SPE-175287-MS

Water Analysis - A Key Tool for Reservoir Monitoring Under Cyclic Steam
Stimulation
Anil Kumar Jain, Khalid Ahmed, Jose L. Ortiz-volcan, and Waleed Al-Khamees, Kuwait Oil Company

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Kuwait Oil & Gas Show and Conference held in Mishref, Kuwait, 11–14 October 2015.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
During the process of Cyclic Steam Stimulation (CSS) variations in reservoir pressure and temperature
occur changing the solubility of reservoir rock minerals in the formation water and therefore during
production phase, produced water brings valuable information about dynamic characteristics of reservoir
rock and fluid. Its analysis may provide an invaluable means for monitoring the reservoir. This paper
describes the process of water analysis where results are interpreted on the basis of the principle that the
solubility of minerals varies with change in pressure and temperature. This also shows the importance of
water analysis as a key tool for reservoir monitoring in fields undergoing cyclic steam stimulation.
Water analysis is also used to optimize impact of produced water on Capex and Opex of oil production
as water is required to be handled and disposed without impacting the environment, and is applied as
troubleshooting tool to identify well problems and to validate log interpretations.
Field examples illustrate application of water analysis in i) mineralogical changes that takes place
during CCS operation for reservoir monitoring and impact of steam on clays, ii) determining compatibility
of injected steam with the formation water and compatibility of effluent with the formation water of
disposal well, iii) surface facility design and water treatment before steam generation, iv) reservoir
description and computing fluid saturation using resistivity of formation water and v) troubleshooting well
problems, e.g. unanticipated water production because of channeling behind the casing and communica-
tion between the layers.
Paper discusses the importance of water analysis at each stage of CSS operation and its application in
reservoir monitoring and describes field experience with water analysis in the surveillance of a CSS
project.

Introduction
Water production is an unwanted occurrence during oil production as it not only affects the oil production
but also imposes the burden of handling and disposing it and increases the capital and operating
expenditures. Its disposal is also not so simple because of environmental issues. A detailed water analysis
is required and accordingly effluent treatment plant and other surface facilities are designed. A good
feature associated with produced water is that being a good solvent it also provides valuable information
2 SPE-175287-MS

about the reservoir rock and fluid. Its analysis is also required for optimizing facility design, material
selection and hydrocarbon recovery (Abdou et al, 2011).
Solubility of minerals in the formation water changes vertically and laterally in the same aquifer
because of variation in rock properties, reservoir pressure and temperature from place to place. Compo-
sition of formation water varies with time also because of intrusion of fresh water from the surface into
the reservoir either by water injection or by recharge of the formation from the surface. With time,
reservoir pressure and temperature changes and therefore composition of the formation water also
changes. These changes can be observed in the produced water, and their analysis becomes very important
for understanding the dynamic behavior of the reservoir.
During Cyclic Steam Stimulation (CSS) process, water is injected in the form of steam to produce
heavy oil. In this process, temperature and pressure of the reservoir changes and therefore solubility of
various minerals also changes in the formation water around the wellbore. When the well is produced
back, temperature of the produced water goes down with time and therefore composition of minerals
associated with it also changes. The changed composition provides dynamic information of the reservoir
that helps in its monitoring. In this paper field examples are discussed and it is shown that the varying
composition of produced water can be used for reservoir monitoring. Water analysis is also required for
prediction of chemical scaling in the formation (incompatibility with injected water), calibration of
resistivity logs and its variation within a field indicated extent of reservoir and aquifer connectivity
beneath in the field (Coleman, Jones and Cox, 1990) and for many other applications. These topics are
also discussed in the paper.
Water Sampling and its Validity
The first requiremnet for a meaningful water analysis is to have a representative water sample. If the water
sample is good then only its analysis will be beneficial otherwise it will give wrong interpretations. Water
sample may be collected in two ways: (i) surface sampling, (ii) downhole sampling directly from the
formation by wireline formation tester. Another potential source of formation water samples that are
usually rejected because of high levels of mud filtrate contamination is samples from core (Coleman,
Jones & Cox, 1990). Surface water samples are usually collected from the wellheads or separators, this
is the water that comes along with oil; water separated from the oil is used for the analysis. When a well
is flowing for quite some time then the wellhead water sample may be considered as a representative
sample from the desired formation and it may be used for the analysis. Surface sampling is less expensive
than downhole sampling and can be done more routinely.
Downhole sample has an advantage of preserving gases in the formation water. Carbon dioxide and
hydrogen sulphide, in particular have an important effect on pH and hence on chemical composition.
Downhole sampling is also done in newly drilled wells; this may be from the water-bearing formations
or oil bearing formation or both. Sample from oil-bearing formation may have associated water also. This
water is used to carry out water analysis. If the well is drilled with oil based mud then this sample should
be considered as a representative one. If the well is drilled with water based mud then the situation is
different. Most of the time samples are found to be contaminated with mud filtrate. Though precaution is
taken during sampling, even then in most of the cases, samples were found to be contaiminated with mud
filtrate. If analysis of contaminated water is used then it may give misleading results. It is, therefore,
necessary to ascertain that the sample being used for analysis is a representative one.
There are many ways to know whether the sample is contaminated with mud filtrate or not. One simple
method is just to calculate percentage of some particular component used in the mud. In case of
water-based mud usually potassium chloride (KCl) polymer is used in drilling of a well in an unconsol-
idated sandstone formation. If percentage of potassium component is found to be more in downhole
sample then it may be concluded that it is contaminated with mud filtrate. So this sample cannot be used
for our purposes.
SPE-175287-MS 3

