Water Formed Scale Book Free

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Water Formed Scale
Oil Field Scale, formation, Prediction, and Inhibition.
Free copy from The Author – No Copyrights
Prepared by
Yasser Kassem
1
http://www.oilprocessing.net/oil/
Preface
I would like to present a simple book in organic scales, and water formed scale.
The book is dedicated to oil and gas engineers and technicians dealing with oil
and gas produced water, water injection and water treatment facilities.
Best Regards
Yasser Kassem
Oct. 2nd, 2019
2
Contents
Chapter 1 ......................................................................................................................................... 5
Fundamentals of Chemistry and water Analysis ............................................................................. 5
1.1 Elements and Compounds..................................................................................................... 5
1.1.1 Pure Substances, Compounds, Elements ....................................................................... 5
1.1.2 Atom: .............................................................................................................................. 5
1.1.3 Atomic Number .............................................................................................................. 6
1.1.4 Atomic Mass Number ..................................................................................................... 6
1.1.5 Atomic Weight ................................................................................................................ 7
1.1.6 Molecules and Molecular Weights ................................................................................. 8
1.1.7 The mole ....................................................................................................................... 10
1.1.8 Ions and Valence .......................................................................................................... 10
1.1.9 Radicals ......................................................................................................................... 11
1.1.10 Equivalent Weights ..................................................................................................... 11
1.1.11 Using Equivalent weights ........................................................................................... 12
Chapter 2 ....................................................................................................................................... 14
Water Formed Scale ...................................................................................................................... 14
2.1 Introduction ......................................................................................................................... 14
2.2 Scale Types .......................................................................................................................... 14
2.2.1 Calcium Carbonate ....................................................................................................... 15
2.2.2 Calcium Sulfate ............................................................................................................. 18
2.2.3 Barium Sulfate .............................................................................................................. 20
2.2.4 Strontium Sulfate.......................................................................................................... 23
2.2.5 Iron Compounds ........................................................................................................... 25
2.3 Predicting Scale Formation.................................................................................................. 27
2.3.1 The value of Solubility calculations .............................................................................. 27
2.3.2 The Basics for Solubility Calculations ........................................................................... 27
2.3.3 Solubility Product Principle .......................................................................................... 28
2.3.4 Saturation Ratio ............................................................................................................ 29
2.3.5 Calcium Carbonate Scaling Calculations ....................................................................... 29
2.3.6 Sulfate Scaling Calculations .......................................................................................... 34
2.3.7 Barium Sulfate Solubility Calculations .......................................................................... 35
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2.3.8 Strontium Sulfate Solubility Calculations ..................................................................... 36

2.4 Example Scale Calculations.................................................................................................. 37
Chapter 3 ....................................................................................................................................... 45
Scale problems & Inhibition .......................................................................................................... 45
3.1 Introduction ......................................................................................................................... 45
3.2 Scale mechanisms................................................................................................................ 45
3.3 Causes of Scales ................................................................................................................... 45
3.3.1 Change in temperature ................................................................................................ 45
3.3.2 Mixing Incompatible water .......................................................................................... 52
3.3.3 Loss of carbon dioxide (increase in pH) ........................................................................ 53
3.4 Field and Lab Examination of Scales.................................................................................... 54
3.5 Qualitative and Quantitative Tests ...................................................................................... 55
Chapter 4 ....................................................................................................................................... 57
Scale Inhibition .............................................................................................................................. 57
4.1 Theory of Scale Inhibition .................................................................................................... 57
4.1.1 Introduction .................................................................................................................. 57
4.2 Complexation ...................................................................................................................... 57
4.3 Adsorption ........................................................................................................................... 59
4.3.1 Threshold Inhibition ..................................................................................................... 64
4.4 Laboratory Evaluation of Inhibitors ..................................................................................... 65
4.4.1 Precipitation Tests ........................................................................................................ 66
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Chapter 1
Fundamentals of Chemistry and water Analysis
1.1 Elements and Compounds

Matter is the “stuff” of which the universe is composed. Matter has two characteristics: it has
mass and it occupies space. Matter is found in three physical “states” (solid, liquid, and gas).
1.1.1 Pure Substances, Compounds, Elements

Substance: a particular kind of matter with a definite fixed composition. Substances cannot be
broken down into simpler substances by chemical reactions are called elements. Most
substances are chemical combinations of elements. These are called compounds. Compounds
are made of elements and can be broken down into elements. Properties of the compound are
not usually related to the properties of the elements that compose it. Compounds have the same
chemical composition at all times.
Matter
Mixtures Pure Substances
1- Variable composition 1- Fixed composition
2- May be separated by physical methods 2- Cannot be separated into simpler substances
3- Different mixtures have different 3- Can only be changed by chemical methods
properties 4- Properties do not vary
4- Example: air
Homogeneous Heterogeneous Element Compounds
mixture mixture Cannot be decomposed Can be decomposed
into simpler substance, into simpler
i.e., (oxygen- Nitrogen - substance, i.e., (CO2-
Sodium) Water)
Table. 1.1. Mixture, substances differences.
1.1.2 Atom:
Atoms are the smallest unit particle of an element.
An atom is composed of a positively-charged nucleus orbited by one or more negatively-charged
particles called electrons. A simplified schematic representation of this arrangement is illustrated
in Figure 1.1. The nucleus is the core of an atom. It has a positive charge because it usually
consists of two particles, the neutron and the proton (hydrogen is the exception with only a proton
in the nucleus). The neutrons are electrically neutral, and the protons are electrically positive. A
nucleus with one proton has a charge of +1 (or simply 1), and a nucleus with two protons has a
+2 charge. Together the neutrons and protons give the nucleus its mass, but the proton alone
gives the nucleus its positive charge.
The particles that orbit the nucleus are electrons. They are very small, with a mass only 1/1835
the mass of a proton or neutron. Each electron is negatively charged, and the charge of one
electron is equal in magnitude (but opposite in sign) to the charge of one proton. The number of
electrons orbiting a nucleus is exactly equal to the number of protons contained in that nucleus.
The equal and opposite charges cancel each other, and the atom as a whole is neutral.
5
The electrons are bound in the atom by electrostatic attraction. The atom remains neutral unless
some external force causes a change in the number of electrons.
Because the nucleus is composed of neutrons and protons that are about 1835 times heavier
than an electron, the nucleus contains practically all the mass of the atom, but constitutes a very
small fraction of the volume. Although electrons are individually very small, the space in which
they orbit the nucleus constitutes the largest part of the atomic volume.
Some of the properties of the atom and its component parts are summarized in Table 1.2. The
masses listed in Table 1.2 are measured in atomic mass units (amu), which is a relative scale in
which the mass of a proton is about 1.0.
Figure. 1.1.Schematic of a Simple Atom (Helium)
Table. 1.2. Properties of the Atom and its Fundamental Particles.
1.1.3 Atomic Number

The number of protons in the nucleus plays such an important role in identifying the atom that it is
given a special name, the atomic number. The symbol Z is often used for atomic number (or
number of protons). Hydrogen has an atomic number of 1. The atomic number is also equal to
the number of electrons.
1.1.4 Atomic Mass Number

The sum of the total number of protons, Z, and the total number of neutrons, N, is called the
atomic mass number. The symbol is A. Not all atoms of the same element have the same atomic
mass number, because, although the Z is the same, the N and thus the A are different. Atoms of
the same element with different atomic mass numbers are called isotopes.
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1.1.5 Atomic Weight

In Table 1.2, the masses of atomic particles are given in atomic mass units (amu). These units
represent a relative scale in which the mass of the isotope carbon-12 is used as the standard and
all others are related to it. Specifically, 1 amu is defined as 1/12 the mass of the carbon-12 atom.
Since the mass of a proton or a neutron is approximately 1 amu, the mass of a particular atom
will be approximately equal to its atomic mass number, Z.
The atomic weight of an element is generally more useful than isotopic masses. The atomic
weight of an element is defined as the weighted average of the masses of all of its natural
occurring isotopes. On this scale, the atomic weight of hydrogen (H) is 1.0 amu, that of helium
(He) is 2.0 amu, and that of magnesium is 24.3 amu. This tells us that the He atom is twice the
mass of H atoms while the Mg atoms are about 24 times heavier than H atoms.
Table. 1.3. gives the atomic weight of selected elements.
Table 1.3. Symbols and atomic weight of selected elements.
7
Figure 1.2. Illustrates Hydrogen, Helium , and Magnesium atoms.

Figure. 1.3. Periodic table of elements.
Figure. 1.2. Hydrogen, Helium , and Magnesium atoms.
1.1.6 Molecules and Molecular Weights

Atoms combine to form molecules, which can be defined as the smallest particle of a compound
which can exist. Thus, atoms have the same relation to elements as molecules have to
compounds.
A molecule of a compound is formed by the union of two or more atoms of the elements of which
the compound is composed. The molecular weight (or formula weight) is the relative mass of a
single molecule compared to the mass of carbon-12 atom. Molecular weight is found by adding
the atomic weights of the elements which form the molecule. An example of calculation is given in
table. 1.4.
Table .1.4. Molecular weight calculation.
Molecular weights, like atomic weights, are also relative weights. A molecular weight of 18 means
that one molecule of water is 18/12 = 1.5 times as heavy as one atom of carbon.
Another example: The chemical formula of sulfuric acid is H2SO4, which means that it contains 2
atoms of hydrogen, 1 atom of of sulfur and 4 atoms of oxygen. Therefore, its molecular weight is:
(2x1)+32+(4x16) = 98
Thus, a mole of H2SO4 contains 98 units of mass, of which two are hydrogen, 32 are sulfur, and
64 are oxygen.
8
Figure.1.3. Periodic table.
9
1.1.7 The mole

A mole is defined as the amount of substance that contains as many elementary entities (atoms,
molecules, or other particles) as there are atoms in 12 grams of pure carbon-12 isotope. “the
number equal to the number of carbon atoms in 12 grams of carbon.”
One mol of something consists of 6.022 x 1023 units of that substance.
According to the definition, one mole refers to 6.02 x 1023 “elementary entities” whose identities
must be specified. We could have a mole of atoms or a mole of molecules (or a mole of ions,
electrons or any particles).
The mass of one mole of atoms of a pure element is numerically equal to the atomic weight of
that element (in amu’s), expressed in grams. For example, 1 mole of elemental sodium contains
6.02 x 1023 sodium atoms and has a mass of 23.0 grams.
Similarly, one mole of ions contains 6.02 x 1023 ions, and this number of ions has a mass equal to
the atomic weight or formula mass expressed in grams. Hence, 1 mole of Mg+2 contains 6.02 x
1023 magnesium ions, has a mass of 24.3 grams.
Another example: If you obtain a sample of pure gold, which has an atomic weight of 197 amu,
and weight 197 grams, you will have one mole of gold, which contains 6.02 x 10 23 atoms of gold.
Thus, one atom of gold weights:
197/(6.02 x 1023) = 3.27 x 10-23 g
When dealing with gases, we have to be careful, since some gases exist as atoms while others
exist as molecules containing two atoms. Oxygen commonly exists as O 2 molecules, so one mole
of oxygen has the mass of 32.0 grams contains 6.02 x 1023 molecules. This concept is further
illustrated in table. 1.5.
Unless otherwise stated, the mass contained in a mole is expressed in grams. However, moles
can also be expressed in other units, such as pounds, tons, or kilograms.
Table. 1.5. Mass of one mole of atoms of some common elements.
Using carbon as an example:

