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Use of ScaleSoftPitzer to calculate deposition, or precipitation,

in a reservoir or core material during long term flow.


Approach will be presented in four steps:
1. Determine whether equilibrium, kinetics, or mass transport is controlling,
2. Relate precipitation to the physical variables in the field or laboratory core,
3. Relate the physical variables that affect scale formation or dissolution to space
and time in the reservoir or core material, and
4. Combine the two into a single description explicitly and implicitly.
Two physical geometries will be examined algebraically, 1
st
(left). linear flow as might
occur in a laboratory column, and 2
nd
(right). radial flow as might ideally represent flow
into or out from a well in a reservoir. Pictorially, these can be represented as follows:
Two flow regimes will be considered for each geometry: A. no gas phase present, as is
common with laboratory cores or in deep reservoirs at pressure, and B. with a gas phase
is present. The difference is important to CaCO
3
, FeCO
3
, FeS, etc., but will no direct
effect upon BaSO
4
, CaSO
4
s, NaCl, etc.
Objective: Express the fractional change in porosity, n/n, in terms of flow conditions,
brine composition, and time. Specifically, the calculation of n/n can be considered to be
composed of four parts, illustrated here for calcite deposition or dissolution:
[ ] [ ]
1
space pore calcite
calcite 2
1
2
dV
1

MW
t Q ) M , Ca ( d
n
n
space pore
of volume
al differenti
Calcite of mole
Calcite of Volume
water produced
of Volume
water produced of Volume
Ca of moles in Change
n
n

+
1
1
]
1

1
]
1

1
1
1
]
1

1
]
1

1
]
1

1
]
1

Summary of approach: the precipitation of, e.g., calcite, d(Ca


2+
,M), will be expressed
as a function of pressure change, dP(psi), which will be expressed in terms of flow rate,
Q(m
3
/s, or B/d) and reservoir properties, such as permeability, k(m
2
, or md) and porosity.
121470613.doc Page 1 of 24
height(m)
r
e
,P
e,equilibium
r
w
,P
w(well)
r,P(pressure)
radius, r(m)
flow, Q(m
3
/s)
1. Relate kinetics and mass transport. First, estimate the average distance, or
time, that brine will flow for half of the amount that can precipitate to precipitate, i.e.,
t
1/2
, and from this show that equilibrium is generally fast compared with reservoir
flow.
The heterogeneous mass transport equation for precipitation in the presence of solid core
material can generally be modeled with a mass transport-type equation. Calcite, CaCO
3
,
will be used as an example precipitate material, wherein the number of moles of calcite
precipitated per liter of brine, d(CaCO
3
), is equal to the change in the molarity of calcium
ions, d(Ca
2+
,M) per second, dt(s):
n
) n 1 ( ) cm / g (
) g / cm ( SSA ) s / cm ( k
n
) n 1 ( ) cm / g (

volume / mass r
) cm / g ( r ) g / cm ( SSA ) s / cm ( k ) s ( k
) M , Ca ( ) s ( k } ) M , Ca ( ) M , Ca {(
V
A
k
) s ( dt
) M , Ca ( d
3
solid 2
m
3
solid
water solid s/w
3
w / s
2
m
1
order st 1
2 1
order st 1 m equilibriu
2
t
2
brine
solid
m
2


+ + +
+
Where k
m
(cm/s) is a mass transfer coefficient for the ions in solution and can be
estimated by any many dimensionless groups, e.g., the Sieder and Tate heat/mass trasfer
analogy, A
solid
(cm
2
) is the surface area of the solid reservoir material with a corresponding
volume of brine, V
brine
(cm
3
), SSA(cm
2
/g) is the specific surface area of the reservoir
material, r
s/w
(g/cm
3
) is the ratio of the solid mass to the corresponding volume of water,

solid
is the density of the solid, and n is the porosity of the reservoir.
k
1st order
(s
-1
) is a first order rate constant for precipitation. For illustration purposes, assume

solid
2.5 g/cm
3
, n = 0.25, and k
m
= 0.001 cm/s (a conservative estimate):
k
1st order
(s
-1
) 0.0075 SSA(cm
2
/g)
-Typically, when we measure SSA of core material by BET isotherm the value is on the
magnitude of to 1.0 m
2
/g = 10
4
cm
2
/g, but a range of values will be examined for radial
flow (a similar table would apply to linear flow):
SSA (cm
2
/g) K
1st order
(s
-1
) t
1/2
(sec) Dist. Traveled
(cm) at v = 90
ft/d
*
(r 2 ft)
Dist. Traveled
(cm) at v = 360
ft/d
*
(r 0.5 ft)
10,000=1 m
2
/g 75. 0.009 0.00029 0.00115
1,000 7.5 0.09 0.0029 0.0115
100 0.75 0.9 0.029 0.115
10 0.075 9.0 0.29 1.15
*
v(ft/d) = Q(ft
3
/d)/{n A(ft
2
)} = Q(ft
3
/d)/{2 n r(ft) b(ft)}, with b(ft) representing the
reservoir thickness. In this table, b = 20 ft; Q = 1,000 B/d have been assumed.
121470613.doc Page 2 of 24
Flows at less than r = 0.5 ft from the center of the well bore are probably under the
influence of the packing, etc., but kinetics may be important in this region for some wells.
Otherwise, these calculations illustrate that the distance for equilibrium to be complete is
generally very small ( 1 cm, or less) compared to the travel distances. Near well bore
effects (e.g., r < 1 ft.) are not known and probably need to be tested experimentally.
2. Relationship of pressure change to flow rate using Darcys law.
A. Linear one dimensional flow: First, the relationship will be developed in one
linear dimension, x, and then the corresponding results for radial flow will be
given in 2. B, below.
) m ( dx
) m ( dh
) m ( A
s
m
K
s
m
Q
2
3