Ternary Plot may also be used to find out whether the sample is contaminated or not. An example of
this plot is shown in Figure 1 where composition of three samples is shown. Three components – sodium
(Na), potassium (K) and calcium (Ca) are plotted on three axes. Sample-1 has high percentage of
potassium that is major component of mud. It clearly shows that this sample is highly contaminated with
the mud filtrate while Sample-2 is very good representative one and Sample-3 shows that sample is
moderately contaminated. So, analysis data of Sample-2 should be taken into consideration for all
interpretation

Figure 1—Ternary diagram showing water samples contaminated with drilling fluid

Downhole samples are required to have a base data and are taken at the time of drilling itself. But for
regular monitoring of CSS wells, wellhead surface sample is taken.
Chemical Composition of Water
Water analysis is consists in determining physical properties such as total dissolved solid (salinity), total
suspended solids, pH, conductivity, resistivity, hardness, specific gravity and hydrogen sulphide, and
chemical properties determining various cations and anions in it. Frequently used chemical property of
water is salinity, but ionic composition of water is also needed for many purposes. All formation water
is chemically characterised by its composition in terms of dissolved solids. Most commonly found
dissolved solid is sodium chloride. Other commonly found dissolved solids are potassium chloride,
calcium chloride, magnesium chloride, strontium chloride, sodium sulphate, sodium carbonate and
sodium bicarbonate. Solids present in formation water are usually defined in terms of cations and anions.
Concentration of dissolved solids is often expressed in terms of mg/litre or ppm. Cations include sodium,
potassium, calcium, magnesium, barium, strontium, iron ions and anions include chloride, sulphate,
bicarbonate, carbonate, and hydroxide. Analysis of these components is called as API 12 ion water
analysis. Apart these cations and anions, some additional components such as boron, aluminium, silicon,
phosphorus and lithium are also determined. Sometimes oil in water is also being determined.
Water Analysis Method
Most of the chemical composition of water are identified by inductively coupled plasma (ICP) atomic
emission spectroscopy or ion exchange chromatography. These techniques consist of determining ions of
sodium, potassium, calcium, magnesium, barium, strontium, dissolved iron, sulphate (as total sulphur),
phosphorus, silicon, boron, aluminium and lithium. Chloride is determined by potentiometric titration and
sulphate is usually determined by gravimetry. pH and bicarbonate determinations are measured by ion
selective electrode.
Specific gravity and density are determined by densitometer on a filtered and undiluted sample. The
temperature is recorded and the results are reported at 60°F. Conductivity is performed on filtered and
4 SPE-175287-MS

undiluted sample using conductivity meter and noting the temperature. The resistivity at 60°F is calculated
from conductivity values.

Stiff & Ionic Concentration Diagram (Schoeller Diagram)

A Stiff diagram is one of the graphical representations of cations and anions present in the formation
water. A polygonal shape is created from four parallel horizontal axes extending on either side of a vertical
zero axes. Cations are plotted in milli-equivalents per liter (meq/l) on the left side of the horizontal axis,
and anions are plotted on the right side. Milli-equivalent per liter can be calculated by multiplying valency
with mg/l and deviding by molecular weight.
Stiff diagrams are useful in making a quick visual comparison of water from different sources.
Different formation waters are characterised by their uniquely distributed solids. Relative distribution of
dissolved solids distinguishes various formation waters. Water contained in producing formations may
have composition different from any other water, even those in the immediate vicinity of that formation.
When comparing Stiff diagrams of different waters it is important to prepare each diagram using the same
ionic species, in the same order, on the same scale. Figure 2 depicts the Stiff diagram of three different
reservoir of the same field. Concentration of Na, Ca, Mg and Fe ions are plotted on left side and that of
Cl, HCO3, SO4 and CO3 are plotted on right side. These plots are on linear scale. The same plot can also
be made on logarthemic scale. Shape of all three is different. By visual inspection only, it can be said
easily that these samples belong to different reservoirs.

