13

3.0

Mass Transport in Porous Solids

The relative transport of different species through gases and

liquids in a solid matrix is important in many mass transfer
operations e.g. leaching, drying, absorption and catalytic
reaction in
membranes.

solid

catalysts,

separation

of

fluids

by

solid

Recall, diffusion is mass transfer of a substance from one part

of a system to another as a result of random molecular motion or
a concentration gradient.
Solute will flow from the region of
high concentration to a region of low concentration. The molar
flux is directly proportional to the concentration gradient.
CA
(49)
x
The proportionality constant is the diffusion coefficient DAB or
NA

= D AB

diffusivity of A through B. This relation is called Ficks first

law.
Diffusion through a solid matrix can be classified into two
types:
1) Diffusion that is not a function of the solid structure.
2) Diffusion in porous solids where the actual structure and
interstices are important.
The former will be covered next year in CHNG 3001 - Transport
Phenomena III.

Figure 5. A porous solid.

14
3.1

Liquid Diffusion Dependent on Structure of Solid

This is mainly concerned with porous solids that have

interconnected pores or voids. The diffusion is greatly affected
by the shape of the voids. Voids are filled up with the liquid
(water) and the concentration of solid (salt) in water at
boundary 1 is cA1 and at boundary 2 is is zero (Fig 5).
Salt
diffuses to point 2. The salt takes a very tortuous path that is
unknown and greater than z2-z1 by a factor called the
tortuosity. At steady state:

NA

D AB

(c A1 c A 2 )
( z 2 z1 )

(50)

is the open void fraction and DAB is the diffusivity of salt in

water.
Tortuosity, , must be found experimentally. may be
separated into a shape factor that corrects for the longer path
and a separate a length angle factor for the fact that many
pore angles are at an angle with the surface.
The tortuosity, the open void fraction, and the diffusivity may
be combined into an effective diffusivity.

Deffec

3.2

D AB

(51)

Gaseous Diffusion Types in Porous Soilds

With gases different mechanisms of diffusion are possible since

the pores can be quite small and which form of diffusion occurs
depends on the diameter of the pores or capillaries and the mean
free path , which is defined as:

= 3.2 x P (

R T 0.5
)
2 M

(52)

P is pressure in atmosphere, M is the Molecular weight. The mean

free path is the average distance a molecule will travel before
colliding with another molecule (Fig. 6).

15

Figure 6. Diffusion in capillaries: a) Knudsen diffusion, (b)

molecular (Fick's) diffusion, (c) transition diffusion.
(a)

Knudsen Diffusion

This shows a gas molecule diffusing through a capillary of

diameter d.
This is called Knudsen diffusion.
The total
pressure on both sides is constant, but pA1 > pA2 .
In a),
is very large compared to d. Flow occurs by molecular reflection
from the walls so diameter d is important.
The diffusivity is
pressure independent and from gas kinetic theory is given by
DKA = 9.7 x 10-3 (T/MA)

(53)

The flux equation over length L is

N A = DKA

dp A 1
dc
= DKA
dz
dz R T

DKA
RT L

( x A1 x A 2 )

(54)

Diffusion of A is completely independent of B since A collides

with the wall not B.
When the Knudsen Number (Kn = /2r) is
greater than 10 diffusion is primarily Knudsen.
(b)

Molecular Diffusion:

When Kn < 0.01 (i.e. d is very much larger than the mean free
path), then molecular diffusion holds.
Molecular-molecular
collisions predominate.
As Kn gets smaller, molecular-wall
collisions have little effect and Ficks law predictions become
increasingly accurate. Recall the basic mass transfer equation
with diffusive and convective contributions, which for a gas is;

16
N A = D AB

dx A P
dz R T

Defining a flux ratio:

N A = D AB

dx A P
dz R T

xA (N A + N B )

= 1 +

(55)

NB
NA

1
(1 x A )

= D AB

dp A 1
dz R T

1
(1 x A )

(56)

Integrating along a path of length L;

NA

D AB P
RT L

ln

(1 x A 2 )
(1 x A1 )

(nb for equimolar counter diffusion

applies.)

(57)
= 0 and Ficks law

(c) Transition Region Diffusion

When and d are intermediate in size between the two limits for
molecular and Knudsen diffusion, the transition or mixed type
diffusion occurs. Both types of collision are important.
The
loss in momentum due to molecule to wall collisions in length dz
is:

(dp A ) knud ( g A) = N A (

RT
) ( g A) dz
DKB

(58)

where A is capillary cross sectional area.

