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■ INTRODUCTION
In recent years, demand for domestic petroleum feedstock in
production from shales is typically associated with low
molecular weight gases, shale rocks can also contain
North America and the depletion of conventional reservoirs considerable amounts of heavier species and, in general,
worldwide has prompted increased global interest in unconven- complex mixtures that may include water and brine coexist as
tional petroleum reservoirs. Tight oil formations previously vapor, liquid, and surface-adsorbed phases.2,11 Among other
considered to be too impractical and expensive for large-scale things, condensation and size exclusion are known factors that
production are now considered important fuel sources. Some of complicate fluid behavior in shale pore networks, nonetheless,
the most formidable challenges in procuring petroleum from current understanding of the behavior of petroleum mixtures in
these reservoirs stem from their low permeability, and, in shale shale nanonetworks is mostly speculative.12−14
rocks, the affinity of hydrocarbons to the organic medium in Of particular interest for petroleum community are
which it is generated.1 It has been shown that these types of retrograde fluids, which exhibit anomalous phase transitions
nanochannels, which can approach molecular dimensions, and solubility properties under high pressures and temperatures
constitute significant proportions of the material’s porosity; that fall inside the saturation curve of the PV phase
accordingly, such pore networks are the key components of diagram.15−17 Fluid mixtures exhibiting these properties have
hydrocarbon storage and mediation of fluid flow in shale been known for over a century, but recently interest has
formations.2 As demand for hydrocarbon production from shale increased as condensation of larger hydrocarbons in shale gas
formations increases, so does the demand for understanding formations has generated optimism with respect to increasing
phase behavior and dynamics of petroleum compounds in production of heavier hydrocarbons as well as consternation
carbonaceous nanoconfined spaces.3−8 about the proclivity for condensates to seal pores and inhibit
Kerogen in shale oil formations is a compressed amalga-
mation of large organic molecular networks which decompose Received: November 6, 2014
over time rendering free hydrocarbons confined to nanoscale Revised: April 14, 2015
pore systems defined by the remaining organic solid.9,10 While
Scheme 1
gas production.15,16 Retrograde condensation is highly sensitive simulations performed the Andersen thermostat (which
to the concentration of fluid components and oil-wet networks produced comparable results). Statistics were taken from the
with high surface area to volume ratios can drastically alter fluid final 9 ns of the production runs.
compositions; consequently, adsorption and fluid phase Solid walls for the pore with 4 nm square cross sections were
behavior of retrograde mixtures, which depend on the constructed as L-J spheres with radius of 0.5 nm in a face
migration history of the fluid, is complex.17 centered cubic (fcc) lattice 4 particles thick. To mimic a
Given the obscure nature of deep subterranean pore strongly oil-wet surface, interaction parameters were derived
networks, especially at the nanoscale, computational modeling such that the 2 nm thick layer of the coarse grained surface
is a naturally attractive way to examine physics involved in these particles produced a force field comparable to that produced by
types of systems. For nanochannels with significant solid stacks of associated dodecane molecules in the OPLS-UA force
surface area involving fluid particles with high Knudsen field. This resulted in LJ spheres with σ of 0.47 nm having an ε
numbers, accounting for molecular interactions at interfaces is of 3.2 kJ/mol which corresponds well with parameters used in
crucial. Consequently, molecular dynamics (MD) simulations similar coarse grained hydrocarbon models for dodecane.34−36
suitable for examining nanoscale systems are increasingly Solid particles were held in place using harmonic constraints in
practicable as computational resources become more readily all directions.