Figure 2—Stiff diagram of three different reservoir of the same field

Schoeller Diagram (Ionic Concentration Diagram) is another way of graphical representation. It is a

semi-logarithmic diagram of the concentrations of the ionic constituents in water. On horizontal axis, ions
are kept at equal space while on vertical axis ionic concentration in meq is plotted. A simple modified
Schoeller plot with ionic concentration in mg/l on semi-log scale on vertical axis has been used in this
paper and will be used to compare ionic composition of different layers of the same well (Figure 5 & 7).
SPE-175287-MS 5

Important Features of the Formation Water and Rock of the Field under
Consideration

Composition of Formation Water

Water analysis of hundreds of downhole samples was done in the reservoir under consideration. Depth of
the reservoir varies from 450 ft to 850 ft, accordingly water properties also vary with the depth. Water
properties varies areally also as rock composition varies from place to place. Average ionic concentration
of various components in the field is given in Table 1.

Table 1—Average values of ionic component of formation water

(all values are % of TIDS)
Component Value

Na⫹ 20-28
K⫹ 2-3
Ca⫹⫹ 6-8
Cl- 49-61
SO4-- 0-12
HCO3- 1-3
Mg⫹⫹ 3-4
Ba⫹⫹ ⬍0.01
Sr⫹⫹ 0.14-027

Resistivity of water changes with salinity but at higher salinity (total dissolved solids), it does not
change much and becomes almost constant but specific gravity continuously increases with salinity
(Figure 3). It is observed in the field that Mg and Sr ions increase with depth (Figure 4).

Figure 3—Change in resistivity and specific gravity of formation water with total dissolved solids
6 SPE-175287-MS

Figure 4 —Magnesium and Strontium lons increases with depth of the reservoir

Salinity changes with depth in the same well, but relative distribution of dissolved solid remains the
same. Salinity will be minimum in the top and maximum at the bottom. Figure 5 shows the ionic
distribution of four water samples that were collected at different depth of same formation in the same
well. The sample collected at 815 ft has minimum concentration of each component while the lowest
sample collected at 1170 ft has maximum concentration. These concentrations increase with increasing
depth but relative distribution of components remains the same.

Figure 5—Ionic Concentration of Different components at Different Depth of the Same Well

In the same well, salinity varied from formation to formation. One interesting point is that salinity of
water within the same formation increases with depth, but it does not mean that salinity of lower
formations at all depths will be higher than the upper formation salinity. Shallower formations may have
higher salinity than deeper formations and also sometimes different formations may have same salinity.
One such field example is given in Figure 6 where salinity variation with depth in three different
formations of the same well is shown.
SPE-175287-MS 7

Figure 6 —Plot of depth vs. salinity of three different reservoir of the same well

If we take samples from different wells at different places in the field but in the same reservoir,
concentration of components may vary. Ionic concentration of various component of three wells is plotted
in Figure 7. These samples are from three different part of the field. Sulphate concentration is different
in all the cases. It is because of different reservoir setting.

Figure 7—Ionic concentration of three wells from different of the field in the same reservoir

Mineralogical Composition of the Formation Rock

The field under consideration consists of unconsolidated sandstone. Mineralogical analysis of the
reservoir rock of the field suggests that the main constituents of the formation rock are quartz, K-feldspar,
calcite, dolomite and clays. Quartz (including amorphous silica) is the main constituent of the reservoir
rock; in some part of the formation, it is up to 70%. K-feldspar is present up to 5-6%. Calcite is almost
absent but at some places it is up to 1-2% within the sand. Dolomite is also very low, however at some
places it is up to 10% in the reservoir in streaks. Clays up to 9% are found in the reservoir sand. Illite and
smectite together make about 70% of the total clay present in the reservoir.
Water Life Cycle during Cyclic Steam Stimulation (CSS)
Cyclic Steam Stimulation
During CSS process, steam is first injected into a well to heat the viscous oil around the wellbore to reduce
its viscosity and after soaking for a few days, oil and water is produced from the same well. CSS process
is shown in Figure 8. Pressure and temperature around the well bore increases during injection and
decreases during soaking and keep on decreasing during production period. Water is a good solvent and
solubility depends upon pressure, temperature and saturations. Mineralogical changes take place during
the process and because of this produced water analysis becomes an important tool for monitoring
dynamic characteristics of the reservoir under CSS.
8 SPE-175287-MS

