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PROCEEDINGS, Thirty-Eighth Workshop on Geothermal Reservoir Engineering
Stanford University, Stanford, California, February 11-13, 2013
SGP-TR-198
IMPACTS OF ROCK-BRINE INTERACTIONS ON SANDSTONE PROPERTIES IN LOWER
MIOCENE SEDIMENTS, SOUTHWEST LOUISIANA
Masoud Safari-Zanjania, Christopher D. White
a, Jeffrey S. Hanor
b
Louisiana State University aCraft & Hawkins Department of Petroleum Engineering
bDepartment of Geology and Geophysics
2107 Patrick F. Taylor Hall
Baton Rouge, Louisiana, 70803, United States
E-mail: [email protected]
ABSTRACT
Reinjection of cooled geothermal fluid is an essential
part of geothermal reservoir management, and has
been discussed in many recent reservoir studies.
Geothermal fluid reinjection can improve heat
recovery and maintain pressure. Reinjection may
have unfavorable consequences, such as calcite and
silica scaling in reservoir and injection facilities.
However, the impact of brine-rock interactions on
reservoir properties has not been addressed as fully
for reinjection. In this paper, interactions between
geothermal fluid and reservoir rocks in the West
Hackberry field, Cameron Parish, Louisiana are
examined using geochemical modeling. The
Hackberry Field comprises Miocene sediments on the
flank of a salt dome. These sandstones are variably
cemented with calcite, pyrite, and pyrrhotite. The
field is 1.4-2.1 km deep, with initial temperature and
pressures ranging from 65 to 75 °C and 15 to 27
MPa, respectively. The brine is cooled down to the
estimated output temperature of power plant and re-
equilibrated. Then, reinjected brine-rock interactions
with declining reservoir temperature are simulated,
and the effects on reservoir properties like porosity
and permeability are investigated. Geochemical
reactions between different sampled brine and
reservoir rock compositions have been modeled as
the reservoir is chilled.
Keywords. Geochemical model, geothermal reservoir,
rock-brine interaction, geothermal fluid
reinjection, West Hackberry Field
INTRODUCTION
The transition from fossil fuels to renewable
sources seems mandatory for world’s future
economy. High price and political issues
accompanied by crude oil and also environmental
pollution and climate instability caused by fossil fuels
such as oil, coal and natural gas, have attracted the
considerations of energy industry toward renewable
sources like wind, solar, and geothermal energy.
Almost thirty percent of the world’s current
producing electricity by geothermal power plants is
concentrated in the United States; its 3,187 MW of
installed geothermal capacity is more than any other
country in the world. The majority of geothermal
power plants in the US are located in California and
Nevada. There are also power plants in Hawaii, Utah,
Idaho, Alaska, Oregon and Wyoming. More than 140
projects in 15 states comprise one-third of the land
area of the US. Over 5,000 MW of power potential
was identified under development by April 2012.
(International Market Overview Report, GEA, 2012).
Louisiana is one of the states that recently have
started to develop geothermal source of energy.
Independence of power plant to providing fuel and
production reliability has made the geothermal power
plants as an appealing source of energy to provide
emergency electricity in the time of hurricanes.
Heat flowing form the earth’s core and mantle
and from radioactive isotopes decaying in the earth’s
crust is the energy source for geothermal power
projects. Water adsorbs heat from the rock and
transports it to the earth’s surface, where using
turbines and generators heat energy has been
converted to electrical energy. Moreover, direct
applications of geothermal fluids, which decrease the
need for electricity production and burning of fossil
fuels, have gained importance over the years
Geothermal often cannot compete with fossil
fuels commercially. The cost of drilling enough wells
to supply full plant capacity is almost equivalent to
purchasing most of the fuel required for the next 20
years in a fossil-fired plant (Gallup, 2009). On the
other hand, after operating the geothermal power
plant the costs will be mostly the maintenance
expenses. Therefore, a geothermal power plant has to
work reliable for a long period of time to be
profitable.
