Professional Documents
Culture Documents
J6 - Pore Size Distribution From Challenge Coreflood Testing by Colloidal Flow
J6 - Pore Size Distribution From Challenge Coreflood Testing by Colloidal Flow
Downloaded from Academia.edu
chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77
a b s t r a c t
The transport of colloidal and suspension particles and the resultant particle retention occur in a wide range of
porous media. The micro scale pore throat size distribution is an important characteristic of porous media, allowing
for evaluation of important transport properties. An effective method based on micro scale modelling for the deter-
mination of overall pore throat size distribution (PSD) by injection of colloidal particle suspensions into engineered
porous media with monitored inlet and breakthrough particle concentrations is developed. The treatment of inlet
and outlet colloidal particle concentrations obtained in coreflooding results in a good agreement between the mod-
elling and experimental data. Yet, some deviation was observed between the obtained PSD and that calculated by
the Monte Carlo simulation based on the Descartes’ theorem.
© 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Pore size distribution; Porous media; Suspension; Colloid; Size exclusion; Monte Carlo; Challenge testing
1. Introduction porous materials; the last but not the least is environmental
unfriendliness of mercury for the case of mercury porosimetry.
The pore size distribution (PSD) is an important character- The challenge testing method, which was recently signifi-
istic of the porous media allowing prediction of transport cantly improved, utilises the injection of particle suspension
and volumetric properties (Amix et al., 1964; Dullien, 1992; into porous media (Purchas and Sutherland, 2002; Rideal,
Bedrikovetsky, 1993; Selyakov and Kadet, 1996). Different 2007, 2009). Since particle cannot pass the pore throat with
methods for determination of PSD have been applied exten- the size smaller than the particle size, the maximum size
sively in many industrial sectors: chemical and environmental of passed-through particle determines the maximum pore
engineering, petroleum, natural gas, food, medical and phar- throat size. Besides the maximum pore throat size, the inlet
maceutical, etc. and breakthrough concentrations for different size particles
Presently, there are two commonly used methods in the allow determining the overall PSD curve, but only for thin
industry for the determination of PSD: porosimetry and chal- filters or membranes (Aimar et al., 1990; Frising et al., 2003;
lenge testing. The method of porosimetry suggests injection Rideal, 2009). The method is based on calculation of the parti-
of non-wetting phase in the core under increasing pressure. cle capture probability in a single sieve and cannot be applied
During the displacement, the injected phase fills the pores in for deep bed filtration. Yet, usually the reservoir rock sam-
decreasing order of their radii and the curve “injection pres- ple sizes vary as 0.5–10 cm; a thin slice can be submitted to
sure versus phase saturation” allows calculating PSD (Amix flow only for highly consolidated cores. To the best of our
et al., 1964; Brakel et al., 1981; Dullien, 1992; Yortsos, 1999). knowledge, there is no available in the literature method to
Different options of the method use mercury, gas and other determine the overall PSD of core plugs from particle size dis-
non-wetting displacing fluids. Disadvantages of the method tribution in the injected and produced suspensions.
include: it underestimates concentration of thin pores because Determination of PSD from challenge testing data, i.e. using
high pressures must be applied in order to force the non- inlet and breakthrough concentrations of different size par-
wetting fluid into thin pores; it can be destructive under ticles, is an inverse problem for suspension flow in porous
high pressure hence not applicable for deformable and fragile media. Since pore and particle sizes affect the passage of
∗
Corresponding author. Tel.: +61 8 83033082.
E-mail address: pavel@asp.adelaide.edu.au (P. Bedrikovetsky).
Received 2 February 2011; Received in revised form 7 August 2011; Accepted 18 August 2011
0263-8762/$ – see front matter © 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2011.08.018
64 chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77
particle through porous media, the pore size is an ade- 2. Description of the problem
quate length scale for modelling in order to determine PSD
(Payatakes et al., 1973, 1974). Presently used mathematical Let us consider the challenge testing, which includes sus-
models for transport of particulated suspensions in porous pension flow in porous specimen measuring inlet and outlet
materials on micro scale include random walk equations concentrations of each size particles (Fig. 1). Fig. 2 illustrates
(Cortis et al., 2006; Shapiro, 2007; Yuan and Shapiro, 2010), the definition of the pore throat size as a radius of the min-
population balance models (Sharma and Yortsos, 1987a,b,c; imum sphere inscribed between three neighbouring grains.
Santos and Bedrikovetsky, 2006; Bedrikovetsky, 2008), equa-
tions for resident time distributions (Fan et al., 2008; Lin et al.,
2009), different versions of Boltzmann model (Shapiro and
Wesselingh, 2008; Tang et al., 2010) and direct micro scale
modelling (Biggs et al., 2003; Rong et al., 2010). These models
are widely used in chemical, environmental and petroleum
engineering (Bergendahl and Grasso, 2000; Mays and Hunt,
2005; Gitis et al., 2010).
In the present work, the PSD is determined from the chal-
lenge testing for “long” engineered porous columns where the
deep bed filtration occurs. In order to avoid cumbersome and
expensive characterisation of particle–rock interaction, it was
proposed to use the liquid and particle materials that promote
net repulsion between particles and rock, so size exclusion Fig. 2 – Formation of the pore throat by three tangent grains.
chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77 65
Particle passes the pore if the particle size does not exceed
the pore size:
rs < rp . (1)
having radii between rs and rs + drs . The total concentration of For triangular pores, the conductance is calculated from
retained particles (x, t) is obtained as exact solution of the one dimensional viscous steady state
flow of Newtonian fluid (see Landau and Lifshitz, 1987): k1 =
∞ √
9 3rp4 /20.