Figure 8 —Cyclic Steam Stimulation Process

Water life cycle of the CSS consists of three stages – injection phase, soaking phase and production
phase. Involvement of water is always there in all the stages and therefore its analysis is required at each
stage for one reason or the other.
Injection Phase
During injection phase, first requirement is availability of water. Source of water may be either sea,
sewage, effluent or wellbore. Water from these sources cannot be sent directly to the boilers; otherwise
it may choke the boiler. Water has to pass through treatment facility where proper chemical may be
applied to make desired quality of water. Treatment plant and boiler also create some rejected water that
cannot be used and we have to get rid of this by either throwing it in the sea or dumping it into some
disposal wells. In both cases, this reject is to be treated again. If reject is to be injected in some disposal
well, then compatibility of reject with the formation of disposal well is required. For all this water analysis
is required.
After generating the steam, next stage is to inject it in to the formation. Usually wet steam is used for
CSS where 80% of water is kept in vapor phase and rest 20% in liquid phase. Prior to steam injection,
compatibility test is done to see what quality of steam is the most suitable for the formation water. This
also involves water analysis of steam and formation water.
During injection, pressure and temperature of the formation increase and steam interacts with
formation fluid and rock and that changes the composition of the formation water.
Soaking Phase
In this phase, the well is kept closed for a few days to soak/transfer the heat to the oil in the formation
so that its viscosity may be reduced. With time, steam condenses into water and pressure and temperature
of the formation goes down. Condensed steam (hot water) mixes with formation water and therefore
salinity and water saturation around the wellbore changes. The varying temperature affects solubility of
various rock minerals. Initially solubility of some of the minerals increases but later it decreases and they
precipitate in the formation. Steam also affects clays present in the formation. Some of the clays like illite
and smectite may swell and choke the formation. Dissolution of silica in water varies with temperature
and magnesium ion reacts with hydroxyl to form magnesium hydroxide that may also precipitate in the
reservoir. Precipitation of magnesium hydroxide is affected by pH and temperature of the formation.
Steam with optimum pH is used to avoid Mg(OH)2 precipitation and also corrosion of the surface
facilities.
Production Phase
After sufficient soaking period, well is allowed to flow. Condensed steam is produced first followed by
formation water along with oil. During this process, salinity of the produced water changes. Initially the
salinity of produced water remains low as it is only condensed steam and it keeps on increasing with time
as condensed steam mixes with the formation water. Temperature and pressure of the reservoir also goes
SPE-175287-MS 9

down with production. Many dissolved minerals come along with water. Solubility of minerals varies as
the reservoir pressure and temperature goes down. This property gives important information about the
dynamic changes in the reservoir. Produced water also needs to be disposed of that also needs treatment
in the same way as it is done for reject of the boiler.

Reservoir Monitoring
Reservoir pressure of the field is about 240 psi and temperature is 90 °F. Oil viscosity varies from 100
cp to 2000 cp. Cyclic steam stimulation (CSS) was applied in seven isolated wells of the field under
consideration. 80% quality steam was injected in the wells at about 420 psi wellhead pressure. The
temperature of the steam was around 450 °F. The quantity of steam injected was in the range of 15,000
to 20,000 barrel per day (cold water equivalent). After injection, wells were kept shut-in for about two
weeks for soaking and then they were put on production.
Since water is always in the center stage of whole CSS process and therefore its analysis is also needed
at each stage for various reasons. The produced water can be analyzed to determine whether mineralogical
changes are occurring over the life of CSS. In the CSS process, during injection phase, temperature and
pressure of the formation increases and during soaking and production phase, it decreases; pH of the
reservoir water also changes. Solubility of minerals depends on temperature, pressure and pH and
therefore concentration of various minerals in produced water also changes. Monitoring and analysis of
these changes are quite useful to understand the dynamic behavior of the reservoir rock. Produced water
can also be analyzed over the life of steamflooding in the same way.
Solubility of Calcite, Magnesite and Dolomite
Experiments conducted to see the solubility of calcite (CaCO3), magnesite (MgCO3) and dolomite
(CaMg(CO3)2) in fresh water at different temperature and was discussed in detail by Morey (1962).
Solubility of calcite remains almost constant up to 300 °F and thereafter starts decreasing rapidly and
become almost insoluble at 800 °F (Figure 9). Maximum solubility of calcite at any temperature is 21
ppm. Solubility of magnesite first increases with increasing temperature and reaches to maximum of 13
ppm at 300 °F and then it decreases (Figure 10). It is interesting that at about 300 °F, magnesite (MgCO3)
starts changing into brucite (Mg(OH)2) and if temperature continues to increase, MgCO3 is completely
replaced by Mg(OH)2.

Figure 9 —Solubility of CaCO3 remains almost constant up to 300 °F and thereafter starts decreasing rapidly (by Morey, 1962)
10 SPE-175287-MS

Figure 10 —Effect of temperature on solubility of MgCO3 and Mg(OH)2 (by Morey, 1962)

Dolomite consists of carbonates of calcium and magnesium CaMg(CO3)2. Solubility of CaCO3 of

dolomite increases linearly with temperature up to 400 °F, then decreases sharply (Figure 11). The amount
dissolved at 400 °F is 18 ppm, almost the same as was found during calcite alone. Solubility of MgCO3
of dolomite increases up to 212 °F, then decreases. The maximum solubility was found to be 8 ppm at 230
°F. When MgCO3 come in contact with water it converts into Mg(OH)2 at 300 °F. The same reaction takes
place as above when dolomite comes into contact with water at 350 °F. As the temperature increases, the
solubility of Mg(OH)2 decreases and becomes almost zero at 650 °F.

Figure 11—Effect of temperature on solubility of dolomite (by Morey, 1962)

All the solubility values are measured by Morey in lab using fresh water, but in the formation under
actual field conditions these solubility values changes because of presence of rock and mineral water.
Changes in calcium ion were monitored in all the seven CSS wells of the field. It was found that
calcium ion remains almost constant during production phase of CSS as was before CSS except one well
(Well-2) where it fell sharply from 7% (before steaming) to 1.9% after steaming during production phase.
It means perhaps precipitation of calcite took place at higher temperature in Well-2. From XRD analysis,
it was found that the producing zone has calcite up to 3% and dolomite up to 38% in this well while in
other wells they are almost absent. So the main reason of less calcium ion in produced water in Well-2
may be because of the presence of high calcite that is still precipitating in presence of fresh water.
Magnesium Precipitation in the Formation
Travers and Novel (1929) were among the first who experimented on the effect of temperature on the
solubility of Mg(OH)2 in water but their temperature range was from 0° to 200° C. Carlson et al (1953)
conducted the experiment for a wider range of temperatures (Figure 12). It was concluded that solubility
of Mg(OH)2 decreases with increasing temperature and at about 250 °F, it becomes almost nil. Larson et
al (1959) also referred the work of Travers and Nouvel in their paper and worked to find out the optimum
pH and temperature at which water can flow in pipes without scaling of magnesium hardness. They
showed that maximum allowable magnesium hardness decreases with increasing temperature at constant
SPE-175287-MS 11

pH and also decreases with increasing pH at constant temperature (Figure 13). The study was conducted
for the pH in the range of 8.6 to 9.8.

Figure 12—Solubility of Mg(OH)2 at various temperatures (by Carison, Peppler & Wells, 1953)

Figure 13—Max. recommended Mg hardness at various recorded temperatures and pH values, hardness as CaCO3 to avoid scalling (by
Larson, Lane & Neff, 1959)

Dolomite (calcium magnesium carbonate; CaMg(CO3)2) and magnesite (magnesium carbonate;

MgCO3) are the main source of magnesium ions in the formation water. As discussed above, magnesite
(MgCO3) starts changing into brucite (Mg(OH)2) at 350 °F and if temperature continues to increase,
MgCO3 is completely replaced by Mg(OH)2. Solubility of magnesium hydroxide in water is very low
compared to other magnesium salts, it is about 12 mg/l at 10°C. At the same temperature, solubility of
magnesium carbonate is 600 mg/l and magnesium sulphate is of 309 mg/l. Magnesium cations present in
the formation water of the field under consideration are in the range of 400 – 2000 mg/l.
In all the CSS wells almost neutral water (pH⫽7) was injected. Steam temperature was around 450 °F.
Magnesium, strontium, sulphate and bicarbonate ions in the produced water before and after steam in four
of the CSS wells are shown in Table 2.

Table 2—Ionic concentration of wells before and after steaming in produced water
Mgⴙⴙ, mg/l Srⴙⴙ mg/l SO4-, mg/l HCO3-,mg/l

Before After Before After Before After Before After

Well no. steaming steaming steaming steaming steaming steaming steaming steaming

Well-1 680 12 35 0.68 1270 20 630 190

Well-2 755 1 10 ⬍0.05 1210 11 50
Well-4 425 4 32 0.32 1580 52 290 64
Well-6 585 2 76 2.3 1460 42 465 73
12 SPE-175287-MS

Before steaming, magnesium level of the produced formation water was in the range of 425 - 755 mg/l.
But after steaming, it reduced in the range of 1 to 12 mg/l only. The reason for this is that the hydroxyl
ion of condensed steam reacted with magnesium ions presented in the formation water and form
magnesium hydroxide at higher temperature. Since solubility of magnesium hydroxide is very low, so it
got precipitated in the formation itself. The same was the case with strontium. Sulphate ions also
decreased after steaming, it indicates that sulphate of strontium and barium might have precipitated in the
formation. This phenomenon was also observed during compatibility study in the lab and will be discussed
in section 5.6.
Figure 14(a) and 14(b) show the variation of magnesium ion (in percentage of TDS) and temperature
with time of Well-4 and Well-6. It is interesting to note that the concentration of magnesium ion droped
down drastically compare to the original level during early stage of production phase as the temperature
was higher in the wells and it remained low till the temperature of the wells was above 145-150 °F (much
above the reservoir temperature 90 °F). When temperature went down further then the concentration of
magnesium ion increased again. The same phenomemon was observed in other two wells also. It is clear
from here that at higher temperature magnesium hydroxide precipitation takes place in the formation.