,
_

,
_

Darcys Law in one dimension, x


SI units of measurement are self consistent and will be given initially, but equations
with common field and laboratory units will be presented and used.
Q(m
3
/s) = fluid flow rate
K(m/s) = hydraulic conductivity
A(m
2
) = cross sectional area of flow
dh(m) = hydraulic head in meters
dx(m) = length of porous medium
The hydraulic conductivity can be expressed in terms of intrinsic permeability, k(m
2
):
) s m / kg s Pa (
) s / m ( g ) m / kg ( ) m ( k
s
m
K
2 3 2



,
_

k(m
2
) = intrinsic permeability or simply called, permeability
(kg/m
3
) = fluid density; (kg/m
3
)
water
10
3
kg/m
3
at 25 C, 1 atm, and IS = 0
g(m/s
2
) = acceleration due to gravity = 9.8 m/s
2
often taken to be 10 m/s
2
.
(kg/m s) = dynamic viscosity, (kg/m s)
water
10
-3
kg/m s at STP and TDS =
0
Then, by substituting k(m
2
) for K(m/s) Darcys law in SI units becomes:
) m ( dx
) m ( dh
) m ( A
) s m / kg s Pa (
) s / m ( g ) m / kg ( ) m ( k
s
m
Q
2
2 3 2 3



,
_

1 darcy = 10
-12
m
2
= 1 m
2
= 10
-8
cm
2
10
-5
m/s = 10
-3
cm/s , or
1 mdarcy = 10
-15
m
2
= 10
-3
m
2
= 10
-11
cm
2
10
-8
m/s = 10
-6
cm/s
121470613.doc Page 3 of 24
*
___these are permeabilities; these are hydraulic conductivities of water at STP
Note that k(m
2
) = 1 darcy is the SPE preferred unit for permeability, but many still use
millidarcy, md, as the unit of permeability.
Darcys law can be rearranged to calculate the head loss, dh(m of water), first in SI units:
) m ( dx ) m ( A
) s m / kg s Pa (
) s / m ( g ) m / kg ( ) m ( k
s
m
Q ) m ( dh
1
2
2 3 2 3

'

,
_

g = 9.8 m/s
2
10
-3
kg/m s
1 g/cm
3
= 10
3
kg/m
3

For illustration, a specific column will be assumed: 1 ft length with cross sectional area of
1 in
2
with permeability of 100 md flowing at 10 ml/min:
Q = 10 ml/min = 1.66x10
-7
m
3
/s
k = 100 md = 10
-13
m
2

A = 1 in
2
= 6.45x10
-4
m
2
dx = 1 ft = 0.305 m
{ }
{ }
head pressure water of psi 115 m 1 . 80 ) m ( dh
s / m 10 x 32 . 6 s / m 10 x 06 . 5 ) m ( dh
m 305 . 0 m 10 x 45 . 6 s / m 10 x 8 . 9 s / m 10 x 66 . 1 ) m ( dh
m 305 . 0 m 10 x 45 . 6
s m / kg 10
) s / m 8 . 9 m / kg 000 , 1 m 10
s / m 10 x 66 . 1 ) m ( dh
1
3 10 4 8
1
2 4 7 3 7
1
2 4
3
2 3 2 13
3 7


'

The hydraulic conductivity, K(m/s) = 9.8x10


-7
m/s, is about equal to 100 md. Also, a
water head of 80.1 m high can be converted to psi using the density of water, as will be
done below (80.1 m 115 psi of pressure head.)
121470613.doc Page 4 of 24
Customary field units: Q, A, dh, etc., can be expressed in customary field units as
follows:
Q(m
3
/s) = Q(B/d) 1.84x10
-6
[(m
3
/s)/(B/d)]
k(m
2
) = k(md) 10
-15
m
2
/md
A(m
2
) = A(ft
2
) (0.3048 m/ft)
2
Since the ratio, dh/dx must be unitless, both will be expressed in ft and then the
head, dh, will be converted to dP(psi):
dh(ft of water) = 2.29 (ft/psi) dP(psi)
dx(ft) = dx(ft)
Note that:
) ft ( dx
) psi ( dP
psi
ft
29 . 2
) ft ( dx
) ft ( dh

,
_

is unitless, as required.
Substituting and collecting terms:
) ft ( dx
) psi ( dP
) ft ( A ) md ( k 10 x 133 . 1
d
B
Q
2 3

,
_


We will most commonly use this equation to calculate dP(psi) in common units:
) ft ( dx
) ft ( A ) md ( k
) d / B ( Q
4 . 879 ) psi ( dP
2


(1.
For example, again with the above core and noting that 10 ml/min = 0.091 B/d, the
pressure drop across the column with the above formula in common units would be:
psi 115 ft 1
ft 00694 . 0 md 100
d / B 091 . 0
4 . 879 ) psi ( dP
2


