Oilfield Chemicals Training Manual

OILFIELD CHEMICALS
TRAINING MANUAL
PART 5
5.
SCALE
5.1
Problem
Scale is that hard deposit of the inorganic mineral constituents of water which precipitate
from the water. Scale may adhere to metal and other surfaces in the oil and gas
production system, or may be deposited as sludge.
The major problems caused by scale formation are:
Reduced oil production
Well plugging
Reduction in pipe carrying capacity
Impedance of heat transfer
Increase in operational safety hazards
Localization of corrosion attack
Increases in operational costs
In production operations, scale problems may be encountered whenever water is produced
with oil and gas due to the destabilization of water caused by changes as the fluids pass
through the production processing equipment. These problems are reviewed in detail in
the following section.
In water injection operations, scale problems are often encountered in the initial period as
injected water contacts the formation water around the base of the well. In operations
where produced water, seawater or additional make-up water is used, careful examination
of scaling tendencies of the waters should be made.
The deposition of scale can have very significant financial impact on an oil and gas
production system due to the cost of stimulating a well or cleaning (or at worst replacing)
damaged equipment, as well as loss of production during any workovers. For an offshore
well the total cost of a workover could be $0.5 MM US while for a satellite well, the cost
could be in excess of $3.0 MM US. Prevention of scale deposition is therefore of great
interest to oil and gas producers.
August 19, 1997
Nalco/Exxon Energy Chemicals, L.P.
Scale
5.2
Theory
5.2.1
General Mechanism
Scale deposition is a complex crystallization process. Most natural waters contain
considerable quantities of dissolved impurities, which are present as ions. Combinations
of some of these ions form compounds that have low solubility in water. When the
waters limited capacity to dissolve these compounds is exceeded (supersaturated), then
these compounds can precipitate as solids.
It is now believed that for crystallization of a compound from water to occur, three
conditions must be fulfilled simultaneously.
These are:
1. supersaturation
2. nucleation
3. adequate contact time for crystal growth
5.2.2
Supersaturation
A solution is saturated if it is in equilibrium with its solute (i.e. dissolved compounds).
Supersaturation is when a solution contains higher concentrations of dissolved
compounds than the equilibrium concentration. Supersaturation can come about for a
number of reasons such as:
1. Changes in temperature of a water
2. Changes in pH of a water
3. Changes in pressure on a water
4. Changes in agitation
5. Comingling of incompatible waters
6. Changes in concentration of solute i.e. mineral ions
The degree of supersaturation in the bulk solution does not always indicate what can
occur in localized areas.
It is important to appreciate that a stable solution can become supersaturated, and so
unstable, by relatively minor changes such as:
Increasing or decreasing the temperature of the water may destabilize the water
and cause scale formation.
Raising the pH of aerated water containing iron will destabilize calcium carbonate
and iron oxide.
Reducing the pressure of CO2 from produced water will destabilize calcium
carbonate.
5.2.3
Nucleation
Nucleation is the initial formation of a precipitate. There are two mechanisms:
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Scale
1. Homogeneous nucleation which does not require the presence of a foreign

substance; this is not a likely mechanism because in nature it is not likely that
environments free from foreign nucleating sites will be experienced.
2. Heterogeneous nucleation which requires the presence of a foreign substance to
trigger nucleation. The foreign substance can be one of a number of things, for
example:
a) Foreign scale nuclei or corrosion products
b) Welds/stress points on metal surfaces
c) Corrosion sites on metal surfaces
d) Scratches on metal surfaces
e) Small particles of suspended solids
The mechanism of nucleation can be described as follows:
In a supersaturated solution, the individual ions are in constant motion and move in and
out of the sphere of influence of other ions or molecules.
Ions are electrically charged and consequently are attracted to ions of opposite charge,
and so form groups. These groups of ions are called clusters and are continuously
forming and then breaking up.
If these clusters become sufficiently large they become more stable and instead of
breaking up they continue to grow and become what is known as crystallites.
The formation of crystallites from clusters is known as the process of nucleation.
Once nucleation reaches the crystallite stage the process will continue to produce crystals.
5.2.4
Precipitation, Crystal Growth and Adherence
Although nucleation may occur in a supersaturated solution, it is not inevitable that
adherent scale will also form. There are several factors that can influence the fate of the
crystal nuclei. These will not be discussed extensively here, but there are two aspects
worth noting.
5.2.4.1 Contact Time
For scale to form after a solution has become supersaturated and nucleation has occurred
there must be sufficient contact time between the supersaturated solution and the
nucleating sites on the metal surfaces. The time required varies depending upon the
degree of supersaturation (the higher the degree of supersaturation the shorter the contact
time), type of mineral (the less soluble the shorter the time), temperature, pressure and
agitation.
5.2.4.2 Crystal Growth
Many of the variables mentioned above (degree of supersaturation, temperature, flow
velocity, etc.), have an influence on the mechanism and kinetics of crystal growth.
Despite extensive study, crystal growth is still not fully understood. Certain relationships
are clear however.
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Scale
1. The rate of precipitation from a scale-forming solution varies according to the

crystalline form that the solid adopts.
2. Scale deposits change with time. There is a continuous process of dissolution and reprecipitation taking place at the surface. This results in deposits gradually becoming
harder as time passes.
3. Under certain conditions, although large amounts of precipitate are formed, little or no
adherent scale is deposited. This may be because of a kinetic effect or because of
features of the crystal morphology.
5.3
Oil and Gas System Scale Problems
The potential for scale problems exist whenever the fluid produced from a reservoir
contains water. Initially the production from a well will be dry, that is, will only contain
hydrocarbon. However, as the well matures and more and more hydrocarbon is extracted
from the reservoir the water table in the reservoir rises, water begins to be produced, and
the potential for scale deposition increases.
A simplified diagram of an oil and gas production system is shown in Figure 1.
Choke
4.
Gas
Separators
6.
5.
3.
Production
Flowlines
Downhole
Safety
Valve
Effluent
Treatment
(Typ.)
Oil
Water
Lines
8.
Surge
Tank
7.
Well
2.
Gas Flotation
Media
Filters
Reservoir
Injection
Pumps
1.
Figure 1
The main areas that can experience scale problems are:
1. Reservoir Perforations at the Well Bore
There are many fields that inject seawater into the reservoir to maintain pressure and
maximize extraction of hydrocarbon. Figure 5A-1 (found in the Appendix at the back
of this section) shows the analyses of sea and various formation waters. As can be
seen, many of the natural formation waters contain barium and strontium but no
sulfate, while seawater contains sulfate but no barium/strontium. When these waters
commingle in the well bore or reservoir perforations area, precipitation of barium
sulfate or strontium sulfate may occur (sometimes calcium sulfate as well). There is
normally no potential for scaling from the natural formation water alone at this point
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Scale
because the temperature and pressure conditions are the same as the reservoir which
by definition are stable for the formation water.
2. Well Tubulars
As the produced fluids pass up the well to the surface there can be changes in
temperature and pressure which can:
a) Destabilize the natural formation water. In certain fields the water contains
bicarbonate and is saturated with carbon dioxide. If the pressure drops in the
fluids as they pass up the well then calcium carbonate precipitation may occur.
Alternatively, the temperature of the produced fluids may decrease as they pass up
the well to such a point that some of the minerals begin to precipitate such as
barium sulfate.
b) Destabilize further the mixture of sea water and formation water causing further
deposition of barium sulfate, strontium sulfate etc.
3. Downhole Safety Valve
This area suffers from the same potential scale problems as described above. In
addition, since the downhole safety valve causes a restriction in the diameter of the
well tubulars, there is a significant pressure drop and turbulence created which can
cause further destabilization of the produced fluids.
4. Choke
The choke is a pressure reducing/flow control valve. An indication of the high
pressure drop and turbulence induced in this area is that the diameter of many well
tubulars are 4 while the diameter of the choke is typically 1. The choke can
therefore suffer from similar scale problems as described in (2) and (3) together with
the severe agitation induced by flow restrictions due to smaller diameter valves.
5. Production Flow Lines
In production flow lines scale problems can be experienced due to:
a) Destabilization of natural formation waters due to reductions in pressure (causing
scale formation) and secondly, changes in temperature of produced fluids. Some
systems have production coolers while some others have heat exchangers that may
promote precipitation of scale.
b) Destabilization of mixed sea/formation waters is due to reduction in pressure and
changes in temperature. These changes can obviously induce further precipitation
of barium and strontium sulfate.
6. Production Separators
7. Water Lines
8. Effluent Treatment Systems
All of these parts of the oil and gas production system can experience scale problems,
similar in nature to those described in 5. above, due to the inevitable change in
temperature and pressure experienced as effluent water is processed through the system.
In certain systems with gas flotation units the considerable agitation present in the units
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Scale
can induce further destabilization.

