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Fuel 203 (2017) 208213

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Fuel
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Full Length Article

Porosity and permeability of Green River oil shale and their changes
during retorting
Alan K. Burnham
Consultant to Total Exploration and Production, United States
Energy Resources Engineering, 367 Panama St., Stanford University, Stanford, CA 94305, United States

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Estimate compaction and porosity 1.E+02


Porosity
during diagenesis as a function of 0.51
organic content. 1.E+01 0.42

 Calculate porosity as a function of oil 0.28


shale grade and kerogen conversion 1.E+00 0.19
Permeability, mD

during in-situ retorting. 0.11


 Estimate permeability from porosity 1.E-01

using simple engineering 5


correlations. 1.E-02 10
15
25
1.E-03 35
45
55
65
1.E-04
0.0 0.2 0.4 0.6 0.8 1.0
Fraction retorted
Permeability calculated from porosity using a modified Kozeny-Carman
relation as a function of oil shale grade and fraction retorted.

a r t i c l e i n f o a b s t r a c t

Article history: Oil shales are organic-rich mudstones that generally have little porosity and permeability until kerogen is
Received 2 March 2017 transformed into oil and gas. A simple mathematical model is reported for how porosity and permeability
Received in revised form 19 April 2017 values for the Green River Formation change during retorting under confinement. Unlike when retorted
Accepted 26 April 2017
unconstrained, during which numerous fractures occur due to the limited tensile strength of retorted oil
shale and the permeability increases from micro or nano-Darcy levels to Darcy levels, fracture permeabil-
ity is minor when constrained by lithostatic loads typical of in-situ retorting, so permeabilities increase
Keywords:
only to the milli-Darcy level. The permeability increase is related to an increase in both porosity and pore
Green River oil shale
Porosity
diameter, and measured permeabilities are consistent with measurements and calculations of those
Permeability properties and inter-relationships developed for naturally matured petroleum source rocks.
Retorting 2017 Published by Elsevier Ltd.
Compaction

1. Introduction wanes every few decades as the price and perceived supply issues
for conventional crude oil rise and fall. More recently, production
Although oil shale retorting has been a source of small amounts of natural petroleum (oil and gas) from mature source rocks and
of shale oil for centuries and is important in certain localities, glo- adjacent or interbedded fine-grained yet more permeable layers
bal interest in oil shale as a potential source of shale oil waxes and has greatly increased the knowledge of porosity and permeability
of organic-rich fine-grained rocks. The combination of historical
and recent information gathered for oil shale processing and for
Address: Energy Resources Engineering, 367 Panama St., Stanford University, production of tight oil and shale gas purposes provides some more
Stanford, CA 94305, United States. general insights that can be useful for both applications, although
E-mail address: aburnham@stanford.edu

http://dx.doi.org/10.1016/j.fuel.2017.04.119
0016-2361/ 2017 Published by Elsevier Ltd.
A.K. Burnham / Fuel 203 (2017) 208213 209

the primary intended application for this work is to develop a new 0.3
algorithm for permeability as a function of grade and extent of BH1 850-950 ft (R8)
kerogen decomposition for modeling fluid flow during in-situ oil BH1 950-1150 ft (MZ)
shale processing. BH1 2136-2250 ft (R0-L0)
As in any field, measurement methodologies improve over time. 0.2
Consequently, historical information must be critically evaluated.
However, measurements from the 1960s and 1970s are still among
the best available for some conditions. The current paper attempts
to combine the best of the old literature with more recent mea- 0.1
surements to draw a more comprehensive picture of how porosity
and permeability evolve over the transformation of kerogen under
lithostatic load typical of in-situ retorting, which can be approxi-

Porosity
mated as constant volume. This information is used to develop 0.0
and validate a new, simple algorithm for how porosity and perme- 0 10 20 30 40 50 60 70
ability evolve during retorting at constant volume. More general 0.3
relationships for volume versus mechanical load during retorting BH1 1890-2135 ft (R1-R2)
are still in the development stage. BH1 1151-1347 ft (L5-R6)
The approach developed here combines three simple aspects to
calculate permeability as a function of grade and extent of retort- 0.2
ing. First, an empirical relationship is developed to account for
how the greater ductility of kerogen affects initial porosity as a
function of kerogen content. Second, a correlation is developed
0.1
between total porosity and the matrix permeability of both raw
and retorted shales as expected by Kozeny-Carman and similar
relationships. Third, it is shown that retorting under lithostatic
load corresponding to a few hundred meters overburden yields 0.0
porosities as a function of kerogen conversion roughly equal to 0 10 20 30 40 50 60 70
those calculated at constant volume. These three relationships
are used to create an algorithm for and a plot of permeability as
Grade, gal/ton
a function of conversion for various oil shale grades, which is Fig. 1. Porosity versus grade for five intervals in the Green River Formation in the
needed to model the dissipation of pore pressure generated within Piceance Basin.
the formation during in-situ oil shale retorting.

