AN EXPERIMENT ON MONOMERIC AND POLYMERIC SILICA PRECIPITATION

RATES FROM SUPERSATURATED SOLUTIONS

TABLE OF CONTENTS

ABSTRACT

1. INTRODUCTION

2. BACKGROUND
2.1 Silica scaling
2.2 Previous studies and mitigating measures
2.3 Operation difficulties and field tests

3. DESCRIPTION OF WORK
3.1 Assessment of Malitbog sector scaling
3.1.1 Scaling potential evaluation
3.1.2 Data on injection wells
3.2 Silica experiment
3.2.1 Experimental design
3.2.2 Sampling and analytical methods
3.2.3 Results

4. DISCUSSION
4.1 Results of experiment
4.2 Relevance of experimental results to Malitbog
4.3 Future work

5. SUMMARY AND CONCLUSIONS

ACKNOWLEDGEMENTS

REFERENCES

APPENDICES

I. Sample of WATCH print-out to determine scaling potential

II. Data for calculation of mixed brine in Separator Station 51 at 10 bar-g
III. Data for calculation of mixed brine in Separator Station 52 at 10 bar-g
IV. Data for calculation of mixed brine from Separator Stations 51 and 52
V. Malitbog production wells scaling potential
VI. Silica experiment results
 AN EXPERIMENT ON MONOMERIC AND POLYMERIC SILICA
PRECIPITATION RATES FROM SUPERSATURATED SOLUTIONS

Erlindo C. Angcoy Jr.

Technical Services Sector, Geoservices Department
PNOC-Energy Development Corporation
Merritt Road, Fort Bonifacio, Taguig City
PHILIPPINES
angcoy.ec@energy.com.ph

ABSTRACT

Experimental solutions initially supersaturated with amorphous silica were allowed

to polymerize while being pumped through a column packed with silica gel. The
concentrations of silica monomers and polymers in the solutions were monitored at
the inlet and outlet of the column. Results of experimental runs conducted at 50°C
with pure water and saline solutions (0.1 M, 0.2 M, 0.3 M and 0.4 M NaCl)
showed shorter induction time and faster polymerization with increasing salinity
consistent with theory and past studies. In all runs, monomeric silica dropped to
saturation for amorphous silica in the column whereas the concentration of
polymerized silica changed little. A solution of 0.3 M NaCl at 90°C also showed
lesser tendency for polymeric silica than monomeric silica to precipitate on the
surface of the silica gel in the packed column. However, higher temperature and
salinity allowed polymers to grow large enough to deposit in the source tank. In
the column, some of the polymeric silica lost either by precipitation or filtration
from solution in the void spaces of the column. The experiment demonstrates that
amorphous silica scaling from geothermal brine can be mitigated by allowing
dissolved silica in excess of amorphous silica solubility to polymerize provided
that factors affecting polymerization rate and polymer deposition rate are known.

1. INTRODUCTION

Harnessing geothermal energy entails overcoming the difficulties encountered in its various stages of
development. Whereas geothermal projects are spurred forward after establishing the heat source and
permeability, addressing problems associated with the chemical composition of the geothermal fluids
is as critical for successful exploitation. Geothermal water undergoes cooling and degassing during
the process of extracting the heat. These changes favour the formation of different scales along the
fluid path (Arnórsson, 2004) which are often detrimental to geothermal operations. Amorphous silica
is one of the major and most common scaling problems as its solubility decreases with decreasing
Angcoy 3 Report 5

temperatures. Depending on the conditions, amorphous silica scales may form anywhere from the
production wells, surface facilities to downstream of injection wells.

Injecting the fluids back to the reservoir is either an integral part of field management and/or
compliance to environmental regulations. As spent geothermal waters are injected, silica may
precipitate to cause mild to severe decline in injectivity of wells (Messer et al., 1978; Hauksson and
Gudmundsson, 1986; Itoi et al., 1989; Malate and O’Sullivan, 1993; Alcober et al., 2005). High costs
both in drilling wells and treatment to restore well injectivity make it important to maintain injection
well capacities in a sustainable period. In this study, we establish potential amorphous silica scale
formation in the aquifer receiving brine in the Malitbog sector of Tongonan Geothermal Field,
Philippines with the aid of the speciation program WATCH. The scale formation, which deteriorates
the injectivity of the wells, provided the motivation to investigate the precipitation rates of the
different silica species in a controlled experiment.

2. BACKGROUND

The theory and mechanism of amorphous silica scaling, studies conducted in the past and their
applications to address problems encountered in the geothermal industry are reviewed. As silica is the
most abundant oxide in the earth’s crust coupled with the need to understand its behaviour as applied
to sciences and engineering, it is a subject of considerable study through the years. For detailed and
comprehensive discussions on silica chemistry, readers are referred to Iler (1979) and Dove and
Rimstidt (1994). General information on Malitbog geothermal operations and field tests in relation to
the study topic is provided in this report.

2.1 Silica scaling

The term silica is a short convenient form of silicon dioxide (SiO2) and may refer to any of its nine
natural or engineered earth system forms (polymorphs). In studying geothermal fluids, the silica
phases of most interest are quartz, chalcedony and amorphous silica. Quartz is the most stable and
common form in nature and is invariably present as secondary mineral of most geothermal systems.
Reaction of quartz with aqueous solution can be expressed as:

SiO2,quartz + 2H 2 O ⇔ H 4 SiO4,aqueous (1)

In most high-temperature reservoirs, aqueous silica concentrations are controlled by quartz solubility
(Fournier and Rowe, 1966). Quartz solubility is temperature dependent. Accordingly, aqueous silica
concentrations in geothermal reservoirs are determined by the reservoir temperature (point 1 on Figure
1). As the reservoir water rises to the surface, it boils by depressurization and cools down and in the
process it gives off heat to the steam that forms. The steam formation increases the silica
concentration of the water. This causes the water to become quartz supersaturated. Experience shows,
however, that quartz precipitation from supersaturated solution is very slow. Silica only precipitates at
appreciable rate if the effects of cooling and steam formation are sufficient to produce amorphous
silica supersaturated solution (point 2 on Figure 1). To prevent deposition of amorphous silica in
geothermal installations it is common to keep its temperature above that corresponding with saturation
for amorphous silica. This limits the amount of heat that can be extracted from the fluid discharged
from production wells. It is therefore common to cool the water past the saturation levels (point 3 in
Figure 1) making it supersaturated with respect to both quartz and amorphous silica. Quartz and
amorphous silica solubilities have been investigated numerous times over a wide range of
temperatures, pressures, and solution compositions which are summarized in the works of Chan
(1989) and Gunnarsson and Arnórsson (2000).
Angcoy 4 Report 5

Dissolved silica in typical conditions of geothermal reservoir waters (<600°C, 6-8 kbar) were
determined by Zotov and Keppler (2002) to be all on monomeric form (monosilicic acid), H4SiO40. A
monomer may also be written as Si(OH)40 showing a central Si atom with 4 separate bonded –OH , or
silinol, groups. The silinol groups between two monomers form the Si-O-Si bonding into dimers, an
initial step called a condensation reaction towards formation of higher molecular weight polymers:

Si(OH)4 + Si(OH)4 ⇔ ( HO)3 Si - O - Si(OH)3 + H 2 O

0 0
(2)

Since equation (2) shows no ionized species, it is alternatively written in two reactions to manifest the
effect of cations and pH (Fleming, 1986):

H 4 SiO4 ⇔ H 3 SiO4 + H +
0 -
(3)

H 4 SiO4 + H 3 SiO4 ⇔ H 6 Si2 O7 + OH (4)

0 - 0 -

2,500
When the monomeric concentration
exceeds amorphous silica saturation level,
the growth of polymers and scale
Unionized silica as SiO2 (mg/kg)

deposition are functions of combined 2,000

chemical and physical processes following Quartz

Amorphous silica
two dominant and essentially competing
pathways: (1) molecular deposition upon 1,500
Cooled
solid surfaces and (2) particle deposition geothermal
3
which follows homogenous nucleation and water

growth of suspended particles (Weres and 2 No silica

1,000 scaling zone
Apps, 1981; Klein et al., 1991). The two Amorphous silica
supersaturation
mechanisms compete for the supply of 1
excess Si(OH)4 in solution such that the
500 Aquifer
dominant one tends to slow down the
other.

Molecular deposition involves not only 0

chemical bonding of dissolved silica 0 100 200 300

directly to solid surfaces like pipe walls, Temperature ( C) o
forming hard, dense, difficult to remove,
Figure 1: Solubility curves of quartz and amorphous
vitreous, and often dark-coloured scale. It
silica as a function of temperature. Point 1 is the
also refers to the mechanism in which the
silica concentration in aquifer initially in equilibrium
growing polymer surface is a solid to
with quartz. During adiabatic boiling and subsequent
which the monomer and silicate ions
cooling of the aquifer water, aqueous silica
migrate by circulation and diffusion
concentrations increases and amorphous silica
(heterogenous nucleation). This
saturation is reached in point 2. Further adiabatic
mechanism is a slow process and
boiling and cooling of the aquifer water will lead to
dominant at supersaturation ratio <2
supersaturation with respect to amorphous silica at
(silica concentration/equilibrium solubility
point 3.
at the given condition) or at high flow
velocity such that nucleation occurs further downstream. The rate of molecular deposition of
monomeric silica is a function of temperature and the density of silinol groups ionized to –Si-O- on the
solid growth surface, or to an –OH group in a corroded iron. Salinity accelerates deposition by
increasing the extent of surface ionization and decreasing the solubility of amorphous silica.

In particle deposition, the starting process is termed homogenous nucleation since the polymers
develop spontaneously in solution. The decline of monomeric silica concentrations in solution (from
initial supersaturation to saturation level) as analyzed by the molybdate method has been the principal
method of studying polymerization processes. The rate of decline of monomeric silica is a strong
Angcoy 5 Report 5

function of initial supersaturation such that it is often instantaneous or very rapid if the ratio is >2.5
but exhibits a plateau called induction period which can last from minutes to hours if the ratio is <2.5.
Induction period and polymerization rate are subjects of a lot of studies (summarized by Chan, 1989;
Gunnarsson and Arnórsson, 2005). In general, at a given supersaturation level, induction will be
shorter at a lower temperature, higher salinity, and higher pH (except in very basic solution when
solubility of amorphous silica is high). The rate by which the monomers disappear to form polymers
(polysilicic acid) is usually expressed as (Bohlmann et al., 1980; Weres et al., 1982; Fleming, 1986):

= k (C − Ce )
dC (5)
−
n

dt

where C = monomeric silica concentration;

Ce = concentration corresponding to amorphous silica saturation at the reaction
temperature;
k = reaction constant;
n = reaction order.