(x, t) = ˙(rs , x, t)drs . (5)
0 Likewise, the inaccessible flow fraction through thin pores
(Fig. 4), fns , is defined by
The retained particle concentration can also be distributed
according to rp since both rp and rs take effect in particle cap- rs
Uns k1 (rp )H(rp , x, t)drp
ture. Therefore, we introduce ˙ - (rp , rs , x, t) as the distribution fns = = o∞ . (11)
U k1 (rp )H(rp , x, t)drp
of retained particle concentration over the pore and particle o
radii:
The flow through inaccessible areas in large pores, fnl , is
∞
(rs , x, t) = (rp , rs , x, t)drp . (6)
- ∞
o
rs
k1 (1 − (rs /rp ))H(rp , x, t)drp
fnl [H, r] = ∞ . (12)
The curvilinear pore throat presented in Fig. 2 may be o
k1 H(rp , x, t)drp
approximated by a circle or a triangle, leading to two defini-
tions of a single pore throat’s cross-sectional area: The accessible conductance formula obtained from k1
replacing rp by rp -rs is described below in Eq. (13) for the two
S1,o (rp ) = rp2
considered pore throat approximations:
S1,i (rp ) = √ . (7)
S1, (rp ) = 3 3rp2
⎨ k1a,o (rp ) = 8 rp4 (1 − j)2 (1 + 2j − j2 )
⎧
Here index i = o corresponds to a circles for cylindrical capillary √
k1a,i (rp ) = .
⎩ k1a, (rp ) = 9 3 r4 (1 − j)2 1 + 2j − 1 j2 − 4 j3
⎪
The radius of inscribed circle in the accessible area for tri- k1, 3 9
angular pore is equal to rp -rs , which also results in expression
(8) for accessibility factor (Ilina et al., 2008; Panfilov et al., 2008; 3.2. Governing equations for suspension flow in
Bedrikovetsky, 2008). porous media
The particle capture kinetics requires the definition of the
accessible and inaccessible flow fractions fa and fn , respec- In this section, the governing equations of suspension
tively. For the PTM, the accessible flow fraction is defined by transport in porous media with brief derivations follow
∞ Bedrikovetsky (2008).
Ua rs
k1 (rp )(j)H(rp , x, t)drp The main assumptions of the model for transport of the
fa = = . (9)
colloidal material in porous media include: no particle coagu-
∞
U k1 (rp )H(rp , x, t)drp
o
lation or attrition, negligible external filter cake, particle–rock
where = (j) is the flux reduction factor, which is the ratio repulsion leading to size exclusion mechanism of the particle
between fluxes via the accessible and the overall pore cross capture, no diffusion, one pore is blocked by just one particle
section and k1 = rp4 /8 is the pore conductance determined (no bridging), homogeneous porous media (Herzig et al., 1970;
from the Poiseuille’s flow in a circular tube Sharma and Yortsos, 1987a,b,c; Grenier et al., 2008; Rebai et al.,
2010; Daniel et al., 2011). Low retention process is considered,
r4 dp k1 dp i.e. the amount of retained particles is negligibly smaller that
q1 = − =− (10)
8 dx dx the number of vacant pores available for the particle capture.
The accessible porosity is the total of accessible pore cross Substituting the expression for retention rate (19) into mass
sectional areas per unit of the porous media cross section balance equation (16) yields
∞ ∂ ∂
{a [H, rs ]C(rs , x, t)} + U {C(rs , x, t)fa [H, rs ]}
a [H, rs ] = s1,i (rp )(j)H(rp , x, t)drp . (15) ∂t ∂x
rs
1
= − fns [H, rs ]C(rs , x, t)fa [H, rs ]U, (21)
l
where s1,i (rp ) is the cross-sectional area of a single pore throat
having radius rp and (j) is the area accessibility fraction. Here
round brackets are used for functions of scalar variables and System of two Eqs. (20) and (21) for two unknowns describes
square brackets are used for the functionals of functions. size exclusion deep bed filtration. The initial conditions for the
The population balance equation for colloidal particles in clean bed process include zero suspension concentration and
porous media for the above assumptions accounts for sus- initial uniform PSD for pores:
pended particles flowing via accessible area and retained
particles distributed throughout the overall porous space: t = 0 : C(rs , x, 0) = 0, H(rp , x, 0) = H0 (rp ). (22)
1
q1 (rp )H(rp , x, t)C(rs , x, t)fa [H, rs ]t. (17) Since the injected carrier water flux exceeds the post-
l
inlet water flux carrying particles, the post-inlet concentration
It is assumed that particles are not captured in inaccessible exceeds the injected particle concentration. Eq. (23) deter-
areas of larger pores (1) under the particle–grain repulsion. The mines the post-inlet concentration and provides the boundary
suspended particles are captured by smaller pores only. condition for population balance equation (21).
The rate of retained rs particles being removed by smaller rp
pores, rp < rs , is equal to the overall particle flux from chambers 3.3. The analytical solution
into these pores
In this section we show that the assumption of low retention
∂
(rp , rs , x, t) filtration results in linearization of the governing system (16),
1
- = q1 (rp )H(rp , x, t)C(rs , x, t)fa [H, rs ]. (18) (19) and (20) causing separate independent filtration of particle
∂ l
populations with different sizes. This feature finally enables
Integration of (2) in rp for all smaller pores yields the expres- determining the pore size distribution from the effluent and
sion for the retention rate of rs particles inlet particle size distributions (Section 6.2). The linearized
flow can be described by explicit analytical formulae.