• 1 mole C = 12 g
• 1 lb-mole C = 12 lb. = 5448 g = 5448/12 = 454 g-mol
• 1 ton-mole C = 12 tons. = 24000 lb = 2400/12 = 2000 lb-mole or 908000 g-mole
1.1.8 Ions and Valence

As previously stated, atoms are made up of protons, neutrons, and electrons. Each atom has an
equal number of protons and electrons, so their charge balance out and the net charge is zero. If,
however, an atom should loss or gain electrons, an imbalance in charge will result since the
number of protons in nucleus stays constant. Therefore, if an atoms gains electrons it will have a
10
net negative charge. If it loses electrons it will have a net positive charge. Whenever this
happens, the atom is no longer called an atom. It becomes an ion which may be defined as an
atom or group of atoms containing an electrical charge. A positively charged ion is called a cation
while a negatively charged ion is called an anion.
The amount of charge is called the valence and is a measure of the element’s chemical
combining power. When hydrogen ionizes it loses its electron and has a net positive charge or
valence of +1.
H – e- → H+
Calcium ionizes by losing 2 electron and thus the calcium ion has a valence of +2.
Ca – 2e- → Ca2+
Chlorine ionizes by gaining 1 electron and chlorine ion has a valence of -1.
Cl + e- → Cl-
The formula of hydrochloric acid, HCl, tells us that one atom of hydrogen combines with one atom
of chlorine. The sum of the valence must be zero since compounds have a net charge of zero.
H+ + Cl- → = HCl ……. (+1) + (-1) = 0
Similarly for salts

Ca2 + 2Cl- → CaCl2 ……. (+2) + [2 x( -1)] = 0
1.1.9 Radicals
A radical is a group of atoms found in a certain compounds which reacts as a unit, i.e., as if it
were a single atom or ion. The radicals in the compounds following are enclosed in parentheses.
H2SO4 --- CaCO3 ---- BaSO4
If these compounds were ionized we would find that the radicals behaves as polyatomic ions:
SO4-2 (sulfate ion) ------------------ CO3-2 (Carbonate ion)
1.1.10 Equivalent Weights

When elements combine to form a given compound they do so in a fixed and invariable ratio by
weight. This ration can be predicted by means of equivalent weight. For and element or ion:
Equivalent weight = Atomic weight / Valence
The valence of an element is the charge it exhibits when it is ionized.

Some elements, such as iron, have more than one equivalent weight because it can exist in more
than one valence state. For example, iron has two different equivalent weights because it can
exist as either ferrous ions (Fe+2) or ferric ion (Fe+3).
The equivalent weight of the compound is:
Equivalent weight = Molecular weight / Net positive valence
A compound has no charge. The net positive valence of a compound is the total number of
positive charges that would result if the compound were ionized in aqueous solution.
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1.1.11 Using Equivalent weights

One of the main uses of equivalent weight is to permit us to easy determine the quantity of
reactants and products in a chemical reaction.
If two elements, A and B will combine to form compound C, they will do so on an equivalent
basis. One equivalent of A will combine with one equivalent of B to form one equivalent of C.
For example:
1 Equivalent Ca+2 + 1 Equivalent CO3-2 = 1 Equivalent CaCO3
(20 ) + (30 ) = ( 50)
Similarly for ferric chloride:

Fe+3 + 3Cl- = FeCl3
Weight reacting = 56 + 3 (35.5) = 162.5
Equivalent weight = 18.7 + 35.5 = 54.2
No of equivalents = 3 + 3 = 3
We see that one atomic weight of irons combined with three atomic weights of chlorine to give
one mole of FeCl3. More important, however, 3 equivalents of iron have combined with 3
equivalents of chlorides to give 3 equivalents of ferric chloride. Equivalents always combine on
one-to-one basis.
Some examples of equivalent weights are given in tables 1.5, 1.6, and 1.7.
12
Table. 1.5 .Equivalent weight of some elements and compounds.
13
Chapter 2
Water Formed Scale
2.1 Introduction
Solubility is defined as the limiting amount of a solute which can be dissolved in a solvent under a
given set of physical conditions.
The chemical species of interest to us are present in aqueous solutions as ions. Certain
combinations of these ions are compounds which have very little solubility in water. The water
has a limited capacity for maintaining these compounds in solution, and once this capacity, or
solubility is exceeded, the compound precipitate from solutions as solids. Therefore, precipitation
of solid materials which may form scale can occur if both of the following conditions are satisfied:
1- The water contains ions which are capable of forming compounds of limited solubility.
2- There is a change in physical conditions or water composition which lowers the solubility
below the concentration presents.
Solid precipitates may either stay in suspension in water, or they may form a coherent scale on
the surface such as a pipe wall. Formation plugging may occur by filtration of suspended particles
from the water. Alternatively, a solid scale may form on the formation face. Either is undesirable.
The difficulty of removal varies with the type of plugging which has occurred.
Scale formation frequently restricts flow through injection and flow lines, and tubing strings. It
cause pump wear or plugging and creates additional rod load when formed on sucker rods. Fire
tubes in all types of heaters fail prematurely when scale formation results in overheating.
Corrosion is often more severe under scale deposit.
Water formed scales are responsible for many production problems and their effective control
should be one of the primary objectives of any efficient water handling operation.
2.2 Scale Types

Few types of many scales are found in oilfield waters. These scales are listed in table ….
Table. 2.1. Common oilfield scale.
14
2.2.1 Calcium Carbonate

Calcium carbonate scale can be formed by the combination of calcium and other carbonate or
bicarbonate ions as follows:
Ca+2 + CO3-2 → CaCO3 ↓ Eq. 2.1
Ca+2 + 2(HCO3-) → CaCO3 ↓ + CO2 + H2O Eq. 2.2
2.2.1.1 Effect of CO2 Partial Pressure

The presence of CO2 increases the solubility CaCO3 in water. When carbon dioxide dissolves in
water, it forms carbonic acid, which ionizes according to the following series of equations:
CO2 + H2O ↔ H2CO3 Eq. 2.3
H2CO3 ↔ H+ + HCO3- Eq. 2.4
HCO3- ↔ H+ + CO3-2 Eq. 2.5
Only a small percentage of the bicarbonate ions dissociate at the pH values found in most
injection water to form H+ + CO3-2 , as shown in figure 2.1.
Bicarbonate ions are usually greater than carbonate ions present under normal circumstances.
Therefore, it is thought that equation (2.2), is the more accurate expression for the precipitation of
calcium carbonate.
As the concentration of CO2 in solution is increased, the reaction shifts to the left, resulting in less
CaCO3 precipitation. The water also becomes more acidic (the pH decreases) with the addition of
CO2 to the water.
The amount of CO2 that will dissolve in water is proportional to the partial pressure of CO2 in the
gas in contact with the water.
Partial Pressure of CO2 = (Mole Fraction of CO2 in Gas) x (Total Pressure) Eq. 2.6
Mole Fraction of CO2 in Gas = %CO2 in Gas /100 Eq. 2.7
Hence, if a two-phase (gas + water) system is operating at 100 psia and the associated gas
contains 10 mol % CO2 , the partial pressure of CO2 in the gas is:
(0.1)x(100) = 10 psia.
So, if either the system pressure or the percentage of CO 2 in the gas were to increase, the
amount of CO2 dissolved in the water also would increase.
Figure 2.2 illustrates the effect of CO2 partial pressure on the pH of water containing little or co
dissolved minerals. This data should not be applied to brines since the presence of dissolved
minerals changes the relationship between pH and the amount of dissolved CO2. The effect of
CO2 pressure on the solubility of CaCO3 in pure water is shown in figure 2.3.
This data illustrated that CaCO3 solubility increases with increase CO2 partial pressures. The
effect becomes less pronounced as the temperature increases.
The reverse is also true. It is one of the major cause of CaCO3 scale precipitation. At any point in
the system where a pressure drop is taken, the partial pressure of CO 2 in the gas phase
decreases, CO2 comes out of solution, and the pH of the water rises. This shifts reaction 2.2 To
the right and may cause CaCO3 precipitation.
15
Figure 2.1. Ionization of carbonic acid as a function of pH.
Figure 2.2 Effect of CO2 partial pressure on the pH value of water.
16
Figure 2.3. Effect of CO2 partial pressure on calcium carbonate solubility.
2.2.1.2 Effect of Total Pressure

The solubility of calcium carbonate is a two phase system increases with increase pressure for
two reasons:
1- Increased pressure increases the partial pressure of CO 2 and increases the solubility of
CaCO3 in water as previously explained.
2- Increased pressure also increases the solubility due to the thermodynamic consideration.
Pressure drops are one of the primary causes of calcium carbonate scale deposition in
production systems. In addition to decreasing the solubility of CaCO 3 due to the loss of CO2 and
the thermodynamic pressure effect, pressure drops across chokes and valves induce turbulence
in the water which helps to overcome supersaturation effects and initiate precipitation.
In single phase (all water) systems, such as water injection system, increased pressure increases
the solubility of calcium carbonate solely due to thermodynamic considerations.
2.2.1.3 Effect of Temperature

Contrary to the behavior of most materials, calcium carbonate becomes less soluble as
temperature increases- The hotter the water gets, the more likely CaCO3 scale will form.
Hence, a water which is non-scaling at the surface may result in scale formation in an injection
well if the downhole temperature is sufficiently high. This is also the reason that CaCO 3 scale is
often found on the fire-tubes of heating equipment.
The solubility of CaCO3 scale in pure water at 1 atmospheric CO2 partial pressure as a function of
temperature os shown n figure 2.4.
Methods for calculating the temperature at which CaCO3 scale may be anticipated are given in a
later section.
17
Figure 2.4 Calcium carbonate solubility.
2.2.1.4 Effect of Dissolved Salts

Calcium carbonate solubility increases as the salt content of the water increases. For instance,
adding 200,000 mg/L NaCl to distillate water increases the CaCO 3 solubility from 100 mg/L to 250
mg/L.
Actually the higher the total dissolved solids (not counting calcium or carbonate ions), the greater
the solubility of CaCO3 in the water and lower the scaling tendency up to a maximum of about
200,000 mg/L.
2.2.1.5 Summary of Factors affecting CaCO3 scale formation

