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SPE/DOE 35394
Permeability Damage in Diatomite Due to in-situ Silica Dissolution/Precipitation
C.J. Kohl, P.C. Dagenaisl, D.C. Larson2 and A.S. Murer2
1Mobil Exploration and Producing Technical Center, 2 Mobil Exploration and Producing, U.S.

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temperature (due to increased depth in the field), Opal A

converts to Opal CT (crystobatite-trydimite), then to quartz.
These conversions, which are aqueous dissolutionprecipitation reactions, result in a more c~stallographically
structured mineral. The Iaek of structure in the Opal A results
in a highly unstable mineral which dissolves, particularly at
higher temperature, more readily than the structured forms of
silica
Produced water from field operations and laboratory
waterflood experiments contain measurable amounts of
dissolved silica. Concentrations of dissolved silica typically
range from 100 to 1000 ppm. Diatomite has low permeability
(typically in tie 0.5 to 3 md range) because of its grain size
and relatively small pore throat diameter. Although the
concentration of dissolved silica appears insignifkartt, the very
small pore throat diameters in diatomite do not require large
amounts of mineral deposition to effectively block the
movement of fluids. These observations, in conjunction with
the field experience of hot water injectivity reduction during
the course of waterflooding diatomite reservoirs, prompted a
study to ascertain the impact of in-situ silica dissolution and
precipitation on permeability.
Equilibrium aqueous silica concentration is temperature
dependent. The dissolution-precipitation reaetions take on
more import in light of the thermal EOR processes currently
being considered for the diatomite. During the course of
thermal EOR projects there exists a non-uniform temperature
profile between injection and production wells. Consider the
simplified scenario of a reservoir under therrnrd EOR process
depicted in Fig. 1. As hot water or steam is injeeted, a
temperature profile is established in the reservoir with the area
around the injeetion well being relatively hot and the area
around the producer remaining at the resenoir temperature.
Silica will be dissolved by the hot water in the vicinity of the
injector. As this hot, silica-laden brine @aversesthe reservoir
towards the cooler region of the production well, the fluid is
cooled and precipitation of silica occurs. Due to the small
pore throat sizes of the diatomite, these reactions may lead to
dramatic changes in the posity and permeability across the
reservoir as silica is dissolved and later deposited.
Here, we tacitly assume the likely situation that
permeability decreases as porosity decreases due to in-situ

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Abstract
It has been observed in Mobils California diatomite thermal
recovery projects that water injectivity decreases gradually
with time. Several factors, such as reservoir fill-up or high
suspended solids concentration in the injection fluid, may
effect such decrease. Due to the inherently low permeability of
diatomite, small amounts of in-situ silica dissolution and/or
precipitation can also have a drastic effeet on the marnx
permeability and consequently the injectivity. In this study, we
outline an experimental program designed to ascertain such
behavior and to elucidate qualitative and quantitative results to
further our understanding of the problem, Furthermore,
transient flow experiments were performed to obtain silica
dissolutiort/preeipitation data at various temperatures. It is
shown that the silica reaetion can be modeled approximately
as fret-order kinetics. Numerical model results indicate that
this kinetic data can be used to model diatomite permeability
damage data obtained in rhe laboratory. Our current effort to
simulate field-scale permeability damage using the
experimentally-derived silica kinetic model will also be
distmased
Introduction
The diatomite reservoirs in California are currently being
produced by primary and waterflood operations. The low
recoveries and large volumes of oil in place have spurred an
effort to investigate the effectiveness of thermal recove~
processes for these fields. Diatomite is composed of the
siliceous frustules or shells of diatoms, a type of algae, The
silica forming these frustules is amorphous (i.e. noncrystalline) and is known as Opal A. With increased

511

PERMEABILITY

DAMAGE IN DIATOMITE DUE TO IN-SITU SILICA DISSOLUTION/PRECIPITATION

The data, shown in Fig. 4, can be fitted to the following

Arrhenius-type rate equation:

silica precipitation. Although we gain permeability near the

injection well due to silica dissolution, we lose permeability
where silica is precipitated. The net effect on the overaJl
permeability of the reservoir is uncertain without detailed
analysis, but we conjecture that a net decrease in permeability
is most probable (since permeability is additive in its inverse,
i.e.,

kW = ~dx/Jdx/k(x)).

Fig.

m=l.9x10A

Modeling of Slllca Dissolution/Preclpltation and

Permeability Damage
As state4 the objective of this work is to determine the effects
of silica dissolution and precipitation on the permeability of
the diatomite. To this end, the study is divided into three parts.
First, we obtain experimentally the rate constant of silica
dissolution/precipitation from diatomite samples obtained
from Mobils reservoirs. Second, we describe the modeling of
silica transport and mass balance with water flowing through
diatomites a whole core piug flow experiment has been
performed and its &ta have been used to determine the
correlation between porosity and permeability. Finally, the
model is tested under field scale conditions and compared with
field injectivity data.