Which is the same as with SI units confirming the unit conversions.
Customary laboratory units: To convert the above expression in common field units to
common laboratory units make the following substitutions:
Q(B/d) = Q(ml/min) (1 B/159,000 ml) (1440 min/d) = 9.06x10
-3
Q(ml/min)
dx(ft) = dx(in) (1 ft/12 in) = 0.083 dx(in), commonly the column length
A(ft
2
) = A(in
2
) 0.00694
121470613.doc Page 5 of 24
psi 115 in 12
in 1 md 100
min / ml 10
3 . 95
: above as data same the using example, For
) in ( dx
) in ( A ) md ( k
min) / ml ( Q
3 . 95 ) psi ( dP
or ), in ( dx 083 . 0
) in ( A 00694 . 0 ) md ( k
min) / ml ( Q 10 x 06 . 9
4 . 879 ) psi ( dP
2
2
2
3

2. B. Radial flow: Darcys law in SI units in homogenous radial flow at steady state
conditions is given in SI units by Howard B. Bradley, ed., Petroleum Engineering
Handbook, 1992, SPE, Ch. 26 by Daniel M. Bass, Jr., page 26.13):
) r / r ln( ) s m / kg (
)} Pa ( P ) Pa ( P { ) m ( b ) m ( k 2
) s / m ( Q
w e
w e
2
3

where r
e
and P
e
refer to the equilibrium, or steady state,
reference radius and pressure, normally taken to be constants at about r
e
610 m (2,000
ft) into the formation, r
w
and P
w
refer to the pressure at the well, r and P refer to any
arbitrary radius and pressure, and b(m) is the zone thickness. We will only use the
differential of this equation and therefore the specific values for r
e
and P
e
will not enter
into the final equations. Rearranging:
)) r ln( ) r (ln(
) m ( b ) m ( k 2
) s m / kg ( ) s / m ( Q
) Pa ( P ) Pa ( P
e w
2
3
e w




Taking r
e
and P
e
as constants and letting P
w
P and r
w
r and taking the differential of
both sides {dln(r) = dr/r}:
) m ( dr
) m ( b ) m ( r 2 ) m ( k
) s m / kg ( ) s / m ( Q
) Pa ( dP
2
3




Conversion to customary units with: 14.7 psi = 1 atm 10
5
Pa, or dP(Pa) =
dP(psi)x6.8x10
3
; Q(m/s) = Q(B/d) 1.84x10
-6
; r(m) = r(ft) 0.305; k(m
2
) = k(md) 10
-15
;
and
w
(kg/m s) 10
-3
kg/m s,

(2. ) ft ( dr
) ft ( b ) ft ( r ) md ( k
) d / B ( Q
141 ) psi ( dP
305 . 0 ) ft ( dr
305 . 0 ) ft ( b 305 . 0 ) ft ( r 2 10 ) md ( k
} s m / kg 10 ) s m / kg ( { 10 x 84 . 1 ) d / B ( Q
10 x 8 . 6 ) psi ( dP
15
3 6
3


121470613.doc Page 6 of 24
b(m)
r
e
,P
e
r
w
,P
w
r,P
The slope of the pressure head vs. radius can be calculated at various radii, an illustrating
for 1,000 B/d flow, 100 md, at r = 1ft, with b = 20 ft:
ft
psi
70
ft 20 ft 1 md 100
d / B 000 , 1
141
) ft ( b ) ft ( r ) md ( k
) d / B ( Q
141
) ft ( dr
) psi ( dP



This can be compared with Darcys law in linear flow by using the area of the formation
at r = 1 ft and b = 20 ft, where A(ft
2
) = 2 r b = 2 (3.14) (1 ft) (20ft) = 125.6 ft
2
,
using Equation 1, above:
ft
psi
70
ft 6 . 125 md 100
d / B 000 , 1
4 . 879
) ft ( dx
) psi ( dP
2


That is, this is a characteristic of the reservoir rock when viewed as an instantaneous
slope.
3. Set Saturation Index (SI) = 0 and obtain d(M
2+
,M) vs. dP(psi). Use calcite as
an example. Relate the physical variables that affect scale formation or dissolution
to space and time in the reservoir or core material. This is done with the SI equation,
illustrating with calcite. Calcite is used as an example, because of the common
minerals it is the most complicated to model due to ionization and possible gas phase.
The equation will first be developed without a gas phase present. It will be shown
that the results for other minerals, such as BaSO
4
, will be much more clear-cut.
Calcite precipitation with no gas phase present. The saturation index, SI, is defined as
the ratio of the ion products in molar units, M, divided by the solubility product. If the
K
sp
is expressed explicitly as a function of TDS, then concentrations can be used see
e.g., J. E. Oddo and M. B. Tomson, J. Pet. Tech. 34:1583-1590, 1982, for a discussion of
activities versus concentration in the saturation index equation:

'

+
) TDS , P , T ( K
) M , CO ( ) M , Ca (
log SI
sp
2
3
2
10
Using the first and second ionization constants of carbonic acid in brine and substituting
for the reaction written as a solubility product of calcite solid:
CaCO
3,cr
+ H
2
CO
3,aq
Ca
2+
+ 2HCO
3
-
121470613.doc Page 7 of 24
b(ft)
r
e
,P
e
r
w
,P
w
r,P
r =1ft