For molecule to molecule collisions:

(dp A ) molec ( g A) = N A (

RT
) (1 x A ) ( g A) dz
D AB

(59)

Summing for total momentum loss:

(dp A ) ( g A) = N A (

RT
) ( g A) dz +
DKA

NA (

RT
) (1 x A ) ( g A) dz
D AB

(60)

Rearranging:
NA = {

Integrating:

(1 x A )
D AB

1 1 P dx A
} { }
DKA
R T dz

(61)

17

NA

= (

D AB P
) ln
RT L

{1 x A 2
{1 x A1

+
+

D AB
}
DKA
D AB
}
DKA

(62)

This reduces to

Knudsen equation at low pressure

Molecular diffusion equation at high presure

DAB/DKA is proportional to 1/P hence at high pressure NA is
independent of P.
At low pressure the flux NA is directly
proportional to P (Fig. 7).

Figure 7. Effect of total pressure P on the diffusion flux NA in

the transition region
3.3

Dispersion in Porous Solids

When solid packing is present there is an extra diffusion

mechanism that is essentially a random process of sidewise
deflection and mixing due to the presence of the solid
particles. Attention will be concentrated on the transverse
(radial) component of this type of diffusion rather than on the
longitudinal component.
A simple and elegant model of the effect was put forward by

18
Baron (1952) and Ranz (1952).
For simplicity consider a twodimensional bed of spherical particles, each of diameter d, as
illustrated in Fig. 8.

Fig 8. Sideways deflection of fluid due to packing

If attention is fixed on a particular molecule of the fluid
moving upwards through the bed, it will be seen that each time
it moves through a layer of particles it undergoes a lateral
displacement of the order d, and the sign is a matter of
chance. After it has progressed a distance z in the direction of
flow, it will have undergone approximately
n=z/d
deflections.
The total lateral deflection will now be of the order
y = d d...,
(63)
where this is summed up to n terms. The mean value of y is
clearly zero (deflection is as likely to the left as to the
right), but the mean square deflection is
_____
(y)2 = zd
(64)
According to the celebrated Einstein diffusion equation the
mean square displacement in a time t is related to the
diffusion coefficient by
_____
Dt = (y)2/2t
(65)
Since t = z/u, where u is the fluid velocity, we finally obtain
Dt = ud
(66)
as an expression for the transverse diffusion coefficient'
arising from the sidestepping effect caused by the packing.

19
Analysis in three dimensions gives a factor of 11.2 in place of
8. This is in good agreement with a large numbers of
experiments.
At values of a particle Reynolds number (Re =
usd/ : is kinematic viscosity) above 100 the results of
Wilhelm and his collaborators (1950) are in good agreement with a
value of the coefficient in the above equation of about 11.
Accordingly the equation 65 is rearranged and written
ud = 11
(67)
Dt
The L.H.S. of Eqn 67 is a dimensionless group known as the Peclet
number, Pe, which is the ratio of convective transport to
diffusive transport.
In this case it is for transverse
diffusion, hence Pet. The experimental work of Fahien and Smith
(1955) has shown that the value of Pet varies across the radius
of a bed and the value of 11 represents a mean.
The magnitude of the transverse 'diffusion coefficient' arising
from the above mechanism is usually a good deal larger than the
molecular diffusion coefficient.
For air, for example, at a
Reynolds Number of 100, Dt works out at about 0.76 cm2/s, some
four times larger than the molecular diffusion coefficient. At
all higher Reynolds Numbers the effect due to the packing is much
greater. However the transverse diffusion effect caused by the
packing is a factor which can be masked the effects of transverse
temperature gradients owing to heat removal.
So much for the transverse diffusion, the packing also gives rise
to a dispersion or diffusion effect in the longitudinal
direction. Experimental results obtained by a number of workers
are shown in Fig. 9 as a longitudinal Peclet number (Pel =
usd/Dl) plotted against the particle Reynolds number.

20

Figure 9. Longitudinal dispersion in gases in packed beds.