(l-~oPr (x-xo).............................(5)

(we)=-(l_@#)p,

where X XO is the change in silica mass fraction given by

Eqn. (A-9) in Appendix A.
It is reasonable to assume that the permeability of the rock
is affected by changes in the porosity. Here, we assume one of
the simplest forms of porosity-permeability relationship

Rate of Sitica Dissolution/Precipitation. We begin with the

measurement of the rate of silica dissolution and precipitation
and the assumption of fmt order kinetics 1%

k(x,f) =

ce)................................................(l)

ax

km(l) =

The equilibrium silica concentration, Ce, is obtained from

batch experiments by measuring silica concentration of
saturated water@atomite mixture. Assuming steady-state and
boundary condition of C(x = O)= Ci , the solution to (2) is
simply.

{}

Ci-C~

__~

- T

................................................(6)

........................................m
jdx/j-&

It should be pointed out that we do not know a priori

whether Eqn. (6) describes the actual pcmsity dependence of
diatomite as silica is dissolved or precipitated. An experiment
described in the next section, was performed to determine the
validity of Eqn. (6), and if valid, the value of the porositypermeability factor (7) for the diatomite core in this study.

=m(c-ce) .......................................(2)

~ c(L)-ce

+)

fhe ovemll (or effective) permeability of a one-dimensional

system is simply given by the spatial average of k(x,r):

A series of experiments has been performed to ascertain the

reaction rate catstant (m). The experimental setup is shown in
Fig. 3, where water is injected into a diatomite core plug of
length L.. The effluent water is collected and its silica
concentration measured by inductively coupled plasma
analysis.
The one-dimensional mass balance for silica in solution
can be given by
X+VK

exp(1192 /l) (see-]).........................(4)

Non-isothermal Silica Transport and Rock Mass Balance.

Here, our objective is to model the relationship between silica
dissolution/precipitation and the change in porosity as hot
water is injected into the pous medium (i.e. diatomites.)This
mathematical problem is comprised of three differential
equations and has been solved by Make and 0SuHivan3; for
brevitys sake, the governing equations and boundary
conditions are given in the Appendix. The reader is referred to
refenme 3 for a more detailed derivation of the results.
As water is injxted into the diatomite, silica is dissolved or
precipitated depending on whether the water is super- or
under-saturated. As this happens, the porosity is altered as
described by the following equation3~4

shows qualitative

temperature, porosity and permeability profiles expected in the

situation described in Fig. 1.

;=.m(c.

SPE 35394

Siiica Deposition Experiment

Fig. 5 shows the schematic of an experiment designed to
ascertain the behavior of diatomite as silica is deposited in the
rock matrix. As shown, water is injected into a pack of
diatomite sand maintained at 400F (204C); as water ieaves
the sand pack, it is supersaturated with silica and enters into
the coider, constant temperature (120F or 49C) diatomite
core plug. Due to this supersaturation, the dissolved silica
comes out of solution and is deposited in the diatomite core
plug as the water traverses the plug. The ionic content of the
injection water is same as that obtained from field injection
watq its composition is shown in Table 1. llte injection watez

.........................................(3)

The slope of the plot of the logarithmic term in Eqn. (3) vs.
(-LW) is the reaction rate constant, m(T), for a given
temperature. Five sets of experiments with various flowmes
have been done with temperature ranging from 12(YFto 350F

512

SPE

33394

C.J, KOH, PC. DAGENAIS,

DC. LARSON, A.S. MURER

is adjusted so that data collected before the initial reservoir

fill-up when injectivity is significantly higher are excluded.
Since injectivity is directly proportional to the average
reservoir permeability, we believe that the injectivity reduction
observed in these wells is at least partially due to in-situ silica
precipitation. Although there is no exact quantitative
similarity, we ea.nsee that the permeability reduction observed
in the field is qualitatively captured by the model predictions.
In fact, both graphs show that the typical time scale of
permeability reduction is of the order of hundreds of &ys.
The general shape of the curves between these two plots is
similar, but there is one qualitative difference that should be
pointed out. The model predicts that the permeability, and
therefore the injectivity, should eventually approach zero; field
data show that there is a minimum injectivity of roughly 24
bbl/psi.D (0.05-0.09 m3/kPa.D). This discrepancy is due to the
fact that the model treats the reservoir as a homogeneous
matrix with properties obtained from laboratory experiments.
In reality, the reservoir is not homogeneous and contains
regions of higher permeability and larger pore throats such as
natural fractures. These regions are not subject to the same
permeability reduction mechanism (at least not the same
magnitude) due to silica deposition. Consequently, the
reservoir will have a minimum overall perrneabilit y (and
hence injectivity) greater than zero.