'

'

+
TDS , T
sp 1
2
10
aq , 3 2
2 1
3
2
10
) P (
K K
K
log
) M , CO H (
) M , HCO ( ) M , Ca (
log SI
where the (P)
T,TDS
implies that the T and TDS are held constant for a particular brine and
steady state flow conditions. To an excellent approximation the pressure dependence of
equilibrium constants can be taken to be a linear function of the pressure (this is
equivalent to assuming the partial molal volume change of reaction is independent of
pressure):
pK -log
10
(K) = b(psi
-1
) P(psi) + constant
These b-values have been tabulated for individual reactions by the late Dr. Shiliang He of
the BCC, but we will use ScaleSoftPitzer 7.0 to calculate b-values, because SSP 7.0
automatically includes the effects of T, P, and Composition on the b-values although the
specific values of b are not too sensitive to T, P, and Composition.
The conclusion that precipitation is essentially at equilibrium versus flow in a column or
reservoir is equivalent to setting the SI equal to zero as flow occurs:
SI
calcite
= 0.00
constant ) psi ( P b 303 . 2
) M , CO H (
) M , HCO ( ) M , Ca (
ln
gas no
calcite
aq , 3 2
2 1
3
2
e
+

'


+
This equation will be used for differentiation to relate d(Ca
2+
,M) dP(psi), i.e., as the
pressure drops how much must calcium precipitate in order maintain SI = 0.00? The
precipitation reaction for calcite in the absence of a gas phase:
Ca
2+
+ 2HCO
3
-
CaCO
3,cr
+ H
2
CO
3,aq
From this equation, the amount of calcite solid to precipitate is given by the change in
calcium concentration in solution, d(Ca
2+
,M), and for every calcite mole that precipitates
two bicarbonates are lost and one carbonic acid is produced:
d(CaCO
3
,M) = (Ca
2+
,M)
o
- (Ca
2+
,M)
where the superscript, (Ca
M ,
)
o
, implies initial conditions. It is possible to either take the
derivative, dSI/dP=0 or simply take the differential of the following. The differential is
used to imply a limiting process as the pressure changes from P(psi) to {P(psi)-dP(psi)}:
constant ) psi ( P b 303 . 2
)]} M , Ca ( ) M , Ca [( ) M , CO H {(
)]} M , Ca ( ) M , Ca [( 2 ) M , HCO {( ) M , Ca (
ln
gas no
calcite
2 o 2
aq , 3 2
2 2 o 2 o 1
3
2
e
+

'

+

+ +
+ + +
121470613.doc Page 8 of 24
Taking the differential of both sides and simplifying algebraically, yields an expression
similar to adding resistor in parallel (with the exception of 4 over the bicarbonate
concentration):
[ ] ) psi ( dP b 303 . 2
) M , HCO ( ) M , Ca ( ) M , CO H ( ) M , Ca ( 4 ) M , CO H ( ) M , HCO (
) M , CO H ( ) M , HCO ( ) M , Ca (
) M , Ca ( d
or
dP b 303 . 2 ) M , Ca ( d
) M , CO H (
1
) M , HCO (
4
) M , Ca (
1
gas no
calcite
3
2
aq , 3 2
2
aq , 3 2 3
aq , 3 2 3
2
2
gas no
calcite
2
aq , 3 2
3
2

1
1
]
1

+ +


1
1
]
1

+ +
+ +
+
+
+
+
Just as with resistors, the term in brackets reduces essentially the smallest
concentration of the three, ). M , CO H ( or ), M , HCO ( ), M , Ca (
aq , 3 2 3
2 +

For typical brines:
) 10 (K , 10 ) M , HCO ( ) M , CO H (
0 . 6
1
pH 0 . 6
3 aq , 3 2



if the pH > 6, the (HCO
3
-
,M) will typically be larger than the carbonic acid, etc. If
the pH, (HCO
3
-
,M) and (Ca
2+
,M) are measured, the above equation can be used to
estimate the aqueous carbonic acid.
The ratio in brackets has units of molarity, M:
) M , HCO ( ) M , Ca ( ) M , CO H ( ) M , Ca ( 4 ) M , CO H ( ) M , HCO (
) M , CO H ( ) M , HCO ( ) M , Ca (
) M ( R
3
2
aq , 3 2
2
aq , 3 2 3
aq , 3 2 3
2
gas no
calcite
+ +
+
+ +

For example, if pH = 5.5, (Ca


2+
,M) = 0.005 M, and (HCO
3
-
,M) = 0.025 M, then

M 079 . 0 10 M 025 . 0 10 ) M , HCO ( ) M , CO H (
5.5 - 6 pH 6
3 aq , 3 2


, and
M 0045 . 0
M 025 . 0 M 005 . 0 M 079 . 0 M 005 . 0 4 M 079 . 0 M 025 . 0
M 079 . 0 M 025 . 0 M 005 . 0
) M ( R
gas no
calcite