For gases, at low Reynolds numbers (< 1), Pel increases linearly
with Reynolds number, giving:
ud = K.usd = K.Sc-1.ud
(68)
Dl

DAB
where Sc is the Schmidt number (DAB/).
Since the Schmidt number is approximately constant for gases and
the voidage of a randomly packed bed is usually about 0.4, the
longitudinal diffusivity is proportional to the molecular
diffusivity.
This is consistent with the hypothesis that
molecular diffusion predominates at low Reynolds numbers.
Assuming the proportionality constant, which is found to be
approximately 0.7, is a tortuosity factor, , because the
molecules must negotiate a tortuous path around the particles, we
get the relationship:
Dl

= D AB

(69)

At Reynolds numbers greater than about 10 the longitudinal Peclet

Number becomes approximately constant, giving:
Dl dus/
(70)
That Pel has a value of about 2 was predicted by Aris and
Amundson (1957), who modelled the phenomenon with the interstices

21
in the packing acting as a series of mixing chambers.
In the intermediate range of Reynolds numbers, the effects of
molecular diffusivity and of macroscopic mixing are approximately
additive, and the dispersion coefficient is given by an equation
of the form:
Dl

= D AB + 0.5ud

(71)

However, the two mechanisms interact and molecular diffusion can

reduce the effects of convective dispersion. This can be
explained by the fact that with streamline flow in a tube
molecular diffusion will tend to smooth out the concentration
profile arising from the velocity distribution over the crosssection. Similarly radial dispersion can give rise to lower
values of longitudinal dispersion than predicted by equation 71.
As a result the curves of Peclet versus Reynolds number tend to
pass through a maximum as shown in Fig. 10.

Figure 10. Longitudinal and radial mixing coefficients for argon

in air.
The extent to which the longitudinal effect must also be brought

22
into consideration in reactor design depends very much on the
ratio of the reactor length to the size of the particles. If this
ratio is 100 or more, as it usually is, it seems that the effect
of longitudinal diffusion is trivial!
However in shallow beds
the effect can be quite significant.

Figure 11. Longitudinal dispersion in liquids in packed beds.

A comparison of the effects of axial and radial mixing for gaseos
is seen from Fig. 11.
It is seen that molecular diffusion
dominates at low Reynolds numbers, with both the axial and radial
dispersion coefficients Dl and Dt equal to approximately 0.7
times the molecular diffusivity.
At high Reynolds numbers, if
Pet =11 and Pel = 2, the longitudinal diffusion coefficient due
to the packing is actually some 5 times greater than the radial
diffusion coefficient.
Dl/Dt 5
(72)
It should be borne in mind, however, that reactors are usually
much longer than they are wide and the longitudinal concentration
gradients are therefore often much less steep than the radial
ones. Moreover, when it is said that the effect of longitudinal
diffusion is trivial, this means in comparison with the transport
due to the bulk flow.

23
The experimental results for dispersion coefficients in gases
show that they can be satisfactorily represented as Peclet number
expressed as a function of particle Reynolds number, and that
similar correlations are obtained, irrespective of the gases
used. However, it might be expected that the Schmidt number would
be an important variable but it is not possible to test this
hypothesis with gases as the values of Schmidt number are all
approximately the same and equal to about unity.
With liquids, however, the Schmidt number is variable and it is
generally about three orders of magnitude greater than for a gas.
Experimental results for longitudinal dispersion show that over
the range of Reynolds numbers studied (10-2 < Re < 103) the Pel is
fairly constant and is of the order of unity. Comparison of this
result with the corresponding ones for gases (Fig. 10), shows
that
the
effect
of
molecular
diffusion
in
liquids
is
insignificant at Reynolds numbers up to unity. This difference
can be attributed to the very different magnitudes of the Schmidt
numbers.
4.0

Heat Transport in Porous Solids

For heat and mass transfer between a single spherical particle

between and a stagnant fluid, experiments have shown that the
heat
and
mass
transfer
coefficients
reach
limiting
low
theoretical values given by:
Nup = Shp = 2
(73)
where the Nusselt number, Nup = h.d/k and
Sherwood number, Shp = kc.d/DAB are with respect to the fluid.
Kramers (1946) has shown that, for conditions of forced
convection, the heat transfer coefficient can be represented by
the following equation:
Nup = 2.0 + 1.3Pr0.15 + 0.66Pr0.31.Rep0.5
(74)
where Rep is the particle Reynolds number usd/ based on the
superficial velocity us of the fluid, and