Figure 14(a)—Change in Mgⴙⴙ concentration (% of TDS) with temperature of Well-4

Figure 14(b)—Change in Mgⴙⴙ concentration (% of TDS) with temperature of Well-6

Dissolution and Precipitation of Silica

Solubility of quartz and amorphous silica increases sharply with temperature at constant pH of liquid
phase of steam as shown in the Figure 15 (Hong, 1994). Morey et al (1964) concluded in their experiment
that in nearly neutral solution the solubility of amorphous silica is 115 ppm at 25°C. Konrad B Krauskopf
(1956) did a detailed laboratory study to understand the effect of temperature, pH and salinity on the
solubility of silica. Most or all of the dissolved silica was in the form of mono-silicic acid, H4SiO4. The
crystalline forms of silica have lower solubility, quartz the least of all. Precipitation could occur as
temperature and pH drop between injector and producer during steamflood. The solubility of amorphous
silica is little affected by pH in the range of 0 to 9, but increases rapidly as the pH rises above 9. Silicate
ion is present in appreciable amounts only at higher pH (over 9); in more acidic solutions the silicic acid
SPE-175287-MS 13

is essentially un-ionized. Amorphous silica has almost no effect on the water salinity. It has about the same
solubility in fresh water as in sea water.

Figure 15—Maximum silica solubility in neutral water (from Hong, 1994)

Solubility of silica increases with pressure at constant temperature. (Fournier and Rowe, 1977).
Presence of carbon dioxide and hydrogen sulphide affect the solubility of silica because during steam
injection, carbon dioxide and hydrogen sulphide are produced and these gases dissolve in condensed water
and make it somewhat acidic. (Thimm, 2008).
During cyclic steam injection, silica concentration in produced water was analyzed. Production and
reservoir temperature went down with time. It was observed that silica concentration also decreased. One
such example of a well is shown in Figure 16. As discussed above, with increasing temperature,
dissolution of silica increases but when temperature of the reservoir goes down during production phase
this dissolution decreases. The same thing happened in this well. Initially more silica dissolved in the
reservoir during injection and soaking phase but later when temperature went down, dissolved silica
started precipitating in the reservoir itself.

Figure 16 —Temperature and silica concentration in water decreases with production (Well-1)

Dissolution and precipitation of silica of four CSS wells was analyzed and compared (Figure 17). At
higher temperature, silica concentration was maximum in produced water of well-1 and minimum in
Well-4. During production phase, as the temperature goes down, maximum precipitation of silica took
place around the wellbore of Well-1 and minimum precipitation took place around the wellbore of Well-4.
It is interesting to note that dissolution and precipitation varied from place to place in the field. It depends
on the rock properties and formation water chemistry at these places. The reservoir area near to Well-1
is more prone to this dissolution and precipitation of silica than that near to Well-4.
14 SPE-175287-MS

Figure 17—Variation in silica concentration of wells from different part of the field

Effect of Steam on Clays

Seven to nine percent of the formation rock consists of clays. From the XRD, it was found that smectite
and illite are the main constituents of these clays (90% of the total clays), kaolinite is about 5% of total
clays and rest is calcite. Some of the SEM pictures of the clays present in the formation are shown in
Figure 18. A study to understand the steam effect on clay mineral was done and found that in presence
of fresh water (in the form of condensed steam), smectite swells and reduces the porosity and permea-
bility. Kaolinite moves in the pore structures and also causes significant permeability reduction. Calcite
produces carbon dioxide, causes precipitation of siderite and kaolinite which cause plugging of pores
around the wellbore. This is confirmed by pre and post SEM images carried out during flooding
experiments in the laboratory. Increasing pH or salinity of the water somewhat reduces the formation
damage but does not stop/control the damage completely. However, these damages can be controlled by
using permanent clay stabilizers.