On some platforms the drain system can feed sea or rain water into the effluent water
system causing further mixing of incompatible water leading to deposition of scale.
5.4
Scale Species Found in Oil and Gas Production Systems
The scale species normally

encountered in oil and gas
production systems are:
3000
2800
calcium carbonate
2600
calcium sulfate
2400
barium sulfate
2200
strontium sulfate
2000
iron deposits
5.4.1
Calcium Carbonate Scale
Calcium Carbonate scale is the most
common of the scaling species
encountered in natural formation
waters in the North Sea reservoirs.
In oil field waters, calcium carbonate
scale can be formed by the
combination of calcium ion with
bicarbonate ions.
CONCENTRATION (ppm)
Calcium Sulfate
Hemihydrate
CaSO4.1/2 H2O
1800
1600
1400
1200
1000
800
600
Calcium Sulfate
Gypsum
CaSO4.2H2O
Calcium Sulfate
Anhydrate
CaSO4
400
200
Calcium Carbonate
100
Ca++ + 2 (HCO3-)
Ca(HCO3)2
50
Ca(HCO3)2
CaCO3 20 40
+
60
80 100 120 140 160

CO
+ H2O
2
TEMPERATURE OC
180
Figure 2
5.4.1.1 Effect of CO2
The presence of CO2 increases the solubility of CaCO3 in water. As the CO2 in solution
is increased, the reaction above shifts to the left resulting in less precipitation as the pH
decreases.
The amount of CO2 that will dissolve in water is proportional to the partial pressure of
CO2 in the gas over the water.
Partial pressure CO2 is equal to the mole fraction of CO2 times the total pressure. For
example, if the water system operates at 1500 psi and the gas contains 10 mol % CO2 the
partial pressure of CO2 in the gas will be:
10 x 1500 psi = 150 psi
100
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Scale
If either the system pressure or the percentage CO2 in the gas increases, the amount of
CO2 in solution also increases.
It is the reverse of this situation that may lead to CaCO3 scale formation. Wherever there
is a pressure drop in the system, the partial pressure of CO2 decreases, CO2 comes out of
solution, and the pH of the water rises.
5.4.1.2 Effect of Temperature
Calcium carbonate has an inverse solubility relating to temperature.
Solubility of CaCO3 decreases with temperature rise. This has implications in water
injection systems where cold sea or other source water is injected into a hot formation, as
well as in production heater treaters.
Figure 2 shows the effect of temperature upon the solubility of CaCO3.
5.4.1.3 Effect of Dissolved Salts
The solubility of CaCO3 increases as the level of dissolved salts increases, up to a
maximum of about 20% dissolved salts. For example, CaCO3 solubility in fresh water is
about 100 mg/l CaCO3 solubility in 20% NaCl solution is about 250 mg/l
(Figure 3).
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Scale
250
CaCO3(ppm)
200
150
100
50
0
50
100
150
200
250
300
350
400
450
500
550
600
NaCl (grams / liter)
Figure 3
5.4.1.5 Summary
The potential for CaCO3 scaling:
a)
b)
c)
d)
increases as the temperature increases

increases as the pH increases
increases as the partial pressure of CO2 decreases
increases as the total dissolved solids decreases
Although a major problem in oil and gas systems it is possible to remove calcium
carbonate deposits by the application of inhibited acid solutions, usually HCl.
5.4.2
Barium Sulfate Scale
The mixing of two incompatible waters - seawater that contains about 2,800 ppm sulfate
with no barium and formation waters that may contain barium but no sulfate, often causes
barium sulfate scale in oil field systems. The reaction is as follows:
Ba++
+
(Formation Water)
SO4=
(Sea Water)
BaSO4
Barium Sulfate is considerably less soluble, than any of the other commonly encountered
scale forming compounds.
Barium sulfate is about 25 times less soluble in water than calcium carbonate and is about
1,000 times less soluble in water than calcium sulfate. Furthermore, unlike most other
scale, the chemical removal of barium sulfate scale is difficult and costly and as a result,
pure barium sulfate deposits must be removed mechanically or the fouled equipment must
be discarded. In oil field systems, barium sulfate is sometimes deposited with other
scales such as calcium carbonate. When this occurs it is often possible to remove the
scale by the action of acid, which dissolves the calcium carbonate scale and weakens the
matrix allowing mechanical removal of the barium sulfate.
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Scale
The solubility of barium sulfate in water is influenced by a number of factors.

The solubility increases with temperature.
In distilled water at 250C about 2.3 mg/liter BaSO4 dissolves.
5.4.2.2 Effect of Salts
The solubility increases in the presence of mineral salts.
In 5% NaCl at 25 0C about 17.7 mg/liter BaSO4 dissolves.
In 10% NaCl at 250C about 30.0 mg/liter BaSO4 dissolves.
The combination of increasing temperature and salt content helps significantly to improve
solubility.
In 10% NaCl at 950C about 65.0 mg/liter BaSO4 dissolves.
Pressure increase will also improve slightly the solubility of barium sulfate in water.
5.4.3
Strontium Sulfate
Strontium is frequently found along with barium in many formation waters. As a result
strontium sulfate scale is encountered in some oil field systems. Rarely is strontium
sulfate scale found on its own but it is often associated with barium sulfate.
Sr++
(Formation Water)
SO4=
(Sea Water)
SrSO4
Strontium sulfate exhibits similar solubility characteristics to barium sulfate but is

significantly more soluble in water than barium sulfate.
In distilled water at 250C about 135.0 mg/liter SrSO4 dissolves.
The solubility of strontium sulfate in water reaches maximum solubility at about 400C
with decreases in solubility above this temperature.
In distilled water at 50C ... 121 mg/liter SrSO4 dissolves.
Like barium sulfate, the solubility of strontium sulfate is improved by the presence of
other mineral salts.
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Scale 10
In distilled water at 250C ..... 135 mg/liter SrSO4 dissolves.