24
Pr is the Prandtl number Cp/k /.
This expression has been obtained on the basis of experimental
results obtained with fluids of Prandtl numbers ranging from 0.7
to 380.
5.0 Aquifers and Hydrocarbon Reservoirs
Water, crude oil and natural gas are often trapped under pressure
in underground porous natural reservoirs, confined between
impermeable rock layers.
A typical natural porous medium is sandstone. The terms "sands"
and "sandstones" are used interchangeably although they should be
kept separate.
Sands are unconsolidated and made up of quartz
grains with little or no cement. Sandstones are made up of one
or several types of minerals; quartz is almost always the
dominant mineral and the grains are either partially or
completely cemented.
5.1 Hydrocarbon Reserve Estimation
In its simplest form the recoverable reservoir oil volume is
shown by the following formula.
Recoverable stock-tank oil (bbl) = A.t.F
(75)
where:
A = area of producing formation, acres
t = formation thickness, ft
F = recoverable oil, bbl/acre-ft
When
the
porosity,
permeability,
and
interstitial
water
saturation have been determined along with their relationship to
the oil, a slightly more detailed formula can be utilized.
Recoverable stock-tank oil = A.t.7.758eff(l-Sw)R
(76)
FVF
where:
A = Area of prospective reservoir, acres
t = producting formation thickness, ft
7,758 = bbl/acre-ft
eff = effective porosity, fraction
Sw = interstitial water, fraction

25
FVF

=
formation volume factor - the ratio of oil
removed from reservoir to oil recovered in stock
tank after gas has dissipated.
R = estimated recovery percent expressed as a decimal.
Natural-gas liquids are hydrocarbon liquids which are gaseous or
in solution with crude oil in the reservoir and which are
recoverable as liquids by the process of condensation or
absorption that takes place in field separators. The most common
type is the wet gas, or gas condensate.
Recoverable solution gas = recoverable stock tank oil x Gs Rg (77)
where:
GS = gas volume liberated from each barrel of in-place
oil as it is produced as a barrel of stick-tank
oil.
Rg
= recovery factor in decimal form
Natural-gas reserve estimation is divided into nonassociated gas
and associated gas. Nonassociated gas is that gas that is not in
contact with crude oil in the particular reservoir. Associated
gas is in contact with oil and production of the gas is
significantly affected because of the production.
5.2 Properties Of Reservoir Rocks
The estimation of optimum production rates, well spacing, and
production allocations relies on core analysis data. The basic
information required to make production estimations are:
1. Effective thickness of the formation
2. Thickness of the producing zone
3. Capacity of the reservoir to store fluids
4. Void space within the rock
5. Extent to which the void space is occupied by oil and gas
6. Permeability of the reservoir rock
7. Position of the gas, oil and water contacts
The reservoir properties required for evaluation from core

26
analysis, wireline well-logging and drill-stem testing are:Porosity
Total porosity includes all the pore space in a rock while
effective porosity includes only the pore space which is
interconnected and effective as a void which can be filled or
drained of fluids. Porosity depends to a large extent on the
surface texture, roundness, and uniformity of the grain size. The
lower the grain sphericity, the higher the porosity is, so
spherical grains are not desirable for maximum porosity.
To
emphasize what porosity means potentially, a porosity of 1% is
equivalent to 77.58 bbl of fluid per acre-foot.
As a general
guide, the formation should contain at least 8-10% porosity
before it can be considered commercially interesting.
Grain Orientation
Problems in reservoir engineering develop when cross bedding and
graded bedding are encountered.
Permeability
Permeability is a measure of a rock's ability, under a potential
gradient, to conduct fluids. Like porosity, however, it depends
on rock properties such as grain shapes, grain and cement
texture, angularity, and size distribution.
Saturation
Ideally, a petroleum reservoir is formed in such a way that the
fluids in it are separated simply by the force of gravity. Thus
from the top to the botton of the reservoir there will be gas,
oil and water.
In practice, gravity plays a large part but
nearly always, water is found in the oil zone as a thin film on
rock grains and in more inaccessible capillary pores which cannot
accept invasion of the more viscous oil. Such water is classified
as connate water; it is present before the oil migrates into the
reservoir. The connate water may amount to as much as 50% of the

27
fluids in the reservoir.
Relative Permeability
Relative permeability is the ability of a rock to allow fluid to
pass through it under a potential gradient [P = (p + gh)] when
there are two or more phases such as oil, gas, and water present
in the rock's pore space. How much and which phase fluid will be
produced depends on the permeability of the rock and on the
degree of saturation of each of the fluid phases, shown typically
in Figures 12.