However, results are not consistent and reaction orders from 1 to 8 have been reported for the
maximum rate at 6<pH<9. Others also propose different mechanisms of how the monomers
polymerize leading to development of different forms of polymerization rate equations (summary in
Chan, 1989). Despite the differences, most authors agree that polymerization continues until the
monomeric silica concentration falls to the solubility of amorphous silica.

Polymers continue to grow until they reach a critical size (<50 Å but sometimes down to 10-20 Å) for
them to be considered colloidal particles. The colloids may deposit to a solid surface driven by
transfer processes such as diffusion, flow turbulence and gravity. When the colloids are deposited
along with monomeric silica (Iler, 1979), deposition rate are much faster than deposition involving
monomers only and the deposits are much more dense and hard than those formed by coagulated
colloids only. Simultaneous deposition of colloids and monomeric silica creates worse scaling
problems than deposition of monomeric silica only as the depositing colloids are cemented together by
the monomers (Weres and Apps, 1982). If the solution is static or flowing very slowly, the colloids
may coagulate and form flocs which could either precipitate or remain suspended as semi-solid
material. In some cases, the colloids are very stable in solution and do not precipitate (Klein, et al.,
1991).

2.2 Previous studies and mitigating measures

Similar studies on silica chemistry have recently been carried out with objectives and methodology
similar to those of the present study. Bohlmann et al. (1980) simulated geothermal brines under
controlled conditions at specified supersaturation, pH, temperature and salinity and passed through
columns with various substrates. They observed that once thoroughly coated with silica, the
deposition behaviour was identical and independent of the type of substrate. They also observed that
more than half the silica removed from solution was deposited as monomers. Polymerized silica had
little tendency to deposit. Weres et al. (1982) studied experimentally and theoretically silica
polymerization with the purpose of predicting its pattern under conditions typical of geothermal
brines. Fleming (1986) studied condensation polymerization between monomer and silica surfaces in
the absence of nucleation (seeding with colloidal amorphous silica particles of known surface area).
Amorphous silica precipitation behaviour was investigated by Carroll et al. (1998). They observed
slower rates in laboratory tests than in field experiments. The cause was considered to be due to
chemical impurities in the geothermal brine. Gallup (1998) demonstrated that Fe and Al silicate scales
were significantly less soluble than pure amorphous silica. It may require higher brine temperature to
mitigate them.
Angcoy 6 Report 5

Conducting local field experiments is common as results using actual geothermal brines often deviate
from laboratory experiments. In their study of injection problems caused by downhole silica scaling,
Nishiyama et al. (1985) observed the scale deposition was concentrated at the upstream part of the
column only and that brine with high polysilicic acid concentration caused small decrease in
permeability. Axtmann and Grant-Taylor (1986) recognized that in slightly silica-supersaturated
brine, monomeric silica initially deposited on growing colloidal surfaces so they concluded that it was
favourable to use a fluidized bed prior to injection. Mroczek and McDowell (1990) found that with
rapidly polymerizing brine, deposition rate across gravel beds were lesser compared to brine
containing only monomeric silica. Mroczek et al. (2000) allowed brine with excess monomeric silica
only to pass across a column packed with zirconia beads and used the results to numerically model and
predict the lifetime of reinjection aquifers. The tests of Rothbaum et al. (1979) showed that deposition
of polymerized silica only changed the physical appearance of the scale but had no effect on the
chemical content. It was however argued that these observations were probably due to the high
turbulence of the flowing brine. Dunstall and Brown (1998) and Zipfel et al. (1998) explored how
hydrodynamics affects the behaviour of silica scaling.

The results of these studies helped develop other approaches to control silica precipitation from
geothermal brines aside from avoiding supersaturation. The exact fields utilizing the methods are
widely cited in Weres and Apps (1982) and Arnórsson (2004). These include: (1) lowering the pH by
acidification, (2) brine aging to convert monomeric silica to colloidal silica, (3) use of inhibitors, (4)
precipitation of the silica with lime or by bubbling CO2 through the solution, (5) mixing the brine with
steam condensate and (6) removal of colloidal silica by coagulation and settling. There is no single
standard solution to all silica scaling problems. Often a combination or slight modification of any of
these methods has been adapted depending on the experience gained.

2.3 Operation difficulties and field tests

Malitbog is located south of the Tongonan 0 1 2 km TONGONAN Production pad

Geothermal Field (Figure 2). This field forms GEOTHERMAL Injection pad
4RC4 FIELD
the northern reservoir of the 107,625 hectares Power plant

geothermal reservation called Greater Tongonan 405

408 Upper Mahiao
Major fault
Impermeable block
Geothermal Field in the island of Leyte, central 410

Philippines. Malitbog is the major outflow 110 401 403

region of the Tongonan reservoir (Alvis-Isidro 101

1R5
1R3
300B
South Sambaloran
et al., 1993) and its artificial recharge by Tongonan-I 1R8
503
injected brine helps maintain the average well 305
5R7D
discharge enthalpies in this sector below 1,600 5R1
509
MAHANAGDONG
kJ/kg (Dacillo and Siega, 2005). All spent Malitbog
5RB
MN2 GEOTHERMAL
FIELD
geothermal brine from Malitbog is injected into MGB3

3 wells (5R1D, 5R4 and 5R7D). As of August MGDL

Mahanagdong-B
MG3D
2006, flow measurements using tracers showed MG1
MG5D
that 73% of the total brine (~250 kg/s) flows
MG2D
into wells 5R1D and 5R4 of Pad 5R1 at a Mahanagdong-A
temperature ~160°C. Most of the Malitbog MG-RD1
brine is preferentially distributed to Pad 5R1
injection wells and lesser flow to injection well
5R7D of Pad 5R7 to counteract the observed
decline in output of the central and eastern Figure 2: Map of the Greater Tongonan
Malitbog production wells (Herras, 2006). Geothermal Field, Leyte, Philippines
Thus, maintaining high injection capacities in
Pad 5R1 wells is of utmost importance not only for environmental compliance but also to achieve field
management objectives.
Angcoy 7 Report 5

Limited silica scale (3-8 mm/yr) forms in the 1999 2000 2001 2002 2003 2004 2005 2006

140 140
surface facilities conveying the brine from the After workover
After workover
and acidizing
120 120
steam separators to the injection wells.
Observations show decreased injectivity in wells 100 100 After workover

Flow (kg/s)
and acidizing
5R13D

5R1D and 5R4 (Figures 3 and 4). The steep 80 Before workover 80
quenched

decline in Figures 3 and 4 after workover of 60 60

these wells is attributed to pressure build-up in a 40 40

shallow two-phase permeable zone. This 20 20 5R13D
unquenched
behaviour was initially observed in 2003 when 0 5R1D Water flow 0
well 5R4 acceptance improved after quenching 5R1D Wellhead pressure (WHP)

WHP (MPa-g)
1.6 1.6
the blow-out of well 5R12D that was eventually 1.2 1.2
0.8 0.8
controlled through relief well 5R13D. Starting 0.4 0.4
March 2005, continuous quenching was done by 0 0

injecting in well 5R13D a mixture of river water, 1999 2000 2001 2002 2003 2004 2005 2006

main power plant condensate and brine dumped Figure 3: Malitbog injection well 5R1D water
from the main brineline to Pad 5R1. However, it flows and wellhead pressures
is observed lately that only well 5R4 positively
responds to quenching. The gradual decline is attributed to deterioration of permeability by deposition
of amorphous silica in the receiving formation; but the brine injected in Pad 5R1 is slightly amorphous
silica-supersaturated (oversaturation ratio of 1.1-1.2). The idea of silica deposition was substantiated
when mechanical cleaning coupled with leaching by acid (HCl and HF) of the injection wells showed
significant improvements in injectivity compared to mechanical cleaning alone.

Studies of silica scaling in Malitbog started in 1999 2000 2001 2002 2003 2004 2005 2006

220 220
1996 by tests using a chemical inhibitor to keep After workover
5R12D blowout
quenched
200 and acidizing 200
polymerized silica suspended in solution (Garcia
180 180
et al., 1996). The residence time from the 5R13D
Flow (kg/s)

quenched
160 160
nearest separator station to the shallowest Pad
140 140
5R1 wellbore loss zone is 23 min. Using a
120 120
polymerization vessel, it was determined that the 5R13D
100 100
onset of silica polymerization in untreated brine Before workover
unquenched

80 80
was 45-55 min. In 2004, the above conditions 5R4 Water flow
and acidizing

60 60
were simulated in a field test set-up that allowed 5R4 Wellhead pressure (WHP)
WHP (MPa-g)

1.2 1.2
brine to flow through a column packed with 0.8 0.8
broken rocks. The field test set-up was used to 0.4 0.4

evaluate different mitigating measures (Alcober 0 0

et. al, 2005, Angcoy et al., 2005) which 1999 2000 2001 2002 2003 2004 2005 2006

included: (1) brine pH modification by addition Figure 4: Malitbog injection well 5R4 water
of H2SO4 and (2) addition of silica inhibitors. flows and wellhead pressures
Acidification yielded clean rock formations but
posed increased risk of corrosion while the inhibitors reduced deposition by 80-85%.

3. DESCRIPTION OF WORK

3.1 Assessment of scaling in Malitbog sector

This section aims to establish the type of scales that may precipitate from Malitbog brine as it is
disposed off into injection wells. The use of geochemical tools is emphasized (analyses retrieved from
PNOC-EDC integrated computer databases) but data on injection wells (from Reservoir Engineering
Department of PNOC-EDC) are also presented to support the results obtained from the geochemical
evaluation.
Angcoy 8 Report 5

3.1.1 Scaling potential evaluation

The saturation state of the geothermal fluids SEPARATOR STATION 51

1st Flash

from Malitbog with respect to some common

10 bar-g
Production
wells

scale-forming minerals was assessed with the aid

501 High-pressure steam
508D to Main Power Plant
510D
511D

of the speciation program WATCH 2.3 2nd Flash

5 bar-g

(Arnórsson et al., 1982 and Bjarnason, 1994). Low-pressure steam

to Bottoming Cycle Plant

The detailed background and calculation 145 kg/s Pad 5R7

methods of the program are discussed in

90 kg/s
SEPARATOR STATION 52
1st Flash
10 bar-g Injection well

Arnórsson et al. (1982). In general, the program

5R7D
Production
wells

computes the chemical composition of the

503 High-pressure steam
509 to Main Power Plant
513D
514D 55 kg/s

aquifer fluid based on the chemical analyses of

517
2nd Flash
5 bar-g

water and steam samples collected at the surface. Low-pressure steam

to Bottoming Cycle Plant

The program can also be used to compute the 190 kg/s

245 kg/s
Pad 5R1

resulting chemical composition when a fluid is Injection well Injection well

cooled conductively or by adiabatic boiling from

5R1D 5R4

a reference temperature. During adiabatic Figure 5: Simplified diagram of Malitbog fluid

boiling, the geothermal fluid may undergo collection and injection system
varying degree of degassing.