In 10% CaCl at 250C ......... 313 mg/liter SrSO4 dissolves.
In 10% NaCl at 200C .......... 630 mg/liter SrSO4 dissolves.
Both barium sulfate and strontium sulfate are soluble in concentrated sulfuric acid.
5.4.4
Calcium Sulfate Scale
The reaction for calcium sulfate precipitation is:
Ca++
SO4=
CaSO4
In the oil field, calcium sulfate precipitates mainly as gypsum CaSO4.2H2O. A high
temperature form of CaSO4 known as anhydrite may also precipitate under certain
conditions.
Gypsum scale is encountered less often than calcium carbonate because it is more soluble
than calcium carbonate.
Gypsum solubility increases up to 380C (1000F) then decreases with temperature (Figure
2).
Dissolved salts, other than Ca++ or SO4= ions, increase the solubility of gypsum and
anhydrite, up to a salt concentration of about 15%. Further increases in dissolved salts
decrease solubility. For example, adding 15% NaCl to distilled water will treble the
solubility of gypsum (Figure 4).
8
CaSO4 mg / l X 1000
3
0
50
100
150
200
250
300
NaCl (grams / liter)
Figure 4
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Scale 11
5.4.4.3 Effect of Pressure

A pressure drop can cause CaSO4 precipitation.
5.4.5
Iron Compounds
Iron ions may occur naturally in produced waters or occur as a result of corrosion.
Formation waters usually contain low levels of iron, say 5 to 10 mg/l. Higher levels are
normally due to corrosion.
Dissolved gases such as CO2, H2S or oxygen contribute to corrosion leading to the
formation of various iron compounds.
CO2, reacts with iron to form FeCO3 (Siderite). This could scale depending upon the
system pH. Above pH 7 scale is more likely.
H2S forms iron sulfides, which are quite insoluble and form a thin adherent scale.
Suspended iron sulfide forms black water. The solubility of iron sulfides depends upon
pH and H2S concentrations. The relationships are quite complex.
Ferrous hydroxide, ferric hydroxide and ferric oxide are common scales that can occur in
an oxygen environment.
Fe2O3.xH2O is practically insoluble above pH 4 whereas Fe(OH)2 remains in solution
even at pH 8.0.
Iron scales can also be formed by bacterial action due to gallionella ferruginea. These
bacteria take Fe++ from the water and precipitate Fe+++.
The chemistry of iron compounds is complex due to the two possible valence states.
Suffice to say that avoidance of oxygen in the system will prevent many iron scale
problems.
5.5
Scale Prediction Using Solubility Data
Solubility calculations can be used to predict the formation of some types of scale,
principally those occurring due to physical changes to the water conditions.
Calculating a scaling tendency acts a guide only, a high-predicted positive tendency to
scale should cause some alarm and promote chemical treatment. Absolute values are not
necessarily important.
5.5.1
Field Water Analyses
Calculated scaling tendencies can only be as good as the values obtained in the water
analysis (Figure 5A-2). Valid results can only be obtained if water samples are analyzed
immediately after being taken or special precautions are taken to preserve the sample.
Many of the critical parameters change as a sample ages.
Ideally, analysis should be done at the system pressure and temperature. This is not
possible and some assumptions have to be made.
Values that change on standing are:
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Scale 12
Temperature - the temperature of the water at the point of concern should be

accurately known.
pH - dissolved gases evolve when pressure is reduced, pH changes.
Loss of dissolved gases - affects the HCO3-/CO3-- balance, as well as affecting the
sulfide content.
Oxidation - Fe++ is oxidized to Fe+++ with precipitation.
Turbidity - insoluble iron compounds precipitate, scale deposits on vessel walls.
5.5.2
Calcium Carbonate Solubility Calculations
The calculation used to predict CaCO3 scaling is based on the Stiff and Davis extension to
the Langelier Theory. The original Langelier Theory calculated the saturated index for
fresh waters, Stiff and Davis extended this theory to cover oil field brines.
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Scale 13
The equation is:

S.I. =
pH
(K + pCa + pAlk)
Where
S.I. = Scaling index
pH
= Actual pH of the water in the system
= An empirical constant which is a function of salinity, composition and

water temperature. This is derived from a graph (Figure 5A-3).
pCa = The negative logarithm of the calcium ion concentration in moles per
liter and is derived from a graph (Figure 5A-4).
pAlk = The negative logarithm of the total alkalinity, titrated to a methyl orange
endpoint and expressed in terms of titratable equivalents per liter. This
is derived from Figure 5A-4.
When S.I. is negative the water is undersaturated with CaCO3 and scaling is unlikely.
When S.I. is positive CaCO3 scaling is probable.
When S.I. is zero, the system is balanced at the CaCO3 solubility saturation point.
In order to make a CaCO3 solubility calculation it is necessary to have the following data:
Na+, Ca++, Mg++, Cl-, CO3-2, HCO3-, SO4-2 concentrations
pH, temperature
Values of K as a function of ionic strength
A chart for the deviation of pCa and pAlk.
A step by step method for calculating the S.I. is given in Figure 5A-5.
5.5.3
Calcium Sulfate (gypsum) Solubility Calculations
The calculation used most frequently to predict gypsum solubility in oil field brines is that
devised by Skillman, McDonald and Stiff. This is applicable for temperatures up to 800C.
Above 800C more complex methods such as that devised by Carlberg and Matthews are
available for temperatures up to 1250C.
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Scale 14
The method of Skillman, et. al., is based on the thermodynamic solubility measurements:
S = 1000
x 2 + 4K X
where:
S
= calculated solubility of gypsum (Meq/L)
= Solubility product constant which is a function of water composition and

temperature. Values of K are obtained from a graph correlating ionic
strength. Values of K as a function of ionic strength are given in
Figure 5A-6.
= Excess common ions concentration, expressed in moles per liter. This is