The experiences of high pressure drop in the
reservoir and high annual steam decline rates in
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excess of 25% in some areas of the Geysers steam
field, California, have shown the importance of
reservoir management in the geothermal fields
(Goyal and Conant, 2010). Reinjection of cooled
geothermal fluid not only is an environmental
prerequisite for disposal of the geo fluid, but it also
can maintain reservoir pressure and improves heat
recovery from matrix rocks (Ungemach, 2003).
In the case of high salinity geo fluid, corrosion
and scale forming may cause serious problems in
production and surface facilities and also reinjection
process. The Salton Sea geothermal field in southern
California (USA) is a well-known field for its hyper-
saline, 200,000–300,000 mg/L total dissolved solids,
brines (Gallup, 2009). In this field, corrosion problem
has been successfully controlled by materials
engineers. Also, new technologies created by
production engineering and chemistry efforts like
crystallizer–clarifier and brine acidification, has
effectively solved scale forming problem (Gallup,
2009).
Although, considerable efforts have been done to
solve the scaling problem in production and surface
facilities, the impact of scaling and rock-brine
interactions on reservoir properties has not been
addressed as fully for reinjection. In this paper,
interactions between geothermal fluid and reservoir
rocks in the West Hackberry field, Cameron Parish,
Louisiana are examined using geochemical modeling.
GEOLOGIC SETTING
The West Hackberry salt dome is located in
north-central Cameron Parish, southwest Louisiana
and constitutes the western half of a larger, 16-km-
long salt ridge. The dome is an elongate shallow
piercement dome which intrudes Tertiary and older
sediments (McManus and Hanor, 1988).
Ground elevation in the area is a few meters
above mean sea level (m.s.l). Caprock consisting of
calcite, anhydrite and pyrite (Howe and McQuirt,
1935) is developed on top of the dome and extends to
an elevation of -600 m m.s.l. The top of salt occurs at
an elevation of -700 m m.s.l. (McManus and Hanor,
1988). Mineralogical analyses of the salt stock
indicate that it is composed of 95 percent halite, 4
percent anhydrite, and
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Table 1: The brine compositions that have been used
in the models, all concentrations are in
mg/kg.
Brine number
1 2 3
Specific gravity (gr/cm3) 1.192 1.161 1.127
pH 4.80 6.35 5.80
CO2 1,258 407 279
HCO3- 49 569 110
Ca2+
6,208 208 10,470
Mg2+
1,023 53 1109
Na+ 84,814 82,394 49,500
K+ 857 832 861
Cl- 145,973 128,488 99,379
SO42-
159 39 1
Fe2+
0 3 0
Table 2: The rock compositions that have been used
in the models by mass percentage.
Plug number
1 2 3
Sampling depth (m) 1,524 1,835 2,134
Quartz 84 35 31
K-feldspar 0 3 11
Plagioclase 13 1 9
Calcite 3 53 12
Pyrite 0 4 0
Siderite 0 0 2
Analcime 0 0 4
Kaolinite 0 0.6 2
Illite 0 0.8 5
Smectite 0 2.6 24
Modeling process
The rock-brine reactions have been modeled
with titration paths. In titration reaction paths, the
program repeatedly adds a small aliquot of reactants
and then recalculates the system’s equilibrium state
as it steps forward in reaction progress (Bethke and
Yeakel, 2012).
The initial and final temperatures of geofluid
have been assumed to be 150 and 25 °C, respectively.
Although, the highest measured temperature in
studied area was 75 °C, for generalization purposes
and compatibility with required brine temperature for
binary geothermal power plants, the final temperature
has been assumed to be 150 °C. First, the brine has
been cooled down to 25 °C. Then, the earliest
geochemical reaction between brine and rock has
been modeled at reservoir temperature; with brine
temperature rising from 25 to 150 °C. Next, reaction
steps were modeled using a constant temperature of
150 °C.
Rock-brine geochemical reactions have been
modeled in two different ways; in the first case, after
the earliest rock-brine interaction, the resulting
minerals are separated and next reaction step happens
between the minerals resulting from last reaction step
and initial brine composition. In the second case,
after the earliest rock-brine interaction, the resulting
fluid is separated and next reaction step happens
between the brine resulting from last reaction step
and the initial rock composition. Figure 2 shows a
schematic drawing for these two cases of modeling.