available. Fluid dynamics and phase phenomena of nano- For simulations of the ethane/heptane fluid inside nano-
confined Lennard-Jones (L-J) fluids, united atom molecular channels, stochastic temperature control was employed through
models, and to a larger extent, water, have been examined by the Langevine dynamics integrator, which is necessary for
MD,18−23,24 and more so by Monte Carlo methods.25 Surface nonequilibrium simulations, particularly when center-of-mass
interactions of confined methane, CO2, and some other motion is an important factor.37−39 While this can result in
hydrocarbons have seen some treatment by MD,26−29 however, nonconservation of momentum, we believe this is not an issue
similarly confined multicomponent petroleum fluids in non- in our study because we do not examine extremely non-
mineral organic media still remain relatively unexplored by equilibrium simulations, but in the case of pressure gradients,
molecular simulation. quasi-static systems. Consequently, weak stochastic temper-
In this study, we examine liquid/vapor and adsorption ature coupling was used in these cases, with the inverse friction
behavior of a simple model system, a mixture of 70/30 wt % constant set at 50 ps to minimize dampening of dynamics while
ethane/heptane, the retrograde phase behavior of which was maintaining the desired temperature. In order to modulate
first thoroughly demonstrated by Kay in 1938.15 First, large pressure, which could vary from one end of a channel to
simulations of the mixture (154 494 ethane molecules and another, pistons composed of 2 nm thick layers of L-J spheres
19 683 heptane molecules) were performed for prograde (310 in an fcc lattice were placed on two ends of the pore/fluid
K) and retrograde (365 K) isotherms in order to gain insight system, moving in the positive and negative z directions. Piston
into the molecular behavior involved in retrograde phase particles were restrained in the x and y directions and assigned
transitions. Subsequently, the same fluid confined to solid, oil- high association energies with each other, forcing fcc layers to
wet nanotubes 60 nm long with a square cross sectional width remain intact and allowing for acceleration in the z direction to
of 4 nm was examined under variable pressures induced by create pressure in the system. Association energies between
accelerating pistons on either side of the simulation cell as piston and fluid particles were set to approximate hard-sphere
illustrated in Scheme 1. Finally the same type of system was
interactions as were energies between pistons and solid pore
used to simulate pressure gradients through shorter (40 nm)
walls. The piston induced pressure system was used for both
tubes in order to examine condensation processes relevant to
equilibrium and quasi-equilibrium simulations involving nano-
extraction from organic shale.
■
channels.
In principle, grand canonical Monte Carlo simulations are
METHODS best suited to examine adsorption behavior of fluids, never-
All MD simulations were performed in parallel using the OPLS- theless, for the purposes of this study, relevant information
UA force field30 as implemented in GROMACS 4.6.3 about the effects of pressure on phase phenomena of the
software.31 Interaction cutoffs were set to be 1.5 nm with the confined fluid could be adequately obtained by MD using a
function switched to begin continuously decaying to zero at 1.2 large enough fluid volume. Because a highly parallelized MD
nm. In preliminary investigations, an integration time step of 3 code is readily available in GROMACS, we were able to
fs, while producing higher bond energies (see Supporting examine a large number of simulations over large ranges of
Information, Figure S1), produced vapor/liquid phase behavior pressures for long time periods using MD. Accordingly, data
nearly identical to what was observed using shorter time steps, presented here are for confined fluids, technically calculated in
and the long time step was used for all simulations. Equilibrium the NVT ensemble, but effectively, under mobile piston
simulations of bulk fluids were performed in the NPT ensemble pressures, in the NPT ensemble.
using the velocity-Verlet integrator, the MTTK barostat,32 and Ensuring that large simulations of adsorption in narrow pores
the Nose−Hoover thermostat under strong coupling con- have converged to true equilibrium states proved tedious
ditions for 45 ns.33 Initial configurations were obtained from especially for systems with significant phase separation. For
B DOI: 10.1021/jp511125e
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article
example, initial rapid expulsion due to starting too far from In Figure 1a, contours for heptane illustrate how a single
equilibrium may be followed by condensation of droplets component fluid should behave; for a pure fluid with strict
outside the pore, prohibiting the proper amount of heptane phase transitions, there are two main regions, a broad region of
from re-entering the pore on any reasonable time scale. We lower densities and a narrower region, well separated, at higher
were generally able to avoid said problem using the stepwise density. The probability profiles are unimodal and approx-
equilibration from high to low pressure and most simulations imately Gaussian in shape, indicating only one phase at each
converged, such that average numbers of adsorbed particles did pressure. The gradual shift in the distribution centers between
not change for the final 25 ns after a total of 250 ns. For the 2.5 and 10 bar is followed by a sudden increase at 12.5 bar.