simply the difference between the calcium concentration and the sulfate
concentration.
The calculated gypsum solubility (meq/L) is compared with the actual concentration of
Ca++ and SO4-- ions present in the water (expressed in meq/L). If S is less than the
smaller of the two concentrations (Ca++ or SO4--) then the formation of gypsum scale is
unlikely.
NOTE: For these comparisons, S, and Ca++ and SO4-- concentrations must all be
expressed in milliequivalents per liter. An example calculation is given in Figure 5A-7.
5.5.4
Calculation of Barium Sulfate Solubility
Similar calculations can be used to estimate the solubility of BaSO4 for waters containing
sodium and chloride ions and small amounts of magnesium and calcium.
It is usually necessary to carry out compatibility testing in the specific waters of interest.
5.5.5
Compatibility of Mixed Waters
One of the major causes of scaling in oil field operations is the mixing of incompatible
waters. The individual waters may be quite stable at all system conditions but once
mixed, reactions between dissolved ions may form insoluble products.
For example, seawater contains a large amount of SO4-2 ions; formation water contains a
proportion of Ba++ ions. When the two mix BaSO4 precipitates. In any two waters,
depending upon the amount of each ion present, the temperature, pH and ratio of one to
the other, the potential for scaling may exist.
Mixing two or more incompatible waters on the surface would be obviously undesirable.
Surprisingly few formation plugging problems are experienced when injecting seawater
into the formation where incompatibility would be anticipated. This is probably because
there is only a small area of contact between the injection and formation waters and little
mixing occurs.
Severe problems occur after break through of the injection water into producing wells.
Here there is ample opportunity for mixing.
The usual approach when attempting to predict the scaling tendency of mixed water is as
August 19, 1997
Scale 15
follows:
a) Obtain an analysis of the waters to be mixed.
b) Calculate the composition of the mixed water by proportion, assuming no
precipitation.
c) Calculate the scaling tendency as previously described.
The scaling tendency, otherwise described as supersaturation, is important when
considering the effect of mixing ratios of two incompatible waters.
There are two main issues to be considered when evaluating the scaling tendency of
mixed waters:
1. Maximum amount of scale
The maximum amount of scale can be shown to take place where a mixture of
typically 90% formation water mixes with 10% seawater.
This is the maximum weight of scale that will form.
However, the driving force for scale formation is the degree of supersaturation.
2. Maximum Supersaturation
Calculations show that the maximum supersaturation, where the amount of barium
sulfate exceeding its solubility limit is the greatest, occurs around a 50:50 mixture of
formation water to seawater. The exact ratio varies with the water composition.
In practice it is at high (maximum) supersaturation that we find it most difficult to
inhibit scale formation, thus testing under such conditions provides the most severe
test.
Note that the supersaturation varies from model to model and program to program
in its exact definition.
5.5.6
Scaling Prediction by Computer
A range of software packages have been developed to carry out calculations of scaling
tendency. Using a computer to perform these calculations has the following advantages:
By including more factors into the calculations, the results can be made more
reliable. Using the Stiff-Davis relationship would give full agreement with
observations for a relatively simple brine/CO2 system. However, oil field waters
and the conditions to which they are exposed are complex. Extension of the basic
equation for scaling tendency allows some of the complexities to be taken into
account.
Alternatively, a more empirical approach can be adopted. The basic relationships

can be modified using experimental data on scale formation gathered from various
oil field water compositions.
The use of computer programs for scale prediction has become the industry standard. As
with all computer models, the results are only as good as the initial input. If scale
prediction software is to give useful results, good sampling techniques and good
August 19, 1997
Scale 16
analytical practice is very important.
5.6
Control of Scale Deposition
There are four general methods for preventing scale precipitation:

1. Control of physical variables. This is usually not applicable to oil production
systems.
2. Removal of scale forming species. This is usually not utilized in oil production
systems. However, although very expensive, sulfate removal plants are available and
have been installed in several sea water injection systems.
3. Avoidance of incompatible waters. This is possible in certain circumstances.
4. Use of Scale Inhibitors. This is the best method for the prevention of scale
deposition in oil production systems.
5.6.1
Scale Inhibitor Mechanisms
Scale inhibitors can work in one or more of three ways:
1. By interfering with the nucleation process (see 5.2.2). A nucleation type inhibitor
diffuses in the bulk liquid to reach the ion clusters either in the liquid or on a solid
substrate. The inhibitor ions are of a sufficiently large size to be able to disrupt the
scaling ion clusters and prevent their further growth to the critical size where
crystallites would form. If the formation of crystallites can be prevented then scaling
will not occur. A good nucleation inhibitor ion needs to be of a critical size but still
be able to diffuse in the water at an acceptable rate.
2. By interfering with crystal growth (see 5.2.2). Crystal growth occurs on active sites
that occupy a small percentage of the crystal surfaces. A good crystal growth
inhibitor has a strong affinity for such active sites and is able to diffuse over the
surface to other active sites as they form. This type of inhibitor has to be sufficiently
small to be able to do this, but sufficiently large in order not to be absorbed into the
growing crystals. If the inhibitor is absorbed into the crystal it can be considered
advantageous in that the resulting scale may be soft, friable and easily removed.
3. By modifying crystal surfaces. Molecules that are neither nucleation nor crystal
growth modifiers are able to absorb strongly to crystal surfaces and prevent
attachment of crystals. This action is analogous to the action of dispersants on
organic deposits.
5.6.2
Types of Scale Inhibitors (Antiscalants)
Scale inhibitors can be classified in two main groups - Inorganic and Organic.
5.6.2.1 Inorganic Scale Inhibitors
These are the least expensive scale inhibitors. All are polyphosphates of some kind.
However, to varying degrees all inorganic scale inhibitors suffer from a phenomenon
known as reversion and are no longer in common use.
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Scale 17
5.6.2.2 Organic Scale Inhibitors

There are numerous specialty organic antiscalants, each with somewhat different
properties.
A carefully selected organic scale inhibitor will be designed to perform under field
conditions and not to revert or precipitate at high concentration levels.
There are three main types of organic inhibitors:
Phosphate Esters
This group is generally very effective at low dosage rates on all scales, and effective in
high brine concentrations. However, they are limited in that they are not effective at
temperatures much above 93 - 980C, because hydrolysis of the ester starts to occur at a
significant rate, the carbon - oxygen bond is broken. When this occurs, the product loses
effectiveness and precipitation of orthophosphate may occur.
Their general structure is:
O
R1
CH2
OH
OH
Phosphonates
Phosphonates are effective at high temperatures up to about 1500C.
A major deficiency of many phosphonates is that they have a tendency, especially at high
pH, to precipitate in the presence of high levels of Ca++ and Mg++ ions. Special
phosphonates have been developed to eliminate this problem. The precipitation problem,
however, can be used as an advantage in precipitation squeeze applications where the
product is intentionally precipitated in the formation to extend the squeeze life.
A typical phosphonate structure is:
O
HO
O
(CH2)
OH
(CH2)
CH2
OH
OH
OH
O
OH
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Scale 18
Organic Polymers
There are numerous polymeric antiscalants based upon polymeric acrylates,
methacrylates, mallets, vinyl sulfonates, phosphinocarboxylates etc., and co-polymers
thereof.
The various permutations of monomers, molecular weights, ratios of respective
monomers, chain branching etc., gives an almost unlimited number of polymers with
varying degrees of antiscalant effect.
Polymers have the highest thermal stability of the organic inhibitors, and will function at
very high temperatures.
Although many polymers become ineffective in the presence of greater than 2,000 ppm
Ca++ ions, there are a few which show compatibility at calcium levels greater than
30,000 ppm.
Similar to phosphonates, precipitation of calcium and magnesium salts is a disadvantage
with some polymers.
Their structure is typically:
CH2
CH2
CH2
CH
CH
CH
COOH
COOH
COOH
Polyacrylate
5.6.3
Selection of a Suitable Scale Inhibitors
In selecting the best scale inhibitor to treat a particular problem, the type of scale to be
prevented, the water chemistry, the temperatures and the method of chemical application
must all be taken into account.
Downhole squeeze application is used to place inhibitors in the reservoir to prevent
downhole and surface scale. These inhibitors need sufficiently high temperature
tolerance and compatibility with formation waters at relatively high concentrations and
low pH. Their adsorption / desorption characteristics are also important to the success of
the squeeze. Squeezes can also be designed to deliberately precipitate inhibitors.
Surface (or topside) application of scale inhibitors is used to control surface scale, and
the inhibitor will be required to work at lower temperatures and higher pHs than are
found downhole.
Usually, laboratory tests have to be designed to take into account the means of
application, the conditions prevalent where inhibition is required, the composition of the
scaling water, the means for determining residual inhibitor levels and the compatibility of
the chosen chemical with other chemicals in the system.
August 19, 1997
Scale 19
For both squeeze and surface application, general screening methods can be used such as
a threshold test, tube blocking test, or tube deposition test. While these tests may be
sufficient for surface applications, together with tests for compatibility, monitoring etc.,
more stringent tests are required for downhole application.
For downhole squeeze application perhaps the most important feature of an inhibitor is its
stability and solubility in the sea water or formation water at downhole temperatures.
Any uncontrolled precipitation at such temperatures may cause plugging in the formation
as the inhibitor solution is applied to the well reservoir.
Assuming we have chosen an inhibitor sufficiently effective against the scale present, the
next most important criteria is the rate at which it will return in the production fluids after
a squeeze application. These features are examined by carrying out core studies where
the rates of adsorption and desorption of the proposed chemical on and from the reservoir
formation can be quantified. These test methods will now be briefly discussed.
5.6.3.1 Thermal Stability
Various concentrations of the inhibitor chemical in seawater, or mixtures of sea water and
formation water, are subjected to temperatures equivalent to the reservoir temperature for
varying periods of time. The appearance of the test solutions is noted. Any precipitate or
strong discoloration is noted and such a chemical would then be considered unacceptable.
Analytical analysis of the scale inhibitor residues can also be conducted.
5.6.3.2 Threshold Test
In this test mixtures of incompatible waters at various mix ratios are heated to formation
temperature or topside temperature with and without the addition of inhibitor.
For example, seawater containing SO4-- would be mixed with formation water
containing Ba++,Sr++; or, one water would contain Ca++ and the second water HCO3-.
Various similar combinations can be worked out to simulate the scaling conditions
prevalent in the system.
At the end of the test the solutions are filtered and the soluble scalant ions analytically
determined.
In this way the percentage inhibition for each inhibitor can be calculated for comparison.
The best inhibitors being those where no scaling ions are precipitated.
5.6.3.3 Tube Blocking Test
In this test the two incompatible waters are separately pumped via a mixing chamber
through a fine capillary tube held at the required temperature.
Pressure transducers before and after the capillary indicate the rate of pressure build up,
and finally complete blocking of the capillary.
A good inhibitor will allow such a system to run for a long period of time, whereas
untreated waters will block the tube within a short period of time.
August 19, 1997
Scale 20
5.6.3.4 Tube Deposition Test