In summary the, the likelihood of forming calcium carbonate scale:
• Increases with temperature

• Increases with partial pressure of CO2 decreases.
• Increases as pH increases.
• Increases as total dissolved salts decreases.
• Increases as total pressure decreases.
2.2.2 Calcium Sulfate

The precipitation of calcium sulfate from water results from the reaction:
Ca+2 + SO4-2 → CaSO4 ↓
2.2.2.1 Forms of Calcium Sulfate

Many calcium sulfate deposits found in the oilfield are gypsum. According to Oddo and Tomson,
the most likely scale to form from brines will be gypsum at temperatures less than 176 0F (800C).
Between 1760F (800C) and 2500F (1210C), any of the three types of calcium sulfate may form,
with gypsum being more likely at the low end of the temperature range and anhydrite more likely
at the high end. Hemi-hydrate is commonly found in this temperature range in non-turbulent
systems with high ionic strengths. Above 2500F (1210C), any calcium sulfate formed will almost
certainly be anhydrite.
18

Gypsum solubility in pure water increases with temperature up to about 100 0F (380C), then
decreases with temperature as shown in figure 2.5.
This is a quite different from the temperature-solubility behavior of CaCO3. First, gypsum is
considerably more soluble than CaCO3 in the normal temperature range of interest. Second, the
maximum in the gypsum curve tells us that an increase in temperature could either increase or
decrease the solubility of gypsum depending on which part of the temperature curve we’re
concerned with. This is decidedly different from CaCO3 where an increase in temperature always
decreases the solubility.
Note that above about 1000F (380C), anhydrite becomes less soluble than gypsum, so it could
reasonably be expected that anhydrite might be the preferred form of CaSO4 in deeper, hotter
wells.
Actually, the temperature at which scale changes form from gypsum to anhydrite or hemi-hydrate
is a function of many factors, including pressure, dissolved salt content, flow conditions, and the
speed at which different forms of CaSO4 can precipitate from solution.
Predicting which form of calcium sulfate will precipitate under given set of conditions is very
difficult. Even though anhydrite would be expected above 1000F (380C), in preference to gypsum
due to its lower solubility, gypsum may be found at temperature up to 2120F (1000C).
It is often difficult to precipitate anhydrite directly from solution. However, with the passage of
time, gypsum can dehydrate to form anhydrite.
Above 2120F (1000C), anhydrite will precipitate directly in a stirred or flowing stream. If the system
is quiescent, hemi-hydrate solubility becomes limiting. Conversion to anhydrite could be expected
with time.
Figure 2.5 Solubility of calcium sulfate in pure water.
19

The presence of NaCl or dissolved salts other than calcium or sulfate ions increases the solubility
of gypsum or anhydrite just as it does for calcium carbonate up to a salt concentration of about
150,000 mg/L. Further increases in salt content decreases CaSO 4 solubility. (Refer to figure 2.6)
2.2.2.4 Effect of Pressure

Increase pressure increases the solubility of all forms of calcium sulfate due to the
thermodynamic considerations.
Pressure drops are one of the primary causes of calcium sulfate scale deposition in production
systems. In addition decreasing the solubility due to the thermodynamic considerations, pressure
drops across chokes and valves induce turbulence in the water which helps to overcome
supersaturation effects and initiate precipitation.
The effect of pressure and temperature on anhydrite solubility is shown in figure 2.7. Note that
pressure effect decreases as temperature increases.
2.2.2.5 Effect of pH
pH has a little or no effect on the solubility of calcium sulfate.
Figure 2.6 Solubility of gypsum in NaCl brines.
2.2.3 Barium Sulfate

Barium Sulfate is the least soluble of the scales we have discussed thus far.
Ba+2 + SO4-2 → BaSO4 ↓
Table 2.2 compares the solubility of the three scales mentioned thus far, in distilled water at 77 0F
(250C)
Scale Solubility (mg/L)

Gypsum 2080
Calcium Carbonate 15
Barium Sulfate 2.3
Table 2.2 Comparative solubilities at 250C.
20
The extreme insolubility of BaSO4 makes it very likely that scaling will occur if both Ba+2 and
SO4-2 ions are present in water.
Most barium sulfate scales also contain some strontium sulfate.
Figure 2.7. Effect of pressure and temperature on CaSO4 (anhydrite) solubility.

Barium sulfate solubility increases with temperature up to to 2120F (1000C). The solubility in
distilled water increases from 2.3 mg/L at to 770F (250C) to 3.9 mg/L at to 2030F (950C) as shown
in figure 3.8. The increase is fairly substantial percentage wise, but barium sulfate is still quite
insoluble even at this higher temperature.
Above to 2120F (1000C).the solubility decreases with temperature in water with TDS (Total
dissolved salts) less than about 50,000 ppm. The solubility in higher salinity waters shows
normal solubility behavior and increases with temperature as shown in figure 3.9.
Because of the increase in solubility over normal temperature ranges, barium sulfate usually
presents no downhole scaling problems in injection well if it is non-scaling at surface conditions. It
is more commonly a problem in producing or water supply wells.

The solubility of barium sulfate in water is increased by foreign dissolved salts just as the in the
case of calcium carbonate and calcium sulfate. The addition of 100,000 mg/L of NaCl to distilled
water increases the solubility of BaSO4 from 2.3 mg/L to 30 mg/L at 770F (250C). Maintaining
100,000 mg/L of NaCl and increase the temperature to 2030F (950C), will increase BaSO4
solubility to about 65 mg/L.
21
Figures 2.8 and 2.9 illustrates the effect of salinity on BaSO4 solubility over a wide range of
temperatures. The data in figure 2.8 is plotted as a function of molar ionic strength rather than
sodium chloride concentration. An ionic strength of 1.0 is equivalent to a sodium chloride
concentration approximately 60,000 mg/L. Ionic strength is defined later in this chapter with a
calculation example.
As a rule of thumb, you can assume that BaSO4 solubility will double as the temperature is raised
from 770F (250C) to 2030F (950C) regardless the dissolved salt concentrations. The effect of
dissolved salts is much more pronounced, as mentioned above in the addition of 100,000 mg/L
NaCl example.
Figure 2.8 Barium sulfate solubility in NaCl solutions.
22
Figure 2.9 Effect of temperature on Barium sulfate solubility at atmospheric pressure.

Increased pressure increases the solubility of barium sulfate due to the thermodynamic
considerations.
Pressure drops are one of the primary causes of barium sulfate scale deposition in production
systems. In addition decreasing the solubility due to thermodynamic considerations, pressure
Figure 2.10 shows the effect of pressure and temperature on barium sulfate solubility in pure
water.
pH has a little or no effect on the solubility of barium sulfate.
2.2.4 Strontium Sulfate

Strontium Sulfate is considerably more soluble than barium sulfate, with a solubility of 129 mg/L
in pure water at a temperature of 770F (250C).
Sr+2 + SO4-2 → SrSO4 ↓

Strontium Sulfate solubility decreases with temperature. In pure water the solubility decreases to
68 mg/L at 2570F (1250C).
2.2.4.2 Effect of Dissolved Solids

The solubility of SrSO4 in water increases as the NaCl content of the water increases up to a
maximum of approximately 175,000 mg/L. Further increases in salinity result in decreasing
solubility. In brines containing calcium or magnesium, the apparent solubility of SrSO4 is greater
than a NaCl brine of equivalent ionic strength. Refer to figure 2.11.
23
Figure 2.10 Effect of pressure and temperature on barium sulfate solubility in pure water.
Figure 2.11. Strontium sulfate solubility in NaCl solution.

Strontium sulfate solubility in NaCl brines slightly increases with pressure.
Pressure drops are one of the primary causes of strontium sulfate scale deposition in production
systems. In addition decreasing the solubility due to thermodynamic considerations, pressure
24
Until the advent of seawater injection in the middle east, pure SrSO4 scales was seldom
observed and was not considered as a major problem in water injection operations. However,
serious SrSO4 scale problems have occurred in producing wells in number of middle east fields
after breakthrough of seawater, due to mixing of sulfate-bearing seawater and the strontium in
formation waters in the producing wellbores.
In a majority of cases, however, strontium co-precipitate with barium to form (Ba,Sr) SO4 scale.
pH has a little or no effect on the solubility of strontium sulfate.
2.2.5 Iron Compounds

Iron ions present in water may be either naturally present in the water or the result of corrosion.
Formation waters normally contain only a few mg/L of natural iron and values as high as 100
mg/L are rare. Higher iron contents are invariably the result of corrosion. Precipitated iron
compounds are a common cause of deposit formation and injection well plugging, as well as
being indicative of serious corrosion problem.
Corrosion is usually the result of CO2, H2S, or oxygen dissolved in the water. Most of the scales
containing iron are corrosion products. However, iron compounds can also form by precipitation
of natural formation iron even if corrosion is relatively mild.
Carbon dioxide can react with iron to form iron carbonate scale. Whether or not scale actually
forms will depend on the pH of the system. Scale formation is much more likely above pH 7.
Figure 2.12 illustrates the solubility of iron carbonate in fresh water.
Figure 2.12 Iron carbonate solubility diagram.
25
Hydrogen sulfide will form iron sulfide as a corrosion product which is quite insoluble and usually
forms a thin, adherent scale. Suspended iron sulfide is the cause of “black water”.
The iron sulfide diagram in figure 2.13 illustrates the concentration of Fe 2+ (ferrous ion) which will
stay in solution at various pH values and H2S concentration in fresh water. Fe3+ (ferric ion) is
seldom found at pH values above 3.0.
Oxygen combines to form several compounds. Ferrous hydroxide, Fe(OH) 2, ferric hydroxide
Fe(OH)3, and ferric oxide Fe2O3, are common scales resulting from contact with air. For example,
when air-free water containing dissolved ferrous iron ions and bicarbonate ions is contacted by
air, ferric hydroxide can be formed.
2Fe+2 + 4HCO3- + H2O + ½ O2 → 2Fe(OH)3 ↓ + 4CO2
Ferrous iron (Fe+2) is oxidized in the presence of air to give ferric iron (Fe +3), and ferric hydroxide
results. This is practically insoluble above pH 4. As shown in figure 2.14, if oxygen can be
excluded, 100 ppm of Fe(OH)2 “ferrous hydroxide” will still in solution at pH 8.5.
“Red water” is the result of suspended particles of Fe2O3, another product of oxygen and iron.
Iron compounds can also result from the action of certain bacteria (gallionella ferrginea) which
live in water in the presence of air. These bacteria take Fe+2 ions from the water and deposit ferric
hydroxide.
In summary, the chemistry of iron compounds is much more complex than that of previously
discussed compounds. This is due primarily to the fact that iron commonly exists in two oxidation
states in water, Fe+2 (ferrous) and Fe+3 (ferric). These two ions form compounds with the same
anions that possess very different solubilities. It is difficult to quantitatively predict the behavior of
iron compounds. It is far more important to prevent their formation.
Figure 2.13 Iron sulfide stability diagram.
26
Figure 2.14 Iron hydroxide stability diagram.
2.3 Predicting Scale Formation