Let us consider steady state of suspended particles along
∂ (rs , x, t) 1
- = UC(rs , x, t)fa [H, rs ]fns [H, rs ]. (19) the core, where the difference between the number of parti-
∂t l
cles entering and exiting the reference volume is captured by
From the assumption that one retained particle plugs one the porous media. Eq. (21) becomes an ordinary differential
pore, it follows that the rp pore plugging rate due to particle equation:
capture is equal to the overall flux of larger particles flowing
d 1
into rp pores from chambers U {C(rs , x)fa [H, rs ]} = − fns [H, rs ]C(rs , x)fa [H, rs ]U, (24)
dx l
∞
∂H(rp , x, t) ∂ Let us discuss the initial stage of size exclusion deep bed
=− (rs , x, t)drs
∂t 0
∂t filtration, where retained concentration is negligible if com-
∞ pared with the vacant pore concentration. It happens either
1
=− UC(rs , x, t)fa [H, rs ]fns [H, rs ]drs , (20) at small injection times, or at injection of diluted suspensions
l 0 or at small filtration coefficient (small particle size). Since it
68 chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77
is assumed that one pore is plugged by one particle and vice The steady state distribution of suspended particles in the
versa, the conditions of particle capture do not change during overall core is established after arrival of the suspension front
low retention filtration, i.e. the pore concentration remains to the core outlet (Herzig et al., 1970). As it follows from (21),
intact. The same conclusion can be drawn from Eq. (20) for the velocity of the front is Ufa /a , so the constant value of the
pore plugging rate – the time variation of the PSD tends to zero effluent concentration (29) is established for t > La /Ufa .
when either injected concentration tends to zero, the correla-
tion length l (inter chamber distance) tends to infinity or the
4. Laboratory procedure for forcing
particle size does not exceed the minimum pore size.
suspensions through porous media
The initial PSD for pores is uniform. So, the assumption of
low retention filtration leads to constant PSD during the injec-
In this section, the conditions of particle–grain repulsion and
tion, i.e. H(rp , x, t) = H0 (rp ). Therefore, flow fractions become
the consequent absence of particle retention due to attach-
functions of particle size only and will be denoted as fj (rs ),
ment are established by tests in a simplified one-grain-layer
j = a, ns and nl further in the text. In this case, Eq. (24) is solved
engineered porous media. Then the laboratory procedures
independently for each particle size, i.e. the particles of the dif-
developed for the flow of colloidal suspensions through glass-
ferent sizes filter independently from each other and deposit
bead-packed porous media are discussed.
as a bunch of mono disperse suspensions.
Boundary condition (23) becomes
4.1. Preliminary study
C0 (rs )(fa (rs ) + fnl (rs ))
C(rs , 0) = , (25)
fa (rs ) An experimental method is developed where particle reten-
tion in porous media occurs exclusively due to particle strain-
Eq. (24) becomes ing. Operational conditions are experimentally determined for
the purpose of eliminating particle retention via mechanisms
dC(rs , x) 1 other than straining, in particular retention via attachment.
= − fns (rs )C(rs , x), (26)
dx l The objective of this preliminary study is to design and
construct a micro model unit that provides the visual obser-
Solving ordinary differential equation (26) subject to ini-
vation of colloidal suspension flow through porous media.
tial condition (25) yields the value of the pre-outlet particle
This experiment allows the determination of the solution
concentration
chemistry that promotes the particle–surface repulsion forces
C0 (rs )(fa (rs ) + fnl (rs ))
x
between porous structure and suspended colloids and, there-
C(rs , x) = exp −fns (rs ) , (27) fore, minimises the particle attachment.
fa (rs ) l
In the developed experimental method, a colloidal suspen-
The outlet upstream particle flux is equal to the down- sion of spherical, fluorescent carboxyl latex microspheres is
stream particle flux immediately after the core injected through an engineered porous medium. The yellow-
green (rs = 4.9 m) and blue (rs = 2.3 m) fluorescent latex
C(rs , x)fa (rs )U = CL (rs )U, (28) microspheres (Polysciences Inc., Warrington, PA) are selected
as the colloidal particles held in suspension. The surfaces
where CL (rs ) is the particle concentration measured in pro- of these colloids are grafted with carboxyl functionalised
duced suspension sample. Further in the text CL (rs ) is called groups by the manufacturer. This creates a negatively charged
the effluent (breakthrough, outlet) concentration. Since the hydrophilic colloidal surface possessing a net negative charge
water flux carrying particles upstream the outlet is lower than when in an alkaline solution. The net charge of the sur-
the downstream flux, the pre-outlet concentration is higher face prevents coagulation of colloids and reduces electrostatic
than the breakthrough concentration. The pre-outlet particle attraction to the porous media. The colloid concentration is
flux is dissolved in the overall water flux after passing the core held constant at 20 ppm in all the preliminary tests.
outlet. A single layer of sieved and cleaned spherical glass
From (27) and (28) follows that beads (Ballotini Bead, Potters Industries Pty. Ltd., Australia) is
adopted as a 2D porous medium. The main component of the
L porous medium, silica (SiO2 ), has a net negative surface charge
CL (rs ) = C(rs , x)fa (rs ) = C0 (rs )(fa (rs ) + fnl (rs )) exp −fns (rs ) ,
l in alkaline solutions (SiO4 4− ). Silica is also selected because
(29) it represents the fundamental material of sandstone reser-
voirs. According to the manufacturer, the glass beads have
Formula (29) connects the injected concentration with that a reported chemical composition: 72.0% SiO2 , 15.0% Na2 O,
measured after the core outlet. It will be used further in the 7.0% CaO, 4.2% MgO, 0.4% Fe2 O3 and 0.3% Al2 O3 . These glass
text for determining PSD H0 (rs ) from the values of the break- beads are packed homogeneously with a theoretical porosity
through concentration CL (rs ) as obtained in laboratory tests for of 39.6%. Two sizes of beads are chosen for the tests with mean
different injected particle sizes rs . radii 150 m and 300 m, respectively.