cally 515% carbonate and 2040% illite by weight, but the R0


2. Porosity versus grade and L0 zones have noticeably lower porosity. The upper zones
are typically 2040% carbonate and less than 15% illite [6], and
Many years ago, Tisot [1] reported porosities for several sam- the porosity trends are almost inversely related to depth, which
ples of Green River oil shale from the Mahogany Zone. Porosity may be related to nahcolite deposition and dissolution. For the
was determined by comparison of bulk and grain densities for purposes here, the effect of organic matter on porosity is qualita-
cores, although the procedure for measuring grain density was tively the same for all depth and mineralogy variations.
not described in enough detail to be sure all porosity was accessed. The porosity of shale versus depth is often described by Athys
The porosity was about 10% for lean oil shale with 1 wt% Total law, or more rigorously, as a function of effective stress via Terza-
Organic Carbon (TOC) and dropped linearly to zero for organic con- ghis principle [7]. Given that immature kerogen, particularly Type
tent greater than 6 wt% TOC. However, subsequent helium pyc- I, is softer than mineral grains, it is plausible that compaction
nometry measurements at Lawrence Livermore National might be greater for shale with more organic content, although
Laboratory (LLNL) on a variety of samples from the Piceance and variability with mineralogy also occurs. Youngs modulus and com-
Uinta Basins indicated that porosity of 15% still existed for sam- pressive strength calculated from the sonic log (Schlumberger
ples with 7 wt% total organic carbon (TOC) [2]. So Tisots data SonicScanner, chirp sampling 300 Hz to 8 kHz) using correlations
should not be considered definitive. of Horsrud [8] are shown in Fig. 2 for the R0-R2 interval of the
Rock porosity can also be determined from well logs. Smith Garden Gulch Member. Similar values for Youngs modulus were
et al. [3] estimated porosity over 50-ft intervals by comparing grain provided in the logging report using shear and compressive wave
density measurements with neutron log densities. Values from 1 to velocities in classical elastic wave propagation equations. These
9% were obtained, with the higher values attributed to dissolution properties are for a wellbore temperature of 4045 C, based on
of nahcolite nodules. More recently, characterization of a wellbore temperature logs of the measurement interval, which softens the
near the center of the Piceance basin by Schlumberger Combinable organic matter much more than the inorganic crystals.
Magnetic Resonance (CMR) provided a more direct measurement Both modulus and strength decrease as oil shale grade
of the porosity via free water content over a 1500-ft thickness of increases, which is consistent with both the literature [9] and
the Green River Formation [4]. Results for a few selected intervals nanoindentation studies showing that the inorganic crystals are
are shown in Fig. 1. The wt% TOC is approximately half the grade in stiffer and stronger than kerogen [10]. The grade dependence is
gal/ton. The middle portion of the formation (including the leached more pronounced for the carbonate-rich Piceance Creek Member
zone) is not shown, because the porosity has major contributions than for the clay-rich Garden Gulch Member. Typical mineral mod-
due to dissolved nahcolite nodules. uli at zero porosity are 3050 GPa, which indicates the effect of
Using the USGS L-R nomenclature [5], the intervals are sepa- porosity on the sonic log moduli at low grade. The high-grade
rated into two groups, which have zero-organic-matter intercepts modulus limit of 0.8 GPa, for which kerogen is the continuous
of about 16 and 26%, respectively. The porosity is not simply phase, is the same as high-density polyethylene at 40 C [11] and
related to either depth or mineralogy. The R0-R2 zones are typi- less than polystyrene, polycarbonate, polyethylene terephthalate,
210 A.K. Burnham / Fuel 203 (2017) 208213

2.5 with coal being the large-scale example, are obviously load-
bearing, as are organic-rich lamina in lacustrine oil shales. The
0.8+1.3*exp(-gpt/12) depth (or effective stress) and organic content (either kerogen vol-
Young's modulus, GPa