2.3.1 The value of Solubility calculations
Solubility calculations or scaling indexes may be used to predict the formation of certain types of
scales. The value obtained from these calculation procedures should be taken merely as
guidelines. They indicate the degree of “scaling tendency”, or the likelihood of scale formation.
Simplifying assumptions have been made in the derivation of each equation; solubility in naturally
occurring waters is a complex phenomenon.
It should be emphasized that if scale formation is indicated by calculation, it serves as an alarm. If
you are looking at possible water source, you should avoid those which show scaling tendencies
or make a provision for treatment in your planning. Similarly, one should avoid mixing waters
which would result in a composite analysis which exhibits scaling tendencies under system
conditions.
A calculated scaling tendency in an existing system should focus attention on the fact that scale
formation is likely and you should begin inspecting the system for signs of scale formation
immediately. The following section is a summary of some of the published scale prediction
equations, which are used for oil field waters.
2.3.2 The Basics for Solubility Calculations

All scale prediction methods are based on laboratory measurements of the solubility of a specific
compound at equilibrium conditions. Normally, solubilities are measures in synthesized water
over a range of temperature and atmospheric pressure.
27
2.3.3 Solubility Product Principle

When a sparingly soluble salt is added to water, cations and anions from the crystal lattice of the
solid pass into solution until the solution becomes saturated. In the saturated solution the
equilibrium exists between the ions in solution and ions present in the solid crystal lattice.
Using barium sulfate (BaSO4) as an example:
BaSO4 → Ba+2 + SO4-2
Solid Solution
At a given temperature and pressure the product of the activities of the ions in the saturated
solution is constant and is called the “Thermodynamic solubility product constant”, K SP.
KSP = a Ba+2 x a SO4 -2 Eq. 2-8

Where
a Ba+2 = Barium ion activity
a SO4 -2 = Sulfate ion activity
The activity of an ion is defined as the product of the ion concentration and the activity coefficient.
a Ba+2 = C Ba+2 x Y Ba+2 Eq. 2.9
a SO4 -2 = C SO4 -2 x Y SO4 -2 Eq. 2.10
Where
C Ba+2 = Ba+2 Concentration, moles/L
C SO4 -2 = SO4 -2 Concentrations, moles/L
Y = activity coefficient, where it is a function of temperature, pressure, and ionic strength.
At saturation, the resulting solubility product is defined as the ion product constant, or “conditional
solubility product constant, Kc” and is defined in equation 2.11.
Kc = KSP / ( Y Ba+2 x Y SO4 -2 ) = (C Ba+2)( C SO4 -2 ) at saturation Eq. 2.11
Where
Kc = conditional solubility product constant, molar units.
Based on this principle, it is possible to evaluate a solution with respect to the possibility of the
precipitation of a given salt at a given temperature and pressure by comparing the value of ion
product constant at those conditions with the product of the measured concentrations of the ions
in the solution.
If we have a solution which contains a given amount of dissolved BaSO 4, and the measured
concentrations of Ba+2 and SO4-2 are CBa+2 and CSO4 -2 , the possibilities are as follows:
1. The solution is saturated with BaSO4 (Solubility limit)

(C Ba+2)( C SO4 -2 ) = Kc Eq. 2.12
2. The solution is under saturated with BaSO4. . Precipitation cannot occur

(C Ba+2)( C SO4 -2 ) < Kc Eq. 2.13
28
3. The solution is supersaturated with BaSO4. Precipitation can occur

(C Ba+2)( C SO4 -2 ) > Kc Eq. 2.14
Thus, precipitation can occur only in the last case.
2.3.4 Saturation Ratio

Continuing with the example of BaSO4 dissolved in water, the saturation ratio (sometimes called
the supersaturation ratio) is defined as the ratio of iron product to the ion product constant.
SR = IP/Kc = (C Ba+2)( C SO4 -2 ) / Kc Eq. 2.15
Where
IP = Ion product
SR = Saturation ratio
(C Ba+2) and (C SO4 -2 ) = Measured concentration of Ba+2 and SO4-2 in solution.
Thus, it is also possible to express the conditions necessary for precipitation in the term of the
saturation ratio:
1. SR = 1 The solution is saturated with BaSO4.

2. SR < 1 The solution is undersaturated with BaSO4.
Precipitation cannot occur
3. SR > 1 The solution is supersaturated with BaSO4.
Precipitation can occur
2.3.5 Calcium Carbonate Scaling Calculations

2.3.5.1 Calcium Carbonate Saturation Indexes
It is common to express the degree of supersaturation, and hence the likelihood of precipitation of
CaCO3 from the solution in terms of the saturation index, which is defined as follows:
Saturation Index = log10 (IP/Kc ) Eq. 2.16
Although there is agreement as to the definition of the saturation index “stability index”, equations
uses two abbreviations (SI) and (Is).
The saturation index, which we will refer to as SI, is a measure of the degree of supersaturation,
and thus the driving force available to cause precipitation. The larger the value of SI, the greater
the likelihood that scale will occur. It does not predict the amount of scale which will precipitate.
Figure 2.15 illustrates the relationship between the supersaturation ratio and the saturation index.
2.3.5.2 Langelier Saturation Index

This is a well known index was developed to predict whether a fresh saturated with dissolved
oxygen would form calcium carbonate scale or be corrosive.
The Langelier saturation index is calculated from the following empirical equation:
SI = pH - pHs Eq. 2.17
where
SI = Stability Index
29
pH = Actual pH of water
pHs = pH at which water would be saturated with CaCO3.
pHs = pCa + pAlk M + Ct Eq. 2.18
pCa = log [1 / (Moles Ca+2 /liter)] Eq. 2.19
pAlk M = log 1 / (equivalent M alkalinity / liter) Eq. 2.20

M alkalinity = total alkalinity = CO3-2 + HCO3- , equivalent / L Eq. 2.21
where
Ct = a constant which is a function of the total dissolved solids and temperature.
As previously explained, if SI > 0, precipitation of CaCO 3 is indicated. A negative value of SI

indicates that the water is corrosive if dissolved oxygen is present. This index indicates the
tendency of ware to precipitate calcium carbonate, but it does not indicate the amount of
precipitate.
Figure 2.15 Saturation index (SI) versus saturation ratio (SR).
2.3.5.3 Ryznar Stability Index

Ryznar developed an empirical equation for calculating the stability index of fresh water at
atmospheric pressure.
SI = 2pHs – pH Eq. 2.22
Ryznar’s stability index value always positive. They can be interpreted as follows:
1- Stability index < 6.5 indicates CaCO3 scale formation. The smaller the index, the larger
the amount of scale formed.
2- Stability index > 6.5 indicates corrosion if dissolved oxygen is present. The larger the
index, the more sever the anticipated corrosion.
30
2.3.5.4 Stiff and Davis Method

Stiff and Davis empirically extended the Langelier method to apply to oilfield brines. Their
equation is as follows:
SI = pH - pHs Eq. 2.23
where
SI = Stability Index
pH = Actual pH of water
pHs = pH at which water would be saturated with CaCO3.
pHs = K + pCa + pAlk Eq. 2.24
SI = pH - K - pCa - pAlk Eq. 2.25
Where
SI = Stability index. If SI is negative, the water is undersaturated with CaCO 3 and scale formation
is unlikely. If SI is positive, scale is likely to form.
K = A constant which is a function of salinity, composition and water temperature. Values of K are
obtained from a graphical correlation with ionic strength and temperature of water. (Figure 2.16)
pCa = log [1 / (Moles Ca+2 /liter)] Eq. 2.26

pAlk M = log 1 / (equivalent M alkalinity / liter) Eq. 2.27
M alkalinity = total alkalinity = CO3-2 + HCO3- , mg/ L Eq. 2.28
u =0.5 (C1Z12+ C2Z22+ C3Z32 +…..+ CnZn2) Eq. 2.29
where
C = Concentration of the ion in moles/liter.
Z = Valence of the ion.
In order to calculate SI we must know the temperature, pH, and the HCO 3- and CO3-2
concentrations. In addition, a complete water analysis is necessary to enable calculation of ionic
strength.
It is essential that values of pH, HCO3- and CO3-2 be measured in the field immediately after
sampling, since these parameters change very quickly once the sample is removed from a
pressurized system. Valid calculations cannot be made from laboratory analyses.
Unfortunately, even field measurements of pH values will not suffice when attempting to apply
this method to downhole conditions in production and injection wells. The pH must be calculated.
Equations are given in the following section which enable estimation of pH values at elevated
pressures and temperatures.
Values of K as a function of ionic strength in Figure 2.16, the curves are based on experimental
data in the following range:
• Molar ionic strength: 0 – 3.6

• Temperature: 32, 86, and 1220F (0,30 and 500C)
• Pressure: 1 atmosphere(14.7 psig , 101.3 KPa).
All curves outside of this data range were extrapolated.

Figure 2.17is a chart for determination of pCA and pAlk .
31
The results of calculations may be summarized as follows:
If SI is negative, the water is undersaturated with CaCO3 and scale formation is unlikely.
If SI is positive, the water is supersaturated with CaCO 3 scale is likely to form.
If SI = 0, the water is saturated with CaCO3.
An example calculation is given later in this chapter.
2.3.5.5 Oddo and Tomson Method

The equation developed by Oddo and Tomson enable the calculation of the saturation index. Is,
and considers the effect of total pressure as well as varying CO 2 partial pressure. They also
developed equations which permits the calculation of pH.
The equation here were published 1994.
Any System (Gas Phase Present or Absent) where the pH is Known
Is = log [(Ca+2)(HCO3-)]+pH–2.76+9.88 x10-3 T + 0.61x10-6 T2 –3.03x10-5 P– 2.348 u0.5