Accordingly, a clear distinction between vapor and liquid
lower pressures at 310 K, equilibration times of 500 ns were
phases is predicted for pure heptane between 10 and 12.5 bar at
required.
505 K. This is below the experimental value of 16 bar,15 which
■ RESULTS
Simulations of Unconfined Fluids. In order to
is not surprising considering the OPLS-UA force field was not
parametrized for hydrocarbons at high pressures.
In Figure 1b, profiles of ln(ρ) vs density probability for the
quantitatively examine phase separation in NPT simulations binary ethane/heptane system exhibit some marked differences
of bulk fluids, each simulation cell was divided into a number of between the two isotherms. At 310 K, distributions are
smaller cubes, 3375 (153) for the simulations of the ethane/ narrower. The high density tail above 20 bar increases slightly
in both area and density as pressure increases, but the two
heptane mixture and 525 (53) for smaller simulations of pure
phases are never distinct in the density plot under coexistence
heptane. The populations and particle densities in each small
conditions. There is a sharp transition to the liquid state at 30
cube were calculated for 200 frames over 9 ns trajectories at bar, similar to what is seen in the single component system. At
equilibrium for each pressure and corresponding frequency 365 K, the range of pressures in which phases coexist is
histograms were constructed (see Supporting Information broader, consistent with experimental observation for isotherms
Figure S2). Figure 1 shows selections from density histograms closer to the critical temperature. Interestingly, at the higher
for pure heptane (Figure 1a) and for the 70/30 wt % ethane/ temperature, the high density portion of the profiles, while
heptane mixture (Figure1b) at 310 K (upper panel) and 365 K increasing in area, decreases in density as the system is
(lower panel). compressed. Along the 365 K isotherm, at lower pressures, the
two phases cover distinct regions of density which merge with
increasing pressure, eventually coalescing into a single phase at
72.5 bar. Again, phase transition pressures predicted for both
isotherms are underestimated, in both cases by approximately
10 bar.15
Ethane and heptane density profiles are examined separately
for each isotherm in Figure 2. At 310 K (Figure 2a), density
distributions for ethane generally follow the same trends as
those of entire fluid (Figure 1b), the main difference being that
the high density tails do not overlap with the liquid phase. In
the heptane distributions at 310 K, a sudden phase separation is
evidenced by the leftward shift of the low density portion of the
contour above 20 bar accompanied by an increase in the area of
the high density region of the curve. For heptane, the high
density portion does span the liquid density region. These data
indicate that condensation in the saturation envelope is almost
exclusively due to the larger molecule. Importantly, at 310 K, in
both components, regions of highest density increase upon
compression, in both volume and density, until the phase
transition point.
In contrast, at 365 K (Figure 2b), distributions for the ethane
component are bimodal and for pressures above 45 bar, the
high density components coincide with the uniform distribu-
tion seen at the highest pressures. Both low and high density
regions in the ethane component increase in density upon
compression, while for heptane, the density of the most
compact regions decreases, as observed in the entire fluid
(Figure 1b). At 365 K, while the densest regions appear to be
composed primarily of heptane at lower pressures, as pressure
is increased, condensed regions increase in ethane concen-
tration, with a concomitant reduction in heptane density.
The different behavior seen in the density distributions for
Figure 1. Profiles of ln(ρ) vs probability where ρ is particle density in the system at 310 and 365 K can be easily understood from
OPLS united atoms/nm3 at selected pressures for (a) pure heptane at visualizations of the MD trajectories. In Figure 3, snapshots of
505 K and (b) the 70/30 wt % ethane/heptane mixture at 310 K (top the simulations at the two different temperatures over relevant
panel) and at 365 K (bottom panel). pressure ranges are illustrated. At 310 K, as pressure is
C DOI: 10.1021/jp511125e
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article
comparison to those in oil-wet pores. Figure 4 shows density condensation, exclusion of heptane from the pore surface
profiles obtained from simulations of the ethane/heptane results in heptane accumulating outside the narrow pore
(Supporting Information, Figure S5). For subcritical pressures,
association with the surface is diminished for both species, but
still more so for heptane.