The formula show that the larger are the injected particles, In order to examine the attachment and straining of col-
the higher is the fractional flow through small inaccessi- loids moving through a single layer of glass beads, the micro
ble pores fns , the lower is the fractional flow via large pores model housings are designed to support the observation
fa + fnl = 1 − fns and the lower is the exponent term in (29). under an optical microscope. The housings are milled out
Finally, the lower is the effluent concentration CL . The efflu- of polyvinyl chloride (PVC) plastic and are designed in such
ent concentration vanishes when the particle size reaches the a way that two glass slides are held in place to contain the
maximum pore size, where the fractional flow via large pores porous media in a single layer. The deionised ultrapure MilliQ
fa + fnl becomes zero. water (resisitivity of 18.2 M × cm at 25 ◦ C) after degassing in
chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77 69
Fig. 5 – Images of particles strained in porous media: (a) different salinities and (b) different pH levels.
vacuum at pressure ≈ 10−2 Pa is used for the preparation of particles through a 3D pore structure is developed. A plas-
a colloidal suspension. The salinity, acidity and alkalinity of tic column with a packing space of 47 mm in diameter and
the prepared suspensions are adjusted with the addition of L = 50 mm in length to simulate the dimensions of core sam-
NaCl(aq), HCl(aq) and NaOH(aq), respectively. ples is constructed. The column design has incorporated
The effect of colloidal suspension salinity on the parti- homogenised sections to negate the end effects, allowing for
cle retention is investigated under three different NaCl(aq) the particle suspension to be injected as a piston-like front
concentrations (0 mM, 10 mM and 100 mM) at constant acid- into the packing matrix. A 30 m sized stainless steel mesh is
ity/alkalinity. A proportional increase in particle attachment utilised to contain the porous media within the column. The
with salinity is observed throughout these experiments, as application of distribution plates ensures the rigidity of the
shown in Fig. 5(a), where the images of colloid particles are packed glass beads. An exploded diagram of the resulting col-
small bright “points” while the images of glass beads are semi- umn with its components is demonstrated in Fig. 6(a). Fig. 6(b)
transparent large circles. Simultaneously, the particle–grain shows the photo of the column.
interaction force was calculated for three salinity values using Monodisperse suspensions of yellow-green fluorescent
DLVO theory (Landau and Lifshitz, 1980; Khilar and Fogler, polystyrene latex microspheres used in the preliminary study
1998). Three plots of the force versus the particle–surface are taken as colloidal particles in these experiments. Five sizes
separation distance show that the increase in retention is of microspheres are used in these experiments. Table 1 sum-
due to an increased depth of the secondary minimum and marises the specific physical characteristics of the colloids,
a reduced energy barrier to the primary minimum (Tufenkji where rs denotes the mean radius of the colloid particle, is
and Elimelech, 2004, 2005). The same results were obtained by the standard deviation, and s is the particle density.
Kuznar and Elimelech (2007). Glass beads similar to those used in the preliminary exper-
Colloidal particle retention by glass beads is investigated iments are utilised as the porous media in all experimental
using suspensions with five different pH levels (2.79, 4.26, 7, procedures. The glass bead sizes, as reported by supplier, are
8.48 and 10.38) at constant salinity. The monotonic decrease 10–80 m. A thorough sieving process is performed to reduce
in attachment is found to occur with increased alkalinity. The the size range of the glass beads; the size variation after the
colloid retention in the unit is comparatively low in all alka- sieving becomes 10–66 m. A complete washing procedure is
line resident solutions, as shown in Fig. 5(b). The high particle also performed to remove organic impurities using acetone,
retention in acidic conditions is due to the reduction in the hexane and hydrochloric acid.
strength of the electrical charge on the surface of the glass Colloids are held in suspension solution made up with
beads and the colloidal particles. 0.1 M sodium hydroxide and degassed ultrapure MilliQ water
In order to minimise the colloidal particle attachment,
the resident solutions with high pH and pure water must
Table 1 – Size distributions (mean radius <rs > and
be employed so that the physical capture mechanisms standard deviation 0 ) and densities of the colloidal
would dominate. The above conclusions indicate that net particles.
repulsion exists between the porous media and the colloidal
Type <rs >, m 0 , m s , g cm−3
suspensions.
1 1.789 0.339 1.055
2 2.297 0.457 1.055
4.2. Experimental procedure
3 2.976 0.342 1.055
4 4.915 0.796 1.055
Using the outcomes of the preliminary study, an experimen- 5 9.844 0.059 1.055
tal setup and procedure simulating the flow of suspended
70 chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77
(a) (b)
7 8
6 7
6
5
5
f(rp ) 4
f(rp)
4
3
3
2
2
1 1
0 0
0 0.5 1 1.5 0 0.5 1 1.5
rp (µm) rp (µm)
Nolan & Kavanagh (close packed c) Nolan & Kavanagh (close packed d)
Fig. 7 – Validation of the Monte Carlo model for pore size distribution using Descartes’ theorem: (a, b) treatment of data by
Nolan and Kavanagh (1994) (♦); results of modelling ().
the results, is applied. The method is suitable for modelling Section 6 to validate the method for PSD calculation from the
phenomena with significant input uncertainty and studies suspension flow test.
systems with a large number of coupled degrees of freedom.