pH is equal to 8.4 while the production water pH remains

approximately the same (ranging from 8.2 to 8.7.) The
pressure drop and flowrate is monitored in order to determine
permeability changes over the duration of the experiment.
The equations that describe this situation are the ones
shown in Appendix A under isothermal condition ( 120F). By
measuring the inlet silica concentration ( Ci), the effective
permeability of the core plug can be calculated using Eqn. (7).
The best value of y is obtained by minimizing the difference
between the experimentally measured permeability and the
predicted values. Fig. 6, which demonstrates the steady
decline in permeability as silica is deposited, shows the
comparison of the results for the best match where y = 9.
Comparison with Field Data
Hot waterflood using hydraulically fractured injection and
production wells can be modeled approximately using the
equations described by Malate and OSullivan (Appendix). To
ascertain the significance of silica deposition andJor
precipitation in the field, typical field data found in Mobils
diatomite waterflood are used to numerically calculate the
reservoirs effective permeability as a function of time. Since
injectivity is directly proportional to the reservoirs effective
permeability, field injectivity data are compared with the
calculated permeability.
Table 2 shows the data used in the model. These are
averaged values from a number of patterns. Note that the
injection water comes from the produced water of Tulare
steamflood (after filtration but no chemical treatment). From
the data shown, the injection water silica concentration is
higher than the equilibrium value obtained from laboratory
measurements. This higher concentration is most likely due to
super-saturation of silica from the hotter steamflood produced
water (i.e., the hol produced fluid from the steamflood
contains a significant amount of silica and has not reached
equilibrium by the time it is injected into the diatomite at
130F or 54C.)
As we are assuming a one-dimensional model, the fluid
particle velocity in Eqn. (A-1) can be approximated by
V = Qpl / (FHFL) where FH and FL are the fracture height
and length respectively.
Fig. 7 shows the reduction in permeability (~ = initial
permeability) as a function of time for various injection silica
concentrations. For the parameters used in this study, it is
clear that a significant degree of permeability damage can
result in a matter of months. Detailed analysis of the model
indicates that the decrease is due to deposition of silica
contained in the injection water near the injection well (near
the fracture face in the case of a 1-D model), Due to
diatomites low permeability and inherently small pore throats,
a relatively small amount of silica deposition can cause a
disproportionately large reduction in permeability. We can
also see that the rate of permeability damage is quite sensitive
to the injection silica concentration. For example, a 50%
permeability drop RX@CS~ut 9(M)*YS when Ci = 285 ppm
but is reduced to about 350 days when Ci =315 ppm.
Fig. fl plots the general trend of injectivity vs. time for a
number of Mobils diatomite injection wells (using the same
time scale as Fig. 7 for ease of comparison.) Note that Day O

Conclusions
Ithasbeen observed that sigrdlcant injectivity loss takes place

in Mobils diatomite water injection wells. Laboratory

experiments and modeling results suggest that in-situ
precipitation of silica is likely to be partially rtxponsible for
such loss. The silica precipitation is due to the relatively high
silica concentration found in the injection water (high
compared to equilibrium concentration at reservoir
temperature.) To minimize the loss of injectivity due to silica
deposition, the injection water should contain a minimal
amount of dissolved silica. One possibility is to inject water
that has been sufficiently cooled to below reservoir
temperature (i.e. dropping out any excessive silica) so that it
will not precipitate silica upon contact with the cooler
reservoir.
Nomenclature
C = concentration, ppm
FH = hydraulic fracture height
FL = hydraulic fracture length
k = permeability, L2,~2
L = length of core plug, L, m
-1

m = rate constant, t-l ,WC

Q = water injection rate, m3 / see

t=time, sec
T = temperature, K
U = thermal ffont velocity, L / t, m / sec
V. fluid particle velocity,L / t, m /see
x = distance, L,m
a=(l-#o)pr
/(1-4. )P.

513

PERMEABILITY

DAMAGE IN DIATOMITE DUE TO IN-SITU S1LICA DISSOLUTIOWPRECIPITATION

SPE 35334

the governing equations and boundary conditions and

highlight some of rhe key results.

P=p,m/(1-40)P,
9= porosity - permeability factor
# = porosity
X = silica mass fraction

The one-dimensional, transient silica mass balance is given

M

p= density, m / L3, kg/m3

~+v~=m(cce)

Subscripts
e = equilibrium value
~ = effective
i=valueatx=O
1= liquid
r= rock
s = silica
O=origirtal value att=O

..................................(A -1)

The energy balance equation, assuming thermal conduction is

negligible, is given by
~+
a
The

Refemncee
The authors wish to thank T. K. Ellison, S. E. Sommer and
M. A. Thomsen for providing valuable comments and
reviewing the manuscript.