+0.77 u Eq. 2.30
Where
Ca+2 = Calcium ion concentration, moles/L
HCO3- = Bicarbonate ion concentration, moles/L
T = Temperature, 0F
P = Total absolute pressure, psia
u = Molar ionic strength, moles/L
Gas Phase Absent
These equations are applicable in water injection system and in production systems where the
system pressure is greater than the bubble point pressure of the fluids.
1- Determine Caq, the amount of CO2 dissolved in the water. This can be determined directly
by on-site titration, or it can be calculated using equation 3.31.
Caq = log PCO2 - 2.212 – 6.51 x 10-3 T + 10.19 x 10-6 T2 – 1.29 x 10-5 P – 0.77 u0.5
– 0.059 u Eq. 2.31
2- Calculate Is or the pH as desired from the following two equations
Is = log [(Ca+2)(HCO3-) / Caq ]+3.63 +8.68 x10-3 T+8.55x10-6 T2 –6.56x10-5 P– 3.42 u0.5
+1.373 u Eq. 2.32
pH = log [(HCO3-) / Caq] + 6.39 – 1.198 x 10-3 T + 7.94 x 10-6 T2 – 3.53 x 10-5 P – 1.067
u0.5 +0.599 u Eq. 2.33
3- It is also possible to calculate the change in Is or pH in a system without a gas phase

using the following equations:
ΔIs = 8.68 x 10-3 ΔT + 8.55 x 10-6 Δ(T2) - 6.56 10-5 ΔP Eq. 2.34
ΔpH = 1.198 x 10-3 ΔT + 7.94 x 10-6 Δ(T2) – 3.53 10-5 ΔP Eq. 2.35
32
Gas Phase is Present and the pH is Unknown
1- Calculate fg, the fugacity coefficient of CO2 gas.
Eq. 2-36
2- Calculate yg, the mole fraction of CO2 in the gas phase at the specified T and P. Given
that yt is the mole fraction of CO2 in the gas at the surface.
Eq. 2.37
where
BWPD = Barrels of water per day
BOPD = Barrels of oil per day
MMscfd = Million standard cubic feet per day.
3- Calculate the ionic strength.
Eq. 2.38
Where all ions concentrations are in mg/L and are obtained from a water analysis.
4- Calculate Is or the pH as desired.
Eq. 2.39
Eq. 2.40
This method is said to be valid over the following data range:
• Molar ionic strength: 0-4.0

• Temperature: 32-392 0F (0-2000C)
• Pressure 0-20,000 psig
33
2.3.5.6 Estimation of the amount of CaCO3 scale formed

It is possible to estimate the maximum amount of scale which could form, assuming the system is
at equilibrium.
If a solution is supersaturated with a salt (such as CaCO 3, CASO4, BaSO4 or SrSO4), precipitation
can be expected.
Stiff and Davis
Maximum amount of scale can be precipitated in pounds per thousand barrels (PTB) =
Eq. 2.41
Where
G = Ca+2 + HCO3-, moles/L
X = Ca+2 - HCO3-, moles/L
Table. 2.3. Calcium carbonate scaling severity
Oddo and Thompson
Eq. 2.42
Eq. 2.43
2.3.6 Sulfate Scaling Calculations

Traditional approach to Sulfate Scale Solubilities
Solubility values for CaSO4, BaSO4 or SrSO4, can be calculated using the following equation,
providing values of conditional solubility products, Kc, are known for each compound:
Eq. 2.44
The actual concentration of CaSO4 in solution is equal to the smaller of the Ca+2 or SO4-2
concentrations (expressed in meq/liter) in the water of interest, since the smaller concentration
controls the amount of calcium sulfate which can be formed.
The calculated calcium sulfate solubility, S (meq/liter), is compared with the actual concentration
to determine if scale formation is likely.
This formula can be used to calculate the solubility of any divalent salt such as CaSO 4, BaSO4 or
SrSO4.
34
Table. 2.4. Interpretation of sulfate scale calculations
2.3.6.1 Calcium Sulfate (Gypsum) Solubility Calculations

The data measured by Skillman, McDonals and Stiff has widely used to estimate the solubility of
gypsum in oil field brines. They measured ion product constant in simulated oilfield brines over
the following range:
• Temperature: 50,95,122 and 176 0F (10,35,50 and 80 0C)

• Ionic strength: 0-6.0 moles/L
• Pressure: 1 atmosphere (101.3 KPa)
The following procedure is recommended to assess the possibility of gypsum precipitation from a
given brine:
1- Calculate the molar ionic strength using equation 2.38.
2- Obtain appropriate value of KC for the temperature of interest from figure.2.18.

3- Determine the excess common ion concentration, X, in moles/liter. This is simply the
difference between the calcium concentration and the sulfate concentration.
4- Calculate the solubility of gypsum in meq/liter by solving equation 2.44.
5- Calculate the actual concentration of gypsum in the water, which is equal to the smaller
of the Ca+2 or SO4-2 concentration expressed in meq/liter.
6- Compare the calculated solubility with the actual concentration to determine if
precipitation of gypsum is likely.
An Example calculation is given in this chapter.
2.3.7 Barium Sulfate Solubility Calculations

It is possible to estimate the solubility of barium sulfate for waters which contain predominately
sodium and chloride ions and very little magnesium or calcium ions using the solubility data
measured by Templeton. Molar conditional solubility product constant calculated from his data
are presented in figure 2.19 over the following range:
• Temperature: 77,95,122,149,176 and 203 0F (25,35,50,65,80 and 95 0C)

35
The solubility can be calculated using equation 2.44.
, and the probability of BaSO4 precipitation evaluated using the same procedure as previously
outlined for gypsum.
Because BaSO4 has such limited solubility, the appearance of Ba+2 and SO4-2 ions in any water
indicates a danger of scale formation.
2.3.8 Strontium Sulfate Solubility Calculations

The solubility of strontium sulfate in sodium chloride solutions can be calculated in the same
manner as the solubilities of the other sulfate scales.
The following equation is based on Jacques and Bourland data and can be used to estimate
values of Kc.
log Kc = X/R Eq. 3.45

where
Kc = Conditional solubility product constant, molar units
X = 1/T
Eq. 2.46
The units are:
T = 0K = 0C +273
P = Total pressure, psig
u = Ionic strength, moles/L
The coefficients of the equation are:
The equation applies over the following range:
• Temperature: 100- 300 0F (38- 149 0C)

• Pressure: 100-3000 psig
Kc values measure by Fletcher, French and Collins for strontium sulfate is given in figure 2.20.
Their data was measured over the following range:
• Temperature: 50,75,122 and 156 0F (10,35,50, and 69 0C)

• Ionic strength: 0.1-5.25 moles/L
36
2.4 Example Scale Calculations

Ionic Strength, CaCO3 Scaling Index and CaSO4 Solubility
Temperature = 60 0C ; pH =7.04
Calcium Carbonate Scaling Index Calculation

K = 2.24 from figure 2.16.
pCa =1.67 from figure 2.17.
pAlk = 2.05 from figure 2.17.
SI = pH – (K+pCa+pAlk) = 7.04 – (2.24 + 1.67 + 2.05) = +1.08
SI > 0, so CaCO3 scale is likely.
Calcium Sulfate Solubility Calculation
Kc = 9.2 X 10-4 from figure 2.18.

4 Kc = 36.8 x 10-4
Actual CaSO4 Concentration = 36.3 meq/L
S > Actual, so CaSO4 scale is unlikely.
37
Figure 2.16. Values for Stiff and Davis K for CaCO3 Scale calculation.
38
Figure 2.17. Conversion of mg/L Calcium and Alkalinity into pCa and pAlk.
39
Figure 2.18. Calcium sulfate (Gypsum) Conditional Solubility Product Constants.
40
Figure 2.18. (Continued) Calcium sulfate (Gypsum) Conditional Solubility Product Constants.
41
Figure 2.19. Barium sulfate Conditional Solubility Product Constants.
42
Figure 2.20. Strontium sulfate Conditional Solubility Product Constants.
43
Figure 2.20. (Continued) Strontium sulfate Conditional Solubility Product Constants.
44
Chapter 3
Scale problems & Inhibition
3.1 Introduction
Wells producing water are likely to develop deposits of inorganic scales. Scales can and do coat
perforations, casing, production tubular, valves, pumps, and downhole completion equipment,
such as safety equipment and gas lift mandrels. If allowed to proceed, this scaling will limit
production, eventually requiring abandonment of the well.
Technology is available for removing scale from tubing, flow-lines, valves, and surface
equipment, restoring at least some of the lost production level. Technology also exists for
preventing the occurrence or reoccurrence of the scale with conventional inhibitor technology
3.2 Scale mechanisms

As brine, oil, and/or gas proceed from the formation to the surface, pressure and temperature
change and certain dissolved salts can precipitate. This is called “self-scaling.” If a brine is
injected into the formation to maintain pressure and sweep the oil to the producing wells, there
will eventually be a commingling with the formation water. Additional salts may precipitate in the
formation or in the wellbore (scale from “incompatible waters”). Many of these scaling processes
can and do occur simultaneously. Scales tend to be mixtures. For example, strontium sulfate is
frequently found precipitated together with barium sulfate.
3.3 Causes of Scales

Many types of scales form in petroleum producing operations. This module discusses the most
common and most disabling types: the water-formed deposits. Other types of scales, such as
those formed by corrosion or bacteria, are covered in other courses. Water-formed deposits are
seldom pure compounds. They are usually mixtures of compounds in a mixed-crystal lattice or as
layers of different compounds. As a starting point, we will discuss the scale compounds barium
sulfate (BaSO4), calcium sulfate (CaSO4), calcium carbonate (CaCO3), and strontium sulfate
(SrSO4).
Water-formed scales can form for a number of reasons. Defining the cause of the scale is
essential to selection of the best remedy. Sometimes, a simple change in the production system
is enough to prevent scale formation. In other cases, chemical inhibitors must be added. The
common causes of water-formed deposits are
• Change in temperature
• Mixing of incompatible waters
• Loss of carbon dioxide (increase in pH)
• Drop in pressure
3.3.1 Change in temperature