+ +

which is approximately equal to the smallest term, (Ca


2+
,M) = 0.005 M. Finally,
d(Ca
2+
M ,
)
gas no
calcite
R (M) ) b 303 . 2 (
gas no
calcite
dP(psi) (3.
This is the central equation relating calcite precipitation to the system pressure via
the brine composition when there is no gas phase present.
121470613.doc Page 9 of 24
Calcite precipitation in the presence of a gas phase. If the calcite precipitation takes
place in the presence of a gas phase, the detailed form of the d(Ca
2+
M ,
)-term is slightly
different:
Ca
2+
+ 2HCO
3
-
CaCO
3,cr
+ CO
2
+ H
2
O
In this case the CO
2
is free to equilibrate with the gas phase and this can be expressed
using the gas phase CO
2
mole fraction, y
CO2
, and Henrys law constant, K
H
, in the SI
equation:
constant ) psi ( P b 303 . 2
y ) psi ( P
) M , HCO ( ) M , Ca (
ln
phase gas
calcite
2 CO
2 1
3
2
e
+

'

+
Differentiating, as before, but assuming y
CO2
is constant:
(4. ) psi ( dP
) psi ( P
1
b 303 . 2 ) M ( R ) M , Ca ( d
: brackets in term the as ) M ( R Defining
(psi) dP
) psi ( P
1
b 303 . 2
) M , Ca ( 4 ) M , HCO (
) M , HCO ( ) M , Ca (
) M , Ca ( d
or
) psi ( dP
) psi ( P
1
b 303 . 2 ) M , Ca ( d
) M , HCO (
4
) M , Ca (
1
phase gas
calcite
phase gas
calcite
2
phase gas
calcite
phase gas
calcite
2
3
3
2
2
phase gas
calcite
2
3
2

,
_

,
_

+
1
1
]
1

,
_

+
1
1
]
1

+
+
+
+
+
+
+
The
phase gas
calcite
b term expresses the net pressure dependence of the equilibrium constants.
The 1/P(psi) term accounts for the loss of CO
2
to the gas upon lowering the pressure, P,
and the functional form, dP/P, means that it is the fractional change in pressure that is
important to this term.
Barite and related precipitation. If the precipitation takes place via simpler
stoichiometry, such as BaSO
4
, the result is more straight forward but the result is similar:
121470613.doc Page 10 of 24
) psi ( dP b 303 . 2 ) M ( R ) M , Ba ( d
) M ( R ratio, barite the as defined is brackets in term the If
) psi ( dP ) b 030 . 2 (
) M , Ba ( ) M , SO (
) M , SO ( ) M , Ba (
) M , Ba ( d
or
) psi ( dP b 303 . 2 ) M , Ba ( d
) M , SO (
1
) M , Ba (
1
barite barite
2
barite
barite
2 2
4
2
4
2
2
barite
2
2
4
2


1
1
]
1


1
1
]
1

+
+
+
+
+
+
+

If barium and sulfate are equal molarity then the R
barite
term is simply one half the
concentration, as expected.
For CaSO
4
s and NaCl equations similar to the barite equation are obtained, although for
FeCO
3
and FeS equations similar to CaCO
3
are obtained.
4. Combine the SI equations with Darcys equation. Equations 3 and 4 that relate
change in concentration to changes in pressure can now be substituted into
Equations 1 and 2 that relate changes in pressure to flow rate and reservoir
permeability.
Precipitation in a linear column with no gas phase present, using calcite as an
example. From the beginning section:
[ ] [ ]
1
]
1

1
]
1

+
nAdx
1 MW
t Q ) M , Ca ( d
n
n
calcite
calcite 2
,
but d(Ca
2+
M ,
) is related to dP(psi) by Equation 3 and dP(psi) is related to core properties
and distance via Equation 1:
d(Ca
2+
M ,
)
gas no
calcite
R (M) (-2.303
gas no
calcite
b ) dP(psi), but

) ft ( dx
) ft ( A ) md ( k
) d / B ( Q
4 . 879 ) psi ( dP
2


, thus
d(Ca
2+
M ,
)
gas no
calcite
R (M) (-2.303
gas no
calcite
b )
) ft ( dx
) ft ( A ) md ( k
) d / B ( Q
4 . 879
2

[ ]
1
1
]
1

1
]
1


1
]
1

) ft ( dx r n
1 MW
t Q ) ft ( dx
) ft ( A ) md ( k
) d / B ( Q
5 . 882 ) b 303 . 2 ( R
n
n
2
column
calcite
calcite
2
gas no
calcite
gas no
calcite
121470613.doc Page 11 of 24
The quantity inside the first brackets has the units of mole of calcite precipitated per liter
of flow, d(Ca
2+
,M). Therefore, the product, Q t, with time in days, t(d), must have the
units of liters, Q(liters/day) = Q(B/d) 159 liters/B the value of Q(B/d) inside the braces
has already been corrected to units of B/d. The next quotient is the molar volume of
calcite, (L/mole): MW
calcite
/
calcite
= (0.100 kg/mole)/(2.71 kg/liter) = 0.0369 (L
calcite/mole calcite). The product, r
2
dx, must have the units of liters pore space,
(r(ft)
2
dx(ft) (28.3 L/ft
3
). Making these substitutions:
(5.
)} ft ( A ){ md ( k n
) d ( t )} d / B ( Q {
b R 421
n
n
3 . 28 ) ft ( r n
) d ( t
mole
L
0369 . 0
) ft ( A ) md ( k
159 ) d / B ( Q
5 . 882 ) b 030 . 2 ( R
n
n
2 2
2
gas no
calcite
gas no
calcite
2
column
calcite
caldite
2
2
gas no
calcite
gas no
calcite