2.0 ume fraction or wt% TOC) effects can be combined into a single
empirical formula
0.076(304.8/DTCO)3.23
1.5
u u0 ead=1k
b
1
where u is porosity, u0 is porosity at zero depth, d is depth, k is
1.0
kerogen volume fraction, and a and b are empirical constants. As
an example, this equation is fitted visually to two intervals for the
0.5 Garden Gulch Member of the Green River Formation. The parame-
ters are not tightly constrained by the data, but good fits shown
in Fig. 3 are obtained for parameters listed in Table 1. Similar results
0.0
could be derived for other intervals in Fig. 1 if desired. Although the
0 10 20 30 40 50
Uniaxial compressive strength, MPa

20 depth does not change during in-situ retorting, this more general
formulation would be useful for basin modeling applications.
6.5+9.5*exp(-gpt/12)
16
3. Permeability of oil shale

12 0.77(304.8/DTCO)2.93 Although there has been a resurgence of interest in the perme-


ability of organic-rich shales due to the recent increase in oil and
gas production from source rocks, permeability measurements of
8
Green River oil shale date back many years [1,1618]. These early
measurements report negligible permeability for raw shale and
4 focused on the porosity and permeability after kerogen conversion,
combustion, and carbonate decomposition. Later, Sandvik and
Mercer [19] quantified permeability for three samples with 15%
0
TOC and found pico to nano Darcy values.
0 10 20 30 40 50
Most studies of retorted and burned shale were conducted
Grade, gal/ton under unconfined conditions, where fracture permeability domi-
nates the permeability increase for oil shale grade >13.5 gal/ton
Fig. 2. Mechanical properties of illitic oil shale from the Garden Gulch Member of
the Green River Formation calculated from sonic log transit times using correlations [1]. Without fractures, permeability of typical retorted shale is less
from Horsrud [8]. DTCO is the compressive wave travel time (ls/ft), and the dotted than 1 mD. Recent X-ray tomographic studies by Kobchenko et al.
line is a correlation with grade in gal/ton (gpt).

0.30
polymethylmethacrylate, and Nylon at room temperature [12]. The R1 Zone
compressive yield strength is also lower than most common room- R1 Zone calc
temperature polymers, with polyethylene being the closest [13]. In 0.25
R0-L0 zone
other words, kerogen is softer than most common synthetic
R0-L0 zone calc
polymers. 0.20
Burnham [14] and White et al. [15] report macroscopic Youngs
Porosity

moduli measurements (static values from stress-strain measure-


ments) for cores from the same well and interval as a function of 0.15
temperature and grade. The core properties are visco-elastic-
plastic, so slightly different values were obtained for the loading 0.10
and unloading portions of the hysteresis curves. In addition, there
is some uncertainty in the grade of the cores. Nevertheless, it is
certain that the Youngs modulus for oil shale grade >42 gal/ton, 0.05
where kerogen is the continuous phase on average, is 12 GPa at
4050 C. Similarly, 1020 gal/ton oil shale had a modulus of about 0.00
5 GPa at that temperature. These values agree well with those 0.0 0.2 0.4 0.6
determined from the sonic log. The nanoindentation work of
Eliyahu et al. [10] yield somewhat higher modulus values for
Kerogen volume fraction
kerogen, but those measurements are affected by uncertainties in Fig. 3. Comparison of measured dependence of porosity on organic content with
Poissons ratio and finite deformation, which are significant for that calculated from Eq. (1).
visco-elastic-plastic materials. Even so, their kerogen values are
substantially smaller than for the mineral components, a result
which is qualitatively consistent with Fig. 2, even though the Table 1
low-grade, mineral-rich modulus in Fig. 2 is greatly affected by Parameters for visual fits of Eq. (1) to two intervals in the Garden Gulch Member of
porosity. the Green River Formation.
Whether kerogen is primarily load bearing or pore filling has Interval Depth, m u0 a b
been debated extensively in the literature, with a likelihood that
R0-L0 651686 0.5 0.0016 0.7
it intermediate between those extremes in a manner than relates R1 614651 0.6 0.0011 0.5
to the geometric dispersion of the organic matter. Organic layers,
A.K. Burnham / Fuel 203 (2017) 208213 211

[20], Saif et al. [21], and Tiwari et al. [22] provided an incremental
Thomas 1966 6.9 MPa
understanding of this fracture formation, and Tiwari et al. estimate
0.6 AMSO cores 16.4 MPa
permeabilities of hundreds of Darcies for rich oil shale. Other stud- swelling?
AMSO cores 0.12 MPa
ies [23,24] examined permeability of rubble columns under load to Retorted LETC
determine whether compaction of rubble chimneys would shut off Raw LETC
permeability as the shale became plastic during kerogen transfor- Retorted (calc) compaction
mation, but those are only indirectly relevant to this work. 0.4
Raw (calc)