Temperature change is a contributing factor in the deposition of barium sulfate and, in some
cases, calcium carbonate. Deep gas and condensate wells in the Gulf of Mexico and parts of
45
Texas are plagued by the deposition of barium sulfate in lower reaches of the wells and in the
subsurface safety valve (SSSV). These wells produce very little water, maybe only 10 barrels
per day. The problem is attributed to the drop in temperature when gas expands in the tubing. If
formation water is saturated with respect to barium sulfate, then some deposition can be
expected as the temperature drops (Figure 3.1).
Figure 3.1 Effect of temperature of the solubility of BaSO4 in water.
The effect of temperature on the solubility of calcium carbonate is inverse to that shown for
barium sulfate (Figure 3.2).
The solubility of calcium carbonate decreases with increasing temperature. The data in Figure 3.2
were obtained in a closed container in the presence of carbon dioxide. The decrease in solubility
with temperature is greater if carbon dioxide is released from the system. The reasons for this will
be discussed later. From Figure 3.2, one would presume that injecting a water saturated with
CaCO3 into an injection well would cause scale formation
because of the increased temperature as the water descends into the well. This seldom results in
problems for the injection well because the well bore and formation near the injection well are
soon cooled by the injected water. Furthermore, calcium carbonate precipitates slowly because
its solutions easily exceed saturation. Note that the solubilities of CaCO 3 are about
1,000 times those of BaSO4. In producing wells, the temperature decreases as water rises in the
tubing, causing an increase in the solubility of CaCO3. At the same time, carbon dioxide is
released from the water due to a decrease in pressure as the water rises in the production tubing.
This causes a decrease in the solubility of CaCO3. Generally, the loss of CO2 predominates and
CaCO3 precipitates in the upper reaches of the tubing. Because CaCO 3 precipitates slowly, it also
leaves scale on surface equipment. Fortunately, computer programs are available that give the
equilibrium conditions for CaCO3 solutions at any temperature and pressure. With this
information, the scaling tendency can be predicted.
46
Calcium carbonate scaling in produced waters also results when a water incompatible with the
formation water is injected. Complexities arise in predicting incompatibility. Although a water may
be compatible as injected, it can become incompatible through interactions with minerals in the
oil-producing formation. This is especially true of calcareous formations.
Figure 3.2 Effect of temperature of the solubility of CaCo3 in water.
Calcium sulfate solubility increases with temperature below 860F (300C), but the solubility
decreases with temperature above 860F (Figure 3.3).
Calcium sulfate exists in three forms: gypsum (CaSO4 • 2H2O), which contains two water
molecules; hemihydrate (or, subhydrate, CaSO4 • 1/2H2O); and anhydrite (CaSO4). Only gypsum
and anhydrite occur in scales and in petroleum reservoirs. Anhydrite absorbs water very strongly
at temperatures below 1220F (500C), making it a good drying agent. The
crystalline form of the anhydrite and resulting gypsum are exactly the same except for the
presence of water in the latter. Plaster of Paris is made by slurrying anhydrite in water.
Anhydrite absorbs the excess water and converts to a dry, cohesive mass of gypsum. Calcium
sulfate scales sometimes occur in producing wells even though only formation water is produced.
The reasons for this are not clear. It is presumed, however, to be caused by the dissolution of
anhydrite in the formation, which precipitates as gypsum when the temperature of the water is
lowered. Calcium sulfate precipitates as anhydrite if the temperature is greater than 1220F (50
0C). Certain salts cause anhydrite to precipitate at temperatures as low as 1040F (400C). An
injected water need contain neither calcium ions or sulfate ions to be incompatible with the
47
formation water if the petroleum reservoir contains gypsum or anhydrite deposits. Cool injected
water can dissolve large quantities of anhydrite then precipitate it as the water is heated by the
reservoir. This problem occurs extensively in West
Texas. There plugging of the formation near the well bore is common with resulting losses in
production.
Figure 3.3 Effect of temperature of the solubility of CaSO4 in water.
Strontium sulfate (SrSO4) is the rarest of the water-formed scales to be discussed here, but it is a
problem in some areas. The solubility of SrSO4 in water (114 mg/l at 7 0F) is less than CaSO4
(2080 mg/l) but greater than BaSO4 (2.3 mg/l) under comparable conditions. The change in
solubility of SrSO4 with temperature is the same as gypsum in that solubility increases with
temperature up to 1040F (400C) but decreases at higher temperatures (Figure 3.4).
SrSO4 scales result from the injection of water that is incompatible with the formation water.
An example would be injecting a water, such as sea water, that is high in sulfate into a formation
where the water contains high levels of strontium.
Higher pressures increase the solubility of all the scales discussed above. The main reason for
the increase in solubility is that the volume of a system composed of scale and water decreases
when the scale dissolves. This can be expressed simply as shown in Figure 3.5, which illustrates
the effect of pressure on the solubility of anhydrite (CaSO4). A secondary factor in increasing the
solubility is that water is compressed to a volume decrease of about 2 percent on the application
of 500 bars hydrostatic pressure. This decrease in volume increases the salt concentration per
unit volume, and higher salt concentrations increase the solubility of scales. The effect of
pressure on solubility decreases with increasing temperature and total dissolved solids (TDS) of
the water. In the case of CaCO3, higher partial pressures of carbon dioxide (CO2) increase the
solubility. This effect of CO2 applies only to CaCO3 and not to BaSO4, CaSO4, or SrSO4.
48
Figure 3.4 Effect of temperature of the solubility of SrSO4 in water.
Figure 3.5 Effect of pressure on the solubility of CaSO4 (Anhydrite) in water.
49
Carbon dioxide increases the solubility of CaCO3 as shown in Figure 3.6. The reverse condition
also applies. A loss of CO2 from solution results in the precipitation of CaCO3.
The loss of CO2 can occur as the result of increasing the temperature or dropping the pressure.
In some cases, CaCO3 scales in producing systems have been controlled by preventing release
of CO2 from the system. Because of the effect of the loss of CO 2, CaCO3 scaling can result from
the production of produced water only. It can also result from injection of an incompatible water.
Sea water is almost saturated with CaCO3.
The solubility of BaSO4 with increasing salt concentration (in molality) is shown in Figure 3.7.
The increase in solubility is greater at low salt concentrations. The solubility of CaSO 4 goes
through a maximum at about 3.0 m (molality) salt concentration, presumably because the added
salt ties up sufficient water molecules to encourage the precipitation of anhydrite.
The solubility of CaCO3 also goes through a maximum with salt concentration at about 2 m
(molality) because the solubility of CO2 decreases with increasing salt concentration (Figure 3.8).
Figure. 3.6. Effect of pressure on the solubility of Calcium carbonate.
50
Figure 3.7. Effect of salt concentration on the solubility of barium sulfate
Figure. 3.8. Effect of Salt Concentration on the Solubility of Calcium Carbonate at 25°C
51
3.3.2 Mixing Incompatible water

Incompatible waters are those that produce a precipitate when mixed. Incompatible waters can
be waters produced from different zones and then commingled in the producing systems, or they
can be a formation water and an injected water. Most often, the injected water contains an ion
that reacts with an ion in the formation water to cause precipitation and scaling when the two
waters mix in a producing well. Examples of incompatible waters are given in table 3.1.
Table 3.1 .Incompatible ions.
The illustration in Figure 23 gives only the ions that take part in the scaling reactions. Actual
waters contain other ions that affect the precipitation reactions. Two incompatible waters and their
produced mixture are given in
Table 3.2. Production of a mixture of these waters resulted in severe scaling of the producing well
by CaSO4. Notice that the formation water is high in calcium and the injected water is high in
sulfate, resulting in the precipitation of CaSO4. The injected water in table 3.2 is much lower in the
concentrations of most ions than is the formation water.
Table 3.2 .Composition of incompatible water and the mixture of the two.
52
Therefore, we could conclude that injected water was breaking through to the producing well if
the salt content of the produced water decreased. Also, we could accomplish the same thing by
monitoring the concentration of only one ion; for example, Mg++ in the produced water.
When the Mg++ concentration decreased, it indicates that injected water is breaking through. The
composition of the produced water in terms of the fractions of injected water and formation water
can be calculated from the concentration of Mg++ in each water. For example, the fraction of
injected water in the produced water as shown in Figure 3.2 is given by:
3.3.3 Loss of carbon dioxide (increase in pH)

The loss of carbon dioxide is usually due to the decrease of pressure which decrease the
solubility of CO2 and results is an increase of pH.
The pH of a produced water generally has little effect on scaling by BaSO4, CaSO4, or SrSO4, but
a change in pH by loss of CO2 in a producing well has a large effect on scaling by CaCO 3.
The efficiency of chemical scale inhibitors for all the scales is affected by pH. The high pressures
in many oil producing reservoirs cause large concentrations of CO 2 to go into solution, resulting in
a drop in pH (Figure 3.9).
Figure. 3.9. Effect of CO2 Partial pressure on pH.
Calcium carbonate reacts with hydrogen ions in water, causing the pH of the water to rise.
Therefore, injecting a water into a limestone reservoir generally results in an increase in pH of the
injected water.
53
3.4 Field and Lab Examination of Scales

The first step in controlling a scale problem is to identify the scale with certainty. This is difficult to
do visually because the various scales can occur in different forms and colors (Figures 3.10 to
3.12).
Figure. 3-10. Calcium carbonate and calcium sulfate scale.
Figure. 3-11 Strontium sulfate and Barium sulfate scale
54
Table.3.3 Properties of common scale.
Mixed scales are common. Calcium carbonate mingled with barium sulfate is shown in
Figure 3.12. If two scales have a common ion, such as CaSO4 and BaSO4, the least soluble
compound forms first. If a water is capable of forming both CaSO4 and BaSO4, then BaSO4 is
found in the bottom of a producing well. If there is enough SO 4-2 left to form CaSO4, it will be
found in shallower depths of the well.
Figure. 3-12. mixed calcium carbonate/barium sulfate scale
3.5 Qualitative and Quantitative Tests

Identification of a scale in the field by simple physical or chemical tests requires considerable
experience with various types of scales unless the scale is calcium carbonate. Calcium carbonate
dissolves in a weak acid such as vinegar with the liberation of carbon dioxide. If a scale "fizzes" in
vinegar (acetic acid) and dissolves, then it is calcium carbonate. The other scales require closer
scrutiny as shown in Figure 3.13. The tests given in Figure 38 are not fool-proof but provide an
educated guess of the identity of a scale. Chemical verification is still required if there is doubt or
if the scale is complex.
55
Figure 3.13. Simple Field Tests for Identifying Scales
Discussion board
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Chapter 4
Scale Inhibition
4.1 Theory of Scale Inhibition

4.1.1 Introduction
There are two major chemical methods for preventing, or inhibiting, scale formation. These are
removal of the offending cation (Ba+2, Ca+2, Sr+2) or anion (SO4-2, CO3-2) from solution or addition
of a chemical that prevents crystal growth. The removal of offending ions is accomplished by ion
exchange, precipitation, or complexation. Each of these techniques requires the addition of a
stoichiometric quantity of chemical. Because large amounts of added chemicals are required,
removal of the offending ion is practiced only where the concentration of offending ions is very
small, such as in a boiler feed water.
Preventing crystal growth requires only the addition of a very low concentration of chemical,
maybe only about 2 ppm of an effective chemical. For treating large amounts of water that
contain high concentrations of scale-forming ions, preventing crystal growth is the preferred
method.
• Removal of ions
• Anion exchange
• Cation exchange
• Precipitation
• Complexation
• Acidification (CaCO3 only)
• Prevent crystal growth
• Adsorbed chemicals
In this section, Theory of Scale Inhibition, we will discuss complexation and adsorption.
Complexation is rarely used for preventing scale in produced waters. We include it here because
it is useful for small amounts of water or low concentrations of cations.
Adsorption scale inhibitors are good complexing agents for cations. Understanding this property
is important in the formulation and use of adsorption scale inhibitors. Adsorption scale inhibitors
are the most important to us in preventing scale in oil field produced waters and most of our time
will be spent on this topic.
4.2 Complexation
Recall that complexing agents, or chelating agents, are useful for dissolving scale. They react
with cations to form a new ion that is more soluble.
M++ + X ↔ X M++ Eq. 4.1