Applying the Monte Carlo simulation with Latin Hypercube 6. Treatment of experimental results
selection criteria utilising Descartes’ theorem, the PSD curve
can be determined from the grain size distribution. In this Section, it is verified whether the conditions of low
Let us validate the proposed method for prediction of PSD. retention filtration leading to a simple analytical model (29)
Nolan and Kavanagh (1994) determined the PSD from a packed have been fulfilled during the laboratory tests. Afterwards, the
column of spherical particles with a given size distribution laboratory data are treated using the analytical model.
using geometric 3D simulation. The pore throat sizes were
described by the maximum inscribed radius, geometrically 6.1. Validation of the low retention assumption
restricted by the confining spheres in a packed system. Fig. 7
presents the results of Monte Carlo simulation for the case Let us check whether the assumption of the analytical model
when three grains are chosen according to their probability (Section 3.3) that the PSD during particle straining in the
distribution to generate a single pore radius by Descartes’ the- porous media is invariant have been fulfilled in the laboratory
orem presented in Section 2. The process is repeated 100,000 tests. This occurs when the concentration of pore vacancies
times using Latin-hypercube sampling in a Monte Carlo simu- (thin throats) is significantly higher than the concentration of
lator to generate a PSD, and the predicted curves are smooth. retained particles, i.e. the particle retention and the conse-
On the contrary, the curves obtained by Nolan and Kavanagh quent consumption of vacant throats do not affect the total
and shown in Fig. 7 (a) and (b) exhibit oscillations due to small number of vacancies:
number of Monte Carlo runs. Despite some deviation between
the prediction results by the Descartes’ method and those
(x, t) ≪ h(x, t). (31)
presented by Nolan and Kavanagh (1994), the quality of the
agreement allows for utilisation of the proposed method for
This condition can be satisfied if either the injected con-
the evaluation of PSD from known size distribution of packed
centration is very low, or the injection time in the test is short,
glass beads.
Several other cases (Rouault and Assouline, 1998; Al-
0.8 0.06
Raoush et al., 2003; Reboul et al., 2008) have been investigated
as well and show the same order of magnitude in deviation
0.6
between the Descartes’ prediction and geometric simulation. 0.04
The proposed method aims at an approximate evaluation and
f(r )
f(r )
0.4
cannot substitute high precision geometric simulation.
0.02
After validation of the Descartes’ method, the PSD is
0.2
determined from the grain size distribution for conditions
of laboratory experiments. The size distribution of the glass 0 0
beads adopted as the porous media is determined using a 0 10 20 30 40 50 60 70
Malvern Mastersizer (2000). The measured grain size distribu- r , r (µm)
tion and the calculated PSD by Monte Carlo method are given
Pore Radius from Monte Carlo SimulaƟon Grain Radius
in Fig. 8. The PSD can be approximated by lognormal distri-
bution with the mean of 3.52 m and the standard deviation Fig. 8 – Determination of pore size distribution from grain
of 0.53 m. The obtained PSD curve will be used further in size distribution using Monte Carlo simulation.
72 chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77
or the filtration coefficient is small resulting in low retention exponentially decreases along the core. It allows concluding
concentration even for high suspension concentration. that the blocking is negligible under conditions of the con-
Let us examine whether the inequality Eq. (31) is fulfilled ducted tests (Section 4).
under the conditions of the performed tests. The concen-
tration of vacant (thin) pores is h = pNp /V, where Np is the 6.2. Results of the coreflood tests
number of pores, V is the volume of the column and p is the
fraction of vacant pores. The number of grains for spherical Let us determine PSD for the glass bead packed porous column
grain packing is Ng = (1 − )V/(4rg3 /3). For assumed close and from breakthrough concentrations as obtained from the injec-
dense packing in the column, each pore is formed by four tion of different size suspended particles (Section 4.2) using
grains and each grain is surrounded by eight pores. Hence, the analytical model (29)
Np = 2Ng :
CL (rs ) L
(1 − )V = (1 − fns (rs )) exp −fns (rs ) , (34)
Np = , (32) C0 (rs ) l
(2rg3 /3)
Here the fractional flux via thick pores fa + fnl is substituted by
The suspended concentration is smaller than the injected 1 − fns .
one c(x,t) < c0 , the retained particle concentration is limited Consider n challenge tests using particles with radii rs1 ,
by (x, t) = c(x, t)Ut ≤ c0 Ut. Let us define the dimensionless rs2 , . . ., rsn . The inlet and breakthrough concentrations C0 (rsi )
time tD = tU/L calculated in pore volumes of injected sus- and CL (rsi ) are known from experimental data for each test.
pension. Recalculate the injected concentration c0 measured Assume lognormal distribution for pore sizes as determined
by the number of particles per volume of suspension into vol- by mean pore radius <rp > and standard deviation 0 . It allows
umetric concentration measured in ppm multiplying by the expressing the fractional flow via thin pores fns via <rp > and 0
colloid particle volume (4rs3 × 106 /3). Accounting for (32), the using formula (11). Finally, n tests yield system of n transcen-
condition (31) is transformed to the following form: dental equations (34) for three unknowns – mean pore radius,
standard deviation and dimensionless correlation length l/L.
c0 tD L
r 3
g
× 10−6 ≪ 1, (33) The system is solved by the least square method, i.e. the
2p(1 − ) rs solution minimises the total quadratic deviation between the
experimental data and those predicted by modelling
The product c0 tD in the numerator of (33) supports the
above statement that low retention case corresponds to either n 2
L CL (r )
small injected concentration, or short injection time, or small min (fa (rsi ) + fnl (rsi )) exp −fns (rsi ) − 0 si . (35)
rp
,0 ,l/L l C (rsi )
filtration coefficient. i=1
Substituting the values of parameters, which are typical
for the coreflooding tests described in Section 4 of the present The results of minimisation (35) are shown in Figs. 9–11
work (c0 = 8 ppm, = 0.4, the measured particle size rs = 5.0 m and in Table 2: mean pore size is 3.13 m, distance between
and the grain size rg = 40 m, the fraction of thinner pores chambers l = 0.25 mm. The solid piecewise lines 1,2, . . ., 5 in
p = 0.3, dimensionless filtration coefficient L = 3.0 as calcu- Fig. 9 correspond to breakthrough curves during 5 injections of
lated from experimental data and tD = 7 PVI) yields the value mono sized particles with different sizes presented in Table 1.
of left hand side 0.093, i.e. the condition (33) is fulfilled. Yet, The concentrations are constant over the time intervals where
the breakthrough concentrations in 5 tests stabilize after 4–5 the effluent samples were taken. The stabilised relative break-
PVI. Also, the maximum retention concentration at the inlet through values CL /C0 for type 1 particles almost coincide with
1
model
Table 2 – Summary of pore size distribution results from
0.9 1 exp the model and Monte Carlo simulation.