In all cases, reactions have been modeled for several
steps, until the results for total minerals in the system
show the same trend for two consecutive steps.
Figure 2. Schematic drawing shows two different
cases of modeling.
RESULTS
The authors are aware that some of the mineral
products generated in the Geochemist's Workbench
brine-rock simulations (including muscovite and the
Mg-sheet silicates) are usually associated with high-
temperature hydrothermal or low-grade metamorphic
conditions rather than sedimentary diagenetic
settings. However, these phases can probably be
considered as proxies for more typical diagenetic
products, such as illite and other diagenetic sheet
silicates.
The total amount of minerals in the system
versus reaction progress is considered for brine Brine
1 Plug 3, Figures 3 and 4, for the first and second
reaction steps, respectively. In this Plug, the amount
of smectite is relatively abundant. In the first
reaction, the total amount of quartz, albite,
muscovite, calcite and annite are increased
throughout the reaction. These total amounts include
both the initial concentration of minerals which are
entered to the system and minerals which are
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produced during the reaction. Reaction progress is a
normalized way to show the reaction development. In
the horizontal axis of Figures 3 and 4, 0 is the start
point of the reaction and 1 shows the completion of
the reaction. The program divides this progress into
100 steps and introduces a small fraction of reactants
to the system in each step.
Figure 3: First brine-rock reaction for Brine 1 Plug 3.
For the next reaction, the fluid part of the system
is separated and reacted with new rock composition.
In the second reaction, quartz, muscovite, albite, and
calcite are the minerals with the highest
concentrations. The concentration of pyrite in both
reactions is increased in the first moments of the
reaction and stays constant for the rest of the reaction
path.
Figure 4: Second brine-rock reaction for Brine 1
Plug 3.
Four consecutive reactions between Brine 3 and
rock composition at depth of 1835 m (Plug 2) were
investigated (Figs. 5-8). At this depth calcite with 53
percent, is aboundant and its amount is more than
quartz with 35 mass percent.
In these models, for each reaction, the resulting
fluid from pervious reaction is separated and reacts
with the initial rock composition. In the first reaction,
Figure 5, calcite, quartz, muscovite, pyrite and
saponite-Ca continuously increase during the reaction
path. Calcite and quartz have the highest amounts in
comparison to other minerals.
Figure 5: First brine-rock reaction for Brine 3 Plug 2.
In the second reaction, Figure 6, in addition to
previous minerals, the system has annite. In the next
two reaction steps, Figures 7 and 8, the amount of
minerals versus reaction progress have the same
trend. Calcite and quartz are the minerals with the
highest concentrations.
Figure 6: Second brine-rock reaction for Brine 3
Plug 2.
For comparision purposes, four consecutive
reactions between Brine 3 and rock composition at
depth of 2134 m (Plug 3) were investigated (Figs. 9-
12). In these models, for each reaction, the resulting
minerals from the previous reaction are separated and
react with the initial fluid composition.
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5
Figure 7:Third brine-rock reaction for Brine 3 Plug 2.
Figure 8: Fourth brine-rock reaction for Brine 3
Plug 2.
Figure 9: First brine-rock reaction for Brine 3 Plug 3.
Almost the same trend can be seen in all graphs.
Quartz, muscovite, calcite, saponite, daphnite,
nontronite and dolomite are the dominant products in
the system and the amounts of these minerals
increase during the reaction path. Pyrite also is
produced during the reactions; however, its amount,
around 1 mg/kg, is relatively small.
Figure 10: Second brine-rock reaction for Brine 3
Plug 3.
Figure 11: Third brine-rock reaction for Brine 3
Plug 3.
Figure 12: Fourth brine-rock reaction for Brine 3
Plug 3.
DISCUSSION
Reinjection of cooled geothermal brine is
recognized as an effective way to maintain pressure
and improve heat recovery. Scaling problems caused
by calcite and quartz precipitation is a prevalent
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6
disaster which happens in geothermal power plants
and reinjection facilities with high salinity geofluids.