Figure 12. Relative permeabilities of oil and gas in

unconsolidated sand.
5.3 Wells and Recovery
When a well is drilled through the upper impermeable rock
formation
and
penetrates
the
oil
reservoir,
a
pressure
differential is induced between ground level and the trapped oil
that may overcome the potential energy difference and drive the
oil to the surface, where it is recovered, stored, and processed.
Once this process begins, oil migrates in a radial fashion to the
well bore and from there to the surface through the pipe. A

28
simplified equipment arrangement is shown in Fig. 13.

Figure 13.

Oil recovery: (a) natural oil migration, and (b)

enhanced oil recovery

Recall that low Reynolds number flows such as in porous media are
described by the creeping motion equations.
The pressure field
for an incompressible fluid of density flowing in a porous
medium is described by Equation 3, the Laplace equation and fluid
flow rate through the porous medium is governed Equation 6,
D'Arcy law. When Equations 3 & 6 are cast in terms of a stream
function, , there are a number of closed form solutions with
constant pressure boundary conditions for velocity, pressure and
volumetric flow rate and these are given in Table 2.
This is
very useful.
For instance, the first set of equations can be
used to estimate the flow through a sand filter.
Here, the
second set of equations can be used to predict the radial
migration of a single phase (i.e. water or oil) within a
reservoir towards a well.

29
Increasing amounts of oil can be recovered in several stages,
including the following:
1. Primary recovery, in which as much oil is pumped out as
possible.
2. Secondary recovery, typically by pumping water down selected
wells and displacing more of the oil, which is then produced
at other selected wells (Fig. 13). The "five-spot" pattern
shown in Fig. 14 is frequently used. The duration of a
single waterflood is many years, and it is usually important
to
simulate
the
results
as
accurately
as
possible
beforehand, in order to maximize the production of oil. For
example, if water is pumped down the wells too rapidly, it
can "finger" towards the intended production wells, causing
water to be "produced" instead of oil.
3. Tertiary recovery, in which surfactants are often used in
order to reduce the capillary pressure between the oil and
water, and to make it easier for the residual oil to be
recovered.

Figure 14. Five-spot arrangement of wells for waterflooding.

30
The single phase solutions above are applicable to primary
recovery. The following discussion centers largely on enhanced
oil recovery, in which water and oil flow as two immiscible
phases. Similar equations also govern the underground storage of
natural gas (Fig. 15), typically by the displacement of naturally
occurring water. Perhaps the same concept can be used for carbon
capture and sequestration (CCS).

Figure 15. Gas-storage reservoir.

To recover additional amounts of oil, steam may be injected into
neighboring wells surrounding the oil well, which, in advancing,
converges and displaces the trapped oil toward the oil well,
injection of steam raises the diminished driving pressure p and
also the viscosity significantly, both of which mobilize the
trapped oil for further recovery.
Due to the contact of two immiscible liquids in a capillary under
conditions of enhanced recovery, an interface is formed, across
which a capillary pressure differential pc of approximately
pc = 4/dc
(78)
is induced, where is the oil-water interfacial tension and dc
is the diameter of the pore capillary.
Enhanced recovery
proceeds as long as the driving pressure differential predicted
by Eqn. 78 is bigger than that given by the second set of
equations in Table 2. This is true when

31
dc.dp = .Q.dc = .u.dc > 4
2 drr=R 4LR
2
dc
or equivalently when
Ca = u/ > 8/dc2 0.25/(1-)

(79)

(80)

Here Ca is the dimensionless capillary number, expressing the

ratio of displacing viscous to resisting capillary forces. Thus
Eqn. 80 is a necessary condition for liquid-liquid displacement
and initiation of enhanced recovery. Otherwise, oil remains
trapped in the capillary pores, as droplets of resisting
capillary pressure given by Eqn. 78. Once recovery is initiated,
Eqn. 80 suggests that the speed of recovery, u, is proportional
to the porosity and inversely proportional to the viscosity .

32
Table 2 Flow Through Porous Media.
Notation: A = cross-sectional area; b = width of two dimensional
section; k = permeability; L = length; p = static pressure
exclusive of hydrostatic pressure; Q = volume flow rate; u =
superficial velocity, velocity as if solid media were absent; =
fluid viscosity. All fluid flows are between two reservoirs at
constant pressures of p1 and p2. Incompressible fluid.

33