0.8
MC Modelling Monte Carlo
2 data simulation
0.7
Mean radius (m) 3.13 3.52
0.6 Standard deviation (m) 2.76 0.53
Average relative error 1.94e−4 0.11
c L/c 0
0.5
3
0.4
fns (rs)
fns (rs)
0.2 0.08 shapes. The percolation and effective media models better
represent the topology of the pore network (Bedrikovetsky,
1993; Selyakov and Kadet, 1996; Panfilov et al., 2008). The
0.15 0.06 low retention assumption limits the injection period; the
numerical population balance models can simulate long term
injection processes. The above shows the ways of the improve-
ment of the proposed method.
c L/c 0
0.1 0.04
fns
The key point of the proposed laboratory method is cre-
ation of the environment that provides the grain-particle
repulsion. It excludes various particle capture mechanisms
0.05 0.02 driven by the particle–grain attraction like attachment, bridg-
ing, internal filter cake and avoids cumbersome and expensive
physico-chemical characterisation of grain and particle sur-
0 0 faces, interactions, geometry of retained matter, etc. The only
0 1 2 3 4 5 6
rs particle capture mechanism under the repulsion is size exclu-
sion. The straining mechanism is characterised mainly by pore
Fig. 12 – Maximum pore size that can be determined from and particle size distributions, which suits to the goal of this
challenge coreflood test. research.
Several filtration tests with latex particles in packed glass
counter Pamas (see website). The minimum value 0.01 corre- bead medium with simplified geometry show that low salinity
sponds to Malvern Mastersizer (Mastersizer, 2000). These are and high pH of water promote the grain-particle repulsion.
the values for left hand side of Eq. (34). The modelling curve Therefore, the same glass beads, particle and water have been
CL /C0 (34) allows determining the corresponding particle sizes, used further for column experiments in 3D porous media.
which are 4.39, 4.53 and 4.75 m, respectively. Fig. 12 presents The preliminary repulsion tests have been performed for
the plot of the fractional flow via smaller pores fns (rs ) versus latex colloids and glass beads. More research is required
particle radius and the normalized breakthrough concentra- to determine the injected water composition providing the
tion CL /C0 versus the particle radius. The graph fns versus rs colloid–grain repulsion for the natural reservoir rocks (sand-
in Fig. 12 allows calculating the fractional flow values fns for stones with clays, dolomites, carbonates, etc.), filters and
the above the accuracy values, which are 0.0174, 0.0195 and membranes.
0.0229, respectively. The breakthrough concentration curves for five tests, as
The medium pore size, as determined above by tuning pro- plotted in Fig. 9, stabilise after injecting 5 pore volumes at the
cedure (35) is 3.13 m (Table 2). It corresponds to 50% of pores most. The experiments have been conducted with a minimum
smaller than 3.13 m. Formula (11) and Fig. 12 allows calcu- of 250 mL (7 pore volumes) of injected fluid, i.e. the stabilised
lating that only 0.0048 of the total flux moves via the smaller values have been reached in all tests.
pores. The product in exponent of (34) is −0.96, the normal- The restriction of the colloid concentration measurement
ized breakthrough concentration is 0.383, i.e. the value which is that the minimum volume required for an accurate test is
can be measured with high accuracy. For points 1, 2 and 3, the 50 mL. Therefore, the rig used makes it possible to determine
fractional flow fns is equal 0.0004, 0.0013 and 0.0037; despite only a stepwise breakthrough curve – the concentration values
large value of L/l = 200, the products in exponent of (34) are are constant over the time intervals where a single sample
0.08, 0.26 and 0.74. The corresponding values of normalized was taken. Yet, this does not affect the quality of the results
breakthrough concentrations are 0.93, 0.79 and 0.47, i.e. quite because only the stabilised outlet concentrations are used for
“measurable”. The distribution curve for pore throat sizes is PSD determination, see (34).
located to the left of the distribution curves for fluxes via these The Descartes’ model for pore sizes, used for validation
pores. So, even for large pore radii rp , the corresponding fns is of the proposed method for PSD determination, is based on
small enough for the corresponding particle to be detected the assumption of dense and close packing, where four grains
at the core outlet. It explains why the challenge coreflood test form one pore body. This assumption effectively defines the
allows determining PSD for pores which are significantly larger radius of a pore throat as the maximum inscribed radius of
than the mean value. three mutually tangent grains in the plane formed by the cen-
tres of these spherical grains. If the assumption of densely
7. Discussions packed media is incorrect, more than three grains may con-
struct a pore throat and hence the calculation of PSD using
The proposed method of PSD determining involves matching Descartes’ theorem becomes inaccurate. In the case of close
the analytical model (29) for deep bed filtration with exper- packing not occurring, high permeability streaks may trans-
imental breakthrough concentrations, as obtained from size port the colloidal suspension through the column without
exclusion deep bed filtration tests, and uses PSD as calculated exposure to the matrix pore throats. If the assumption of
from grain sizes to validate the proposed method. spherical grains is inaccurate, the shape of a pore throat
The analytical model uses geometrical description of the becomes more complex and is less likely to be defined by
porous media as a set of parallel capillary intercalated by mix- a curvilinear triangle. In order to ensure that the matrix
ing chambers which is widely used for suspension transport is closely and densely packed, an extensive sieving process
modelling. The main assumption of the model – low reten- is performed to narrow the size distribution. It is reasoned
tion filtration – can be fulfilled in laboratory challenge tests that similar sized particles will reduce the occurrence of
on colloid transport in porous media. Yet, the model (19)–(21) unconstrained matrix particles. Furthermore, the experimen-
presents a simplified description of the pore space geome- tal procedure includes the wet packing of the column, an
try. The network models better represent the pore and throat extended settling period and sonification of the glass beads to
chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77 75
of determining the PSD from transport of different size colloids Bedrikovetsky, P., 2008. Upscaling of stochastic micro model for
through porous media. suspension transport in porous media. Transport Porous Med.