Some research has been done on solving scale
problems in surface facilities, but the impact of
precipitation and scaling on reservoir properties has
not been addressed as fully. In this research the
impact of rock-brine interactions on reservoir
properties has been investigated.
Three brine compositions from West Hackberry
field, Louisiana have been used to model rock-brine
interactions. Cl-, Na
+ and Ca
+ are the species with
highest amount in the brine samples. Brines are
somewhat acidic with pHs equal to 4.80, 6.35 and
5.80, respectively.
Dissolution and precipitation
Three rock samples from the same field have
been used for modeling purposes. Samples were
taken from different depths of 1524, 1835 and 2134
m (McManus, 1991). At the lowest depth, the rock
consists mostly of quartz. Plagioclase and calcite, at
13 and 3 percent respectively, are the other minerals
in the rock. At the depth of 1835 m (Plug 2), the
amount of calcite is considerable. At this depth the
amount of calcite (53 percent) is higher than quartz
(35 percent). Low concentrations of clay minerals are
found at this depth. At the depth of 2134 m (Plug 3),
quartz and calcite, at 31 and 12 percent respectively,
are the main minerals in the rock. Clay minerals at 31
percent make considerable portion of the rock.
Smectite with 24 percent is the main clay mineral.
Almost in all cases that have been investigated in
this paper, quartz and calcite were the two important
minerals which were produced in most rock-brine
interaction model runs.
Quartz is one of the most abundant minerals and
occurs as an essential constituent of many igneous,
sedimentary and metamorphic rocks. The
composition of quartz is normally very close to one
hundred percent SiO2. Quartz is one of the most
stable minerals and it is resistant chemically to most
attacking solutions (Deer et al., 1966).
Calcite, like most carbonates, will dissolve in
most forms of acid. Calcite can be either dissolved by
groundwater or precipitated by groundwater,
depending on several factors, including the water
temperature, pH, and dissolved ion concentrations.
The solubility of calcite in water increases with
increasing partial pressure of CO2 and with
decreasing temperature (Deer et al., 1966). The
dissolution or precipitation kinetics of carbonates is
very fast compared to those of silicates. Therefore,
carbonate phases play an important role in the
evolution of reservoir porosity (Fritz et al., 2010).
In a water injection project the possibility exists
that suspended solids will cause the injection wells to
become impaired (Barkman and Davidson, 1972). In
geothermal reservoirs with high salinity geofluids,
the possibility of forming solid particles in a power
plant’s cooled brine outflow is high. Suspended
particles are the main source of damage to wells and
formations (Ungemach, 2003). With similar
mechanisms, these solid particles can cause clogging
inside the reservoir, especially in vicinity of
reinjection wells.
In addition to solid particles present in reinjected
geofluid, new reactions between brine and reservoir
rocks may produce a considerable amount of solid
particles over the geothermal power plant life time
scale. This is particularly true when dealing with tight
and fine-grained reservoirs and high salinity brines.
On the other hand, dissolution of minerals and
porosity increases are also possible.
In modeling consecutive reactions, the
continuous brine flow into rocks has been simulated.
As it can be seen in Figures 5 through 12, after
second reaction, graphs almost have similar trends.
Apparently, as long as the other conditions of
reaction do not change, considerable changes in
mineral concentrations happen in first reaction steps.
Changes of fluid compositions as a result of brine-
rock reaction in different steps of reaction for Brine 3
Plug 2 and the separating fluid for next reaction (Fig.
13) and Brine 3 Plug 3 and the separating minerals
for next reaction (Fig. 14) show the same result.
Figure 13:Changes of fluid compositions in reactions
of Brine 3 Plug 2.
Figure 14:Changes of fluid compositions in reactions
of Brine 3 Plug 3.