1
1
]
1

1
]
1

Using this last equation for a common laboratory column core we might have:
(Ca
2+
M ,
) = 0.005 M (200 mg/l), as the limiting reagent; therefore,
gas no
calcite
R 0.005
M
Q(B/d) = 10 ml/min x 1440 min/d x 1 B/159,000 ml = 0.091 B/d
t(d) = 30 d
A(ft
2
) = 1 in
2
x 1 ft
2
/144 in
2
= 0.00694 ft
2
k(md) = 100 md
n = 0.25
gas no
calcite
b (psi
-1
) = 9.2x10
-5
psi
-1
04 . 0
00694 . 0 md 100 25 . 0
30 091 . 0
10 x 2 . 9 M 005 . 0 421
)} ft ( A ){ md ( k n
) d ( t )} d / B ( Q {
b R 421
n
n
2
2
5
2 2
2
gas no
calcite
gas no
calcite

That is, 4 % of the pore space would be lost in one month, but in a year a substantial
fraction of the porosity would be lost. Since Q/(nA) = velocity of fluid flow, the loss in
porosity varies with the square of the flow rate; therefore if the flow is reduced to 5
ml/min, porosity loss would be only 1 %.
Precipitation in a linear column with a gas phase present, using calcite as an
example. If a gas phase is present, the change in calcium, d(Ca
2+
), is given by combining
Equations 1 and 4:
2 2
2
phase gas
calcite
phase gas
calcite
)} ft ( A ){ md ( k n
) d ( t )} d / B ( Q {
) psi ( P
1
b 303 . 2 ) M ( R 183
n
n

,
_

(6.
121470613.doc Page 12 of 24
phase gas
calcite
b = -3.45x10
-5
psi
-1
, when there is a gas phase present, and
1/(2.303
phase gas
calcite
b ) = 12.6x10
3
psi, as the pressure below which the 1/P-term
predominates
Precipitation in radial coordinates with no gas phase present, using calcite as an
example. Combining Equations 2 and 3 and simplifying, as above:
2 2
2
gas no
calcite
gas no
calcite
)} ft ( r { )} ft ( h { ) md ( k n
) d ( t )} d / B ( Q {
b R 69 . 10
n
n

(7.
Precipitation in radial coordinates with a gas phase present, using calcite as an
example. Combining Equations 2 and 4 and simplifying, as above:
2 2
2
phase gas
calcite
phase gas
calcite
)} ft ( r { )} ft ( h { ) md ( k n
) d ( t )} d / B ( Q {
) psi ( P
1
b 303 . 2 R 64 . 4
n
n

,
_

(8.
121470613.doc Page 13 of 24
Listing of key equations:
Molar ratios used in equations below:
) M , HCO ( ) M , Ca ( ) M , CO H ( ) M , Ca ( 4 ) M , CO H ( ) M , HCO (
) M , CO H ( ) M , HCO ( ) M , Ca (
) M ( R
3
2
aq , 3 2
2
aq , 3 2 3
aq , 3 2 3
2
gas no
calcite
+ +
+
+ +

) M , Ca ( 4 ) M , HCO (
) M , HCO ( ) M , Ca (
) M ( R
2
3
3
2
phase gas
calcite
+
+
+

, with
pH 6
3 aq , 3 2
10 ) M , HCO ( ) M , CO H (


) M , Ba ( ) M , SO (
) M , SO ( ) M , Ba (
) M ( R
2 2
4
2
4
2
barite
+
+
+


) M , Ca ( ) M , SO (
) M , SO ( ) M , Ca (
) M ( R
2 2
4
2
4
2
anhyrite or
, e hemihydrat
, gypsum
+
+
+


Linear flow:
) ft ( dx
) ft ( A ) md ( k
) d / B ( Q
4 . 879 ) psi ( dP
2


(1.
Linear flow and no gas phase present. Similar equation applies to all sulfates:
d(Ca
2+
M ,
)
gas no
calcite
R (M) ) b 303 . 2 (
gas no
calcite
dP(psi) (3.
Linear flow with a gas phase present:
) psi ( dP
) psi ( P
1
b 303 . 2 ) M ( R ) M , Ca ( d
phase gas
calcite
phase gas
calcite
2

,
_

+
+
(4.
Porosity loss for linear flow with no gas phase. Similar equation applies to all sulfates:

)} ft ( A ){ md ( k n
) d ( t )} d / B ( Q {
b R 421
n
n
2 2
2
gas no
calcite
gas no
calcite

(5.
Radial flow:
) ft ( dr
) ft ( b ) ft ( r ) md ( k
) d / B ( Q
141 ) psi ( dP


(2.
Porosity loss for linear flow with a gas phase present:
2 2
2
phase gas
calcite
phase gas
calcite
)} ft ( A ){ md ( k n
) d ( t )} d / B ( Q {
) psi ( P
1
b 202 . 2 ) M ( R 183
n
n

,
_

(6.
Porosity loss for radial flow, no gas phase present. Similar equation applies to all sulfates
2 2
2
gas no
calcite
gas no
calcite
)} ft ( r { )} ft ( h { ) md ( k n
) d ( t )} d / B ( Q {
b R 69 . 10
n
n