Where: M++ is a cation such as Ca++,or Ba++, Sr++
X is a chelating agent such as EDTA or DTPA
Complexing agents can lower the concentration of a cation so its concentration no longer
exceeds the solubility product constant. They can therefore, be used to prevent scale and to
57
dissolve scale. Complexing agents are commonly added to cooling water and boiler waters for
these purposes.
Complexing agents must be added in a stoichiometric quantity relative to the amount of cation to
be complexed. Most complexing agents such as EDTA and DTPA cost about $1.00/lb so they are
not economical in many cases. Another disadvantage to complexing agents is that they complex
more than one cation. In other words, they are generally not specific for only the cation selected
for complexing. The ability of a complexing agent to complex a given cation is expressed by the
stability constant, K, as previously explained. Using the reaction given in Eq. 4.1, the stability
constant can be expressed as shown in Eq. 4.2. The stability constant is the ratio of complexed
cation to uncomplexed cation and is, therefore, an expression of the strength of the complex.
Eq. 4.1
The stability constants of EDTA for several cations are given in Figure 4. If EDTA is added to a
mixture of the cations given in table 4.1, the Ca++ ions will be complexed first because they form
the strongest complex (log K = 10.59) with EDTA. However, if Ba++ ions are to be complexed,
then sufficient EDTA must be added to complex all of the Ca++ and Mg++ ions first. The amount
of EDTA required might be many times that required to complex only the Ba++. The amounts of
EDTA required to complex Mg++, Ca++, and Ba++, based on mole-for mole addition, are given in
table 4.2.
Table.4.1. Some Stability Constants for EDTA Complexes.
Table.4.2. Amount of Na3EDTA Required to Complex Various Cations.
Suppose a water contains 1 ppm each of Mg++, Ca++, and Ba++ ions. It would require 9.6 ppm
of Na3EDTA to complex the Ca++ but 25.2 ppm to complex the Mg++ because sufficient EDTA to
complex the Ca++ must also be added. Complexing the Ba++ would require 28.0 ppm of
Na3EDTA. Almost all complexing agents behave in this manner. It would be advisable to measure
the amount required experimentally if a mixture of cations is present.
58
4.3 Adsorption
Adsorption is the interaction of a substance with a solid surface. Absorption is the taking up of
one substance by another throughout its bulk. This section is titled adsorption because it is
believed that surface adsorption is the way that some scale inhibitors are able to prevent scale at
concentrations of only 1 ppm or so.
About 80 years ago, it was discovered that some inorganic phosphorous compounds, called
metaphosphates, could prevent CaCO3 scaling in irrigation systems when only 2 ppm were
added to the water. This small amount of metaphosphate could maintain a supersaturation of
over 200 ppm of CaCO3 in solution. A low concentration of metaphosphate could not only prevent
CaCO3 scaling, but it also caused previously-formed CaCO3 deposits to disappear.
Clearly, this was not a stoichiometric phenomenon and so it was called a threshold treatment
because it maintained the dissolved CaCO3 on the threshold of precipitation. The term threshold
treatment today means the use of substoichiometric quantities of scale inhibitor, specifically,
concentrations in the range of 20 ppm, or less. With modern threshold chemicals, we often
observe effective scale inhibition with only 0.5 ppm of inhibitor.
Metaphosphates belong to a family of inorganic phosphates called condensed phosphates,
dehydrated phosphates, or polyphosphates. They are inexpensive and still used in municipal
waters and cooling waters. The preparation of a polyphosphate is written in the following
reactions. The monomolecular phosphoric acid, called orthophosphoric acid, is heated with an
alkali to expel water and form sodium hexametaphosphate, an excellent scale inhibitor. The
orthophosphates have no scale-inhibiting properties at all. In practice, it was found that solutions
of sodium hexametaphosphate rapidly lost their ability to inhibit scale. The reason is that the
hexametaphosphate reacts with water, or hydrolyzes, and reverts back to the inactive
orthophosphate. This loss of scale-inhibiting activity is called reversion.
Formation
6H3PO4 + 3Na2O → Na6(PO3)6 + 9H2O
Reversion
Na6(PO3)6 + 6H2O → 6NaH2PO4
At one time, polyphosphates were widely used in oil fields to inhibit scale. They were found to be
effective against CaCO3, CaSO4, and BaSO4. Because of the reversion problem, solutions of
polyphosphates could not be depended on for long life when squeezed into formations. The rate
of reversion increases with temperature and acidity so the squeezed solutions rapidly lost
effectiveness under downhole conditions (Table 4.3).
Table 4.3. Reversion of Inorganic Polyphosphates at 25 °C
59
To overcome the reversion problem, controlled-solubility, or glassy, polyphosphates were

developed. These contained cations other than sodium to limit their solubility. The glassy
phosphates in pellet form were fractured into formations with propping agents. Although scale
inhibition for up to 4 years was reported, penetration of the pellets and life of the treatment were
very uncertain.
Another disadvantage of the inorganic phosphates was overtreatment. If too much phosphate
was used and reversion occurred, calcium orthophosphate, Ca3(PO4)2, precipitated from solution.
The solubility of calcium phosphate is only 20 mg/l, thus, it is a more offensive scale than is
CaCO3. The glassy, controlled-solubility, phosphates offered a way to avoid overtreatment.
Baskets of the compound were hung from the tubing of producing wells, placed in source water
tanks, and put in flowing streams. The glassy phosphates slowly dissolved to provide inhibition for
a period of time after which the basket was refilled.
Even though their cost was low, disadvantages of the polyphosphates caused them to give way
to the more expensive, but more reliable, organic compounds used today. The use of inorganic
polyphosphates is almost unknown in oil fields today but much of our application technology and
knowledge of the mechanisms of scale inhibition were developed for the polyphosphates.
Several mechanisms have been proposed whereby threshold scale inhibition occurs. Generally,
nucleation is not prevented by scale inhibitors, but the scale nuclei remain very small – in the
order of only a micron (10-6 m) in diameter. Restriction of crystal growth by adsorption on one or
more crystal faces appears to be the dominant mechanism for scale inhibition by threshold
inhibitors. If a CaCO3 crystal is placed in a metastable saturated solution of CaCO 3, the crystal
will grow. However, if the crystal is first immersed in a solution of threshold inhibitor and then
placed in the saturated solution, it will not grow.
Crystals nucleated in the presence of threshold inhibitors have a different form than those
nucleated under normal conditions. In extreme cases, where some scale formation occurs in
inhibited waters, the scale is softer and bulkier and more easily sloughed off than scale formed in
uninhibited waters.
Surfaces treated with scale inhibitor, and then exposed to scale-forming water, have a delayed
tendency to scale. Supposedly, the inhibitor adsorbs on the solid surface and prevents adherence
of scale nuclei.
Scale inhibitors are also good deflocculants. In other words, they cause agglomerations of
crystals to disperse. Scale inhibitor molecules contain ionic groups. These ionic groups impart the
same electrical charge on solids to which they adsorb. The like charges repel one another,
causing the solids to disperse. Very large polymers of the same inhibitors can adsorb on more
than one particle, binding them together. The large, or high molecular weight polymers, are used
as flocculants to aid settling and filtration of solids.
In summation, threshold scale inhibitors are able to adsorb on solid surfaces. As a result of this
adsorption, they are able to prevent crystal growth, change crystal forms, decrease adherence,
and disperse crystals. The result of these effects is that these compounds prevent problems from
scale formation even when present in very low concentrations.
The organic phosphorous, or organophosphorus, scale inhibitors have almost entirely displaced
the inorganic phosphorous compounds from use in the oil field. Other organic compounds
including phosphoric acid esters, polyacrylates, and polyacrylamides are also widely used. The
main reasons for the shift to the organic compounds are that they are more stable and they can
be “tailored” to be very effective under extreme conditions.
60
One of the earliest organophosphorus scale inhibitors was aminotrimethylenephosphonate

(ATMP), which was marketed as Dequest 2000 by Monsanto Chemical Co. (Figure 4.1). The dry
pentasodium salt is called Dequest 2005DN and a 40% solution of the pentasodium salt is
Dequest 2006.
The acid form of ATMP is a strong acid. A 1% solution has a pH of less than 2. It must therefore
be handled in acid-resistant equipment. A 1% solution of the pentasodium salt solution has a pH
of 10 to 11 and is thus less hazardous to handle. The two forms are equal in all respects in their
scale-inhibiting properties when diluted in process water. Properties of the two products are given
in table 4.4.
Figure 4.1. Structure of ATMP and Its Pentasodium Salt
Table 4.4. Properties of Commercial ATMP
61
The compatibility of phosphoric acids and their sodium salts with a wide variety of solvents makes
them readily formulated for a variety of purposes. The phosphonic acids are available in a variety
of molecular weights and copolymers with carboxylic acids. An example of a compound having a
higher molecular weight than ATMP is ethylenediaminetetramethylenephosphonic acid (EDTMP)
shown in Figure 4.2. Any number of the group shown in brackets can be added.
Figure 4.2. Ethylenediaminetetramethylenephosphonic Acid (EDTMP)
Phosphonates resist hydrolysis much better than do the inorganic condensed phosphorous
compounds. ATMP is stable for 90 years in water at pH 7 and 185 °F. A comparison of the
stability of ATMP with sodium pyrophosphate is given in table 4.5.
Table 4.5. Hydrolysis of Dequest and Sodium Pyrophosphate at pH 7.0
The hydrolysis rate of organic phosphonates is constant over all pHs. The rate for condensed
phosphates increases as the pH decreases in water solutions. Organic phosphates rival the
phosphonates in scale-inhibiting properties but are less stable to hydrolysis. They are, however,
more stable than the inorganic phosphorous polymers. The phosphates cost less than
phosphonates and should be considered for applications where stability is not a problem.
Structures of some phosphate groups are given in Figure 4.3. Note that in a phosphate, the
phosphorous is connected to carbon through an oxygen atom while, in a phosphonate, the
phosphorous is connected directly to carbon.
62
Figure 4.3. Structures of Organic Phosphate Esters
Other modern scale-inhibiting chemicals are the polyacrylic acids and polyacrylamides (Figure
4.5). These compounds are effective scale inhibitors when having molecular weights less than
about 20,000. Compounds having molecular weights higher than 20,000 are good flocculants.
Figure 4.5. Structures of Some Scale-inhibiting Polyacrylates
Molecular weight is an important variable in the scale-inhibiting properties of an organic polymer.