For the strongly oil-wet surface, the distribution of heptane is
opposite to what is seen for the nonoil-wet surface. At the oil-
wet surface, there is a higher concentration of heptane at the
surface where the distribution mimics the solid structure. For
the lower temperature, outside of the first adsorption layer,
heptane distribution is fairly uniform and this is generally true
across all pressures. The same is true for ethane and at 310 K,
the fluid exists as a single liquid phase in the narrow, oil-wet
nanotube even at low pressures. At 365 K, however, a different
trend is seen. As the pressure decreases toward the lower region
of the saturation envelope, heptane molecules become
distributed predominantly in the first and second adsorption
Figure 4. Simulated density profiles for heptane and ethane at selected layers. In contrast, for ethane, at pressures above 20 bar,
pressures and temperatures in narrow oil-wet and nonoil-wet molecules are evenly distributed outside the first adsorption
nanotubes with 4 nm cross sectional widths. layer.
Figure 5 illustrates adsorption of each species as a function of
pressure in the first and second adsorption layers of the oil-wet
mixture confined to narrow nonoil-wet pores and oil-wet pores pore (Figure 5a) as well as total accumulation of each species
at the pro-grade and retrograde temperatures. Heptane does inside the pore (Figure 5b). The stoichiometric ratio of ethane
not associate well with the nonoil-wet surface; in fact heptane to heptane atoms (OPLS united-atoms) is approximately 2:1 in
molecules prefer to be separated from the wall by a layer of the bulk fluid and populations inside the nanopore correspond-
ethane at all pressures. Under high pressures, ethane molecules ing to this composition are observed for both temperatures at
pack tightly such that their distribution indicates the molecular high pressures. This is more or less true for the second
structure of the pore surface (a lattice in this case) and to some adsorption layers, but not the case for the first adsorption layer
extent this is even true for the second layer of ethane. In where the ethane/heptane ratio is always lower than the fluid
general, for the nonoil-wet walls, under conditions promoting composition, indicating heptane is absorbed preferentially at
Figure 5. Simulated adsorption isotherms for a fixed amount of the 70/30 wt % ethane/heptane mixture inside an oil-wet nanopore with cross
sectional width of 4 nm and length of 60 nm. Average adsorption was measured for the layer directly adsorbed to the solid lattice, within 0.6 nm,
(L1) as well 0.6 nm further (L2) as indicated by the schematic in the upper left corner of panel a. Simulations were performed between 5 and 30 bar
in increments of 5 bar at 310 K with additional points at 40, 50, and 70 bar. For the 365 K isotherm, simulated pressures ranged between 20 and 150
bar in increments of 10 bar with an additional point at 200 bar. Panel b shows plots of the total number of atoms (OPLS united atoms) in the pore
for each species at each pressure.
E DOI: 10.1021/jp511125e
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article
■
different pressures at the two ends of the simulation cell.
The important trends in heptane accumulation could be
readily seen after 18 ns and these are illustrated in Figure 6. For DISCUSSION AND CONCLUSION
the oil-wet pore, at pressures as low as 10 bar, a notable The parameter set used here (OPLS-UA) underestimates phase
accumulation of heptane occurs at the low pressure end of the transition points at the high pressures examined in this study
tube and this occurs to a significant extent up to 50 bar. and in order to more accurately describe the phase diagram
Similarly to what is seen in the bulk, for pressures in the using molecular simulations, a more robust force field would be
retrograde region, the increased disruption of condensation required. Indeed, all atom models including explicit hydrogen
occurs as pressure increases and for the supercritical pressure atoms and partial charges are known to produce superior
(shown at 110 bar), there appears to be no heptane results. Additionally, for a more detailed description of the
condensation at the pore junction. phase diagram of the bulk fluids, a Monte Carlo method may be
These clogging effects are examined more quantitatively in more appropriate and histogram reweighting might be
Figure 7, where average numbers of heptane and ethane atoms employed in order to access information about other
in 1 nm cross sections of the simulation cell are plotted for a temperatures.