Figure 18 —Some of the clays present in the formation

A means to verify the reaction of condensed steam with clay is to monitor the pH of produced water
over the life of the flood. If the reaction is occurring, Na⫹ will be consumed and H⫹ will be produced.
The result would be a decline in both sodium concentration and pH (Hong, 1994). pH of produced water
of four CSS wells was measured and compared with the pH of formation water of these well. It was found
that pH reduces after steaming as shown in the Table 3. This confirms that swelling of clays is taking place
in the formation.
SPE-175287-MS 15

Table 3—pH of produced water

Well No. Before Steaming After Steaming

Well-1 8.18 7.64

Well-2 8.89 7.73
Well-4 8.45 7.38
Well-6 8.73 7.78

Calcium Sulphate, Barium and Calcium Carbonate Scaling in the Reservoir

When steam is injected, it interacts with formation water and rock and some scaling due to precipitation
of minerals may take place in the reservoir. Compatibility study was done to find if some precipitation of
minerals was taking place in the reservoir or not when different pH steam was mixed with formation
water. It was done in two ways - computer scale prediction study using software and static Jar Test by
mixing injection water with the formation water in various ratios. Effect of temperature, pressure and pH
on the compatibility of injected alkaline steam with the formation water was done and different scenarios
were analyzed. The results of the jar test and computer scaling study indicates that injecting steam boiler
feedwater into the formation will result in BaSO4 and CaCO3 scaling. CaCO3 precipitation increases with
increasing pH and temperature. Precipitation of CaSO4 increases above 100 °F and that of BaSO4 above
212°F. In water analysis of one of the wells (Well-2) it was observed that when well was produced soon
after steaming and soaking, calcium ions in produced water decreased sharply from 7% to 1.9%. It
confirms that precipitation of calcium compound took place in the well.
Precipitation of Mg(OH)2 increases above pH 9.5. Magnesium level is very high in the formation
water, it goes up to 2000 ppm. The high pH is contributed by hydroxyl ion (OH-). If high pH steam is
injected, Mg ion will react with hydroxyl and form Mg(OH)2. Solubility of Mg(OH)2 is very low and
precipitate in the reservoir. The suggested pH of the steam is in the range of 8.5 to 9.5. In this range,
minimum precipitation takes place. If pH increases above 10.5, precipitation increases sharply.
Discussion on pH
pH is one of the key parameters in selection of material for equipment and surface facilities to reduce their
corrosion. It is also an important parameter to understand scaling and precipitation of various salts in the
formation. Use of optimum pH steam in CSS and steamflood projects is required for various reasons. Pure
steam has neutral pH but liberated gases may dissolve in condensed water and reduce the pH. Usually 70
to 80% quality of steam is used in most of the CSS and steamflood projects. pH of the liquid fraction of
the steam affects dissolution and precipitation of silica and magnesium hydroxide and corrosion of the
surface facilities. Corrosion decreases as pH increases up to 11 only, above which corrosion increases.
Dissolution of silica increases sharply above pH 11. During the study, it was found that precipitation of
magnesium hydroxide in the reservoir reduces if liquid fraction pH is in the range of 8.5-9.5, above this
pH precipitation increases. Magnesium ion in the formation water is in the range of 400-2000 mg/l. When
steam of higher pH (⬎9.5) is injected, then there are more chances of converting magnesium ion into
magnesium hydroxide and it may precipitate in the reservoir itself as solubility of magnesium hydroxide
in water is only 12 mg/l.
Computation of Formation Water Produced
During production phase of CSS, regular monitoring of the salinity of produced water is required that
provides us a very good piece of information whether only condensed water is producing or formation
water also starts coming. During this phase, initially salinity of produced water will be low as only
condensed steam will be produced back that has low salinity. Gradually, salinity increases as fresh water
of the condensed steam mixes with the formation water. The change in salinity of the first CSS well
(Well-5) of field under consideration has been shown in Figure 19. When production phase of CSS started,
16 SPE-175287-MS

only condensed steam was produced that was just like fresh water and its salinity was too low.
Subsequently salinity started increasing and reached up to 12000 ppm within four month time. This
increase indicated that now a quite good amount of formation water was coming.

Figure 19 —Variation of salinity with time of produced water during production phase of CSS of Well-5

Hardness of produced water is also one of the indications of arrival of formation water. Higher valency
ions contribute to hardness of water, such as magnesium, calcium and strontium salts. Salts of sodium,
potassium and boron do not contribute to the hardness. Since initially we get condensed steam, so the
hardness of the produced water will be low. Gradually formation water also starts coming so hardness will
increase with production.
Continuous measurement of the salinity is useful to know how much formation water is produced and
how much condensed water is coming back. This may be used in simulation. The above data also tells us
how much of the injected water is retained. We routinely do this.
Some Other Important Use of Water Analysis in CSS
Apart from reservoir monitoring, water analysis is required at each stage of CSS. The field water analysis
was used for material selection and commercial facility design of the field under consideration. It was also
used for reservoir description, computation of saturation of the reservoir in the field and as a trouble
shooting tool.
Effluent disposal and surface facility design
Formation water invariably occurs in petroleum reservoir, but it has no commercial value except
re-injection for pressure maintenance or using it as feed water for generating steam. In case of CSS, there
are two types of water that are required to be disposed of. One is produced water and other is the reject
of steam boiler. These waters may be sent to either some disposal well or to the sea. These waters need
proper treatment before disposal. If water is being sent to some disposal well, compatibility of the
disposed water with formation water needs to be evaluated. If it is being sent to the sea then also proper
treatment is needed so that environmental concerns are addressed. A detailed water analysis was done to
create effluent treatment plant and other surface facilities for commercial development of the field. Cost
of facilities impacts CAPEX and OPEX of the project.
Boiler Feed Water
Steam cost depends upon the composition of water to be used for making steam. Water source may be
either from formation or sea or produced water depending upon availability. Water from the source cannot
be sent to boiler directly. In all the cases, this water needs treatment before sending it to boiler. Otherwise
its pipes may be choked or coroded. For treating the water, detailed water analysis is required. Since
70-80% quality steam is to be used, care should be taken that wet steam generated is of optimum pH.
SPE-175287-MS 17