(7.
Porosity loss for radial flow with a gas phase present:
2 2
2
phase gas
calcite
phase gas
calcite
)} ft ( r { )} ft ( h { ) md ( k n
) d ( t )} d / B ( Q {
) psi ( P
1
b 303 . 2 R 64 . 4
n
n

,
_

(8.
121470613.doc Page 14 of 24
The constant values, b
mineral
(psi
-1
), in the above equations have been determined using
ScaleSoftPitzer 7.0, and are tabulated below. It is recommended to calculate these SI/
(P = 100 psi) for the specific conditions of the brine under study; this is easily done
using SSP 7.0 by changing the pressure by 100 psi, all else constant and reading SI
from the Input sheet (see example Demo sheet at 4,000 psi in the presence of a gas
phase.)
Solid phase
SI/100 psi at 70,000
mg/l TDS, 200 F,
4,000 psi (SSP 7.0)
b-terms (psi
-1
)
*
calcite, no gas -0.0092 -9.20x10
-5
psi
-1
calcite,gas phase -0.0143
**
-3.45x10
-5
psi
-1**
barite -0.0039 -3.90x10
-5
psi
-1
celestite -0.0041 -4.10x10
-5
psi
-1
gypsum -0.0030 -3.00 x10
-5
psi
-1
hemihydrate -0.0042 -4.20 x10
-5
psi
-1
anhydrite -0.0042 -4.20 x10
-5
psi
-1
*
For the net reaction, as written: V
rx
(ml/mole) -2.303RTpK/P -1,020 b(psi
-1
),
and these values are typically -40 to - 90 ml/mole, as expected for solubility in brines.
1 5 1 5 1 5
0 . 7 SSP
phase gas
calcite
* *
psi 10 x 45 . 3 psi 10 x 86 . 10 psi 10 x 3 . 14
) P 303 . 2 /( 1 ) dP dSI ( b