The particle–grain repulsion can be achieved by the correct 75, 335–369.
Bergendahl, J., Grasso, D., 2000. Prediction of colloid detachment
choice of the material and coating of the particles and of water
in model porous media: hydrodynamics. Chem. Eng. Sci. 55,
composition (salinity, pH). 1523–1532.
The geometrical model of a porous space as a set of parallel Biggs, M.J., Humby, S.J., Buts, A., Tüzün, U., 2003. Explicit
capillaries intercalated by mixing chambers, which is widely numerical simulation of suspension flow with deposition in
used for colloidal flows in porous materials, is fully deter- porous media: influence of local flow field variation on
mined by PSD and the inter-chamber distance. Therefore, this deposition processes predicted by trajectory methods. Chem.
model was chosen for determining PSD. Eng. Sci. 58, 1271–1288.
Binder, K., Heermann, D.W., 1988. Monte Carlo Simulation in
The colloidal flow test includes injection of different
Statistical Physics: an Introduction. Springer-Verlag, Berlin.
size particles with measurements of the inlet and sta- Brakel, J.V., Modry, S., Svata, M., 1981. Mercury porosimetry: state
bilised breakthrough concentrations. The analytical model for of the art. Powder Technol. 29, 1–12.
size exclusion deep bed filtration relates the inlet and sta- Cortis, A., Harter, T., Hou, L., Atwill, E.R., Packman, A.I., Green,
bilised breakthrough concentrations with PSD. Finally, PSD P.G., 2006. Transport of Cryptosporidium parvum in porous
is determined from the inlet and stabilised breakthrough media: long-term elution experiments and continuous time
random walk filtration modeling. Water Resour. Res. 42,
concentrations by least square method using the analytical
W12S13.
model.
Daniel, R.C., Billing, J.M., Russell, R.L., Shimskey, R.W., Smith,
The laboratory tests performed in packed glass bead col- H.D., Peterson, R.A., 2011. Integrated pore blockage-cake
umn with 5 types of particles with different sizes show that filtration model for crossflow filtration. Chem. Eng. Res. Des.
the determined PSD curve tunes well 5 experimental points. 89, 1094–1103.
The curve is also in a good agreement with that obtained Descartes, R., 1901. Oeuvres de Descartes par Adam et Tannery,
by the Descartes’ method. The analytical model for triangu- vol. 4, Paris.
Dullien, F.A.L., 1992. Porous Media: Fluid Transport and Pore
lar shape capillary tunes the experimental points and agrees
Structure, 2nd ed. Academic Press, New York.
with the Descartes’ method better than that for circular pore Fan, L., Reti, H., Wang, W., Lu, Z., Yang, Z., 2008. Application of
shape. computational fluid dynamic to model the hydraulic
The proposed method needs more substantial validation. performance of subsurface flow wetlands. J. Environ. Sci. 20,
More experimental points for particle radii between the max- 1415–1422.
imum and minimum pore sizes must be obtained. It is Frising, T., Thomas, D., Contal, P., Bemer, D., Leclerk, D., 2003.
preferable to use high accuracy geometric simulation of the Influence of filter fiber size distribution on filter efficiency
calculations. Chem. Eng. Res. Des. (former Trans IChemE) 81A,
packed column for validation of the results.
1179–1184.
Gitis, V., Rubinstein, I., Livshits, M., Ziskind, G., 2010. Deep-bed
Acknowledgements filtration model with multistage deposition kinetics. Chem.
Eng. J. 163, 78–85.
Grenier, A., Meireles, M., Aimar, P., Carvin, P., 2008. Analysing flux
Many thanks are due to Prof. Y. Yortsos (University of Southern
decline in dead-end filtration. Chem. Eng. Res. Des. 86,
California), Prof. A. Shapiro (Technical University of Denmark)
1281–1293.
and Prof. P. Currie (Delft University of Technology) for long- Herzig, J.P., Leclerc, D.M., Le Goff, P., 1970. Flow of suspensions
term cooperation in suspension flow studies. Prof. A. Shapiro through porous media – application to deep filtration. Ind.
critically revised the text and provided valuable comments. Eng. Chem. 62, 8–35.
Special thanks go to Dr. A. Badalyan for his helpful suggestions Ilina, T., Panfilov, M., Buès, M., Panfilova, I., 2008. A pseudo
and comments. The authors are grateful to A. Zeinijahromi two-phase model for colloid facilitated transport in porous
media. Transport Porous Med. 71, 311–329.
for calculation of DLVO forces. Fruitful discussions with T.
Khilar, K., Fogler, S., 1998. Migration of Fines in Porous Media.
Rodrigues and I. Abbasy (Santos Pty Ltd., Australia) are grate-
Kluwer Academic Publishers, Dordrecht.
fully acknowledged. Kuznar, Z.A., Elimelech, M., 2007. Direct microscopic observation
Financial supports from the Australian Research Council of particle deposition in porous media: role of the secondary
(ARC) Discovery Project 1094299, Linkage Project 100100613 energy minimum. Colloid Surf. A 294, 156–162.
and Santos Pty Ltd are gratefully acknowledged. Landau, L.D., Lifshitz, E.M., 1980. Statistical Physics. Pergamon
Press, Oxford.
Landau, L.D., Lifshitz, E.M., 1987. Fluid Mechanics, 2nd ed.
References Pergamon Press, Oxford.