0.001
0.01
0.1
1
10
100
1000
10000
100000
1000000
1 2 3 4 5
Reaction steps
Ele
men
tal
com
po
siti
on
(m
g/k
g)
Aluminum
Calcium
Carbon
Chlorine
Hydrogen
Iron
Magnesium
Oxygen
Potassium
Silicon
Sodium
Sulfur
0.001
0.01
0.1
1
10
100
1000
10000
100000
1000000
1 2 3 4 5
Reaction steps
Ele
men
tal
com
po
siti
on
(m
g/k
g)
Aluminum
Calcium
Carbon
Chlorine
Hydrogen
Iron
Magnesium
Oxygen
Potassium
Silicon
Sodium
Sulfur
http://en.wikipedia.org/wiki/Ion
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7
As it can be seen in these Figures, the most
significant changes happen between step 1 (the first
interaction between fluid and rock) and step 2.
Although, some changes can be seen in later steps,
potassium decrease in step 2 of Figure 14, in last two
steps there are almost no changes in the amount of
elemental compositions in fluid.
Principal reaction products
Results from the case study show the production
of quartz and calcite in most rock-brine interactions
(Figs. 15 and 16). The ratios of total volume of quartz
after reaction completion to initial volume of quartz
in both Brine 3 Plug 2 and Brine 3 Plug 3 in all
reaction steps are greater than 1; quartz precipitates.
This result is also correct in case of calcite. For Plug
3 which has lower amount of calcite in comparison to
Plug 2, production of quartz is as high as 37 percent
of the initial amount.
Figure 15: The ratio of total volume to initial volume
in reactions of Brine 3 Plug 2.
Figure 16: The ratio of total volume to initial volume
in reactions of Brine 3 Plug 3.
Effects on porosity and permeability
Some minerals, especially quartz and calcite, are
produced during reaction and increase the ratio of
rock volume to bulk volume. On the other hand,
some minerals, especially albite, anaclime, smectite,
illite, and K-feldspar, are dissolved and increase
porosity (Table 3). In this study, the amount of
dissolution was more than precipitation. Therefore,
an increase in porosity occurs. A volume decrease of
6.85 cm3 has been calculated for Brine 3 Plug 3. In
this simulated experiment, minerals from the
previous reaction products are separated (or “Picked
up”, Fig. 2, top), and reacted anew with the original
brine (Table 3). If one assumes initial porosity of
, the secondary porosity is calculated to be 0.264, a 5.6 percent increase in porosity. Similarly, a
0.53 percent increase in porosity is estimated for
Brine 3 Plug 2. In that simulated experiment, fluid is
separated from previous reaction (refer to Fig. 2,
bottom) and reacted anew with initial mineral
composition (data are not shown here).
Table 3: Change of mineral volume as a result of
brine-rock reaction for Brine 3 Plug 3.
Step 1
Volume
before
reaction
(cm3)
Volume
after
reaction
(cm3)
Volume
difference
(cm3)
Albite 34.406 25.460 -8.946
Analcime 17.643 0.000 -17.643
Calcite 44.268 45.080 0.812
Illite 18.090 0.000 -18.090
K-feldspar 43.025 0.000 -43.025
Kaolinite 7.710 0.000 -7.710
Quartz 117.013 141.100 24.087
Siderite 4.942 0.000 -4.942
Smectite-high-Fe 82.538 0.000 -82.538
Dolomite-ord 0 4.697 4.697
Minnesotaite 0 23.96 23.96
Muscovite 0 82.88 82.88
Nontronite-Ca 0 10.12 10.12
Pyrite 0 5.31E-05 5.31E-05
Saponite-Ca 0 31.31 31.31
Summation 369.63409 364.60705 -5.027
Step 2
Volume
before
reaction
(cm3)
Volume
after
reaction
(cm3)
Volume
difference
(cm3)
Albite 25.460 3.988 -21.472
Calcite 45.080 49.970 4.890
Daphnite-14A 0.000 19.123 19.123
Dolomite-ord 4.697 0.471 -4.226
Muscovite 82.880 83.970 1.090
Nontronite-Ca 10.120 10.150 0.030
Pyrite 0.000 0.000 0.000
Quartz 141.100 159.900 18.800
Saponite-Ca 31.310 36.130 4.820
Minnesotaite 23.96 0 -23.96
Summation 364.607 363.702 -0.905
0.96
0.98
1
1.02
1.04
1.06
1 2 3 4 5
Reaction steps
V t
ota
l/V
in
itia
l
Quartz
Calcite
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1 2 3 4 5
Reaction Steps
V t
ota
l/V
in
itia
l
Quartz
Calcite
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8
Table 3 (cont.): Change of mineral’s volume as a
result of brine-rock reaction for
Brine 3 Plug 3.