Porosity
The early study most relevant to this work is Thomas [17] who
measured the porosity and permeability for cores retorted under Thomas estimates
triaxial confinement from 0.7 to 17 MPa. No apparent cracking 15% compaction
was observed for these confinement pressures. There was an 0.2 for 70 gpt
inverse relationship between confinement pressure and perme-
ability, with a roughly constant permeability of 10 mD parallel to Line from CMR log
the bedding plane for oil shale grades greater than 35 gal/ton and
confinement pressures greater than 5 MPa. 0
Recently, Kibodeaux [25] greatly expanded the published infor- 0 20 40 60 80
mation on porosity and permeability evolution during in-situ con- Grade, gal/ton
fined retorting using cores from inside and outside the retorted
Fig. 5. Porosity for raw and retorted Green River oil shale calculated from the free
region of a field experiment. Those data are shown in Fig. 4 along
volume created by kerogen conversion [1,17] AMSO is American Shale Oil
with data from Thomas, which follow the same trend. The scatter (unpublished data) and LETC is Laramie Energy Technology Center. CMR is
in the data is typical for variability of tight rocks. Three different Combinable Magnetic Resonance from Schlumberger and is presumably a more
calculated curves are also shown, including a modified Kozeny- accurate measure of porosity in a tight rock.
Carman relationship [30u2.5/(1  u)2], the Ergun equation
[110u3/(1  u)], and a cubic power law [200u3]. There is no differ-
ence in the ability of any of these relationships to fit the data well 60
within the measurement variability. All work better than the log-
R0-R3
linear relationship of Li et al. [26]. The dashed line represents their
base case, and they varied the slope and intercept, but their func- 50 Linear (R0-R3)
tional form simply cannot reproduce the correct relationship. Shen
[27] used a similar function but did not disclose parameters.
Given this relationship between permeability and porosity, it is 40
Grade, gal/ton

possible to estimate permeability as a function of kerogen conver-


sion by first calculating the porosity created by kerogen conver-
sion. A comparison of measured and calculated porosities is 30
shown in Fig. 5. This simple volume balance calculation uses the
correlation between organic content and oil shale grade shown in
20
Fig. 6, an assumed kerogen composition of 81% carbon, kerogen
density of 1.05 g/cm3, mineral density of 2.73 g/cm3, and coke
y = 2.178x - 1.30
density of 1.4 g/cm3, which means that 82% of the kerogen volume 10
is converted to porosity. The created porosity is then added to the

0
0 5 10 15 20 25 30
TOC, wt%
Fig. 6. Relationship between total organic carbon and Fischer-Assay oil shale grade
for the Garden Gulch Member of the Green River Formation in the Piceance Basin.

initial porosity (raw shale) as a function of grade, which was


assumed from the CMR log to be

u 0:04 0:12egpt=3 2

where gpt is the oil shale grade in gal/ton and the porosity is in vol-
ume fraction. The resulting permeability versus fraction retorted for
various oil shale grades calculated from the modified Kozeny-
Carman relation, assuming 63% of the immature kerogen porosity
is closed, is given in Fig. 7.
Note in Fig. 7 that the initial permeability ranges from 1
to10 lD depending on the initial porosity determined by oil shale
grade. The measured range of permeability in Fig. 4 varies more,
Fig. 4. Comparison of calculated permeability as a function of porosity with presumably due to variability in porosity at constant grade and
measurements from Thomas [17] and Kibodeaux [25]. The samples of Thomas were the possibility of some fracture permeability. For rich oil shale,
retorted under confinement, and the samples of Kibodeaux were recovered from
core both inside and outside an in-situ retort at an unspecified depth. Orientation of
the permeability of retorted shale increases to about 20 mD, which
the measurements is not well documented and could account for some of the is consistent with the largest permeabilities of Thomas [17] shown
scatter. in Fig. 4. In contrast, the increase in permeability as a function of
212 A.K. Burnham / Fuel 203 (2017) 208213

1.E+02 stant volume condition is approximately correct for retorting


Porosity under modest confinement consistent with overburden thickness
0.51 of 100700 m depth. The initial permeability is inversely related
0.42 to oil shale grade due to a greater degree of compaction and smal-
1.E+01
ler porosity for rich oil shale, but the increase in permeability at
0.28 constant volume is much greater for rich oil shale due to the
greater increase in porosity from kerogen conversion.
1.E+00 0.19
Permeability, mD