This test is very similar to the tube blocking test. The main difference is that instead of
using a capillary, a wider bore tube is used, and after a set period of running time the
amount of scale and its chemical composition are determined.
5.6.3.5 Core Studies
Tests described as core studies are used to predict the behavior of the inhibitor and mixed
fluids within the reservoir, under simulated reservoir conditions. The following areas can
be studied:
1. Squeeze technique:
a) adsorption/desorption isotherms
b) shut in period optimization
c) re-squeeze evaluation (interval before re-squeeze needed)
d) formation damage evaluation
2. Water flooding:
a) compatibility studies
b) products compatibility (simultaneous injection)
3. Product stability:
a) stability at use concentrations with matrix rock
b) effect or need for pretreatment of reservoir (e.g.) spearhead
5.6.3.6 Analysis for Inhibitor Residual
For squeeze application it is essential that the residual level of inhibitor in returning fluids
be known so that a re-squeeze can be carried out when the level drops below that of
minimum effect.
For topside application it is useful to know what the level of inhibitor is throughout the
separation train to ensure that adequate inhibitor is present to inhibit downstream scaling.
In either case, analytical methods have to be devised to accurately determine low levels of
inhibitor in production fluids.
5.6.3.7 Other Tests
Tests for corrosivity, emulsification tendency etc., may also be required to ensure no
problems are encountered during application.
5.6.4
Chemical Application
The success of a chemical treatment program is only as good as the application method.
Adequate consideration has to be given to the correct means for application. Even the
best inhibitor will fail if applied incorrectly.
August 19, 1997
Scale 21
It is not necessary to be concerned with trying to prevent scale formation within the
reservoir proper. It is possible to inhibit scale formation around the well bore but in the
reservoir itself the formation of rock is so large that the use of inhibitors to prevent scale
deposition is impractical. Scale formation within the reservoir is not usually an issue for
concern.
Scale inhibitors function by preventing crystal nucleation or crystal growth. Therefore it
is essential that the inhibitor is present in the fluids upstream of the point where scale
nucleation begins. This is relatively easy to arrange for in surface applications, but to
prevent scale at the perforations in the well bore it is necessary to inject the inhibitor
downhole.
It is thus convenient to consider two areas of application, surface and downhole.
5.6.4.1 Surface
As stated above, surface application is relatively straightforward. Inhibitor should be
dosed continuously. Dosage rates vary according to the particular conditions but are
typically in the range of 5 to 40 ppm.
Note that if scale inhibitor is used to protect the producing wells then the separation
system will also be partially protected. If conditions change through the separation
system it may be necessary to supplement the concentration of inhibitor in the produced
fluids by additional injection of inhibitor to the separation system.
Inhibitor should be applied upstream of the scaling area through an injection quill. It
should be noted that in concentrated form at high temperatures most scale inhibitors are
somewhat corrosive.
Care should be taken that the injection system is compatible with the scale inhibitor and
that the inhibitor is immediately dispersed in the fluids without the possibility of
concentrated solution accumulating in dead areas.
5.6.4.2 Downhole
Downhole application can be sub-divided into two main areas, continuous injection and
squeeze application.
Continuous downhole injection
This technique can only protect the production tubing and equipment downstream from
the point of application.
Below are described four versions of downhole injection, in all these versions it is
essential to ensure that metallurgy is compatible with inhibitor solution, the inhibitor
solution is stable at downhole conditions and injection really is continuous.
1. Gas Lift
Atomized scale inhibitor solutions are injected into the lift gas, and thus enter the
production tubing (Figure 5). This is a convenient means of application to the
production tubing when gas lift facilities are installed. However, scale inhibitors may
gunk out when the lift gas strips the solvents.
August 19, 1997
Scale 22
Production
Tubing
Lift Gas
With
Inhibitor
Gas Lift
Valves
Casing
Packer
Figure 5
2. Via Annular Space
A solution of filtered scale inhibitor is diluted by a side stream of production fluid and
pumped into the annular space and enters the production tubing via a side pocket
mandrel valve (Figure 6). There are a number of disadvantages to the use of this
system.
The main problem is that the system does not give true continuous injection. The
mandrel valve opens and closes on the basis of pressure differential. Typically a
valve may be
open say for 15
minutes every 2
Production Tubing
to 3 hours.
When the valve
is closed no
inhibitor enters
the system and
there is nothing
to prevent scale
crystallites from
forming.
Inhibitor
Solution
Downhole
Injection
Valve
Fluid
Column
Packer
Casing
Formation
In lower
pressure
pumping wells
without a
August 19, 1997
Figure 6
Formation
Figure 7
Scale 23
packer, the inhibitor solution simply falls through the fluid column in the annulus and
returns up the tubing with the produced fluid (Figure 7).
3. Via Concentric or Macaroni String
A small-bore stainless steel tube is installed in the production tubing and scale
inhibitor is pumped down the tube to the well bottom (Figure 8). This technique
although satisfactory for the application of inhibitor is difficult and costly to install
and operate.
Production Tubing
Inhibitor
Solution
Macaroni
String
Casing
Dual
Packer
Formation
Formation
Figure 8
August 19, 1997
Scale 24
3. Capillary Tube
A small-bore stainless steel
tube is clamped to the
outside of the production
tubing and connected to a
downhole valve. Inhibitor is
then pumped down the
capillary and injected via the
downhole valve (Figure 9).
New systems are
contemplated where one or
more capillary tubes are
encapsulated in rubber to
prevent crushing when
running into deviated wells.
Squeeze Application
The application of scale inhibitor
by squeeze technique is greatly
influenced by a number of
important parameters.
Production
Tubing
Capilary
Tubing
Straps
Downhole
Injection
Valve
Casing
Packer
Formation
Figure 9
The most important parameter that cannot be altered is the adsorptive capacity of the
formation. Laboratory and field studies on the adsorption and desorption characteristics
of scale inhibitors on a number of reservoirs have shown that the adsorptive capacity of
the formation can vary by a factor of 20 between formations.
It is therefore advisable that adsorptive capacity studies be carried out on core samples
from the field, since these studies would provide information on the amount of scale
inhibitor required for a satisfactory squeeze treatment. Such information is limited
depending upon how representative the core sample is to the formation.
When to Squeeze
For sulfate scales, it is typical to squeeze as soon as seawater breakthrough occurs. Even
before seawater breakthrough, it may be necessary to squeeze for calcium carbonate
scale. The amount of inhibitor required (the minimum concentration for inhibition) might
vary as the water chemistry changes. However, a worst case scenario is often used in
planning a squeeze. It is difficult to say when to stop squeezing. This will depend on the
operator. In general, the requirement to squeeze diminishes beyond 50% seawater
breakthrough.
There are several controllable parameters that affect the efficiency of any squeeze
treatment. Four main factors are:
1. Quantity of Scale Inhibitor
Core adsorptive capacity studies, if carried out, will have given a value for the amount
of inhibitor capable of being adsorbed by a given volume of rock. This can be
August 19, 1997
Scale 25
expressed as quantity of inhibitor per unit volume of pore space.