For AMP, the monomer is the best inhibitor for BaSO4 and CaCO3 but the dimer is best for
gypsum (Table 4.6). Commercial formulations seldom consist of active ingredients having a
single molecular weight. Usually, a spectrum of molecular weights will be present.
Table 4.6. Effect of Molecular Weight on Scale Inhibition by AMP
63
The effective concentrations of inhibitor found in Figure 16 are for the given conditions only.
Generally, the amount of inhibitor required increases with the degree of supersaturation (Table
4.7), decreases at lower temperatures, and increases with pH (Table 4.8).
Table 4.7. Effect of Degree of Supersaturation of CaSO4 on the Concentration of AMP Required for Scale
Inhibition
Table 4.8. Effect of Temperature and pH on the Inhibition of CaSO4 and CaCO3 Precipitation by AMP
4.3.1 Threshold Inhibition

As stated earlier, threshold inhibition is effective scale inhibition at concentrations of inhibitor less
than the stoichiometric concentration required to complex the offending ions. In actual practice,
the effective concentration of a good scale inhibitor for a particular system is about 5 ppm, or
less. Systems with high pH, high suspended solids, high supersaturation, or high temperatures
might require a higher concentration of scale inhibitor. Generally. the addition
of higher-than-required concentrations of the organic phosphonates, acrylates, and acrylamides
are only wasteful and do no other harm. Table 4.9 is an example of overtreatment with partially
hydrolyzed polyacrylamide (PHPA). One hundred per cent inhibition of CaCO3 precipitation was
obtained from 5 to 20 ppm of PHPA. The excess of inhibitor over 5 ppm is wasted.
Excess concentrations of inorganic phosphorous compounds and organic phosphate esters can
be harmful if the compounds hydrolyze to form orthophosphate. High concentrations of
orthophosphate can precipitate Ca3(PO4)2, thus contributing to scale problems.
Proprietary scale inhibitor formulations usually contain about 20% by weight of the active scale-
inhibiting compound. Frequently, a recommended scale inhibitor dosage is given in terms of the
64
inhibitor as formulated. For example, a 5 ppm dose of inhibitor formulation would be only 1 ppm
of the inhibitor compound. If any confusion exists about the meaning of a recommended dosage,
you should clarify the units before proceeding with the treatment.
If you think the dose refers to pure compound when it actually refers to 20% formulated
compound, then you will overtreat by a factor of five. In the reverse situation, you would
undertreat by a factor of five.
Table 4.9. Inhibition of CaCO3 Precipitation by Partially Hydrolyzed Polyacrylamide
4.4 Laboratory Evaluation of Inhibitors

Scale inhibitor testing is imperative if a large-scale treatment program is anticipated. Cost
effective treatment, of course, is the major goal, but other considerations must be made also.
There are probably some 2000 scale inhibitor formulations on the market, many of which will not
be suitable for the particular system to be treated. Even though we have seen that organic
polymers of phosphonates, phosphates, and acrylates are good scale inhibitors, the purity,
formulation, and average molecular weight of the inhibitor will vary among suppliers.
Some of the factors that require testing for a particular system are listed in Figure 4.10.
Composition of the scale is important because some scale inhibitors are effective against some
scale compounds but are not effective against other scale compounds. Many chemical scale
inhibitors are effective when the degree of supersaturation is low but most are ineffective when
the degree of supersaturation is high. The temperature of the operating system must be
duplicated, if possible. All scale inhibitors have an upper temperature limit above which they are
not effective. The selected scale inhibitor must be compatible in not decreasing the function nor
causing precipitation of other chemicals in the system, such as corrosion inhibitors, biocides,
oxygen scavengers, or emulsion breakers. The scale inhibitor must form clear solutions with the
water in which it is to be used. Downstream effects, such as foaming and oil-water separation,
must not be aggravated by the scale inhibitor. Use of a particular scale inhibitor will require that
large quantities of the concentrated formulations be shipped and stored in bulk or drums. The
effects of local weather on the chemical should be determined to avoid freezing or overheating. A
frozen drum of chemical is useless until thawed. Formulations that contain volatile solvents have
been known to rupture drums when stored in intense sunlight. Finally, the only way to calculate
the cost for using a particular chemical is to determine the concentration at which it is effective.
Most of the tests required are self-explanatory. We will devote most of our time on tests to find
effective scale inhibitors and their effective concentration. These tests are continuously useful
because, even if an effective compound is found, new, more effective formulations might become
65
available. Occasional review of the scale inhibitor program and revision as necessary can result
in great savings in the chemical treatment program.
• Composition of the scale

• Degree of supersaturation
• Temperature
• Compatibility with other chemicals
• Compatibility with the water
• Downstream effects
• Weather
• Cost
Table 4.10. Factors to Consider in Selecting a Scale Inhibitor
There is no definitive simple test for finding an effective scale inhibitor. The test should simulate
the system with which we are concerned as closely as possible. The best test is in the system
itself, but inhibitors should be screened first in a rapid, inexpensive, simple test to select the best
chemicals for the purpose. Broadly, the tests we will consider are divided into static and dynamic
tests. The latter more closely simulate operating conditions but are more expensive and time-
consuming to run.
4.4.1 Precipitation Tests

The simplest scale test is to mix two incompatible waters containing scale inhibitor and measure
the amount of precipitate that forms. The effectiveness of the inhibitor can be expressed as the
per cent of precipitate that was prevented (in the next equation) or the per cent of scale forming
compound retained in solution.
In essence, a precipitation test consists of mixing two volumes of water, one of which contains the
cation and the other the anion of the scale compound. The mixture is capped and stored at
temperature for a predetermined period of time, usually 24 hours, after which the precipitate is
filtered out and weighed. A test is run without scale inhibitor to determine “S” for the equation in
Figure 21. For inhibitor tests, the inhibitor can be put in either water or both, whichever more
closely simulates the actual system. In testing for a squeeze job, the inhibitor would be put in both
waters.
E = [S - F] x 100 / S
where:
E = Inhibitor effectiveness, %
S = Weight of precipitate formed in absence of inhibitor
F = Weight of precipitate formed in presence of inhibitor
The volumes of water that are mixed should simulate those encountered in actual practice. Each
water should have a total dissolved solids content and pH approximating actual conditions.
Several difficulties might be encountered in designing a precipitation test for a particular purpose.
Ideally, we would use the actual waters that we want to inhibit, but this is not always possible. If
two waters are mixing downhole, we can obtain only a mixture of the waters. Also, produced
waters are seldom stable and reliable in behavior because of the presence of hydrocarbons,
66
reduced substances such as iron, unstable compounds, and dissolved gases. It is also likely that
two actual incompatible waters might not form a precipitate when mixed. This is particularly true if
the scale compound is one that readily
supersaturates, such as gypsum or strontium sulfate.
The most reliable and consistent data are obtained by using synthetic waters that simulate the
known compositions of the actual waters. Precipitation can be insured by adjusting the
supersaturation or by seeding the mixture of waters.
The offending ions can be incorporated in the test waters using the compounds listed in Table
4.11. When injected water is produced, a range of compositions and supersaturations are going
to be encountered in production because of the variable ratio of produced water to injected water
that is produced. In this case, it is best to run several tests covering the range of water
compositions that are expected to produce scaling conditions. Remember that precipitation can
be forced in the tests by adding more of the scaling compounds listed in Table 4.11.
Table 4.11. Compounds Added to Test Waters to Simulate Precipitates
For inhibitor additions to the test solutions, it is convenient to make a 1% (wt) stock solution of the
inhibitor. One ml of 1% solution contains 10 mg of inhibitor. So if you wanted to make 1 liter of
solution containing 5 ppm (5 mg/l) of inhibitor, you would add 0.5 ml of the stock solution.
Amounts of 1% stock solution to add for 50 ml of test solution are given below. Remember to add
enough inhibitor for the final volume of test solution. If two 25- ml volumes of water are to be
mixed for a test, then the final volume for which inhibitor concentration is calculated is 50 ml.
Table 4.12. Volume of 1% (Wt) Inhibitor Solution Required for Test Solutions.
67
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2.3.8 Strontium Sulfate Solubility Calculations ..................................................................... 36

Fundamentals of Chemistry and water Analysis

1.1 Elements and Compounds

1.1.1 Pure Substances, Compounds, Elements

Figure. 1.1.Schematic of a Simple Atom (Helium)

Table. 1.2. Properties of the Atom and its Fundamental Particles.

1.1.3 Atomic Number

1.1.4 Atomic Mass Number

1.1.5 Atomic Weight

Table 1.3. Symbols and atomic weight of selected elements.

Figure 1.2. Illustrates Hydrogen, Helium , and Magnesium atoms.

Figure. 1.2. Hydrogen, Helium , and Magnesium atoms.

1.1.6 Molecules and Molecular Weights

Table .1.4. Molecular weight calculation.

Figure.1.3. Periodic table.

1.1.7 The mole

Table. 1.5. Mass of one mole of atoms of some common elements.

Using carbon as an example:

1.1.8 Ions and Valence

Similarly for salts

1.1.10 Equivalent Weights

Equivalent weight = Atomic weight / Valence

The valence of an element is the charge it exhibits when it is ionized.

The equivalent weight of the compound is:

Equivalent weight = Molecular weight / Net positive valence

1.1.11 Using Equivalent weights

Similarly for ferric chloride:

Table. 1.5 .Equivalent weight of some elements and compounds.

Table. 1.6 .Equivalent weight of some elements and compounds.

Table. 1.7 .Equivalent weight of some elements and compounds.

2.2 Scale Types

Table. 2.1. Common oilfield scale.

2.2.1 Calcium Carbonate

Ca+2 + 2(HCO3-) → CaCO3 ↓ + CO2 + H2O Eq. 2.2

2.2.1.1 Effect of CO2 Partial Pressure

CO2 + H2O ↔ H2CO3 Eq. 2.3

H2CO3 ↔ H+ + HCO3- Eq. 2.4

HCO3- ↔ H+ + CO3-2 Eq. 2.5

Mole Fraction of CO2 in Gas = %CO2 in Gas /100 Eq. 2.7

Figure 2.1. Ionization of carbonic acid as a function of pH.

Figure 2.2 Effect of CO2 partial pressure on the pH value of water.

Figure 2.3. Effect of CO2 partial pressure on calcium carbonate solubility.

2.2.1.2 Effect of Total Pressure

2.2.1.3 Effect of Temperature

Figure 2.4 Calcium carbonate solubility.

2.2.1.4 Effect of Dissolved Salts

2.2.1.5 Summary of Factors affecting CaCO3 scale formation

• Increases with temperature

2.2.2 Calcium Sulfate

Ca+2 + SO4-2 → CaSO4 ↓

2.2.2.1 Forms of Calcium Sulfate

2.2.2.2 Effect of Temperature

Figure 2.5 Solubility of calcium sulfate in pure water.

2.2.2.3 Effect of Dissolved Salts

2.2.2.4 Effect of Pressure

Figure 2.6 Solubility of gypsum in NaCl brines.

2.2.3 Barium Sulfate

Scale Solubility (mg/L)

Figure 2.7. Effect of pressure and temperature on CaSO4 (anhydrite) solubility.