Lin, H.-K., Pryadko, L.P., Walker, S., Zandi, R., 2009. Attachment
Aimar, P., Meireles, M., Sanchez, V., 1990. A contribution to the and detachment rate distributions in deep-bed filtration.
translation of retention curves into pore size distributions for Phys. Rev. E 79, 046321.
sieving membranes. J. Membr. Sci. 54, 321–338. Mason, G., Morrow, N.R., 1991. Capillary behavior of a perfectly
Al-Raoush, R., Thompson, K., Willson, C.S., 2003. Comparison of wetting liquid in irregular triangular tubes. J. Colloid Interface
network generation techniques for unconsolidated porous Sci. 141, 262–274.
media. Soil Sci. Soc. Am. J. 67, 1687–1700. Mastersizer, 2000. http://www.malvern.com/LabEng/products/
Amix, B., Bass, R., Whiting, A., 1964. Applied Reservoir Mastersizer/MS2000/mastersizer2000.htm (23.02.11).
Engineering. McGraw Hill Book Co, New York. Mays, D., Hunt, J., 2005. Hydrodynamic aspects of particle
Bedrikovetsky, P., 1993. Mathematical Theory of Oil and Gas clogging in porous media. J. Environ. Sci. Technol. 39, 577–584.
Recovery: with Applications to ex-USSR Oil and Gas Fields. Nolan, G.T., Kavanagh, P.E., 1994. The size distribution of
Kluwer Academic, London. interstices in random packings of spheres. Powder Technol.
Bedrikovetsky, P.G., Marchesin, D., Checaira, F., Serra, A.L., 78, 231–238.
Resende, E., 2001. Characterization of deep bed filtration Panfilov, M., Stepanyants, Y., Panfilova, I., 2008. Mechanisms of
system from laboratory pressure drop measurements. J. particle transport acceleration in porous media. Transport
Petrol. Sci. Eng. 64, 167–177. Porous Med. 74, 49–71.
chemical engineering research and design 9 0 ( 2 0 1 2 ) 63–77 77
Patzek, T.W., Silin, D.B., 2001. Shape factor and hydraulic Selyakov, V.I., Kadet, V.V., 1996. Percolation Models for Transport
conductance in noncircular capillaries. I. One-phase creeping in Porous Media with Applications to Reservoir Engineering.
flow. J. Colloid Interface Sci. 236, 295–304. Kluwer Academic Publishers, Dordrecht.
Payatakes, A.C., Tien, C., Turian, R.M., 1973. A new model for Shapiro, A.A., 2007. Elliptic equation for random walks.
granular porous media. I. Model formulation. AIChE J. 19, Application to transport in microporous media. Physica A 375,
58–76. 81–96.
Payatakes, A.S., Rajagopalan, R., Tien, C., 1974. Application of Shapiro, A.A., Wesselingh, J.A., 2008. Gas transport in tight
porous medium models to the study of deep bed filtration. porous media. Gas kinetic approach. Chem. Eng. J. 142,
Can. J. Chem. Eng. 52, 722–731. 14–22.
Pedoe, D., 1967. On a theorem in geometry. Am. Math. Mon. 74, Sharma, M.M., Yortsos, Y.C., 1987a. Transport of particulate
627–640. suspensions in porous media: model formulation. AIChE J. 33,
Purchas, D.B., Sutherland, K., 2002. Handbook of Filter Media, 2nd 1636–1643.
ed. Elsevier Advanced Technology, Oxford. Sharma, M.M., Yortsos, Y.C., 1987b. Network model for deep bed
Rebai, M., Prat, M., Meireles, M., Schmitz, P., Baclet, R., 2010. filtration processes. AIChE J. 33, 1644–1653.
Clogging modeling in pleated filters for gas filtration. Chem. Sharma, M.M., Yortsos, Y.C., 1987c. Fines migration in porous
Eng. Res. Des. 88, 476–486. media. AIChE J. 33, 1654–1662.
Reboul, N., Vincens, E., Cambou, B., 2008. A statistical analysis of Tang, G.H., Ye, P.X., Tao, W.Q., 2010. Pressure-driven and
void size distribution in a simulated narrowly graded packing electroosmotic non-Newtonian flows through microporous
of spheres. Granul. Matter 10, 457–468. media via lattice Boltzmann method. J. Non-Newton. Fluid
Rideal, G., 2007. Physical measurement of pores by glass bead Mech. 165, 1536–1542.
challenge testing. Filtration 7, 132–137. Tufenkji, N., Elimelech, M., 2004. Deviation from the classical
Rideal, G., 2009. The filtration society: the importance of testing colloid filtration theory in the presence of repulsive DLVO
and standards. Filtr. Separat. 46, 28–30. interactions. Langmuir 20, 10818–10828.
Rong, F., Guo, Z., Chai, Z., Shi, B., 2010. A lattice Boltzmann model Tufenkji, N., Elimelech, M., 2005. Breakdown of colloid filtration
for axisymmetric thermal flows through porous media. Int. J. theory: role of the secondary energy minimum and surface
Heat Mass Transfer. 53, 5519–5527. charge heterogeneities. Langmuir 21,
Rouault, Y., Assouline, S., 1998. A probabilistic approach towards 841–852.
modeling the relationships between particle and pore size Yortsos, Y.C., 1999. Probing pore structures by sorption isotherms
distributions: the multicomponent packed sphere case. and mercury porosimetry. In: Wong, P.-z. (Ed.), Methods in the
Powder Technol. 96, 33–41. Physics of Porous Media. Academic Press, New York.
Santos, A., Bedrikovetsky, P., 2006. A stochastic model for Yuan, H., Shapiro, A., 2010. A mathematical model for
particulate suspension flow in porous media. Transport non-monotonic deposition profiles in deep bed filtration
Porous Med. 62, 23–53. systems. Chem. Eng. J. 162, 974–988.