Step 3
Volume
before
reaction
(cm3)
Volume
after
reaction
(cm3)
Volume
difference
(cm3)
Albite 3.988 0.000 -3.988
Calcite 49.970 48.930 -1.040
Daphnite-14A 19.123 18.544 -0.578
Dolomite-ord 0.471 1.401 0.930
Muscovite 83.970 85.650 1.680
Nontronite-Ca 10.150 10.180 0.030
Paragonite 0.000 0.297 0.297
Pyrite 0.000 0.000 0.000
Quartz 159.900 161.200 1.300
Saponite-Ca 36.13 37.24 1.11
Summation 363.702 363.443 -0.259
Step 4
Volume
before
reaction
(cm3)
Volume
after
reaction
(cm3)
Volume
difference
(cm3)
Calcite 48.930 47.050 -1.880
Daphnite-14A 18.544 17.906 -0.638
Dolomite-ord 1.401 3.064 1.663
Muscovite 85.650 86.180 0.530
Nontronite-Ca 10.180 10.210 0.030
Pyrite 0.000 0.000 0.000
Quartz 161.200 160.900 -0.300
Saponite-Ca 37.240 37.820 0.580
Paragonite 0.297 0.000 -0.297
Summation 363.443 363.131 -0.312
Step 5
Volume
before
reaction
(cm3)
Volume
after
reaction
(cm3)
Volume
difference
(cm3)
Calcite 47.050 45.180 -1.870
Daphnite-14A 17.906 17.260 -0.647
Dolomite-ord 3.064 4.719 1.655
Muscovite 86.180 86.390 0.210
Nontronite-Ca 10.210 10.240 0.030
Pyrite 0.000 0.000 0.000
Quartz 160.900 160.600 -0.300
Saponite-Ca 37.820 38.400 0.580
Summation 363.131 362.789 -0.342
Many studies have been conducted to relate
porosity to permeability. Several different forms that
have been suggested for the porosity function by various authors are shown in Table 4 (Dullien,
1979). Using the equation suggested by Rumpf and
Gupte (1971), the changes of in this specific studied example, for a 5.6 percent porosity increase,
would be equal to 35 percent increase. The calculated
change of using Carman-Kozeny form is equal to a 22 percent increase. In case of 0.53 percent
porosity increase, these quantities for Rumpf and
Gupte and Carman-Kozeny equations would be 2.9
and 1.9 percent, respectively.
Table 4: Different porosity functions for low Reynolds
number flow (See Dullien, 1979 for complete
citations).
Author
Blake (1922), Kozeny (1927), Carmen (1937)
Zunker (1920)
Hulbert and Feben (1933)
Slichter (1898)
Hatch (1934), Mavis and Wilsey (1936)
Rumpf and Gupte (1971)
Assuming that Carman-Kozeny behavior applies
and change in tortuosity and specific surface are
negligible, permeability is proportional to . Percipitation of some minerals like calcite also
may change the elastic module of reservoir rocks as a
result of cementation and therefore the condition of
reservoir’s fractures may change over time as a result
of reinjection.
CONCLUSIONS
In this research the impacts of rock-brine
interactions on sandstone properties have been
investigated. Although the production of quartz and
calcite was observed in the simulations, dissolution
of other minerals results in porosity increase and
therefore a permeability increase. However, porosity
changes caused by rock-brine geochemical reactions
are highly dependent on brine and rock compositions.
Depending on the situation, these reactions could
cause a decrease, an increase, or no change in
reservoir porosity. As a result, geochemical and
geological investigations should be a significant part
of the geothermal resource exploration.
ACKNOWLEDGMENTS
This study was supported by Louisiana State
Board of Regents program enhancement award. The
GDL foundation also is appreciated for a grant which
assisted this research.
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9
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