Figure 5 is a simplified flow diagram of the geothermal fluid collection and injection system in
Malitbog. Table 1 shows the physical characteristics of representative wells 510D and 513D (fed to
Separator Stations 51 and 52, respectively) and their discharge chemistry as analyzed from samples
obtained using a double-wellhead Webre separator. Starting with the known chemical composition of
water and steam samples collected at the wellhead, the fluid composition was calculated at: (1)
reservoir condition taking the quartz equilibrium temperature (Tquartz) to represent the aquifer
temperature, (2) at 10 bar-g assuming adiabatic flashing of the reservoir liquid, (3) at 5 bar-g assuming
adiabatic flashing of the separated brine at 10 bar-g. The objective of these calculations was to see
how the liquid chemistry at 5 bar-g so derived compared with analytical data on samples collected at
these conditions. The calculated composition is almost identical to the analytical data demonstrating
that the model used for the calculations is reliable.

The calculated liquid compositions are compared with the analyses of brine samples in Table 2
(further details in Appendices II, III and IV). The results were obtained by assuming degassing to be
14% and 35% maximum of geothermal fluids in Separator Stations 51 and 52, respectively, showing
good agreement in the components, dissolved gases (except NH3) and pH. If the samples were not
immediately acidified upon collection, some NH3 may have escaped which could explain why the NH3
concentrations are consistently higher in the simulation than in the actual analyses. Acidification
helps keep NH3 in the aqueous solution as it drives the reaction shown below to the right:

+
NH 3 + H 2 O ⇔ NH 4 + OH − (5)

At each stage where the compositions of the geothermal water were calculated, the saturation index,
log (Q/K), of a mineral was obtained from the activity product (Q) and solubility constant (K).
Saturation index value equal to 0 represents equilibrium, <0 undersaturation and >0 supersaturation of
the mineral in the solution. As the geothermal water boils and degasses, it becomes supersaturated
with respect to many hydrothermal minerals known to be present in geothermal reservoirs, such as
quartz, albite and K-feldspar. However, the kinetics of their formation is very slow and poses no
concern to operations. Also, the amount of metallic sulphides that precipitate as a consequence of
boiling and degassing, such as pyrite, marcasite and pyrrhotite is limited by the low concentrations of
Fe and heavy metals in most geothermal waters. Thus the troublesome scale-forming minerals are
Angcoy 9 Report 5

those that can form in quantity due to both fast kinetics and high availability of all their components.
These minerals include amorphous silica, calcium carbonate (calcite or aragonite) and anhydrite.

Table 1: Physical and chemical The saturation indices for amorphous silica, calcite and
characteristics of selected Malitbog anhydrite in variably boiled geothermal water of wells
production wells 510D and 513D are shown in Figures 6 and 7,
respectively (other production wells in Appendix IV).
Well 510Da 513D b At aquifer conditions, the waters are at saturation with
Physical data respect to both anhydrite and calcite within the
Wellhead pressure (bar-g) 12.9 14.4 anticipated limit of error but significantly amorphous
Sampling pressure (bar-g) 12.1 13.9 0 100 200 300

Discharge enthalpy (kJ/kg) 1,376 1,390

Water flow (kg/s) 33.50 42.60 1.0 1st Flash
2nd Flash
brine
Steam flow (kg/s) 13.70 18.00 brine
(at 5 bar-g) (at 10 bar-g)

Vapour chemistry (in mmole/100 moles) SUPERSATURATED

Aquifer
CO2 251 435 water
(at Tquartz)
log (Q/K)

H 2S 19.30 23.10 0.0

Amorphous silica
NH3 1.35 1.90 Anhydrite
Calcite
He 0 0
H2 1.94 3.35
Ar 0.12 0.03 -1.0
UNDERSATURATED
N2 10.63 2.77
CH4 1.73 2.25
Cl 0 0
Na 2.42 1.09 0 100 200 300

Temperature (oC)
Water chemistry (in mg/kg except pH)
Figure 6: Saturation indices of Malitbog
pH (25°C) 6.34 6.01
production well 510D at 14% degassing
Li 20.30 21.10
Na 5,105 5,225 0 100 200 300

K 994 1,114
Ca 285 223
1.0 2nd Flash 1st Flash
Mg 0.14 0.13 brine brine
(at 10 bar-g)
(at 5 bar-g)
Fe 0.18 0.33
SUPERSATURATED
Cl 9,074 9,232 Aquifer
water
SO4 20.50 19.90 (at Tquartz)
log (Q/K)

0.0
HCO3 20.20 19.70 Amorphous silica
Anhydrite
B 159 208 Calcite

NH3 3.06 2.34

SIO2 660 667 -1.0
H 2S 3.59 6.47
CO2_total 21.20 33.80 UNDERSATURATED
a
– Physical data as of 9 Jan 2006, chemistry as
of 19 Aug 2005, representative of 4 production 0 100 200 300
wells fed to Separator Station 51
b Temperature (oC)
– Physical data as of 13 Jan 2006, chemistry as
of 18 Aug 2005, representative of 6 production Figure 7: Saturation indices of Malitbog
wells fed to Separator Station 52 production well 513D at 35% degassing
Angcoy 10 Report 5

Table 2: Comparison of brine sample analyses and silica undersaturated. The calcite saturation
liquid chemistry as calculated using WATCHa index curve of well 513D shows a more
pronounced “hump” than well 510D due to
Well 5R7D Well 5R1D the selection of a higher degassing
Analysis b
Sample c d
Calculated Samplec Calculatede coefficient used in the calculations (0.35 vs
0.14). Cooling either by adiabatic boiling or
pH 6.41 6.16 6.34 6.29
conduction makes the water more
B 199 204 219 228 undersaturated with calcite and anhydrite
SiO2 675 688 707 718 because of their retrograde solubility with
Na 5,822 5,800 5,616 5,941 respect to temperature but more
1,239 1,180 1,166 1,209
supersaturated with amorphous silica.
K
0.05 0.13 0.12 0.13
Mg
After 2nd flashing at 5 bar-g, the brine of well
Ca 326 325 280 340 510D lies just within the amorphous silica
F NAf 1.60 NAf 1.51 saturation level while well 513D is at slightly
Cl 10,632 10,668 10,379 10,578
higher level. Due to its prograde solubility,
only amorphous silica scaling is expected
SO4 27.50 22.79 26.55 24.50 towards temperatures <160°C. The scaling
Fe 0.30 0.34 0.69 0.40 potentials of the brine samples injected in
CO2 15.40 15.88 6.94 6.41 wells 5R1D and 5R7D (Figures 8 and 9,
respectively) were also evaluated using
H2S 5.02 5.37 3.26 2.11 WATCH assuming their conductive cooling
NH3 0.77 6.17 1.71 4.95 or heating in the receiving formation. The
results indicate undersaturation levels of the
a
- Details in Appendices II, III and IV minerals in the brine injected at 5R1D at
b
- In mg/kg except pH temperature ranges of about 160°-250°C and
c
in brine injected at 5R7D 160°-200°C.
– Total composition in water phase at 159°C
Above these temperature ranges, anhydrite or
d
- Separator Station 51 wells 14% degassing calcite may precipitate from the brine
e
- Separator Station 52 wells 35% degassing, Separator Station whereas temperatures below the ranges may
51 to Separator Station 52 brine flow ratio = 22:78
lead to precipitation of amorphous silica in
f
- No analysis available the formation.

0 100 200 300 0 100 200 300

1.0 1.0
SUPERSATURATED SUPERSATURATED

0.0 0.0

UNDERSATURATED
log (Q/K)

log (Q/K)

UNDERSATURATED
-1.0 -1.0

-2.0 -2.0
Amorphous silica
Anhydrite Amorphous silica
Calcite Anhydrite
Calcite
-3.0 -3.0

0 100 200 300 0 100 200 300

Temperature (oC) Temperature (oC)

Figure 8: Saturation indices of brine injected Figure 9: Saturation indices of brine injected
into Pad 5R1 into Pad 5R7
Angcoy 11 Report 5

3.1.2 Data on injection wells

Injection well 5R1D was directionally drilled and completed on 1 August 1982 to a total depth of
952.2 m MD (measured depth from Casing Head Flange). It intersected Mamban Formation which is
a thick sequence of predominantly biotite-bearing hornblende-pyroxene andesite lavas, hyaloclastites
and tuff breccias (Delfin et al., 1995). Petrologic analysis of the rock formations showed the Mamban
Formation to be volcanic breccia intensely altered to quartz + drusy anhydrite + opaques + smectite +
vermiculite + illite + chalcopyrite (Alcober et. al, 2005). Originally targeted as a deep well, continued
drilling was not possible due to complete loss of circulation at shallower depth (Sarmiento, 1986).
The well had one of the highest original injectivity in the field, estimated at 192 l/s-MPa. During its
last mechanical cleaning with acid stimulation in 2004, all obstructions cleared were below the
production casing shoe and within the sections of the perforated liner (565-601 m MD, 815-857 m
MD). In 2000, mechanical cleaning of well 5R1D resulted in minimal capacity recovery (from 98 to
123 kg/s) whereas acidizing registered significant improvements (from 44 to 137 kg/s in 2002 and
from 9.8 to 89.9 kg/s in 2004). Again two years after its last cleaning, it now has a capacity of 6 kg/s
only. Figure 10 shows that at its major and minor permeable zones (553-658 m MD and 767 m MD,
respectively) the temperature in 2001 is between 158° and 165°C that favor the precipitation of
amorphous silica only.