U.=
ax

O. ...... ....... ...... ............ ..............(A.2)

silica rock mass balance is

a
OPl m(C Ct)., ...... ...... ................(A3)
=
(1 @(Jp,
a
The initial and boundary conditions are

References
Boon,J., and BircLG.W; MoctelhngSiJica Transportin
Large-StateLaboratoryExperimen&, CJM Paper No. 85-36-50

1. Stone, T.,

C(x.O)= C.(TD).................... ................. .....(A.4)

C(o,t)= Ci... ..<........ ...... .................... ....... ..(A.5)
T(x.o)= T~.... ............ ...... ....... .. .... ..............(A.6)
T(o, () = T~........ ...... .. .... ........ ............. ........(A.7)
X(x, o) = x~................................................(A-8)

presented at tie 36tJrArmuatTechnical Meeting of the Petroleum

Society of CM, Edmonton, June 2-5, 1985.
2. Malate, R.C.M. and OSullivan, M.J.: Mathematical Modelling of
Sitica Deposition in a Porous Me&m, Geothermics (1992) 21,
No. 3, pp. 37740.
3. Mala@ R.C.M. and OSullivan, M.J.: Mathematieat Modelling of
Non-Isothermal Silica Transport and Deposition in a Porous
Medhum GeAermics (1992) 21, No. 4, pp. 519-544.
4. Itoi, R., Fukuda, M., Jirmo, K., Shirnizu, S. and Tomita, T.:
Nurnerica.1Analysis of rhe Decrease in frrjectivi~ of Wells in the
Otake Geothermal Fiel~ Japan, Proc. 9th New Zealand
Geothermal Workshop (1987), pp. 103-108.

These differential equations are solved by the method of

characteristics. The solution to Eqn. (A-3) provides the mass
fraction of silica in the rock as a function of x and t. Behind
the mass front where x <W:
X- XO= *

AppendlxGovernlng Equations and Boundary

Conditions
The mathematical problem described in this study has been
solved by Malate and OSullivan and the readers are referred
to their paper3 for an in-depth analysis. Here, we simply state

lexp

a/3(Ci - CC)(~t)exp(-~

{[

)]}

......... ... .... ............. .........................(A.9)

Table l-Ionic Content of Injection Water

Sodium (Na+)
Potassium (K+)
Calcium (Ca2+)
chloride (cl-)
Sulfate (S042-)
Bicarbonate (HCf)z-l

133.4ppm
3.9 ppm
0.8 ppm
%.6 ppm
105.7ppm
62,2 Wnl

injection water temperature

reservoir temperature
injection water silica concentration
well spacing
fractureheight
fracture half-length

130F@4C)
100F(38C)
285-315 ppm
130 ft (39.6m)

400 ft(122 m)
150 ft (45<7m)

514

C.J. KOH, P.C. DAGENAIS,

SPE 35294

DC. IARSON,

AS. MURER

Production of Oil and water

Injection of Hot Water

cold

Hot
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water
pump

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maintain
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oonetant

= Distance from injection weii

Fig.

2Ouaiitative
temperature,
porosity
nd
eabllity profflee expected in situation deecrkd
in

%%.

515

of experimental eetup to determino

and preoipltatlon
reectlon
rate

PERMEABILITY DAMAGE IN DIATOMITE DUE TO IN-SITU SILICA DISSOLUTIOWPRECIPITATION

-5

SPE 35394

m x 1.9x104 .(m

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;0

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0.
s
>

0.

0.
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-7
0.002

0.0025

0.00
9ic

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12

TirrN (day)

Fig. 6-Compdeon
of oxperlmental parnteebllity data
vs. modet prediction using * 9
Ffg. 4-Arrtrenlus-typ
experimental data

plot of she

reaction rata

prlmsul
ir
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kwsupply

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injection
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. . .. . .............
. .
.... ....O
.
. .. . . ...!.

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produced
water sampling

0.2 - C,.285~m
--

+ .. . . ... ..% .. . .. . .. . ... ... .. . .. . .

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-----

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o
0

200

400

:
9 ..
600

Tim

\:
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, y-m
800

1000

(day)

F@. 7-plot howlrrg norrrtaltxed permeability for

typfcal range of Injectfon llla concantrattorr.

Fig. Hchematlc
of experimental setup to detarmlna
the affecte on dlatomite permeability
due to lllca
dapoeitlorr

516

C.J. KOH, P.C. Dagenais, DC. LARSON, AS. MURER

SPE 3&94

,.
,:
k
-

,!
.. ..... ...........
$,:

-.
:,
k....
.

\;
. .. .

0. . ..-.

:\

,,

___

--

200

400
Titw

600

800

1000

(day]

E-plot showing water Injeotlvity for various

F@
dlaiomile walla.

517