F DOI: 10.1021/jp511125e
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article
Nonetheless, for the highly lipophilic or systems examined in area to induce condensation at lower pressures than what is
this study, in which Columbic influences are minimal, the seen in the bulk is apparent at 310 K, but the same is not
simple van der Waals type force field provides valuable insights. predicted at equilibrium for low pressures at 365 K in this pore.
MD simulations using the Lennard-Jones force field do appear Sealing due to condensation under pressure gradients at 365 K
to capture the phenomenon of retrograde phase behavior for in the narrow oil-wet pore may be alleviated under retrograde
this binary fluid. For compression along the retrograde conditions, but probably not at low pressures. The models
isotherm, the gradual phase transition in the retrograde region presented here offer some valuable insights into retrograde
is seen as increased disruption of condensed heptane droplets hydrocarbon fluids in narrow oil-wet pore spaces. For
by the high pressure ethane phase resulting in loosely applications to more realistic systems, such as shale, the
associated heptane clouds which persist over long periods of model system should be improved to more accurately predict
time between 62.5 and 72.5 bar. The expansion of the heptane phase diagrams and extended to account for more complex
phase under compression at 365 K is in stark contrast to what is fluids as well as diverse pore shapes, sizes and compositions.
observed for compression of the same fluid at 310 K, in which
liquid density for both components increases with pressure
until the system suddenly transforms to a uniform liquid with a
■
*
ASSOCIATED CONTENT
S Supporting Information
sharp phase transition. The way in which the liquid phase
Figues showing effects of time step on bond energies, predicted
collapses in simulations of the retrograde region presented
particle distributions of unconfined fluids in NPT simulations,
difficulties in examining liquid content based on local densities.
predicted densities for the 70/30 wt % ethane/heptane system,
It should be pointed out, however that the type of collapsing
heptane/heptane radial distribution functions, and truncated
behavior observed here might not be observed with any
snapshots of 70/30 wt % ethane/heptane fluid pressurized in
retrograde fluid. For more complex fluids with a broad range of
nanopores with non-oil-wet solid surfaces and a movie showing
molecular weights, the density of the heaviest components need
MD animation. This material is available free of charge via the
not decrease and a reduction in droplet size might be observed
Internet at http://pubs.acs.org.
■
during compression rather than uniform expansion of the entire
droplet.
Inside the narrow nanopore, nonoil-wet surfaces exhibit a AUTHOR INFORMATION
high preference for the lighter molecule. This was observed at Corresponding Author
both temperatures and all pressures and the nature of the effect *(W.R.W.W.) E-mail: wrww@uwyo.edu.
is not immediately clear. If the effect is purely entropic, it might Notes
be observed to some extent for adsorption in the oil-wet pore The authors declare no competing financial interest.
■
as well. However, no preference for ethane at the oil-wet
surface greater than what can be predicted based on
ACKNOWLEDGMENTS
stoichiometric composition under any conditions is observed.
In any case, there may be an enthalpic component to the effect: We gratefully acknowledge financial support of Hess Corpo-
heptane molecules, having the stronger L-J potential field, ration and the School of Energy Resources and the College of
should preferentially associate with ethane rather than the Engineering and Applied Science at the University of Wyoming.
repulsive wall; consequently, ethane which is lighter and We also thank the Advanced Research Computing Center at
abundant surrounds heptane molecules or aggregates resulting the University of Wyoming for extensive computational
in an ethane layer at the solid surface. resources which made this research possible.
In the oil-wet pore, heptane is preferentially adsorbed to the
pore wall under nearly all conditions studied. At 310 K,
accumulation of heptane at the pore wall under low pressures is
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