+
+
The value the late Dr. Shiliang He tabulated was -3.91x10
-5
psi
-1
.
Collection of conversion factors of use in the this work:
1 ft = 0.305 m 1 B = 159 L 1 d = 1,440 min 1 m
3
/s = 1.84x10
-6
B/d
1 ft = 30.5 cm 1 B = 5.6 ft
3
1 d = 86,400 s 1 ml /min = 0.0091 B/d
1 in = 2.54 cm 1 B = 0.159 m
3
Head of water at = 1.0
g/cm
3
:
1 ft
3
= 28.4 L 1m = 1.43 psi
1 ft
3
= 0.0284 m
3
1 ft = 0.44 psi
1 darcy = 10
-12
m
2
= 1 m
2
= 10
-8
cm
2
10
-5
m/s = 10
-3
cm/s
1 mdarcy = 10
-15
m
2
= 10
-3
m
2
= 10
-11
cm
2
10
-8
m/s = 10
-6
cm/s
121470613.doc Page 15 of 24
Brine # 1 2 3 4 5
Parameters Units Input Input Input Input Input
Select the brines
Select Well Cell H28 is
Sample ID by checking STP calc. pH
Date the boxes on 12/3/2003 Cell H28 is
Operator Row 3. calc. BH T.
Well Name Select T, P Demo Cells H36-38
Location the button are used in
Field on Row 34. calculations.
Na
+
(mg/l)* 19,872 BH T & P WH T & P
K
+
(if not known =0) (mg/l) 500.00 , SI(Top-Bt)
Mg
2+
(mg/l) 54.00
Ca
2+
(mg/l) 6,500.00 0.34 0.35 0.0143
Sr
2+
(mg/l) 700.00
Ba
2+
(mg/l) 49.91 0.12 0.12 0.0038
Fe
2+
(mg/l) 12.00
Zn
2+
(mg/l) 10.00 -1.98 -1.98 0.0010
Cl
-
(mg/l) 43,000
SO
4
2-
(mg/l) 25.00 -1.67 -1.67 0.0030
F
-
(mg/l) 1.00
Total Alkalinity (mg/l HCO3) 281.00 -1.96 -1.96 0.0042
Carboxylic acids (mg/l HAc) 0.00
TDS (Measured) (mg/l) 70,000 -1.36 -1.35 0.0042
Calc. Density (STP) (g/ml) 1.045
CO
2
Gas (STP) (%) 0.62 -0.94 -0.94 0.0041
H
2
S Gas (STP) (%) 0.02
Total H2Saq (STP) (mgH2S/l) 4.32 1.18 1.18 0.0047
pH, measured (STP) pH 7.38
Use pH measured at 7.77 7.77 0.0047
STP to calculate SI? 1-Yes;0-No 0
Gas/Day (103SCF) 8,500 -1.04 -1.04 0.0044
Oil/Day (STB) 0
Water/Day (STB) 100 -0.56 -0.54 0.0143
For mixed brines the B-H Temp in H34 is calculated from the Cp's & Temps for individual wells. Other T&P's must be entered. Inhibitor needed (mg/L)
B-H Temp (F) 200 Calcite NTMP
W-H Temp (F) 200 0.00 0.00
B-H Pres (psia) 4,000 Barite BHPMP
W-H Pres (psia) 3,900 0.00 0.00
Use 30Oil & 0.6gas
to calc. P b.pt.? 1-Yes;0-No 0 5.66 5.67
If No, then Oil grav. API grav. 40.00
and Gas Sp.Grav.: Sp.Grav. 0.81
MeOH/Day (STB) 0
Well Depth (ft) 10,000
Perforation (ft)
Formation
Rock Type Sandstone
Porosity (%) 15.00
Permeability (mD)
Calcite (%)
Clays (%)
QC Checks
, Cations= equiv./liter 1.22
, Anions= equiv./liter -1.22
% Differ = 0.21
Calc TDS= mg/liter 71,009.23
Exp. TDS= mg/liter 70,000.00
% Differ = 0.72
Saturation Index values
pH
Mixed
brine:
Calcite
Barite
Halite
Gypsum
Iron Carbonate
Zinc Sulfide
Hemihydrate
Calcium fluoride
Celestite
Iron Sulfide
Anhydrite
Click here
to run SSP
6.0 the
same as is
done on
the Run
sheet.
Click here to
1. Adjust the value of a
parameter; to
2. A specific value by
3. Adjusting some well
parameter.
For example: Vary BH SI
to 0.00 by adjusting P-
CO2.
121470613.doc Page 16 of 24
From: R. Allen Freeze and John A. Cherry, Groundwater, Prentice Hall, 1979
121470613.doc Page 17 of 24
From Jacob Bears text on hydrology, 1968.
121470613.doc Page 18 of 24
121470613.doc Page 19 of 24
The following three representative data sets is from a large tabulation by US Geological
Survey web site at the this address:
http://pubs.usgs.gov/of/2003/ofr-03-420/Table1.htm
Table 1. Sources, ages, and locations of porosity-permeability data sets.
D=Description
P=Plot (* indicates multiple plots)
X=Spreadsheet
D P X No. Authors and Date Geologic Age Formation Name
35 Kerr and others, 1999 Pennsylvanian Bartlesville (Glenn) sandstone
36 Langford and others, 1990 Oligocene Vicksburg Formation
40 Marzano, 1988 Pliocene widely scattered wells
Location
35 Oklahoma
36 Texas
40 Gulf of Mexico
121470613.doc Page 20 of 24
121470613.doc Page 21 of 24
121470613.doc Page 22 of 24
121470613.doc Page 23 of 24
The following active calculator can be used to test flow in radial coordinates (double click on spread
sheet to activate.
Calculator for pressure change and porosity loss versus radius from well center. Values in yellow may be changed.
t(d) Q(B/d) n(por) h(ft) Pref(psi) rref(ft) b(1/psi) R(M)
365 2000 0.25 20 5000 2000 9.20E-05 0.001
Calculation of the fraction of total in brine needed to fill to 1, 2 ft:
k(1st md) k(2nd md) k(3rd md) k(4th md) Calcite Vpores(L) Moles to fill Flow(L) TotMoles fraction ppt
5 10 50 500 At r=1ft 8.92E+02 2.29E+04 1.16E+08 1.16E+05 0.197
At r=2ft 3.57E+03 9.15E+04 1.16E+08 1.16E+05 0.788
r(ft) P(psi, 1st md) P(psi, 2nd md) P(psi, 3rd md) P(psi, 4th Md) v(ft/d) n/n(1st md) n/n(2nd md) n/n(3rd md)n/n(4th md)
0.300 -176.098 -88.049 -17.610 -1.761 1188.357 31.908 15.954 3.191 0.319
0.675 -159.874 -79.937 -15.987 -1.599 528.031 6.300 3.150 0.630 0.063
1.519 -143.651 -71.825 -14.365 -1.437 234.623 1.244 0.622 0.124 0.012
3.420 -127.427 -63.714 -12.743 -1.274 104.252 0.246 0.123 0.025 0.002
7.696 -111.204 -55.602 -11.120 -1.112 46.323 0.048 0.024 0.005 0.000
17.320 -94.980 -47.490 -9.498 -0.950 20.583 0.010 0.005 0.001 0.000
38.981 -78.757 -39.378 -7.876 -0.788 9.146 0.002 0.001 0.000 0.000
87.727 -62.533 -31.267 -6.253 -0.625 4.064 0.000 0.000 0.000 0.000
197.434 -46.310 -23.155 -4.631 -0.463 1.806 0.000 0.000 0.000 0.000
444.335 -30.086 -15.043 -3.009 -0.301 0.802 0.000 0.000 0.000 0.000
999.996 -13.863 -6.932 -1.386 -0.139 0.357 0.000 0.000 0.000 0.000
Permiability values in millidarcies.
Pressure chage and flow rate vs. radius
-200.0
-150.0
-100.0
-50.0
0.0
0 2 4 6 8 10 12 14 16 18 20
r (ft)

P

(
p
s
i
)
0.1
1.0
10.0
100.0
1000.0
10000.0
v

(
f
t
/
d
)
P(psi, 1st md) P(psi, 2nd md)
P(psi, 3rd md) P(psi, 4th Md)
v(ft/d)
Porosity loss versus radius
0.0
0.2
0.4
0.6
0.8
1.0
0 1 2 3 4 5 6 7 8 9 10
radius, r(ft)
f
r
a
c
t
i
o
n
a
l

p
o
r
o
s
i
t
y

l
o
s
s
,

n
/
n
Dn/n(1st md) Dn/n(2nd md)
Dn/n(3rd md) Dn/n(4th md)
121470613.doc Page 24 of 24