Mbia et al. [33] report that porosity measured by NMR (compa-


rable the CMR used here) were higher than from mercury injection
0.11 alone and comparable to the combination of helium porosimetry
1.E-01 and mercury immersion. They also found that measured perme-
abilities correlated with porosity and BET surface areas as expected
from a Kozeny-Carman relationship.
5 The permeabilities calculated here can be compared to those
1.E-02 10 reported by Aguilera [34] for various unconventional reservoir
15 rocks. In general, the relationship there between porosity and per-
25
meability is flatter, presumably because much of the generated
1.E-03 35
45 porosity is compacted during natural maturation. In this case, the
55 pore throats will remain more nearly constant, whereas for retort-
65 ing in the absence of compaction, the pore throats will tend to
1.E-04 enlarge as a function of kerogen conversion. Nevertheless, the rela-
0.0 0.2 0.4 0.6 0.8 1.0 tionship between permeability and pore-throat diameter from
Aguilera is consistent with that measured for retorted oil shale.
Fraction retorted For retorted 22 gal/ton oil shale from the Mahogany zone, mercury
Fig. 7. Permeability calculated from porosity using the modified Kozeny-Carman
porosimetry determined a porosity of 0.34 and a log-mean average
relation shown in Fig. 4. The legend is the oil shale grade in gal/ton. The right-hand pore diameter of about 0.5 lm [35]. The predicted permeability
scale gives the final porosities for some oil shale grades. The calculation assumes from Aguileras curve is 1 mD, which is within a factor of two from
that the pore size increases along with porosity in a way that can be absorbed into that predicted in Fig. 7.
the Kozeny-Carman coefficients.
Similarly, numerous published scanning electron micrographs
of Green River oil shale (e.g., Mehmani et al. [36]) show negligible
kerogen conversion is relatively small for low oil shale grades, intergranular porosity as large as 1 lm outside the leached zone.
because less porosity is generated. Micro-tomography of a Green River oil shale core with an esti-
mated organic content of 15 wt% and a porosity of 2.5% after
drying had no detectable porosity at the lm resolution scale. Sim-
4. Discussion ilarly, N2 and CO2 gas adsorption isotherms on a Green River oil
shale sample with 25 wt% kerogen indicated a porosity of 1.7%
Extensive measurements of porosity as a function of depth and between 1 and 300 nm [37] Given that the pore throats determin-
kerogen content in the Green River Formation using CMR logs (free ing permeability are only a fraction of the average pore diameter,
water content) show that porosity decreases systematically with the relevant diameter for raw shale with significant organic con-
organic content. This is consistent with the concept that kerogen tent is likely <0.1 lm. The curves of Aguilera would then predict
is more ductile than inorganic grains and presumably deforms into a permeability of 1 lD for 2% porosity. The variability about that
neighboring pore space more easily. The well log trends are value in Fig. 4 could well be due to variations in organic content or
qualitatively consistent with sparse, old data from Tisot [1], but microfractures.
log porosities based on free water content indicate more porosity Given this general agreement between reported permeabilities
survives at for high organic content. This effect can be simply for raw and retorted oil shale and correlations of Aquilera, one
incorporated into an Athy-law compaction relationship, although can have confidence in the permeabilities calculated from porosity
the initial porosity and compaction coefficient will depend on generation and the modified Kozeny-Carman relation for condi-
lithology. tions where fracture permeability is negligible.
That fossil organic matter softens with temperature and is
visco-elastic-plastic is well known [28]. More recently, others have
Acknowledgments
measured the softer nature of kerogen in organic-rich shales using
nano-indentation [29,30], although the elastic moduli reported are
Much of this work was conducted while the author was
substantially higher than from macroscopic measurements and are
employed by American Shale Oil, LLC, a joint venture of Genie
internally variable. Increased compaction with increasing organic
Energy and Total S.A. The work was subsequently expanded with
content during diagenesis has also been noted [31], although not
financial support of Total S.A. in cooperation with the Stanford-
the quantitative type relationship reported here. Eventually, of
Total Enhanced Modeling of Source rock (STEMS) project, a
course, hardening of the organic matter occurs as it expels oil
research collaboration between Total S.A. and Stanford University.
and gas [10], and the portion of the generated porosity that is pre-
The author thanks Total S.A. for its support of both ventures.
served causes a positive correlation between porosity and organic
content for mature organic-rich shales [32].
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