Otherwise there may be scaling or precipitation of various salts in the reservoir that may reduce the
porosity and permeability. Compatibility study was done to solve this problem as discussed before.
Material selection
As mentioned earlier, pH is one of the key parameters in selection of material for equipment and surface
facilities to reduce their corrosion. Chemical composition of formation water is required for proper
selection of production tubing, flow lines and surface facilities. The water pH and salinity values are used
in metallurgical calculations for selection of tubular. (Abdou et al, 2011).
Reservoir Description
Reservoir quality related to diagenesis depends on the mineral dissolution in formation water and
precipitation in the formation that takes place because of reactions occurring under formation pressure,
temperature and rock mineralogy. Variation of formation water composition can indicate isolation of
separate reservoir units, with obvious implications for production planning, aquifer support and injection
schemes. Total salinity varies from reservoir to reservoir as seen in the field (Figure 5 and Figure 6) and
from one place of the reservoir to other. Sometimes some mineralogical changes are also seen from one
reservoir to another that also helps to distinguish one reservoir from other (Figure 7). It is discussed in
section 3.1. This property can be used for reservoir characterization.
Computation of oil saturation and reserves
Water resistivity is one of the key parameter used to compute saturation and to validate the resistivity log.
Resistivity logs are used to determine initial water saturation in reservoirs. Resistivity is controlled by the
ionic concentration of salts in solution and can be calculated precisely from chemical composition
(Coleman, Jones and Cox, 1990). Salinity and pH of water are used for petrophysical evaluation. Archie’s
water saturation equation, from which oil saturation and reserves are frequently computed from logs,
required formation water resistivity as an input (Abdou et al, 2011). Water resistivity was extensively used
for calculating the saturation in the field.
Channeling behind casing
If unexpected water is produced then first thing is to know from where water is coming. It may be because
of channeling or cross-flow from some other zone behind the casing and the less common watered-out
layer without crossflow. Different formation of the same well may have different water composition there
are chances that the water may be from different formation (Figure 5 and Figure 6). A comparison
between mineral compositions of the producing formation water with that of produced water can help in
understanding whether there is any channeling from other water bearing layer.
If steam is injected in lower layer and if it is migrating to upper layer then that can be identified by
measuring salinity and compositional analysis of produced water of upper layer. If it is showing lower
salinity than the expected, then it is a case of cross flow between the layers. Sometimes steam migration
to upper layer may take place due to creation of fractures in the formation. It was seen in one of the wells
in the field under consideration (Jain et-al, 2014). In case of CSS and steamflood, communication between
the layers can be identified by testing the salinity of upper layer.

Conclusions
1. Dissolution of mineral rock depends upon temperature and pressure, and interaction of injectant
with formation water and reservoir rock. During cyclic steam stimulation (CSS) the condensed
steam interact with formation rock and water at changing/varying temperature and pressure.
Because of this the mineral composition of the produced water also keep on changing. These
mineralogical changes become a good tool to monitor the reservoir undergoing CSS.
2. Analysis of produced water of seven CSS wells showed that pH of produced water was reduced
and concentration of magnesium, strontium, and silica ions went down in the initial phase of
18 SPE-175287-MS

production. This might be because of precipitation of some of their compounds. Calcium ion went
down only in one of the wells in which dolomite was higher.
3. Reduction in pH of produced water indicates that clay swelling took place in the CSS wells.
Laboratory experiments also confirmed that the clays present in the formation are affected by
steam and they swell and reduce the permeability of the formation.
4. Water analysis is required at each stage of CSS for various other reasons such as surface facility
design, effluent disposal, boiler feed water preparation, computing oil saturation and reserves, and
as a troubleshooting tool to identify well problems (channeling and interference between layers).

Acknowledgement
Authors are thankful to Dr. S.M. Farouq Ali for his valuable suggestions.

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