equilibrium spontaneous imbibition, for the first time. GEV statistics describes the distribution of extreme events
i.e. of the left and/or right tails of ordinary distributions. For example, GEV was successfully applied to model gas production from US shales by Patzek et al. [
44] and Saputra et al. [
45], Saputra et al. [
46], Saputra et al. [
47]. In these works, the authors argued that gas production from each well is the maximum of what this well could produce by draining gas from matrix blocks and delivering this gas to the wellbore via a network of connected fractures. In our work here, we assume that the volume of each oil droplet that appears externally and then detaches from the outer rock surface represents a maximum that the core surface can retain against surface forces and gravity. Therefore, GEV distribution must be applicable for modeling the distribution of all oil droplets produced during spontaneous imbibition. Our initial development of the GEV paradigm focuses solely on water-wet cores with connate water.
4. Conclusions
We devise a modified Amott cell that reduces the external-surface oil-holdup effect and produces smooth(er) oil-recovery histories. We demonstrate that the combination of our modifications is unique and necessary to eliminate or mitigate experimental artifacts. In contrast, relying solely on the high-frequency data acquisition rate does not guarantee artifact-free data. For low Bond numbers, our method encourages radial flow by non-destructively blocking flow paths from the top and bottom core faces. Therefore, the developed methodology allows for repeated testing of the same samples and reduces experimental uncertainty. Using water-wet Indiana limestone rock samples intially saturated with brine and mineral oil, we demonstrated high reproducibility of the oil recovery curves in both parallel and sequential experimental runs.
Next, we investigated the effect of oil viscosity and rock permeability on the recovery dynamics. For the first time, our findings reliably and repeatedly demonstrate the initial delay in oil production (induction time) in all samples with finite initial water saturation. In our experiments with water-wet Indiana limestone, the delay is influenced by both oil viscosity and rock permeability. As previously reported, the induction time was mainly controlled by rock wettability [
15]. Therefore, our results now reveal other factors, specifically oil viscosity and rock permeability, that contribute to the induction time constituting new insights into previously overlooked physical phenomenon.
For the first time, experimental oil-recovery histories were modeled using the Generalized Extreme Value (GEV) statistics. Our GEV model uses four fit parameters to capture oil-recovery dynamics. Analysis of the GEV-fitting parameters reveals systematic correlations with the physical properties of the oil-rock systems. Specifically, the characteristic capillary-pressure diffusion times, , are shorter for the low-viscosity oil and high-permeability core tests, representing faster oil-production rates. The location parameter, , is larger in experiments with high-viscosity oil, signaling a more pronounced initial production delay. The scale parameter, , is least in tests with higher core permeability, suggesting that in spontaneous imbibition core permeability dominates oil viscosity. Larger shape parameter, , controls decline rate of oil production towards the end of the imbibition process. An extension of this work to the field scale will be introduced in the subsequent paper on the mixed-wet rock-crude oil-reservoir limestone core systems.
Author Contributions
Conceptualization, T.W.P. and C.J.R.; methodology, T.W.P., K.M.K., M.P.Y. and M.M.; software, T.W.P.; validation, T.W.P. and K.M.K.; formal analysis, T.W.P., K.M.K. and M.P.Y.; investigation, T.W.P., C.J.R., K.M.K. and M.P.Y.; resources, T.W.P., K.M.K. and M.P.Y.; data curation, T.W.P. and K.M.K.; writing—original draft preparation, T.W.P., K.M.K., and M.P.Y.; writing—review and editing, T.W.P., C.J.R., K.M.K., M.P.Y., A.G., S.A. and A.Y.; visualization, T.W.P. and K.M.K.; supervision, T.W.P.; project administration, T.W.P., A.G., S.A. and A.Y.; funding acquisition, T.W.P., A.G., S.A. and A.Y. All authors have read and agreed to the published version of the manuscript.