Typical sandstone formation values are 1.5 gal/bbl pore space.
Typical limestone formation values are 0.3 gal/bbl pore space.
However, a proportion of scale inhibitor will be irreversibly adsorbed. It is believed
that the irreversibly adsorbed material chemically reacts with the rock. As a result
subsequent re-treatment generally requires less inhibitor than the initial treatment.
For example, sandstone formations can irreversibly absorb 50 to 75% of the inhibitor
during the initial squeeze treatment.
The volume of formation to contact for a particular squeeze treatment depends upon:
Formation adsorptive capacity
Amount reversibly adsorbed
Rate of desorption
Rate of oil/water production
Total volume of produced fluids
Economic considerations
A desorption curve plotting inhibitor concentration versus pore volumes of flow, from
core studies will provide the best information (Figure 10).
TYPICAL INHIBITOR DESORPTION CURVE
Inhibitor in Effluent (ppm)
500
400
300
200
100
500
1000
1500
2000
Pour Volume of Flow
Figure 10
In the absence of any core data, an approximate estimate of inhibitor quantities has to
be made for the first squeeze.
In calculating the amount of inhibitor the following factors are considered:
a) Well production rate
b) % Water cut.
c) Concentration of inhibitor required to prevent scale deposition.
August 19, 1997
Scale 26
d) Number of days required for inhibitor to be present in the produced water.

e) An estimate of the proportion of inhibitor which will be flushed out immediately
in the initial flow back period.
f) An estimate of the amount of inhibitor which will be irreversibly adsorbed.
g) Production interval length
h) Residual oil saturation
The formula shown below will provide a reasonable estimate of the scale inhibitor
required for control.
General Formula
VSI =
BWPD X # of Days X Treatment Rate X 3

1,000,000
42
Where:
VSI
BWPD
# of Days
Treatment Rate
3
42
=
=
=
=
=
Volume of scale inhibitor

Barrels water per day
Desired treatment life
Required inhibitor concentration in production
Factor (This assumes that 1/3 of the inhibitor is lost to the
formation, 1/3 will immediately come back with the
produced fluid, and only 1/3 will remain in the formation
and come back slowly to provide scale inhibition.)
= Converts barrels to gallons (US)
These calculations are used only for the first squeeze treatment. The information
gained during the first squeeze will be used to determine the quantities required in
subsequent squeezes.
If insufficient scale inhibitor is used then the concentration of scale inhibitor in the
produced fluids will decrease very rapidly to low levels and the frequency of squeeze
treatments will increase.
Alternatively, if excess scale inhibitor is used then the times between treatments will
increase and there will be some loss of excess inhibitor in the initial production.
It is thus better to overtreat than undertreat because of the high cost of lost production
incurred during the lock in time.
2. Concentration of Scale Inhibitor Treatment Solution
Experience has shown that, within certain limits, the more dilute the concentration of
inhibitor in the injected carrier fluid, the better the results from the squeeze treatment.
This is a function of the increased surface area of formation that can be contacted by
the same amount of inhibitor.
Normally, concentrations between 2 and 15% scale inhibitor are used. There is a
lower limit for some inhibitors when using seawater carrier. This is due to an inherent
August 19, 1997
Scale 27
instability with high levels of Ca++ and Mg++ ions. In such cases 10% and above is
the recommended concentration.
3. Volume of Overflush
This is the volume of fluid that is pumped into the formation after injection of the
squeeze solution.
The amount of overflush is most important and has a considerable bearing on the level
of inhibitor in the subsequently produced fluids.
Too much overflush results in the inhibitor contacting too large an area of formation
and the inhibitor is either irreversibly adsorbed, or is released too slowly to be
effective.
Too little overflush results in too rapid a release of inhibitor with a consequential
short interval between re-squeeze treatments.
It is estimated that a penetration of 10 to 13 feet from the well bottom into the
formation, will result in the type of desorption required. For example:
Required penetration
Production interval
Volume
=
=
=
=
=
10 feet
130 feet
r2 h
(3.142 x 10 x 10 x 130 x 0.17811) barrels
7,275 barrels
Assuming a porosity of 20% Then volume required
= (7,275 x 20) bbls = 1,455 barrels

100
Allow sufficient additional volume to displace the production tubing.

Note:
This assumes radial flow. The calculation is not true for fractured formations.
To reduce hydrostatic pressure, gas could be used for overflush instead of sea
water or formation water.
In certain instances, nitrogen gas is used as overflush for scale inhibitor