Figure 10: Temperature and pressure profiles Figure 11: Temperature and pressure profiles
of injection well 5R1D of injection well 5R4

Well 5R4 was vertically drilled and completed on 25 April 1980 to a total depth of 2,342 m (all
vertical depths from Casing Head Flange). It was initially tested as a producer and eventually turned
to an injector in 1996. Its open section starts at 999.9 m intersecting Mamban Formation but its minor
and major permeable zones (1,900-2,000 m and 2,140-2,320 m, respectively) intersect the Mahiao
Sedimentary Complex, which is described as a sedimentary breccia/conglomerate containing
fragments of altered microdiorite, quartz monzodiorite, and minor volcanics. Within the
conglomeratic unit, minor interbeds of sandstone, siltstone and claystone exist and these interbeds
usually mark the contact of Mahiao Sedimentary Complex with the Mamban Formation (Caranto and
Jara, 2006). Figure 11 shows that starting at 600 m depth, it has an almost isothermal temperature.
At this temperature, scaling of amorphous silica, calcite or anyhdrite is not expected. But, on March
1999, blockage was tagged using a 3” Go-Devil tool at 2,224 m, which is within its major permeable
zone. It is possible, however, that the scales were formed when it was still used as a production well.
The encouraging results of mechanical cleaning with acidizing in 5R1D was duplicated in 5R4 in 2001
increasing capacity from 76 to 201 kg/s and suggesting that acid-soluble scales in near-wellbore
formation are decreasing its injectivity.
Angcoy 12 Report 5

Lower downhole survey temperatures in 5R1D may possibly explain the more frequent decline in
injectivity due to amorphous silica deposition (Figure 3). Logging of well 5R4 conducted on June
1996 and June 2001 indicated casing discontinuities in the cased-off sections of ~300-350 m and
~550-580 m. These levels were also intersected during the blow-out of 5R12D in 2003 and eventually
targeted by relief well 5R13D to quench the shallow two-phase high-pressure zone. Since March 2005
cold fluids are injected to 5R13D to maintain quenching. These casing breaks are probable
breakthrough of cold fluids to 5R4 thus generating positive response to quenching. However, it may
also lower its downhole temperature to promote amorphous silica supersaturation since a gradual
decline in its injectivity is still observed at quenched conditions (Figure 4).

3.2 Silica experiment

In view of the results from the preceding section, an experiment was conducted to provide useful
information on amorphous silica scaling in Malitbog. The objective of the experiment was to obtain
data on relative precipitation rates of monomeric versus polymeric silica from amorphous silica
supersaturated solution. Two sets of experiment were carried out. The first set was conducted at fixed
temperature (50°C), atmospheric pressure, initial silica concentration (500 mg/kg) and pH of 6-7 but
salinity was varied by adding 5 M NaCl solution to the initial test solution (0 M, 0.1 M, 0.2 M, 0.3 M
and 0.4 M). The second set of experiments was conducted at 90°C, atmospheric pressure, initial silica
concentration of 500 mg/kg, 0.3 M NaCl and pH of 6-7. This second experiment simulates well
conditions at Malitbog.

3.2.1 Experimental design

The experimental runs were performed using an Cooling cup Pump

oven set at experimental temperature (Figure Filter

12). The silica-supersaturated solution was

pumped from a container across a column
packed with washed silica gel. The solution was
pumped against gravity to prevent channelling in
the column. Pumping across the column from an Column with

experimental solution was continuous for at least silica gel

30 minutes before sampling the discharge. The

same column was used in other experimental pH

solutions. After the column, a three-way valve

meter

was manipulated to direct the outlet solution

either for sampling or for pH measurement. Oven Experimental
solution
The solution did not come into contact with any (50°or 90°C)

glass material to prevent leaching of silica. Figure 12: Set-up of silica experiment
Residence time in the column was fixed by
regularly monitoring the flow rate at 1 ml/min.
The determination of residence time was conducted using an inert visual tracer after completing all
experimental runs. The initial and final weights of the dried column were measured.

The procedures in preparing the solutions and reagents were taken from another silica polymerization
experiment (Gunnarsson and Arnórsson, 2005). Silica stock solution was prepared by dissolving silica
gel in 0.1 N NaOH and filtered using 0.2 µm cellulose acetate filter paper at room temperature. In all
runs, 1 litre experimental solution with target concentration of 500 mg/kg SiO2 was prepared by
diluting the stock solution with deionized water and adding variable amounts of 5 M NaCl solution
depending on the desired ionic strength. The experimental solution after these steps was very basic
(pH≈11). At this pH, all silica species present in the solution were molybdate active and
undersaturated with respect to amorphous silica. The undersaturated solution was kept inside the oven
at the experimental temperature for at least 12 hours.
Angcoy 13 Report 5

The pH of the thermally stabilized experimental solution was lowered to target value of 6.97 by
adding concentrated HCl to oversaturate it with respect to amorphous silica. Prior to acidification, the
experimental solution was buffered with TRIS, (HOCH2)3CNH2, to stabilize its pH. Polymerization of
the silica-supersaturated solution proceeded in the source tank as the solution was pumped across the
column. The solutions at the inlet and outlet of the column were monitored for molybdate active and
total silica concentrations to determine the relative amount of monomeric and polymeric silica in
solution.

3.2.2 Sampling and analytical methods

Sample from inlet of the column was extracted from the experimental solution container using a 10 ml
syringe while sample at outlet of the column was collected into a small vial after passing it through a
0.2 µm cellulose acetate filter. For analysis of monomeric silica concentration, the samples were
immediately brought to room temperature through a cooling spiral and aliquots were drawn using a
pipette. The entire sampling procedure was completed less than 30 seconds to minimize the effect of
cooling to polymerization. For analysis of total dissolved silica, all samples were diluted at least 10
times and acidified with concentrated HNO3. In the first set of experiments, all samples were passed
through 0.2 µm cellulose acetate filter while in the second set of experiments a run was conducted
where filtered samples were duplicated with unfiltered ones.

Monomeric silica concentration was determined using the yellow molybdate method (Franson, 1985).
The absorbance was measured at 410 nm using a Cary, 1E UV-visible spectrophotometer. In theory,
the molybdic acid will react only with monomeric silica in the solution. However, since the samples
in the analytical procedure are diluted to become undersaturated with respect to amorphous silica,
some of the monomers forming the yellow molybdosilicic complex may have also been formed from
the breakdown of silica dimers and trimers (Iler, 1979). Thus in this study, all monomeric silica are
referred to as molybdate active silica. Total dissolved silica concentration was measured using
Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). Solution pH was measured
with buffer-calibrated pH meter.

3.2.3 Results

The results of the experiment are presented in Figures 13-21 and tabulated in Appendix V. After
completing all the experimental runs, the retention time of the solution in the column was determined
visually using a coloured tracer to be ~9 minutes. The first trial of the 90°C run (Figure 19) showed
almost equal total and monomeric silica levels of the inlet solution through time. To determine
whether the polymers grew to sizes large enough to be filtered by the 0.2 μm cellulose acetate filter
membrane or actually depositing in the tank, the experiment was repeated and the filtered samples
were duplicated with unfiltered samples (Figures 20-21). The initial and final dry weights of the
column containing the silica gel did not differ significantly.
 Angcoy 14 Report 5

Time (hours)
0 20 40 60 80 100 120

500 200

Outlet solution SiO2, POLYMERIC (mg/kg)

Initial level

400 160
Silica as SiO2 (mg/kg)

120
300

(64°C)
Polymeric silica
80 lost in column
200 (50°C)

(45°C)

40
100 Total silica, inlet solution
Monomeric silica, inlet solution
Monomeric silica, outlet solution
Amorphous silica saturation levels 0
0
0 40 80 120 160 200
2000 4000 6000 Inlet solution SiO2, POLYMERIC (mg/kg)
Time (minutes)

Figure 13: Experiment results at 50°C, 1 atm, pure water, pH~7.00, 9 minutes retention time,
filtered samples

Time (hours)
0 20 40 60 80 100 120 140 160

500 200
Outlet solution SiO2, POLYMERIC (mg/kg)

400 160
Initial level
Silica as SiO2 (mg/kg)

300 120

Polymeric silica
lost in column
(59°C)
200 (50°C) 80

(45°C)

100 Total silica, inlet solution 40

Monomeric silica, inlet solution
Monomeric silica, outlet solution
Amorphous silica saturation levels
0 0
0 2000 4000 6000 8000 10000 0 40 80 120 160 200
Time (minutes) Inlet solution SiO2, POLYMERIC (mg/kg)

Figure 14: Experiment results at 50°C, 1 atm, 0.1 M NaCl, pH~7.00, 9 minutes retention time,
filtered samples
Angcoy 15 Report 5

Time (hours)
0 10 20 30 40 50 60 70 80

500 200

Outlet solution SiO2, POLYMERIC (mg/kg)

400 Initial level 160
Silica as SiO2 (mg/kg)

300 120

Polymeric silica
lost in column
200 (50°C) 80

(45°C)

100 Total silica, inlet solution 40

Monomeric silica, inlet solution
Monomeric silica, outlet solution
Amorphous silica saturation levels
0 0

0 1000 2000 3000 4000 5000 0 40 80 120 160 200

Time (minutes) Inlet solution SiO2, POLYMERIC (mg/kg)

Figure 15: Experiment results at 50°C, 1 atm, 0.2 M NaCl, pH~7.00, 9 minutes retention time,
filtered samples

Time (hours)
0 5 10 15 20 25 30 35 40 45 50
200
500
Outlet solution SiO2, POLYMERIC (mg/kg)

160
400 Initial level
Silica as SiO2 (mg/kg)

120
300

Polymeric silica
80 lost in column
200 (50°C)

(45°C)
40
100 Total silica, inlet solution
Monomeric silica, inlet solution
Monomeric silica, outlet solution
Amorphous silica saturation levels 0
0
0 40 80 120 160 200
0 1000 2000 3000 Inlet solution SiO2, POLYMERIC (mg/kg)
Time (minutes)

Figure 16: Experiment results at 50°C, 1 atm, 0.3 M NaCl, pH~7.00, 9 minutes retention time,
filtered samples
Angcoy 16 Report 5

Time (hours)
0 5 10 15 20 25 30 35 40 45 50
200
500

Outlet solution SiO2, POLYMERIC (mg/kg)

160
400 Initial level
Silica as SiO2 (mg/kg)

120
300

Polymeric silica
lost in column
80
200 (50°C)

(45°C)
40
100 Total silica, inlet solution
Monomeric silica, inlet solution
Monomeric silica, outlet solution
Amorphous silica saturation levels 0
0
0 40 80 120 160 200
0 1000 2000 3000 Inlet solution SiO2, POLYMERIC (mg/kg)
Time (minutes)

Figure 17: Experiment results at 50°C, 1 atm, 0.4 M NaCl, pH~7.00, 9 minutes retention time,
filtered samples

Time (hours) Time (hours)

0 20 40 60 80 100 120 140 160 0 5 10 15 20 25 30 35 40 45 50

500

Initial level
500

400
Silica as SiO2 (mg/kg)

Silica as SiO2 (mg/kg)

400
300

(90°C)
(59°C)
300
200
(50°C) (73°C)

0 M NaCl
100 0.1 M NaCl 200
Total silica, inlet solution
0.2 M NaCl
Monomeric silica, inlet solution
0.3 M NaCl
Monomeric silica, outlet solution
0.4 M NaCl
Amorphous silica saturation levels
0 100
0 2000 4000 6000 8000 10000 0 1000 2000 3000
Time (minutes) Time (minutes)

Figure 18: Polymerization of tank solutions Figure 19: Experiment 1 results at 90°C, 1 atm,
(starting solutions) at 50°C, 1 atm, pH~7.00, 0.3 M NaCl, pH~7.00, 9 minutes retention time,
varying salinities, filtered samples filtered samples
Angcoy 17 Report 5

Time (hours)
0 5 10 15 20 25

Outlet solution SiO2, POLYMERIC (mg/kg)

Initial level
500
120

New filters
Silica as SiO2 (mg/kg)

400

80

(90°C)
300
Polymeric silica
lost in column or
(73°C) lost in filter
40
200
Total silica, inlet solution
Monomeric silica, inlet solution
Monomeric silica, outlet solution
Amorphous silica saturation levels
100 0

0 400 800 1200 1600 0 40 80 120

Time (minutes) Inlet solution SiO2, POLYMERIC (mg/kg)

Figure 20: Experiment 2 results at 90°C, 1 atm, 0.3 M NaCl, pH~7.00, 9 minutes retention time,
filtered samples

Time (hours)
0 5 10 15 20 25 30
Outlet solution SiO2, POLYMERIC (mg/kg)

Initial level
500
120
Silica as SiO2 (mg/kg)

400

80
(90°C) Polymeric silica
300 lost in column

(73°C)
40
200
Total silica, inlet solution
Monomeric silica, inlet solution
Monomeric silica, outlet solution
Amorphous silica saturation levels
100 0

0 400 800 1200 1600 2000 0 40 80 120

Time (minutes) Inlet solution SiO2, POLYMERIC (mg/kg)

Figure 21: Experiment 2 results at 90°C, 1 atm, 0.3 M NaCl, pH~7.00, 9 minutes retention time,
unfiltered samples
Angcoy 18 Report 5

4. DISCUSSION

4.1 Results of experiment

The results show that monomeric silica concentrations in the solutions flowing from the column
always were at the same concentration. This indicates that monomeric silica easily precipitates on the
surface of the silica gel in the packed column. However, the concentration levels approached
correspond at temperatures significantly lower than the experimental temperatures. Since it is unlikely
that a more stable silica polymorph other than amorphous silica has precipitated in the column, the
results are taken to indicate that cooling of the outlet solution occurred with the result that amorphous
silica equilibration was attained at the lower temperature. The column was kept at the oven
temperature except during sampling of the inlet solution. Thus, it is not likely that the solution cooled
across the column. Significant cooling only occurred when the sample was brought to room
temperature to ensure accuracy of the volumes measured by the pipettes. Probably due to larger
temperature difference, the monomeric silica level in the outlet solutions approached saturation of
amorphous silica at lower temperatures in the 90°C runs (73°C) than in the 50°C runs (45°C).

In contrast to the monomers, the polymerized silica formed in the inlet solutions and pumped across
the column has little tendency to precipitate in the column. Most of it remained in solution when
pumped through the column. In the experiments at 90°C and saline solution, the analyses of the
filtered samples indicated that the polymers grew to a large enough size to be filtered from solution by
the 0.2 μm cellulose acetate filter membrane (Figures 19-20) as confirmed by the analyses of the
duplicate unfiltered samples. In the experiment at 90°C, analyses of unfiltered samples indicated
some polymeric silica (20 mg/kg maximum) was lost either by precipitation or filtration in the void
spaces of the column (Figure 21). But compared to the losses of monomeric silica across the column,
the amount of polymeric silica retained in the column is significantly less. Thus it is important that
polymerization of the excess monomers is fast to use the advantage of polymeric silica observed in the
experiment.

The experiment confirms the results of previous studies that at

about constant degree of supersaturation, pH (buffered
solutions) and temperature, polymerization of monomeric
silica in excess of amorphous silica saturation is a strong
function of salinity. Experiments carried out at 50°C show
that increasing salinity increases silica polymerization rate in
the tank solution (Figure 18). The monomers polymerized
about 10 times faster in the 0.3 and 0.4 M NaCl saline
solutions than in pure water. Silica polymerization rate is also
a strong function of supersaturation. In the 50°C run, the 0.1
M NaCl solution was inadvertently prepared with a lower
supersaturation (~165 ppm) than the solution in pure water
(~220 ppm). The effect of salinity was offset by the low level
of supersaturation such that the two solutions exhibited almost
the same induction time but longer time was required to
closely approach amorphous silica saturation for the 0.1 M
NaCl solution (Figure 18). At the salinity of 0.3 M NaCl
(50°C and 90°C), it was anticipated that increased
polymerization rate due to higher temperature will also be
counteracted by the higher saturation level of amorphous
silica. Thus, supersaturation was increased in the 90°C, 0.3 M Figure 22: Silica gel precipitated
NaCl run by starting at a higher initial silica level to achieve a in the tank at 90°C, 1 atm, 0.3 M
reasonable onset of polymerization of the excess monomers NaCl, pH~7 experiment
after about 5 hours.
Angcoy 19 Report 5

The experiment demonstrated that precipitation of amorphous silica from supersaturated solutions is
decreased if the monomers in excess of saturation are allowed to polymerize. However, the successful
application of this method to mitigate silica scaling requires a balance between both silica
polymerization rate and deposition rate. Silica polymerization is regarded as a precursor to the
precipitation of silica gel (Iler, 1979). At pH~7, the growing polymers in pure water tend to repel each
other because of their negatively charged surfaces. But in saline solutions, the presence of ions
reduces the repulsive forces allowing the polymers to aggregate and gel (Figure 22). In the
experiment, increased salinity increases both silica polymerization and deposition rates. In all saline
solutions of the experiment, the total silica concentration of the inlet solutions slightly declined from
the initial silica levels indicating that some polymers have grown large enough to deposit in the tank.
Growth and precipitation of the silica polymers is enhanced by the presence of electrolytes in solution.
Marshall (1980) observed that the nature of cation and not the anion has greater effect. The decreasing
effect of cations is Mg2+ > Ca2+ > Sr2+ > Li+ > Na+ > K+ (Chan, 1989).

4.2 Relevance of experimental results to Malitbog

Amorphous silica scaling during injection of Malitbog brine to Pad 5R1 wells is probably dominated
by deposition of both monomeric and polymeric silica. The conditions that favour the mechanism of
deposition of both forms of silica are: (1) low degree of supersaturation (maximum of 1.2); (2)
induction period of about 1 hour (Alcober et al., 2005) long enough for the brine to travel away from
the wellbore to the receiving aquifer in the injection well before the onset of polymerization and (3)
presence of cations that may coagulate the polymerized silica to a solid surface rather than to the
colloidal particles in suspension. Monomeric silica deposition and reheating in the formation are not
rapid enough to relieve the slight supersaturation of the brine and to prevent polymerization. In
relatively saline waters, deposition of both monomeric and polymeric silica is relatively fast and forms
hard but microporous scales (Iler, 1979) similar to that observed in the field test of Malitbog (Alcober
et al., 2005). The declining maximum well injectivity achieved after workovers (Figures 3-4) suggests
that the removal and dissolution of the scales is becoming more difficult especially in areas that can no
longer be accessed by acid leaching.

The method demonstrated by the experiment to mitigate amorphous silica scaling can be applied with
greater confidence if (1) silica polymerization is very fast such that no induction period is observed
and (2) the conditions allow the polymers not to precipitate or if precipitated, remain suspended in
solution. To retain the maximum 300 kg/s of Malitbog brine for about 1 hour in order to polymerize
the silica in the brine prior to injection requires an impractically large volume (~1,000 m3). At the
surface, rapid polymerization of the brine is possible by increasing the level of oversaturation by either
brine flashing to low pressure or rapid cooling. Either way, it opens opportunities to cascade the
energy of Malitbog brine for further utilization. If cooling the Malitbog brine is not an option due to
adverse impact to field management, heterogenous nucleation may be induced by seeding or brine
transit through fluidized or packed beds with the objective of stripping the excess silica monomers
from solution before injecting the brine.

4.3 Future work

The experimental procedure needs to be improved so as to allow direct sampling and analyses of
samples without cooling. Analyses of monomeric silica concentrations may also be carried out using
the more sensitive blue molybdate method. After these improvements, silica polymerization and
deposition rates may be investigated with more confidence at various conditions. Laboratory tests
need to be confirmed by field tests to validate the results. For instance, since the silica polymers in
Malitbog brine are likely to precipitate by gravity due to a high ionic strength of the brine (~0.3), field
tests will help gauge the increased risk of deposition. Polymerization and deposition rates may further
be complicated by the influence of trace amounts of iron, aluminium and manganese in the brine
(Gallup, 1998 and Yokoyama et al., 1989).
Angcoy 20 Report 5

5. SUMMARY AND CONCLUSIONS

Potential amorphous silica scale formation in the aquifer receiving brine in the Malitbog sector of
Tongonan Geothermal Field, Philippines was established with the aid of the speciation program
WATCH. An experiment in the laboratory showed that polymeric silica has lesser tendency than
monomeric silica to precipitate from the solution in a column packed with silica gel. Thus allowing
the monomers in excess of the amorphous silica saturation level to polymerize before injection will
possibly mitigate the declining injectivity of wells. Successful application of this method should
consider the conditions that will allow deposition of polymeric silica precipitated due to dissolved salts
in the solution.

ACKNOWLEDGEMENTS

This project was made possible through the fellowship granted by the government of Iceland and the
United Nations University Geothermal Training Programme under the dedicated and esteemed staff of
Dr. Ingvar B. Fridleifsson (Director), Mr. Lúdvík S. Georgsson (Deputy Director), Mrs. Gudrún
Bjarnadóttir and Ms. Thórhildur Ísberg (Administrative Assistants). The author sincerely
acknowledges the critical guidance and support of Dr. Stefán Arnórsson and Ingvi Gunnarsson both at
the Institute of Earth Sciences, University of Iceland and the PNOC-EDC management and colleagues
from the Technical Services Sector who were instrumental in contributing constructive comments and
the necessary data in their simple but invaluable ways.

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 APPENDIX I: Sample of WATCH print-out to determine scaling potential of Malitbog
production wells

ICELANDIC WATER CHEMISTRY GROUP Program WATCH, version 2.3 / 2004

===================================================================================================
STEP 1: Calculation of aquifer conditions from steam and water samples.
Malitbog production well 510D
Water sample (mg/kg) Steam sample

pH/deg.C 6.34/ 25.6 Gas (volume %) Reference temperature deg.C : 267.1 (Quartz)
CO2 21.20 CO2 0.00
H2S 3.59 H2S 0.00 Sampling pressure bar abs. : 13.1
NH3 3.06 NH3 0.00 Discharge enthalpy kJ/kg : 1171. (Calculated)
B 159.0000 H2 13.57 Discharge kg/s : 47.2
SiO2 660.00 O2 0.00 Steam fraction at collection : 0.1797
Na 5105.00 CH4 12.09
K 994.00 N2 74.33 Measured temperature deg.C :
Mg 0.140
Ca 285.00 Liters gas per kg
F 1.340 condensate/deg.C 0.19/25.0 Condensate (mg/kg)
Cl 9074.00 pH/deg.C 0.00/ 0.0
SO4 20.50 Total steam (mg/kg) CO2 0.00
Al 0.0000 CO2 6131.92 H2S 0.00
Fe 0.1800 H2S 365.11 NH3 0.00
TDS 0.00 NH3 12.76 Na 0.00

Ionic strength = 0.26580

Ionic balance : Cations (mol.eq.) = 0.26106104 Anions (mol.eq.) = 0.25596878 Difference (%) = 1.97

Liquid phase components (mg/kg) Vapor phase (mg/kg) Gas pressures (bar-abs.)

B 130.4218 CO2 1119.52 CO2 0.00 CO2 0.213E+01

SiO2 541.37 H2S 68.57 H2S 0.00 H2S 0.652E-01
Na 4187.44 NH3 4.80 NH3 0.00 NH3 0.823E-03
K 815.34 H2 0.39 H2 0.00 H2 0.635E-01
Mg 0.115 O2 0.00 O2 0.00 O2 0.506E-36
Ca 233.77 CH4 2.77 CH4 0.00 CH4 0.462E-01
F 1.099 N2 29.72 N2 0.00 N2 0.465E+00
Cl 7443.06 H2O 0.526E+02
SO4 16.82 Total 0.554E+02
Al 0.0000
Fe 0.1476
TDS 0.00 Aquifer steam fraction = 0.0000

Ionic strength = 0.19629 1000/T (Kelvin) = 1.85

Ionic balance : Cations (mol.eq.) = 0.19268577 Anions (mol.eq.) = 0.18851227 Difference (%) = 2.19

Oxidation potential (volts) : Eh H2S= -0.424 Eh CH4= -0.498 Eh H2= -0.496 Eh NH3= -0.487

Chemical geothermometers (degrees C)

Quartz 267.1 (Fournier & Potter, 1982)
Chalcedony 254.3 (Fournier, 1977)
Na/K 273.0 (Arnorsson et al., 1983)

Activity coefficients in water

H+ 0.650 K+ 0.489 FeSO4+ 0.557
OH- 0.508 Ca++ 0.120 FeCl++ 0.099
H3SiO4- 0.525 Mg++ 0.163 FeCl2+ 0.557
H2SiO4-- 0.107 CaHCO3+ 0.585 FeCl4- 0.525
H2BO3- 0.469 MgHCO3+ 0.525 FeCl+ 0.525
HCO3- 0.525 CaOH+ 0.585 Al+++ 0.022
CO3-- 0.088 MgOH+ 0.597 AlOH++ 0.107
HS- 0.508 NH4+ 0.469 Al(OH)2+ 0.568
S-- 0.099 Fe++ 0.120 Al(OH)4- 0.542
HSO4- 0.542 Fe+++ 0.022 AlSO4+ 0.542
SO4-- 0.078 FeOH+ 0.557 Al(SO4)2- 0.542
NaSO4- 0.568 Fe(OH)3- 0.557 AlF++ 0.107
KSO4- 0.568 Fe(OH)4-- 0.099 AlF2+ 0.568
F- 0.508 Fe(OH)++ 0.099 AlF4- 0.542
Cl- 0.489 Fe(OH)2+ 0.568 AlF5-- 0.088
Na+ 0.525 Fe(OH)4- 0.568 AlF6--- 0.004
 Chemical species in water - ppm and log mole Water pH is 5.223
H+ 0.01 -5.037 Mg++ 0.11 -5.336 Fe(OH)3 0.15 -5.865
OH- 0.05 -5.503 NaCl 1193.30 -1.690 Fe(OH)4- 0.00 -8.238
H4SiO4 865.66 -2.045 KCl 103.91 -2.856 FeCl+ 0.03 -6.518
H3SiO4- 0.17 -5.745 NaSO4- 3.58 -4.521 FeCl2 0.00 -8.852
H2SiO4-- 0.00 -11.412 KSO4- 3.91 -4.539 FeCl++ 0.00 -15.288
NaH3SiO4 0.19 -5.804 CaSO4 4.65 -4.467 FeCl2+ 0.00 -16.157
H3BO3 745.78 -1.919 MgSO4 0.01 -7.200 FeCl3 0.00 -17.439
H2BO3- 0.19 -5.505 CaCO3 0.01 -6.953 FeCl4- 0.00 -18.695
H2CO3 1560.09 -1.599 MgCO3 0.00 -11.306 FeSO4 0.00 -9.956
HCO3- 6.83 -3.951 CaHCO3+ 17.73 -3.756 FeSO4+ 0.00 -17.701
CO3-- 0.00 -9.342 MgHCO3+ 0.00 -7.928 Al+++ 0.00 0.000
H2S 68.02 -2.700 CaOH+ 0.05 -6.068 AlOH++ 0.00 0.000
HS- 0.53 -4.794 MgOH+ 0.00 -7.459 Al(OH)2+ 0.00 0.000
S-- 0.00 -13.713 NH4OH 5.53 -3.802 Al(OH)3 0.00 0.000
H2SO4 0.00 -10.809 NH4+ 2.24 -3.906 Al(OH)4- 0.00 0.000
HSO4- 1.85 -4.719 Fe++ 0.01 -7.040 AlSO4+ 0.00 0.000
SO4-- 6.03 -4.202 Fe+++ 0.00 -20.242 Al(SO4)2- 0.00 0.000
HF 0.63 -4.502 FeOH+ 0.00 -8.859 AlF++ 0.00 0.000
F- 0.50 -4.579 Fe(OH)2 0.00 -10.091 AlF2+ 0.00 0.000
Cl- 6669.78 -0.726 Fe(OH)3- 0.00 -16.714 AlF3 0.00 0.000
Na+ 3717.27 -0.791 Fe(OH)4-- 0.00 -19.877 AlF4- 0.00 0.000
K+ 759.72 -1.712 Fe(OH)++ 0.00 -12.709 AlF5-- 0.00 0.000
Ca++ 225.34 -2.250 Fe(OH)2+ 0.08 -6.057 AlF6--- 0.00 0.000

Logarithms of mineral solubility product constants (K) and ion activity products (Q) in water
log K log Q log K log Q log K log Q
Adularia -14.372 99.999 Albite, low -13.938 99.999 Analcime -11.563 99.999
Anhydrite -8.425 -8.479 Calcite -13.219 -13.566 Chalcedony -1.928 -2.045
Mg-Chlorite -86.296 99.999 Fluorite -11.052 -12.916 Goethite 3.237 -2.686
Laumontite -24.709 99.999 Microcline -14.998 99.999 Magnetite -15.258 -24.927
Ca-Montmor. -72.582 99.999 K-Montmor. -33.869 99.999 Mg-Montmor. -74.087 99.999
Na-Montmor. -34.152 99.999 Muscovite -17.838 99.999 Prehnite -37.927 99.999
Pyrrhotite -11.288 -52.071 Pyrite -29.035 -55.697 Quartz -2.046 -2.045
Wairakite -24.894 99.999 Wollastonite 7.203 5.231 Zoisite -38.758 99.999
Epidote -38.383 99.999 Marcasite -12.809 -55.697 Talc 8.084 4.786
Chrysotile 14.233 8.877 Sil. amorph. -1.612 -2.045

STEP 2: Calculation of brine composition from 1st separator vessel (10 bar-g).

Aquifer liquid boiled to 184.0 °C Degassing coefficient is 0.1400

====================================================================================================
Liquid phase components (mg/kg) Vapor phase (mg/kg) Gas pressures (bar-abs.)

B 162.0251 CO2 76.42 CO2 5424.24 CO2 0.244E-01

SiO2 672.56 H2S 13.04 H2S 297.77 H2S 0.173E-02
Na 5202.13 NH3 5.43 NH3 2.22 NH3 0.258E-04
K 1012.91 H2 0.00 H2 1.99 H2 0.195E-03
Mg 0.143 O2 0.00 O2 0.00 O2 0.000E+00
Ca 290.42 CH4 0.03 CH4 14.08 CH4 0.174E-03
F 1.365 N2 0.16 N2 151.69 N2 0.107E-02
Cl 9246.64 H2O 0.110E+02
SO4 20.89 Total 0.110E+02
Al 0.0000
Fe 0.1834
TDS 0.00 Aquifer steam fraction = 0.1951

Ionic strength = 0.26041 1000/T (Kelvin) = 2.19

Ionic balance : Cations (mol.eq.) = 0.25576815 Anions (mol.eq.) = 0.25057867 Difference (%) = 2.05

Oxidation potential (volts) : Eh H2S= -0.379 Eh CH4= -0.419 Eh H2= -0.398 Eh NH3= -0.447

Chemical geothermometers (degrees C)

Quartz 299.2 (Fournier & Potter, 1982)
Chalcedony 280.5 (Fournier, 1977)
Na/K 271.2 (Arnorsson et al., 1983)
 Activity coefficients in water
H+ 0.691 K+ 0.542 FeSO4+ 0.606
OH- 0.560 Ca++ 0.173 FeCl++ 0.147
H3SiO4- 0.577 Mg++ 0.224 FeCl2+ 0.606
H2SiO4-- 0.158 CaHCO3+ 0.632 FeCl4- 0.577
H2BO3- 0.522 MgHCO3+ 0.577 FeCl+ 0.577
HCO3- 0.577 CaOH+ 0.632 Al+++ 0.045
CO3-- 0.134 MgOH+ 0.643 AlOH++ 0.158
HS- 0.560 NH4+ 0.522 Al(OH)2+ 0.617
S-- 0.147 Fe++ 0.173 Al(OH)4- 0.592
HSO4- 0.592 Fe+++ 0.045 AlSO4+ 0.592
SO4-- 0.120 FeOH+ 0.606 Al(SO4)2- 0.592
NaSO4- 0.617 Fe(OH)3- 0.606 AlF++ 0.158
KSO4- 0.617 Fe(OH)4-- 0.147 AlF2+ 0.617
F- 0.560 Fe(OH)++ 0.147 AlF4- 0.592
Cl- 0.542 Fe(OH)2+ 0.617 AlF5-- 0.134
Na+ 0.577 Fe(OH)4- 0.617 AlF6--- 0.011

Aquifer liquid boiled to 184.0 °C Degassing coefficient is 0.1400

====================================================================================================

Chemical species in water - ppm and log mole Water pH is 5.813

H+ 0.00 -5.652 Mg++ 0.14 -5.241 Fe(OH)3 0.00 -7.703
OH- 0.09 -5.291 NaCl 603.24 -1.986 Fe(OH)4- 0.00 -9.393
H4SiO4 1071.81 -1.953 KCl 44.10 -3.228 FeCl+ 0.18 -5.702
H3SiO4- 1.96 -4.687 NaSO4- 4.60 -4.413 FeCl2 0.00 -11.660
H2SiO4-- 0.00 -9.346 KSO4- 3.09 -4.641 FeCl++ 0.00 -16.731
NaH3SiO4 2.50 -4.674 CaSO4 4.10 -4.521 FeCl2+ 0.00 -17.431
H3BO3 925.45 -1.825 MgSO4 0.01 -6.981 FeCl3 0.00 -18.809
H2BO3- 1.27 -4.680 CaCO3 0.03 -6.478 FeCl4- 0.00 -20.330
H2CO3 90.32 -2.837 MgCO3 0.00 -10.406 FeSO4 0.00 -8.699
HCO3- 10.64 -3.758 CaHCO3+ 10.68 -3.976 FeSO4+ 0.00 -18.828
CO3-- 0.00 -7.878 MgHCO3+ 0.00 -7.951 Al+++ 0.00 0.000
H2S 11.13 -3.486 CaOH+ 0.04 -6.176 AlOH++ 0.00 0.000
HS- 1.86 -4.250 MgOH+ 0.00 -8.060 Al(OH)2+ 0.00 0.000
S-- 0.00 -13.209 NH4OH 2.84 -4.092 Al(OH)3 0.00 0.000
H2SO4 0.00 -13.357 NH4+ 4.29 -3.624 Al(OH)4- 0.00 0.000
HSO4- 0.07 -6.174 Fe++ 0.07 -5.899 AlSO4+ 0.00 0.000
SO4-- 12.02 -3.903 Fe+++ 0.00 -20.049 Al(SO4)2- 0.00 0.000
HF 0.06 -5.538 FeOH+ 0.00 -8.284 AlF++ 0.00 0.000
F- 1.31 -4.161 Fe(OH)2 0.00 -9.548 AlF2+ 0.00 0.000
Cl- 8859.67 -0.602 Fe(OH)3- 0.00 -15.680 AlF3 0.00 0.000
Na+ 4963.44 -0.666 Fe(OH)4-- 0.00 -19.534 AlF4- 0.00 0.000
K+ 988.89 -1.597 Fe(OH)++ 0.00 -13.614 AlF5-- 0.00 0.000
Ca++ 284.94 -2.148 Fe(OH)2+ 0.00 -8.155 AlF6--- 0.00 0.000

Logarithms of mineral solubility product constants (K) and ion activity products (Q) in water
log K log Q log K log Q log K log Q
Adularia -14.997 99.999 Albite, low -14.468 99.999 Analcime -11.767 99.999
Anhydrite -6.931 -7.732 Calcite -11.151 -11.661 Chalcedony -2.298 -1.953
Mg-Chlorite -80.977 99.999 Fluorite -10.657 -11.735 Goethite -1.126 -4.060
Laumontite -24.766 99.999 Microcline -15.900 99.999 Magnetite -22.950 -25.866
Ca-Montmor. -74.047 99.999 K-Montmor. -35.138 99.999 Mg-Montmor. -75.470 99.999
Na-Montmor. -35.349 99.999 Muscovite -18.265 99.999 Prehnite -35.894 99.999
Pyrrhotite -56.973 -70.121 Pyrite -87.795 -78.512 Quartz -2.454 -1.953
Wairakite -23.824 99.999 Wollastonite 8.710 6.764 Zoisite -35.810 99.999
Epidote -37.856 99.999 Marcasite -68.613 -78.512 Talc 11.224 9.395
Chrysotile 18.114 13.301 Sil. amorph. -1.858 -1.953
 Appendix II: Data for calculation of mixed brine in Separator Station 51 at 10 bar-g

Table 1: Determination of brine mixture chemistry from 1st separator vessel of Separator Station 51

W501 W508D W510D W511D Composition at

Mass flow
1st separator
(@ wellhead pressure) kg/s 41.2 38.6 47.2 51.8
First separator vessel brine (10 bar-g, 184°C)a
Water flow kg/s 33.95 31.86 37.99 41.33 145.13
pH (@ 184°C ) 6.01 5.51 5.81 5.42 5.67
B mg/kg 203 160 162 239 193
SiO2 mg/kg 616 613 673 694 652
Na mg/kg 5,793 4,809 5,202 6,048 5,495
K mg/kg 1,197 1,023 1,013 1,224 1118
Mg mg/kg 0.12 0.10 0.14 0.10 0.12
Ca mg/kg 376 246 290 315 308
F mg/kg 1.64 1.70 1.37 1.44 1.52
Cl mg/kg 10,805 8,728 9,247 11,389 10,107
SO4 mg/kg 23.33 20.77 20.89 21.45 21.59
Fe mg/kg 0.44 0.34 0.18 0.33 0.32
CO2 mg/kg 60.3 75.76 76.42 162.03 96.88
H2S mg/kg 9.78 11.5 13.04 20.63 14.10
NH3 mg/kg 3.81 5.3 5.43 8.82 5.99
H3SiO4- moles 3.0E-05 9.2E-06 2.1E-05 8.8E-06 1.7E-05
H2BO3- moles 4.3E-05 1.0E-05 2.1E-05 1.3E-05 2.1E-05
HCO3 -
moles 2.0E-04 9.2E-05 1.7E-04 1.7E-04 1.6E-04
CO3 -2
moles x 2 5.0E-08 6.7E-09 2.6E-08 1.1E-08 2.3E-08
HS- moles 6.3E-05 2.6E-05 5.6E-05 4.0E-05 4.6E-05
a
- Degassing at 14% was selected to calculate the composition of individual well discharges

Table 2: Determination of brine mixture pH from 1st separator vessel of Separator Station 51

Molar concentrations of anions of weak acids in brine mixture at 184°C

pH H3SiO4- H2BO3- HCO3- CO3-2 (x 2) HS- Sum Target Delta

5.67 1.4E-05 1.8E-05 1. 7E-04 1.9E-08 4.6E-05 2.5E-04 2.5E-04a -3.8E-07

a
- Total moles of anions of weak acids in brine mixture
 Appendix III: Data for calculation of mixed brine in Separator Station 52 at 10 bar-g

Table 3: Determination of brine mixture chemistry from 1st separator vessel of Separator Station 52

W503 W509 W513D W514D W515D W517 Composition

Mass flow at 1st
(@ wellhead pressure) kg/s 40.70 42.00 60.60 31.80 35.10 24.70 separator
First separator vessel brine (10 bar-g, 184°C)a
Water flow kg/s 32.35 35.18 48.43 23.38 27.81 20.52 187.67
pH (@ 184°C) 6.06 5.91 5.97 5.83 5.67 6.17 5.93
B mg/kg 220 226 215 188 247 246 223
SiO2 mg/kg 703 577 689 884 710 597 688
Na mg/kg 5,069 5,825 5,401 5,459 5,588 7,307 5667
K mg/kg 1,047 1,036 1,151 1,248 1,186 1,371 1153
Mg mg/kg 0.05 0.19 0.13 0.15 0.15 0.14 0.13
Ca mg/kg 189 535 231 204 228 681 326
F mg/kg 1.64 1.28 1.39 1.47 1.35 1.25 1.40
Cl mg/kg 8,749 10,376 9,542 9,571 9,794 13,143 9996
SO4 mg/kg 19.43 26.25 20.57 19.55 30.91 28.25 23.68
Fe mg/kg 0.60 0.34 0.34 0.36 0.48 0.27 0.40
CO2 mg/kg 18.42 44.30 54.07 47.31 50.83 36.26 42.82
H 2S mg/kg 0.75 5.81 7.03 5.96 6.46 4.61 5.24
NH3 mg/kg 3.33 4.74 4.76 6.68 5.75 3.08 4.71
H3SiO4- moles 3.8E-05 2.3E-05 3.0E-05 2.8E-05 1.6E-05 4.4E-05 2.9E-05
H2BO3- moles 5.0E-05 3. 8E-05 4.0E-05 2.6E-05 2.3E-05 7.9E-05 4.1E-05
HCO3- moles 6.8E-05 1.2E-04 1.7E-04 1.2E-04 8.9E-05 1.5E-04 1.2E-04
CO3-2 molesx2 1.8E-08 2.4E-08 3.7E-08 1.5E-08 9.9E-09 5.8E-08 2.7E-08
HS- moles 5.1E-06 3.1E-05 4.1E-05 2.7E-05 2.1E-05 4.0E-05 2.8E-05
a
- Degassing at 35% was selected to calculate the composition of individual well discharges

Table 4: Determination of brine mixture pH from 1st separator vessel of Separator Station 52

Molar concentrations of anions of weak acids in brine mixture at 184°C

pH H3SiO4- H2BO3- HCO3- CO3-2 (x 2) HS- Sum Target Delta

5.93 2.81E-05 3.86E-05 1.23E-04 2.55E-08 2.88E-05 2.2E-04 2.2E-07a 4.1E-07

a
- Total moles of anions of weak acids in brine mixture
Appendix IV: Data for calculation of mixed brine from Separator Stations 51 and 52 at 5 bar-g

Table 5: Determination of brine mixture chemistry at 5 bar-g (injection to Pad 5R1)

From Separator From Separator Brine mixture to

Station 51a Station 52b Pad 5R1
First separator vessel brine (5 bar-g, 159°C)
Water flow kg/s 55 190 245
pH @ 159°C 6.33 6.16 6.29b
B mg/kg 235 204 228
SiO2 mg/kg 726 688 718
Na mg/kg 5,982 5,800 5,941
K mg/kg 1,217 1,180 1,209
Mg mg/kg 0.14 0.13 0.13
Ca mg/kg 344 325. 340
F mg/kg 1.48 1.60 1.51
Cl mg/kg 10,551 10,668 10,578
SO4 mg/kg 25.00 22.79 24.50
Fe mg/kg 0.42 0.34 0.40
CO2 mg/kg 3.67 15.88 6.41
H2S mg/kg 1.16 5.37 2.11
NH3 mg/kg 4.6 6.17 4.95
H3SiO4 -
moles 7.5E-05 4.8E-05 6.9E-05
H2BO3- moles 0.000106 6.1E-05 9.6E-05
HCO3- moles 2.8E-05 9.5E-05 4.3E-05
CO3 -2
moles x 2 2.0E-08 4.6E-08 2.6E-08
HS- moles 1.5E-05 5.4E-05 2.4E-05
a
- Calculated brine mixture in Table 1, Appendix II adiabatically boiled to 5 bar-g at 14% degassing
b
- Calculated brine mixture in Table 3, Appendix III adiabatically boiled to 5 bar-g at 35% degassing

Table 6: Determination of brine mixture pH at 5 bar-g (injection to Pad 5R1)

Molar concentrations of anions of weak acids in brine mixture at 159°C

pH H3SiO4- H2BO3- HCO3- CO3-2 (x 2) HS- Sum Target Delta

6.29 6.7E-05 9.3E-05 4.6E-05 3.0E-08 2.6E-05 2.3E-04 2.3E-04a -1.2E-05

a
- Total moles of anions of weak acids in brine mixture
 Appendix V: Malitbog production wells scaling potential

0 100 200 300 0 100 200 300

1.0 2nd Flash 1st Flash 1.0 2nd Flash 1st Flash
brine brine brine brine
(at 5 bar-g) (at 10 bar-g) (at 5 bar-g) (at 10 bar-g)

SUPERSATURATED SUPERSATURATED
Aquifer Aquifer
water water
(at Tquartz) (at Tquartz)
log (Q/K)

log (Q/K)
0.0 0.0
Amorphous silica Amorphous silica
Anhydrite Anhydrite
Calcite Calcite

-1.0 -1.0
UNDERSATURATED UNDERSATURATED

0 100 200 300 0 100 200 300

Temperature (oC) Temperature (oC)

Figure 1: W501 saturation indices, Figure 2: W508D saturation indices,

14% degassing 14% degassing

0 100 200 300 0 100 200 300

2nd Flash 1st Flash

1.0 brine brine
1.0 2nd Flash 1st Flash
(at 5 bar-g) (at 10 bar-g)
brine brine
(at 5 bar-g) (at 10 bar-g)
SUPERSATURATED
Aquifer
SUPERSATURATED water
Aquifer (at Tquartz)
water 0.0
(at Tquartz)
log (Q/K)

log (Q/K)

Amorphous silica
0.0
Amorphous silica Anhydrite
Anhydrite Calcite
Calcite
-1.0

-1.0
UNDERSATURATED

-2.0
UNDERSATURATED

0 100 200 300 0 100 200 300

Temperature (oC) Temperature (oC)

Figure 3: W511D saturation indices, Figure 4: W503 saturation indices,

14% degassing 35% degassing
 0 100 200 300 0 100 200 300

2nd Flash 1st Flash

1.0 brine brine 1.0 2nd Flash 1st Flash
(at 5 bar-g) (at 10 bar-g) brine
brine
(at 5 bar-g) (at 10 bar-g)
SUPERSATURATED
SUPERSATURATED
Aquifer
water
0.0 (at Tquartz)
log (Q/K)

log (Q/K)
Amorphous silica 0.0
Anhydrite Amorphous silica
Calcite Anhydrite
Calcite
-1.0 Aquifer
water
(at Tquartz)
-1.0

UNDERSATURATED

-2.0
UNDERSATURATED
-2.0

0 100 200 300 0 100 200 300

Temperature (oC) Temperature (oC)

Figure 5: W509 saturation indices, Figure 6: W514D saturation indices,
35% degassing 35% degassing

0 100 200 300 0 100 200 300

1.0 2nd Flash 1st Flash 1.0 2nd Flash 1st Flash
brine brine brine brine
(at 5 bar-g) (at 10 bar-g) (at 5 bar-g) (at 10 bar-g)

SUPERSATURATED SUPERSATURATED
log (Q/K)
log (Q/K)

0.0 0.0
Amorphous silica Amorphous silica
Anhydrite Anhydrite
Calcite Calcite

-1.0 -1.0 UNDERSATURATED

UNDERSATURATED Aquifer Aquifer
water water
(at Tquartz) (at Tquartz)

-2.0 -2.0

0 100 200 300 0 100 200 300

Temperature (oC) Temperature (oC)

Figure 7: W515D saturation indices, Figure 8: W517 saturation indices,
35% degassing 35% degassing
 APPENDIX VI: Silica experiment results

Table 7: 50°C, pure water, 1 atm, pH~7, 9 minutes retention time, filtered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
0 407 412 5d 11 165 175 10d
d
24 402 415 13 44 161 178 17d
d
100 404 413 10 114 159 172 13d
d
179 392 413 21 189 164 177 14d
244 394 413 18d 254 164 178 14d
d
1,504 394 404 9 1,514 167 189 21d
a a
3,420 235 311 76 3,429 164 312 147b
a a
4,289 231 335 104 4,301 173 339 165b
d
4,534 225 392 167 4,534 173 341 168d
5,709 233 371 138d 5,739 180 355 175d
7,074 228 386 158
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots

Table 8: 50°C, 0.1 M NaCl, 1 atm, pH~7, 9 minutes retention time, filtered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
0 345 339 -6c,d 47 165 166 1d
c
34 348 337 -11 1,074 168 167 -1c,d
c
154 344 336 -9 1,809 166 169 3d
1,062 340 332 -7c,d 2,479 171 190 19d
d
1,791 335 340 5 3,057 167 228 61b
d
2,445 316 326 10 3,929 174 259 85b
a a
3,057 268 282 14 4,434 166 255 89b
a a
3,897 237 257 20 5,404 172 269 97b
4,389 241 274a 33a 5,999 171 268 97d
a a
5,329 218 299 81 6,899 172 283 110b
d
5,924 212 311 99 7,366 166 266 100b
a a
6,844 220 282 62
7,360 210 273a 63a
8,549 204 301 97
9,672 203 293 90
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots
 Table 9: 50°C, 0.2 M NaCl, 1 atm, pH~7, 9 minutes retention time, filtered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
0 377 366 -11c 23 164 164 0
108 379 377 -1c 108 173 159 -14c
338 375 375 0d 356 166 163 -4c,d
1,296 241 301a 60a 1,318 161 273 112b
d
1,888 226 336 110 1,908 164 296 132d
a a
2,798 212 232 19 2,818 162 304 142b
a a
3,278 216 304 88 3,288 159 298 140b
d
4,513 199 320 121 4,558 164 292 128d
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots

Table 10: 50°C, 0.3 M NaCl, 1 atm, pH~7, 9 minutes retention time, filtered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
0 374 353 -21c 32 157 152 -4c
c
84 370 358 -12 472 161 164 3d
c,d
360 355 351 -5 1,636 156 273 117d
d
1,619 213 313 100 2,797 165 276 110d
d
2,688 197 303 106
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots

Table 11: 50°C, 0.4 M NaCl, 1 atm, pH~7, 9 minutes retention time, filtered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
0 371 337 -34c 47 162 151 -11c
69 368 336 -33c 328 158 142 -16c,d
c,d
332 346 321 -25 1,672 156 268 112c,d
d
1,605 205 306 101 2,705 156 278 122c,d
d
2,672 197 284 87
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots
 Table 12: Experiment 1 results at 90°C, 0.3 M NaCl, 1 atm, pH~7, 9 minutes retention time,
filtered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
0 489 457 -33c 37 260 256 -4c
c
32 486 485 -1 65 261 256 -5c
c
58 500 487 -13 260 277 280 4
234 476 481 5 324 268 271 3
302 461 476 15 485 271 281 10
465 473 479 6 1,200 276 262 -13c
1,180 377 383 6 1,532 270 297 27
1,510 355 349 -5c 2,579 280 316 36
2,555 356 337 -20c
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots

Table 13: Experiment 2 results at 90°C, 0.3 M NaCl, 1 atm, pH~7, 9 minutes retention time,
filtered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
c
0 479 446 -33 30 250 237 -13c
c
63 492 461 -31 90 270 251 -20c
366 408 401 -7c,d 396 275 273 -3c,d
d
1,083 345 416 71 1,116 238 271 33d
d
1,261 337 401 64 1,272 274 245 -29c,d
c
1,468 336 318 -18 1,538 275 262 -14c
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots

Table 14: Experiment 2 results at 90°C, 0.3 M NaCl, 1 atm, pH~7, 9 minutes retention time,
unfiltered samples

Inlet solution Outlet solution

Time SiO2, monomeric SiO2, total SiO2, polymeric Time SiO2, monomeric SiO2, total SiO2, polymeric
(min) (mg/kg) (mg/kg) (mg/kg) (min) (mg/kg) (mg/kg) (mg/kg)
0 479 492 13 30 250 239 -11c
c,d
63 492 491 -1 90 270 257 -14c,d
366 408 445 37d 396 275 293 17d
d
1,083 345 462 117 1,116 238 349 110d
d
1,261 337 463 126 1,272 274 384 110d
d
1,527 336 448 113 1,538 275 389 114d
a
- Removed in plot due to low values, b- Excluded in plot since no equivalent analyses from inlet
c
- Set to zero if plotted, d- Used in inlet vs. outlet polymeric silica plots