squeeze treatments.
4. Shut in (Lock in) Time

Laboratory studies and field experience has shown that the adsorption of inhibitor
onto rock formation does not occur instantaneously, but requires a period of time to
reach equilibrium. Only experience with a particular formation will confirm the
minimum lock-in time to give a satisfactory squeeze.
Typically shut-in times are seldom less than 2 hours or greater than 24 hours due to
lost production.
August 19, 1997
Scale 28
Computer Modeling
When the first squeeze on a well has been carried out, and the returns monitored, it is
possible to make more accurate predictions of the behavior of future squeezes by using a
computer model. These programs require a substantial amount of data entry and
computations, and are generally not used on a routine basis.
In order to produce a useful output, this type of model needs accurate water production
and chemical return data, along with detailed information about the well completion and
formation characteristics.
The heart of the program is a routine that generates a specific isotherm for the inhibitor in
the particular well treated. This routine assumes a certain form for the
adsorption/desorption isotherm. Which form is used in the program (Longmuir,
Freundlich, etc.) is decided on the basis of laboratory experiments using rock cores and
the scale inhibitors of interest. Different programs, using different types of isotherm,
would be needed for different classes of chemical. Different forms of isotherm govern the
adsorption/desorption behavior of a chemical on limestone and sandstone.
Once a model of the adsorption/desorption behavior of the scale inhibitor in a specific
well have been established, the effect of changes in the squeeze parameters can be
investigated. The chemical returns can be modeled for squeezes using different amounts
of chemical, different inhibitor concentrations, different lock-in times, etc. It is then
possible to propose changes to the squeeze procedure to increase the squeeze life and/or
improve the efficiency of inhibitor usage.
Miscellaneous Points
Carrier Fluid
Formation water or seawater can be used as carrier fluids. Care should be taken to
ensure good deoxygenation and compatibility of the scale inhibitor with the carrier
fluid. Sterile conditions should be maintained by using an effective biocide.
Surfactant Spearheads
A surfactant spearhead is a pre-flush of water, usually brine water, containing 0.1% to
0.5% surfactant, injected into the formation ahead of the squeeze chemical solution.
The surfactant spearhead may be preceded by a pre-flush containing an emulsion
breaker and there may be a sea water spacer between the two.
The surfactant spearhead may itself contain an emulsion breaker thus obviating the
need for a separate pre-flush containing emulsion breaker.
The aim is that the surfactant spearhead will reduce interfacial tension, assist in
making the rock formation water wet, prevent emulsion blocks, and avoid particle
blocks.
Wettability is the term used to describe whether a solid surface is coated with oil or
water. Most formations are thought to be already water wetted and therefore do not
require a surfactant to make them water wet.
Most formations are composed of a mixture of sandstone, limestone, dolomite and
August 19, 1997
Scale 29
clay in varying proportions.

If a surfactant spearhead is to be used because the formation is considered oil wet then
it is essential that the correct type of surfactant be used. Generally, nonionic and
anionic surfactants are used for this purpose.
It is essential then, that if a surfactant spearhead is to be used, it is of the correct type.
If in doubt do not use a spearhead, more problems may be caused than solved.
Typical Squeeze Procedure
a) Inject the calculated quantity of scale inhibitor as a 10% solution in deoxygenated
formation water, or seawater.
b) Overflush with the calculated volume of deoxygenated formation water, seawater,
nitrogen or produced gas.
c) Shut-in for 12 to 24 hours.
d) Bring the well back on production and commence monitoring of produced water
for the concentration of scale inhibitor.
Notes:
A test method must be available for determining the concentration of scale

inhibitor in produced water.
Injection quality dilution water should be used for the inhibitor solution, or the
solution should be filtered, especially if the permeability of the formation is
considered highly critical.
The injection rate of scale inhibitor solution and overflush normally should not
exceed 2 barrels per minute, and the injection pressure should be below the
fracture pressure, to avoid formation damage.
POTENTIAL PROBLEM AREAS TO BE AVOIDED:
The injection of certain chemicals downhole can damage the production zone.
Pipework could be subjected to corrosive fluids.
Emulsions could be produced in flow back fluids.
Comprehensive laboratory investigations are carried out during product development to

ensure that these problems are minimized, and that we are aware of them. Advice will be
given to help with the application procedures and it is essential that these procedures are
followed.
For example, phosphonates should be diluted in water to a concentration of not less than
10% by volume in order to avoid precipitation downhole of calcium and magnesium
phosphonates.
August 19, 1997
Scale 30
TURBIDITY
THRESHOLD
EFFECT
SEQUESTRATION
EFFECT
CLEAR
TURBID
CLEAR
Mol Ratio phosphonate to calcium
This phenomenon relates to the ratio of Ca++ and Mg++ ions to the available phosphonate
groups available.
At point A in the above diagram we have sub-stoichimetric amounts of phosphonate.
Crystal growth and precipitation are prevented by crystallite adsorption. This is known as
the Threshold Effect.
At point B an equivalent point is reached, where these are present, stoichimetric amount
of Ca++ and Ba++ ions to phosphonate groups. Thus at this point the corresponding
phosphonate molecule can be formed. If this molecule is insoluble under the system
conditions, temperature, pH etc., a precipitate forms.
At point C there is an excess of phosphonate groups to those of Ca++ and Mg++ ions.
These ions then become shared with phosphonate molecules. The lower level of Ca and
Mg in the new molecule gives it solubility and from then on there will be no precipitate.
This is known as the chelation Effect.
The turbid region varies according to the physical condition in the system. The profile for
other types of scale inhibitors (polymers for example), will be different. Dilutions of
scale inhibitor have to be chosen to avoid this turbid region downhole.
The above is just an example of the considerations given during the development of scale
inhibitors. The product not only has to be an effective antiscalant, but also has to be
trouble free in its chosen method of application.
August 19, 1997
August 19, 1997

3,600
11,090
11,200
N. E. CHINA
WESTERN AUSTRALIA
NORTH SEA WATER
10,445
ALASKA
58,692
28,803
GULF OF MEXICO
WEST AFRICA
9,732
CENTRAL ARGENTINA
38,350
3,875
EASTERN VENEZUELA
EAST TEXAS
6,350
7,800
STATFJORD
CORMORANT
9,000
BRENT
SODIUM
Na
400
150
200
155
266
79
125
110
100
120
170
200
POTASSIUM
K
410
550
130
10,700
1,984
102
2,600
280
2,720
140
450
250
CALCIUM
Ca
1,330
220
81
2,200
573
98
1,070
48
24
35
50
50
MAGNESIUM
Mg
36
10
12
93
20
60
15
30
60
BARIUM
Ba
35
390
222
15
45
25
STRONTIUM
Sr
20,100
18,420
7,758
116,000
63,683
15,051
52,000
15,165
18,300
9,700
12,750
14,300
100
560
1,769
37
238
2,269
293
487
220
130
600
1,050
2,700
212
257
CHLORIDE BICARB. SULFATE

Cl
HCO 3SO
4
FORMATION WATER ANALYSIS IN Mg / LITER
APPENDIX
Figure 5A-1
APPENDIX
OILFIELD CHEMICALS WATER ANALYSIS WORKSHEET

COMPANY
LOCATION
TIME
LEASE
Date
WATER SOURCE
TOTAL DISSOLVED SOLIDS:
CATIONS
A.
B.
Column 1
mg/l as compound
Column 2
mg/l as ions
Column 3
meq/l
+
Sodium
Total Hardness, as CaCO3 =
as Na = 23.0 x
++
C.
Calcium, as CaCO3 =
x 0.400
as Ca x 0.050 =
D.
Magnesium, as CaCO3 =
x 0.243
as Mg x 0.0823 =
E.
Barium, as BaSO4 =
x 0.589
as Ba x 0.0146 =
++
++
A.
C.
D.
E.
Subtotal
F.
Total Cations =
F.
ANIONS
-
G.
Chloride, as NaCl =
x 0.607
as Cl x 0.0282 =
H.
Sulfate, as Na2SO4 =
x 0.676
as SO4 x 0.0208 =
I.
Carbonate, as CaCO3 =
x 0.600
as CO3 x 0.0333 =
J.
Bicarbonate, as CaCO3 =
x 1.220
as HCO3 x 0.0164 =
K.
L.
M.
N.
Total Anions =
Total Dissolved Solids
Total Iron, as Fe
Acidity to Phen., as CaCO3
G.
H.
I.
J.
K.
L.
x 0.440
as CO2
OTHER PROPERTIES:
P.
Sulfide, as H2S
S.
Turbidity
Q.
Oxygen, as O2
T.
Temperature F
R.
pH
V.
Spec. Grav.
COMMENTS:
DISTRICT/AREA:
ANALYST:
DIRECTIONS:
Step 1: Complete tests in Column 1, and "Other
Properties".
Step 4: Subtract subtotal from 3K and enter difference in

3A. In Column 3, add 3A to subtotal and enter in 3F.
Step 2: Complete the multiplication steps for Columns 2

and 3, except Line A.
Step 5: Multiply 3A by 23.0 and enter in 2A.
Step 3: In Column 3, add C, D, E to get subtotal. In

Column 3, add G, H, I and J and enter total in 3K.
Step 6: Add Column 2 Cations to get Total in 2F. Add

Anions to get Total in 2K. Add 2F and 2K to get 2L.
Figure 5A-2
August 19, 1997
Solubility Product Constant K X 10-4
APPENDIX
Ionic Strength ( )
(Values of K at various ionic strengths for CaCO3)
Figure 5A-3
August 19, 1997
APPENDIX
Conversion of ppm Calcium and

Alkalinity into pCa and pAlk
pCa = Log
1
Mols Ca / l
mg / l Ca++ or Total Alkalinity
pAlk = Log
1
Equiv Total Alk / l
Calcium
Total Alkalinity
pCa, or pAlk
Figure 5A-4
August 19, 1997
APPENDIX
Calcium Carbonate Solubility Calculation

(Stiff & Davis extension of Langelier Method)
Water Sample Description __________________________________________
Equation: SI = pH - (K + pCa +pAlk)
1. Calculate ionic strength of water.
Concentration
(mg / liter)
Ion
Conversion
Factor
Ionic
Strength
Na+
____________________ X
(2.2 X 10-5) = ________________________X 10-5
Ca+2
____________________ X
(5.0 X 10-5) = ________________________X 10-5
+2
-5
Mg ____________________ X
(8.2 X 10 ) = ________________________X 10-5
Cl____________________ X
(1.4 X 10-5) = ________________________X 10-5
HCO3
____________________ X
(0.82 X 10-5) = ________________________X 10-5
CO 3-2
____________________ X
(2.1 X 10-5) = ________________________X 10-5
SO4-2
____________________ X
(2.1 X 10-5) = ________________________X 10-5
Total Ionic strength ( ) = ______________________ X 10-5
( ) = ______________________
2. Determine K from Figure 5A-2
Temp. = _______0 F;
_________________0C ;
K = __________________
3. Determine pCa from Figure 5A-3

Ca+2
= ______________mg/l;
4. Determine Total Alkalinity
pCa = ___________________
HCO 3- = __________________
CO3
= __________________
Sum
= ______________ mg/l
From Figure 5A-3, pAlk = ______________
5. Add
K + pCa + pAlk = ______________
6. pH
= _________
7. SI = pH - (K + pCa +pAlk)
= ________ - _________ = __________
If SI is negative, scale formation is not likely.
If SI is positive, scale formation is indicated.
NOTE: pH, HCO3- and CO3-2 should be determined in the field on fresh samples.
Figure 5A-5
August 19, 1997
Solubility Product Constant, K X 10-4
APPENDIX
Temperature, 0F = (mg / l)
(CaSO4 Solubility Product Constants)
Figure 5A-6
August 19, 1997
APPENDIX
Calcium Sulfate Solubility Calculation

(Skillman, McDonald & Stiff Method)
Water Sample Description __________________________________________
Equation: S = 1000
X 2 + 4K X
1. Calculate ionic strength of water.

Concentration
(mg / liter)
Ion
Conversion
Factor
Ionic
Strength ( )
Na+
____________________ X
(2.2 X 10-5) = ________________________X 10-5
Ca+2
____________________ X
(5.0 X 10-5) = ________________________X 10-5
Mg+2____________________ X
(8.2 X 10-5) = ________________________X 10-5
Cl____________________ X
(1.4 X 10-5) = ________________________X 10-5
HCO3____________________ X
(0.82 X 10-5) = ________________________X 10-5
CO 3-2
____________________ X
(2.1 X 10-5) = ________________________X 10-5
SO4-2
____________________ X
(2.1 X 10-5) = ________________________X 10-5
Total Ionic strength ( ) = ______________________ X 10-5
( ) = ______________________
2. Determine K from Figure 5A-2
Temp. = _______0 F;
K = _________________ ;
4K = __________________
3. Calculate X:
Concentration
(mg / liter)
Ion
+2
Ca
SO4 -2
Conversion
Factor
M (moles / liter)
-5
(2.5 X 10 ) = ________________________X 10-5

(1.04 X 10-5) = ________________________X 10-5
____________________X
____________________X
Subtract the smaller of the two values of M from the larger value.
X =
M = ________X 10-5
X = _________________ X2 = __________________
4. Calculate S, Solubility of CaSO4 in Brine.

X 2 = __________________
4K = __________________
Total = ______________ = X2 + 4K
X 2 + 4K
= _____________
-X = _______________
Total = ______________ (1000) = S = _______________ meq / l
5. Determine Actual Concentration of CaSO4 in Brine.
Ion
Ca+2
SO4
Concentration
(mg / liter)
____________________
____________________
Equiv.
Wt.
20
48
=
=
mg/l
Equiv. Wt.
= meq/l
_____________________ meq/l
_____________________ meq/l
The actual concentration of CaSO4 in the brine is the smaller of the two values _____________ meq/l
6. Compare Solubility (S) and Actual Concentration of CaSO4.
S = ____________ meq/l Actual = _______________ meq/l
If S exceeds Actual, scale formation is unlikely.
If S is less than Actual, scaling is likely.
Figure 5A-7
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OILFIELD CHEMICALS

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

1. Homogeneous nucleation which does not require the presence of a foreign

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

1. The rate of precipitation from a scale-forming solution varies according to the

Oil and Gas System Scale Problems

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

can induce further destabilization.

Scale Species Found in Oil and Gas Production Systems

The scale species normally

80 100 120 140 160

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

NaCl (grams / liter)

increases as the temperature increases

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

The solubility of barium sulfate in water is influenced by a number of factors.

Strontium sulfate exhibits similar solubility characteristics to barium sulfate but is

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

In distilled water at 250C ..... 135 mg/liter SrSO4 dissolves.

NaCl (grams / liter)

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

5.4.4.3 Effect of Pressure

Scale Prediction Using Solubility Data

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

Temperature - the temperature of the water at the point of concern should be

pH - dissolved gases evolve when pressure is reduced, pH changes.

Oxidation - Fe++ is oxidized to Fe+++ with precipitation.

Turbidity - insoluble iron compounds precipitate, scale deposits on vessel walls.

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

The equation is:

= Actual pH of the water in the system

= An empirical constant which is a function of salinity, composition and

Na+, Ca++, Mg++, Cl-, CO3-2, HCO3-, SO4-2 concentrations

Values of K as a function of ionic strength

A chart for the deviation of pCa and pAlk.

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

= calculated solubility of gypsum (Meq/L)

= Solubility product constant which is a function of water composition and

= Excess common ions concentration, expressed in moles per liter. This is

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

Alternatively, a more empirical approach can be adopted. The basic relationships

August 19, 1997

Nalco/Exxon Energy Chemicals, L.P.

analytical practice is very important.

Control of Scale Deposition

There are four general methods for preventing scale precipitation: