Journal of Petroleum Science and Engineering 171 (2018) 127–139

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Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol

Oilfield scale formation and chemical removal: A review T

a b c,∗ c
Muhammad Shahzad Kamal , Ibnelwaleed Hussein , Mohamed Mahmoud , Abdullah S. Sultan ,
Mohammed A.S. Saadd
a
Center of Integrative Petroleum Research, College of Petroleum Engineering & Geosciences, King Fahd University of Petroleum & Minerals, Dhahran, 31261, Saudi Arabia
b
Gas Processing Center, College of Engineering, Qatar University, PO Box 2713, Doha, Qatar
c
Petroleum Engineering Department, College of Petroleum Engineering & Geosciences, King Fahd University of Petroleum & Minerals, Dhahran, 31261, Saudi Arabia
d
Chemical Engineering Department, College of Engineering, Qatar University, PO Box 2713, Doha, Qatar

A R T I C LE I N FO A B S T R A C T

Keywords: In oil and gas industry operations, scale deposition on the surface and subsurface production equipment can
Scale Removal cause different problems such as formation damage, loss in production, pressure reductions, and premature
Chelating Agent failure of down hole equipment. Due to geochemical processes between injection water, connate water and rock,
Carbonate the complex composition of reservoir fluids make it difficult to control the inorganic scale formation. Carbonate
Sandstone
(calcium), sulfide (iron, zinc), and sulfate (calcium, barium, strontium) scales are more common in oilfield
Organic Acid
applications. The scale formation depends on several factors that include, but not limited to, temperature,
pressures, solution saturation and hydrodynamic behaviour of the flow. This paper reviews different types of
scales that are common in oil and gas production operations, their sources and formation mechanisms. The focus
of this review is on the different chemicals that are used for the removal of different scales. Hydrochloric acid is
one of the classical chemicals used since for most of the mineral scales are soluble in HCl. However, HCl is not
environmentally-friendly and causes corrosion and could be very expensive particularly in high-temperature
conditions due to the need of using many additives to reduce corrosion. This review discusses several alter-
natives to HCl that are more environment-friendly in removing oilfield scale deposits. These alternatives are
mainly organic acids and chelating agents which have been successfully applied in different fields.

1. Introduction
In the last few decades, several solutions have been proposed to
remove and mitigate formation damage to improve the productivity
and injectivity of oil and gas wells. Scales are one of the most severe
forms of formation damage; it can deposit scales in accessible and re-
latively less accessible areas. The scale is an accumulation of different
materials that can lead to clogging and prevent fluid flow in the well-
bore, production tubing, valve, casing, perforations and downhole
equipment (Crabtree et al., 1999). The scale problem can arise any-
where along water paths from surface equipment to the reservoir itself.
The scale deposit can take place in surface water injection facility, in-
jection wells, formation, production well, topside production facilities,
pipelines, and at disposal wells (Bader, 2007). Water is the major source
of all scales and when water is produced along with oil and gas, dif-
ferent types of scale are expected to form in the reservoir or in the
production tubing. The scale can deposit in the form of a thick layer in
the wellbore tubing that reduces the production diameter of the tubing,
which results in clogging and blocking of the flow (Fig. 1). This can
cause a severe increase in the pressure drop and this result in a decrease
in the productivity of the well. The production capacity can reach zero
within a few hours and could cause a huge treatment cost (Olajire,
2015). The precipitation of scale can also cause formation damage in
the reservoir, blockage of different pipelines, enhancing corrosion rate
and can pose a threat to safe production operations (El-Said et al.,
2009). In the case of water injection wells, the scale could deposit in the
formation of pores that can reduce the injectivity with time
(BinMerdhah et al., 2010). Scale deposited in the formation can reduce
the permeability and porosity of the formation. The variation in rock
permeability depends on injection rate and temperature (Haghtalab
et al., 2015; Moghadasi et al., 2004). Several types of scale deposition in
the well and surface facilities cause a decrease in production capacity
and injectivity.
Scale inhibitors (SIs) are a class of specialty chemicals that is used to
slow or prevent scale formation in water systems. There are different
types of scales and they are usually prevented by using scale inhibitors
(Bin Merdhah, 2010; Lu et al., 2010; Tung et al., 2004). In most of the
cases, scale dissolver are required to remove the scale, even after

∗
Corresponding author.
E-mail address: mmahmoud@kfupm.edu.sa (M. Mahmoud).

https://doi.org/10.1016/j.petrol.2018.07.037
Received 24 January 2018; Received in revised form 5 July 2018; Accepted 12 July 2018
Available online 19 July 2018
0920-4105/ © 2018 Elsevier B.V. All rights reserved.
M.S. Kamal et al. Journal of Petroleum Science and Engineering 171 (2018) 127–139

Fig. 1. Typical scale deposition in pipelines (Nasr-El-Din and Al-Humaidan, 2001).

utilizing scale inhibitors as a primary control method. There are dif- Table 1
ferent scenarios where scale inhibitors are not totally effective in scale Typical scale in carbonate and sandstone reservoirs.
prevention such as when scale formation is not predicted accurately in Carbonate Sandstones
advance and when placement of inhibitor is non-optimal owing to re-
servoir heterogeneity (Jordan et al., 2014). Once the scale deposition Scale Type wt% Scale Type wt%
takes place, it must be removed using scale dissolver.
Iron sulfide 29.2 Calcium Carbonate 33.5
Scale deposition in downhole surfaces is initiated due to formation Iron Oxide 28.1 Iron Oxide 30.3
of local brine in the environment and the low solubility of some of the Silicon Oxide 10.4 Silicon Oxide 28.5
inorganic salts that are produced. There are 3 mechanisms that led to Iron Hydroxide 9.0 Iron Sulfide 1.7
the formation of scale deposits both in offshore and onshore. It can be Iron Carbonate 5.5 Iron Carbonate 2.5
Dolomite 4.6 Barium Sulfate 1.1
due to; 1) mixing of two incompatible brines, 2) change in conditions
Calcium Carbonate 3.8 Magnesium Oxide 0.6
(temperature and pressure), and 3) brine evaporation (BinMerdhah Calcium Sulfate 3.6 Aluminum Oxide 0.6
et al., 2010). In oilfield applications, water is of great importance since Chlorite 2.2 Strontium Oxide 0.5
scale will only occur if water is produced. All types of natural waters are Sodium Chloride 1.4 Aluminum Silicate 0.4
rich in ions due to the dissolution of different mineral components. The Barium Sulfate 1.3 Chromium Oxide 0.2
Aluminum Silicate 0.9 Others 0.1
formation contains significant amounts of Ca2+, Mg2+, Sr2+, and Ba2+ Molybdenum oxide 0.2
with total dissolved solids approaching 400,000 mg/L. The scale de-
posit usually starts when two or more incompatible water mix with
each other (Olajire, 2015). The water systems are called incompatible reactivity in acid media and chemical dissolvers. Additionally, the co-
when they interact with each other chemically and precipitate the deposition of mixed scales in the well is also common, where an in-
minerals when mixed. Seawater (if it contains a high concentration of soluble mineral covers a soluble mineral. Another issue in chemical
sulfate ions and low concentration of barium and calcium ions) and scale removal is the precipitation of reaction byproducts following scale
formation water (if it contains a low concentration of sulfate ions and dissolution. This is more common at high pressure and high-tempera-
high concentration of calcium and barium) are typical examples of in- ture conditions where dissolution and precipitation kinetics are com-
compatible brines (BinMerdhah et al., 2010). The mixing of two such petitive.
water can lead to precipitation of barium sulfate and calcium sulfate. Antony et al. reviewed the scale properties and mechanism of scale
Other brine incompatibilities could result in depositing sulfide scales formation during reverse osmosis in water desalination and wastewater
where hydrogen sulfide can react with iron, zinc, and lead. In water treatment (Antony et al., 2011). Li et al. (2017) reviewed the scale
injection wells, the solubility of some salts in saturated injected water formation and control strategy using scale inhibitors (Li et al., 2017).
can reduce as it travels to high-temperature zone. This could also result Kelland (2014) also reviewed several scale inhibitors for oil and gas
in deposition of scale along the well stings. Similarly, a decrease in wells (Kelland, 2014). Scale inhibitors are applied to prevent scale
pressure can lower the solubility of various minerals in the water. For formation, while scale remover (dissolver) is used to dissolve the scale.
every 7000 psi decrease in pressure, the solubility of minerals can de- If the scale problems still arise even after utilizing scale inhibitors as a
crease by a factor of two (Crabtree et al., 1999). The solubility of some primary control method, scale dissolver (remover) is used to remove the
minerals such as carbonates changes with the presence of acid gases, scale. This review discusses the different types of scale dissolvers.
such as CO2 and H2S. Olajire (2015) reviewed the oilfield scale management technology
The scale deposition depends on several factors such as tempera- (Olajire, 2015). The review mainly discusses the thermodynamic and
ture, pressure, chemical reaction equilibria, pH, contact time, eva- kinetic prediction of mineral scale formation. Various chemicals that
poration, and ionic strength (Yap et al., 2010). The scale deposits can be are applied as scale inhibitors in oil and gas industry are discussed in
as a single mineral phase, but usually, scales are composed of the that review. Crabtree et al. (1999) reviewed the physical causes of scale
combination of different elements. Several organic compounds such as formation during production operations (Crabtree et al., 1999). Some
naphthenic acids and their salts, aromatic compounds, sulfur-con- inhibitor systems that are used to prevent the formation of scale are also
taining compounds, resins, paraffin and unsaturated hydrocarbons can mentioned. Although the methods of scale removal by mechanical and
also affect the formation of scale in downhole conditions (Lakshmi chemical methods are compared, the chemicals used have not been
et al., 2013). The most common types of scales encountered in oil and discussed in detail. In addition, there are many recent advancements in
gas production include sulfates (Ba, Sr, Ca), oxides/hydroxides (Fe, oilfield scale removal. This review focuses on different chemicals that
Mg), carbonates (Ca, Mg, Fe), and sulfides (Fe) (Li et al., 2009; are used in oilfield applications for the removal of different types of
Senthilmurugan et al., 2011). The typical scale compositions in sand- scale. The current review has highlighted the conditions for the for-
stone and carbonate reservoirs are given in Table 1. mation of the most common oilfield scales and identified several types
The selection of an appropriate chemical formulation to dissolve of chemicals that are used for the scale removal. In addition, new green
and remove scale is a challenging task due to the diversity of the scale materials that are recently introduced are also reviewed. Future per-
minerals in a single well. The different types of scales have varying spectives of oilfield scales are also discussed.

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M.S. Kamal et al. Journal of Petroleum Science and Engineering 171 (2018) 127–139

Table 2 2.1. Sulfide scales

Different types of scales.
Sulfides 2.1.1. Iron sulfide
Iron sulfide scale is one of the major scales formed particularly in
Pyrrhotite Fe7S8 sour oil and gas wells. Physically, it can vary from viscous fluid to dry
Troilite FeS
black powder. The scale characteristics are usually a function of pH,
Mackinawite Fe9S8
Pyrite FeS2
temperature, scale age, and pressure. Formation of iron sulfide scale
Marcasite FeS2 takes place due to the reaction between hydrogen sulfide and iron.
Greigite Fe3S4 Hydrogen sulfide gas can react with ferric ions and cause iron sulfide
Sphalerite ZnS precipitation. There are various sources of delivery of hydrogen sulfide
galena PbS
and iron in the wells. Hydrogen sulfide can be produced as a free gas in
Carbonates sour wells. The other sources of hydrogen sulfide include, but not
limited to, degradation of drilling mud additives, reduction of sulfate
Calcite CaCO3 ion, thermal degradation of organic sulfur-containing compounds, acid
Vaterite CaCO3
treatment of sour wells, and sulfate-reducing bacteria (SRB) (Chen and
Aragonite CaCO3
Siderite FeCO3 Huang, 1986; Seto and Beliveau, 2000; Singh et al., 1989). Thermal
Dolomite CaMg(CO3)2 degradation of sulfate containing minerals can also generate H2S.
Aragonite CaCO3 The sources of iron are many such as tubular, minerals, clays,
propping agents, formation brine and several other fluids lost during
Sulfates
drilling and completion operations. The main source of iron can be
gypsum CaSO4.2H2O leaching of iron from minerals present in the formation or corrosion
Anhydrate CaSO4 products. During acidizing operation, acid can be contaminated with
Barite BaSO4 iron at any stage starting from the surface tank to well tubulars. This
Hemihydrate CaSO4.5H2O
contamination can lead to deposition of iron in the formation or in the
Celestite SrSO4
wellbore. Acids easily dissolve the rust of the storage tanks (Hall and
Iron scales Dill, 1988). Later, during the acid injection process, acids can also
dissolve corrosion and mill scale products. Iron containing minerals in
Ferrous Hydroxide Fe(OH)2 the formation are another common source of iron in the formation.
Ferrous Hydroxide Fe(OH)3
Hematite Fe2O3
Hematite is a sedimentary mineral and common in sandstone re-
Magnetite Fe3O4 servoirs. Some sandstone contains up to 2 wt% hematite (Ma et al.,
Akaganeite α-FeOOH 2016). The proppant was introduced during hydraulic fracturing pro-
Goethite β-FeOOH cesses and it can also be an additional source of iron in the well. Iron
Lepidocrocite γ-FeOOH
sulfides having iron as a major component are soluble in acids, how-
Hibbingite Fe2(OH)3Cl
ever, if the sulfur ratio is higher it becomes insoluble in inorganic acids
Miscellaneous (Nasr-El-Din et al., 2001a).
Depending upon formation mineralogy, pressure, temperature,
Brucite Mg(OH)2 brine, pH, and time of exposure, there are various forms of iron sulfide
Periclase MgO
Nickel Ferrite NiFe2O4
scales based on the iron to sulfur ratio. Iron sulfide scale can be either in
mono-sulfide phases such as pyrrhotite, troilite, and mackinawite or
disulfide phase such as pyrite and marcasite (Chen et al., 2016). The
2. Scale types and methods of formation iron sulfide scales can be in a soft form such as pyrrhotite or in a hard
form such as pyrite. In the same well, several types of iron sulfide scales
Scale formation differs significantly from one well to another, but it could exist. Hard scales are usually present in the shallower depth. At
can also vary along the depth of the same well. Oilfield scales can be higher temperature, the iron sulfide scale predominantly consists of
classified in different ways; however, the most common scales include, troilite and/or pyrrhotite (Hafiz et al., 2017).
but not limited to, sulfides (mainly iron sulfides), oxides (mainly iron Iron sulfide scale causes many operational problems in oil and gas
oxides), sulfate, and carbonate scales. A relatively unusual scale zinc industry. They are present in all types of well such as producer, injector,
sulfide has been reported (Berry et al., 2012). Table 2 describes the disposal, and supply wells due to the presence of iron and H2S
important and common oilfield scales. The tendency for scaling of some (Elkatatny, 2017). Iron sulfide scale can be accumulated near wellbore
scales, such as calcium sulfate and barite, is independent of brine pH. and can alter the performance of supply wells, injectors, and gas wells
However, the scaling tendency of the majority of scales such as iron (Cusack et al., 1987; Patton, 1993; Walker et al., 1991). It can also
sulfides and carbonates depends on brine pH. It is worthy to mention affect the performance of downhole tools such as production logging
that iron is the most effective ion, which is responsible for balancing the tool. The increased in corrosion rate due to iron sulfide scale poses a
negative charge of the Mg-OH and Si-OH hydroxyl group surfaces. threat to the safe operation of the pipeline valving system. It also causes
Therefore, increasing the pH will cause what is called the ion shielding the precipitation of asphaltene near wellbore area and reduces the ef-
on the edges of Mg-OH and Si-OH hydroxyl group surfaces and the fective permeability of oil flow. Iron sulfide accumulation in the for-
negative value will increase as pH increases (Jones, 1981; Tan et al., mation can also change the wettability of the rock from water-wet with
2013). Most of the scales are either water soluble or acid soluble. oil-wet (Elkatatny, 2017). In production tubing, the formation of iron
However, some scales are neither soluble in water nor in acids. Sodium sulfide scale in the form of thick lining can block the flow. It also causes
chloride is a typical example of water-soluble scale. Calcium carbonate, damage to various wellbore equipment such as heat exchangers, tur-
iron sulfide, and iron oxide are acid soluble scales. bines, production tubing, pipes, pumps, and valves. If not properly
handled, the iron sulfide scale could result in shutting down the well-
bore.
Iron sulfide scale can be coated with oil that results as a diffusion
barrier in the reaction of the acid with scale. To mitigate this type of
scenarios, formulations also contain some surfactants that enhance the

129
M.S. Kamal et al.
Fig. 2. Solubility of different sulfide scales in 1M NaCl at 25 °C (Collins and
Jordan, 2003).
contact between scale and treatment chemical. A long exposure of iron
sulfide scale to H2S will result in scale rich in sulfur that will be difficult
to remove. In addition, other corrosion products can reduce the solu-
bility of iron sulfide scale in non-acidic chemicals. Iron sulfide scales
change the surface charge to more positive making the rock more oil-
wet and alter the relative permeability and reduce productivity. In
sandstone rocks containing iron minerals, the removal of these scales
from the reservoir rock has been reported to enhance oil recovery by
more than 20% (Mahmoud, 2018; Mahmoud et al., 2017b; Mahmoud
and Abdelgawad, 2015).
2.1.2. Other sulfide scales
Some other uncommon sulfide scales, such as zinc and lead sulfides,
are also reported in the literature (Al-Harbi et al., 2017; Berry et al.,
2012). Lead and zinc sulfide scales are deposited in the upper part of
the well, produced water control valve, and in subsurface safety control
valves. These scales were mainly found in the wells located in the Gulf
of Mexico and North Sea (Baraka-Lokmane et al., 2015, 2016; Lopez
et al., 2005). The solubilities of zinc and lead sulfides are much lower
compared to the solubility of iron sulfide in water. Fig. 2 shows the
solubility of three sulfide scales in 1M NaCl at different pH values. At all
pH, the solubility of the iron sulfide is the highest followed by the so-
lubility of zinc and lead sulfides. The solubility of lead and zinc sulfides
increase with an increase in temperature and salinity (Barrett and
Anderson, 1988). This indicates that during the production stage,
cooling of brine could lead to deposition of zinc and lead sulfide scales.
Wurtzite, a form of zinc sulfide scale, was found in a well in the Gulf
of Mexico (Berry et al., 2012). Deposition of zinc sulfide scale takes
place in several ways. The main source of zinc sulfide was believed to
be the formation of brine and different completion fluids. The zinc ions
come from the partial dissolution of formation mineral, such as spha-
lerite (ZnS), in the formation/injected brine. The concentration of zinc
ion in Gulf of Mexico fields is reported to be as high as 245 ppm. Zinc
bromide used in completion fluid as weighting material can also be a
source of zinc. These completion fluids are used for hydrostatic pressure
control. Any fluid loss to the formation during completion operations
can lead to the introduction of zinc ions in the formation. The reaction
of zinc with hydrogen sulfide results in deposition of zinc sulfide scale
in the well. It was reported that in the presence of 2 ppm hydrogen
sulfide a loss of 500 bbl (with a concentration of 17.2 lb/gal) zinc
bromide within the reservoir can deposit a significant zinc sulfide scale
(Biggs et al., 1992).
A similar scale deposition of zinc sulfide has been reported in a field
of North Sea. Hydrogen sulfide gas is the most common source of sul-
fide ion in the downhole environment. The very small concentration of
H2S can cause a significant scale deposition in the presence of zinc ions.
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Journal of Petroleum Science and Engineering 171 (2018) 127–139
Fig. 3. Solubility of sulfate scale (Li et al., 1995).
Degradation of different drilling fluids and corrosion inhibitors can
produce sulfide ions. However, degradation of drilling fluids is not
enough to deposit a significant zinc sulfide scale during several years of
production. Zinc sulfide is primarily affecting the performance of top-
side equipment such as hydrocyclones and low-pressure separators
(Collins and Jordan, 2003). On the other hand, the major source of lead
sulfide scale is the partial dissolution of formation mineral such as
galena (PbS). The concentration of lead ions in Gulf of Mexico field is
around 70 ppm (Collins and Jordan, 2003).
2.2. Sulfate scales
Sulfate scales are common in the applications related to seawater
injection. Sulfate scales are considered one of the hardest forms of scale
having the lowest solubility in acids and are difficult to remove. Sulfate
scales are deposited due to combining of two different waters (one
contains sulfate ion and another with barium, strontium or calcium)
(Chilingar et al., 2013). Fig. 3 shows the solubility product constant
(Ksp) for different sulfate scales. The solubility product constant is an
equilibrium product constant of a solid dissolving in an aqueous solu-
tion. The higher the Ksp values, the higher the solubility of liquid in that
solution. Among sulfate scale, gypsum has the highest solubility pro-
duct constant at all temperatures where barium sulfate has the lowest
Ksp.
2.2.1. Barium sulfate
Barium sulfate scale has a solubility of 2.3 mg/L of water and a
solubility product (Ksp)of 10−9.99 at 25 °C (Kuwahara, 2011; Morris and
Paul, 1990). At the same temperature, the solubility of gypsum is
2080 mg/L (Nasr-El-Din et al., 2004). The barium sulfate scale can form
from two main sources. The first source is the injection of seawater into
the zone where there is an abundance of barium ions causing barium
sulfate scale deposition. This scale deposition takes place due to the
incompatibility of seawater (rich in sulfate ions) and connate water
(rich in barium ions). Drilling operations could also result in deposition
of barium sulfate scale in the production tubing and in the formation.
Barium sulfate is a common weighting material that is used in well
drilling operations. During the drilling operation, some of the barium
sulfates will invade the formation and deposits barite scale in the for-
mation resulting in a reduction in the permeability of the rock (Bageri
et al., 2017).
The BaSO4 scale formation during injection of seawater and for-
mation water in sandstone core is shown in Fig. 4 using SEM micro-
graph. Most of the scaling deposition took place in the front sections of
the cores. It is likely that most of the scaling ions deposited within the
front section of the cores immediately after flooding leaving behind
M.S. Kamal et al.
Fig. 4. SEM images of a sandstone core (a) unscaled core (b) Containing BaSO4
Scale (BinMerdhah et al., 2010).
only a few ions to precipitate in the rear section of the core. During the
production operations, these barite scale particles are produced with oil
and form a scale around the production tubing, casing, and valves.
2.2.2. Strontium sulfate
Strontium sulfate is common with different oil production facilities.
The main reason for strontium sulfate scale formation is the super-
saturation of water containing strontium sulfate (Amiri et al., 2014).
2.2.3. Calcium sulfate
Calcium sulfate has been reported as one of the major scales that can
cause significant problems in producer and injector wells (Al-Khaldi
et al., 2011). Calcium sulfate scale can also be deposited in the reservoir
and can alter the permeability and porosity of the reservoir (Mahmoud,
2014b). Calcium sulfate scale mainly deposits around the electrical
submersible pump in the reservoir (Oddo et al., 1991). The precipita-
tion of CaSO4 is complicated as it has three crystal forms known as
gypsum, hemihydrate, and anhydrite. Gypsum is usually formed at low
temperatures (< 50 °C) while anhydrate typically deposits at high-
temperature conditions. The solubility of calcium sulfate increases with
temperature up to 40 °C (Moghadasi et al., 2007). Further increase in
the temperature reduces the solubility of CaSO4. The prediction of the
exact form of calcium sulfate scale at a given condition is difficult.
However, above 40 °C, the relative solubility of anhydrite is low com-
pared to gypsum. Therefore, at high reservoir temperature anhydrite is
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Journal of Petroleum Science and Engineering 171 (2018) 127–139
Fig. 5. Solubility of carbonate scale (Li et al., 1995).
the predominant form of CaSO4 scale. The solution pH and pressure also
affect the solubility of gypsum in water. Usually, calcium sulfate is less
soluble in high pH solution and low pressures (Carlberg, 1973; Delorey
et al., 1996). The ionic strength can also affect the solubility of CaSO4.
The maximum solubility of CaSO4 is determined by the ionic strength of
the solution. Calcium sulfate scale could be a result of acid stimulation,
water injection, and/or combined hydrocarbon/water production.
However, the main reason of CaSO4 scale is also the chemically in-
compatible water.
2.3. Carbonate scales
The solubility product constant of different carbonate scales is
shown in Fig. 5. Magnesium carbonate has the highest solubility con-
stant at low temperatures, while strontium carbonate has the lowest.
Calcium carbonate scale is the most common among carbonate scales
and is the most widespread in topside production facilities and upper
part of the production tubing (Lakshmi et al., 2013). Calcite is the most
stable form of CaCO3 scale at reservoir conditions. Therefore, calcite is
more common compared to other calcium carbonate scales such as
aragonite and vaterite. The carbonate scale formation is a direct func-
tion of pH, temperature, calcium ion concentration, bicarbonate con-
centration, and ionic strength. The chemical equilibrium between ions
and CO2 in the water determines the calcium carbonate scale deposi-
tion. The calcium carbonate scale deposition can take place through a
combination of calcium and bicarbonate ions. The deposition of CaCO3
scale increases with increasing temperature, the pH, and lowering the
pressure (Hamid et al., 2016; Ramstad et al., 2005). Other than calcium
carbonate, iron carbonate scales have also been reported in the dif-
ferent downhole equipment (Amiri et al., 2013). The main source of
siderite (iron carbonate) scale is also the change in pressure and tem-
perature conditions that leads towards the loss of dissolved CO2. As a
result of this loss, pH of the system increases and solubility of these
minerals decreases in the flowing fluid (Jordan et al., 2014).
Other scale types also exist in the oilfield, but they are not common
such as phosphate scale, silicates scales, and elemental sulphur.
Calcium phosphate scale is very common in water treatment plants and
in cooling water systems. In cooling water, due to the extensive use of
water, the orthophosphate concentration increases. In addition, con-
tamination of water with fertilizers based on phosphates leads to the
formation of calcium phosphate that is insoluble in water (Pierce and
Grattan, 1989). Phosphate scales are not common in the oilfield.
One of the major scales that are commonly found during steam
injection operations are the silicates. In some fields, produced water
that contains lithium is used in the steam operation. During steam,
injection lithium reacts with the silicates and forms lithium silicate
scale. This shows the importance of treating produced water to avoid
M.S. Kamal et al.
scale formation (Zalewski and Bulkowski, 1998). Iron silicate scale was
observed in downstream operations of steam injected reservoirs in a
siliceous reservoir. This type of scale causes corrosion and plugging of
the surface facilities (Daniels et al., 1997). Wang and Wei (2016) re-
ported the formation of silicate scale in steam generator tubing and
calcite was found to be more dominant compared to silicate scales.
Silicate scales can be formed as well during alkaline injection or in
alkaline/surfactant/polymer flooding (Wang and Wei, 2016). Sodium
hydroxide is usually used during water flooding or enhanced oil re-
covery operations to minimize surfactant adsorption. Sodium hydroxide
reacts with quartz to produce silicate scales that are insoluble in water.
Sodium hydroxide dissolves silica first before it precipitates (Basbar
et al., 2013).
Elemental sulphur is present as dissolved species in virtually all
deep sour gas reservoirs. Sulphur precipitation is induced by a reduc-
tion in the solubility of sulphur in the gas phase beyond its thermo-
dynamic saturation point because of the decrease in pressure and
temperature. The change in pressure and temperature occurs during
production operations and can result in sulphur deposition in the re-
servoir wellbore and surface facilities (Hands et al., 2002; Shedid and
Zekri, 2006). The solution to this problem is to control the gas pro-
duction rate that will maintain the sulphur solubility in the gas and
prevents its precipitation (Mahmoud, 2014a).
3. Scale removal chemicals
Both chemical and mechanical methods are used in removing the
scale of oil and gas wells. Scale removal techniques should be eco-
nomical, fast, non-damaging to the wellbore tubing and formation, and
must be able to prevent the precipitation. The strength of the scale and
texture play an important role in the selection of the appropriate re-
moval technique. Mechanical methods have been used frequently to
remove different types of scale deposition. By mechanical means, the
easily accessible scale is milled and removed. This also depends on the
location and nature of the scale. Mechanical methods are only applic-
able if the scale is present in the wellbore and can be easily milled out.
The mechanical methods to remove the scale are expensive due to the
complications that is associated with drilling processes. Mechanical
methods are even not applicable if the scale is present in the formation.
Due to the complexities associated with mechanical methods, the de-
scaling job is preferably carried out using chemical methods.
The chemical methods are more cost-effective in removing different
types of scales and can be used for descaling job in both wellbore and
formation. In chemical methods, several inorganic and organic chemi-
cals are used to remove the scale. The best scale removal chemical can
be selected by knowing the exact composition of the scale, and its
physical/chemical properties. The effective composition of the scale
dissolver in one well might not be effective in other wells due to the
different nature of the scales. Poor selection of chemicals can even
speed up the recurrence of scale. The scale removal efficiency using
chemical methods mainly depends on the accessibility of scale to the
chemicals. Surface area to volume ratio is the critical parameter in ef-
ficiently and cost-effectively in removing scale. Scales having the large
surface area, high porosity, and with hair-like projection have a very
high removal rate since chemicals could have large access to the scale
particles.
Formation permeability can also affect the placement of scale dis-
solvers in the zone affected by the scale since high permeability zone
can divert the scale removal chemicals to another way. Some gelling
materials like viscoelastic surfactant are needed to improve the place-
ment of scale dissolver in the targeted zones. In most of the cases, scales
are usually coated with a hydrocarbon that is hindering the contact of
acid with scales. In such cases, acid-to-scale contact can be improved by
using certain types of surfactants. The selection of surfactant is critical
as it might generate acid-crude oil emulsion.
HCl is the most commonly used acid to remove the scale from oil
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Journal of Petroleum Science and Engineering 171 (2018) 127–139
wells. However, owing to its environmental effect and difficulties in
handling, several other chemicals have been used in laboratory and
field scale. This section highlights several chemicals that have been
used for scale removal. An ideal scale dissolver should be thermally
stable at downhole temperature, have high dissolving capacity, must be
less corrosive, and should not generate free H2S gas after dissolution
(Chen et al., 2016). The scale dissolution performance of different scale
dissolvers is discussed below.
3.1. Hydrochloric acid
Hydrochloric acid is being used in descaling job in the field and
considered as one of the most powerful scale removers since most of the
scale minerals have high acid solubility (Al Tolaihy et al., 2010). The
use of HCl can be very expensive at high-temperature conditions where
additional additives are required to control the reaction rate (Olajire,
2015). Few iron sulfide scales such as troilite and pyrrhotite dissolve in
HCl, while pyrite and marcasite is difficult to dissolve in HCl (Wang
et al., 2013b). Zinc sulfide also dissolves in HCl, however, better per-
formance was achieved using different additives (Berry et al., 2012).
Some oxidizing agents such as H2O2 are required to increase the solu-
bility of zinc sulfide in HCl. Carbonate scales have a very high solubility
in HCl and can effectively be removed using HCl. However, the spent
acid solution containing scale by-products also acts as an initiator for
reformation of scales. Sulfate scales such as barium, calcium, and
strontium sulfates have very low acid solubility. At 25 °C and ambient
pressure, the solubility of calcium sulfate in HCl is only 1.8 wt%
(Moghadasi et al., 2007). The use of some convertor such as Na2CO3
and NaOH can convert gypsum to acid-soluble compounds that can be
removed using an acid. The solubility of calcium sulfate in HCl is below
2% at ambient conditions (Olajire, 2015). Some convertors such as
NaOH, Na2CO3, and KOH are also used to convert several acid insoluble
scales into acid soluble scales.
The generation of H2S and corrosion of production string are major
barriers to the application of HCl. Hydrochloric acid is very corrosive to
steel, particularly at high temperatures. Acid corrosion inhibitors tend
to adsorb on the scale surface that can result in higher metal loss and
reduces the access of acid to the scale (Wang et al., 2013a). The ad-
sorbed inhibitor can also block the pore space and could result in re-
ducing the relative permeability of oil and gas (Crowe and Minor,
1985). The generation of H2S gas by the reaction of HCl and iron sulfide
scale could be a serious issue for well integrity and may cause addi-
tional operational risks (Chen et al., 2009). Hydrogen sulfide sca-
vengers must be added to control the free H2S generated during the
descaling job using acids. The H2S scavengers also hinder the HCl dis-
solution reaction in a similar way as corrosion inhibitors do. The HCl
dissolution capabilities can reduce up to 50% using 5% aldehyde-based
H2S scavengers (Wang et al., 2013a).
The acid loss to formation can cause severe damage to formation
rocks as well. The acid can react with the carbonate formation and
cause an increase in the pH. The iron sulfide scale precipitate once the
pH increases above 1.9 (Wang et al., 2013a). These precipitates can also
clog the near-wellbore area and lower the productivity of the well.
There are some sludging tendencies when the spent acid contacts with
the crude oil (Huang et al., 2002). Therefore, the focus has shifted to
use non-acidic treatments in scale removal. HCl can only dissolve spe-
cific types of scale and is ineffective for other types of scales. For ex-
ample, it can dissolve and remove FeS from the well but unable to
completely dissolve and remove FeS2 (Elkatatny, 2017; Wang et al.,
2015). Owing to the toxicity of H2S and corrosion of production string,
the focus has been shifted to find alternative chemical solutions to re-
move the iron sulfide scale, particularly at high temperatures.
3.2. Organic acids
Different organic acids such as acetic acid, formic acid, maleic acid
M.S. Kamal et al.
Table 3
Chemical structure of some organic acids reported in scale re-
moval application.
Maleic Acid
Formic Acid
Acetic Acid
Glutamic Acid
Succinic Acid
Citric Acid
and citric acid have also been proposed as alternatives to HCl for high
pressure high temperature (HPHT) reservoirs (Da Motta et al., 1998;
Nasr-El-Din et al., 2001b; Smith et al., 2000; Van Domelen and Jennings
Jr, 1995). The majority of the organic acids have very low dissociation
constants compared to HCl (Metcalf et al., 2004). They are an attractive
choice for scale removal owing to lower corrosion rates and long re-
action time. However, organic acids are more expensive than HCl and
their performance in dissolving scale particularly carbonate is not as
effective as HCl (Da Motta et al., 1998). The chemical structure of some
organic acids used for scale removal is shown in Table 3.
Acetic and formic acids are weak acids and they are weakly ionized.
Commercially acetic acids are available up to 100%, however, for field
applications they are normally diluted to 15% (Van Domelen and
Jennings Jr, 1995). At concentrations above 15%, one of the reaction
products (calcium acetate) can precipitate owing to its limited solubi-
lity. The concentration of formic acid is also kept below 15% due to the
limited solubility of calcium formate (Van Domelen and Jennings Jr,
1995). The dissolving capabilities of organic acids are much lower
compared to HCl. The calcium carbonate dissolving capacities of formic
acid and acetic acids are 76% and 58% of the dissolving capacity of
HCl, respectively. The mixture of acetic and formic acids is a viable
option for HPHT wells made of high-alloy steel. A mixture of acetic acid
(5 wt%) and formic acid (7 wt %) is 4 times more efficient compared to
10 wt% acetic acid alone in dissolving calcite scale. Citric acid has been
used in oil field applications specifically as an iron control agent (Hall
and Dill, 1988). Chemically, it has three carboxylic and one hydroxyl
group. The major issue with citric acid is the low solubility of calcium
citrate (0.0018 mol/1000g water) which further decreases with the
increase in temperature (Li et al., 2008). Other organic acids include
maleic acid (dicarboxylic acid and a cis-isomer of butenedioic acid),
glutamic acid (an α-amino acid that contains α-amino and α -carboxylic
acid), succinic acid (dicarboxylic acid also termed as butanedioic acid)
and gluconic acid.
Mixtures of organic acid and mineral acid can have a synergetic
effect in addition to lowering the amount of mineral acid for specific
applications. The mixtures of organic and mineral acids are econom-
ically much better than the HCl-based system. Several types of research
report the use of a mixture of HCl and an organic acid to dissolve scales,
particularly at high temperature to balance the limitations of each class.
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Journal of Petroleum Science and Engineering 171 (2018) 127–139
The organic-inorganic acid mixture is effective for high-temperature
carbonate formation. However, organic acids are not effective in re-
moving several types of iron sulfide scale at different temperatures and
pH conditions.
3.3. Chelating agents
Chelating agents are the molecules that contain electron-donating
group to form a coordination bond with metal ions. Deprotonated
chelating agents are negatively charged molecules that can sequester
metal ions through coordination bond and the process is called chela-
tion. Because of sequestration, stable ring-like structures are formed
that surround the metal ions by capturing all coordination sites of metal
ions and minimizing its interaction with other ions in the solution. The
properties of metal ions and chelating agent determine the stability of
the metal-ligand complex. The affinity of chelating agent for metal is
characterized by its stability constant (a higher stability constant in-
dicates a more stable chelated product). The stability constant depends
on several factors such as the size of the ring, a number of rings, pH of
the chelating agent, and nature of the donor and the central metal atom
(Tariq et al., 2017). Most of the chelating agents sequester ions are
efficient in basic solution. In acidic form, they could not sequester ef-
fectively due to the occupation of hydrogen ions by coordinating
functional group (Fredd and Fogler, 1998). As pH increases, the de-
protonation results in maximum chelating ability. However, at high pH,
the OH− can also occupy the coordination sites and reduce the chela-
tion ability.
Biodegradability of chelating agents is an important consideration
in selecting the chelating agent for a specific application. The chelating
agent can remobilize heavy metal from sediments to drinking and
groundwater (Nowack, 2002; Sillanpää and Kurniawan, 2011). The
biodegradability of chelating agents is related to the number of nitrogen
atom present in the molecule. The chelating agents containing single
nitrogen atom are readily biodegradable. The chelating agents con-
taining more than two nitrogen atoms have poor biodegradability
(Sýkora et al., 2001). The substituent also affects the biodegradability
of chelating agents and increases in the order ‒COCH3, ‒CH3, ‒C2H5,
‒CH2CH2OH, ‒CH2COOH (Sýkora et al., 2001).
Chelating agents are an attractive alternative to organic and in-
organic acids for removal of scale from formations. Chelating agents are
more environmentally friendly, readily biodegradable and less corro-
sive to well tubular and other downhole equipment. The main ad-
vantage of chelating agent is their very low corrosion rate compared to
HCl. Owing to low corrosion, a lesser quantity of corrosion inhibitors is
required. Due to their environmentally friendly nature, chelating agents
are the preferred choice to remove scale from sensitive downhole
equipment such as an electrical submersible pump (Bageri et al., 2017).
However, the cost of the chelating agent itself is higher compared to
inorganic acids. The first successful barium sulfate removal job using a
chelating agent is tested in North Alwin region of North Sea (de Vries
and Arnaud, 1993).
Most of the chelating agents used in the oil industry are aminopo-
lycarboxylic acids. In this group of chelating agents, nitrogen is located
at the center of the molecules and carboxylic acid groups behave as the
arms of the chelating agent. Chelating agents showed superior prop-
erties over several organic and inorganic acids. They have the good
dissolving power, low corrosion, better iron control, low sludging ten-
dencies and are they more environmentally friendly (Almubarak et al.,
2017a). The common chelating agents that have been utilized include
but not limited to ethylenediamine tetraacetic acid (EDTA), hydro-
xyethyl ethylene diamine tetraacetic acid (HEDTA), hydroxyethyl imi-
nodiacetic acid (HIDA), L-Glutamic acid N,N-diacetic acid (GLDA),
Diethylene triamine pentaacetic acid (DTPA), Nitrilotriacetic acid
(NTA), and Methylglycinediacetic acid (MGDA). The structures of these
chelating agents are shown in Table 4.
Chelating agents form stable chelates with alkaline earth metal
M.S. Kamal et al.
Table 4
Chemical structure of common chelating agents used in scale removal appli-
cations.
Chelating Agent Common Structure
Abbreviation
Ethylene diamine tetra acetic EDTA
acid
Hydroxyethyl ethylene diamine HEDTA
tetra acetic acid
Hydroxyethyl imino di acetic HEIDA
acid
L-Glutamic acid N,N-di acetic GLDA
acid
Diethylene tri amine penta acetic DTPA
acid
Nitrilo tri acetic acid NTA
Methyl glycine di acetic acid MGDA
cations and remove the scale from different downhole equipment
(Wang et al., 1999). Chelating agents increase the solubility of in-
organic scale by chelating the metal ions and can prevent the re-
combination of ions that could result in precipitation (Li et al., 2016).
Multiple coordination bonds with metal ions could generate more
stable and water-soluble complexes that result in the dissolution of
scale. The proposed mechanism of scale dissolution using chelating
agent involves mainly two steps for iron sulfide scale. Firstly, the scale
is dissolved using low-pH fluid and Fe(II) ions are generated as a re-
action by-product. In the second step, iron cations are sequestered by
chelation which minimizes the risk of re-precipitation (Yap et al.,
2010).
3.3.1. Ethylene diamine tetraacetic acid (EDTA)
EDTA is one of the earliest candidates of chelating agent for re-
moving scale in oilfield application and most studied for different oil-
field applications (Blanco et al., 1997). EDTA is a hexadentate ligand
having four carboxylic acid groups and two nitrogen atoms for co-
ordination with metal ions. At 500°F and pH 9.5, EDTA thermally de-
grades to HEIDA and iminodiacetic acid in 30 min (Almubarak et al.,
2017b). The primary degradation product HEIDA further hydrolyze to
ethylene glycol and iminodiacetic acid. EDTA has poor biodegrad-
ability, however, can be degraded using certain strains of bacteria
(Grundler et al., 2005). EDTA is used for scale removal and has shown
promising results for removing carbonate, calcium sulfate and a mix-
ture of calcium and barium sulfate scale. EDTA was reported in other
applications as well such as removal of carbonate and sulfate minerals
from boilers and for extraction of metal from ores (Fredd and Fogler,
1998). The poor biodegradability is limiting its application in few
countries.
There are some conflicting results on the use of activator/catalyst
with EDTA to efficiently dissolve different kinds of scales. Lakatos et al.
used different activator such as malonic acid, succinic acid, tartaric
acid, maleic and oxalic acid and found that except oxalic acid, all other
acids have a negative effect on the dissolution capacity of EDTA
(Lakatos et al., 2002b). The oxalic acid was found to have no effect on
the dissolution capacity of EDTA. These results are contradictory to the
reports of Paul and Fieler (1992). They reported that 0.5M oxalic acid
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Journal of Petroleum Science and Engineering 171 (2018) 127–139
increases the dissolution capacity of EDTA. These conflicting results
suggest that optimum conditions such as temperature, pH, and con-
certation (activator/catalyst, EDTA) should be identified to achieve
maximum scale removal efficiency. The calcium sulfate removal using
EDTA increased by increasing the temperature since the solubility of
calcium sulfate increases with temperature. The increase in the con-
centration of EDTA is also directly related to calcium sulfate scale
dissolution capability. The flow rate also affects the dissolution of cal-
cium sulfate scale. EDTA can remove gypsum scales without using any
convertors.
EDTA chelating agent has been utilized to remove barium sulfate
(barite) scales from oil and gas wells. Sodium EDTA showed lower
dissolving power compared to potassium EDTA. A 0.6 M concentration
was reported to be the optimum concentration for removing barite scale
and barite filter cake from oil and water base drilling fluids. The barite
solubility was enhanced in potassium-EDTA by adding potassium car-
bonate, which acts as a converter. Potassium carbonate converted
barium sulfate to barium carbonate in the presence of high pH K4EDTA
(pH above 11). The barium sulfate solubility in potassium-EDTA and
potassium carbonate exceeded 90% (Mahmoud and Elkatatny, 2017).
3.3.2. Hydroxyethyl ethylene diamine tetra acetic acid (HEDTA)
HEDTA is a quinquedentate ligand with three carboxylic acid group
and two nitrogen atoms. Structurally it is as EDTA except OH group
replaces one COOH group. This addition of OH group enhances the
solubility at the cost of stability. HEDTA is used in different scale re-
moval applications. The major drawback of HEDTA is its poor biode-
gradability. HEDTA has higher biodegradability compared to EDTA and
has higher solubility in HCl. HEDTA is a good solution for calcium
carbonate and calcium sulfate scales (LePage et al., 2009).
3.3.3. Diethylene triamine pentaacetic acid (DTPA)
DTPA is one of the promising candidates in removing different types
of scale. It is an octadentate ligand that can form a very strong chelate
in solution and bind to a metal center through five oxygen atoms of
COOH group and three nitrogen atoms (Wang et al., 1999). It has the
highest stability constants among different chelating agents used in
oilfield applications. The higher the stability constant, the more stable
the complex will be. DTPA is also less corrosive as it is usually applied
in basic form. The scale removal reaction using DTPA does not produce
corrosive gases. DTPA (20 wt%) was used to remove iron sulfide scale
with 80% pyrite using K2CO3 as a convertor (Mahmoud, 2018;
Mahmoud et al., 2015; Mahmoud and Hussein, 2017). Up to 85% of the
scale was dissolved in 48 h using selected formulations of DTPA at
158 °F. DTPA is also effective in dissolving calcium sulfate scale without
using convertors. However, its performance in dissolving BaSO4 scale is
poor (Kelland, 2014).
Most of the applications of DTPA reported in the literature for scale
removal are for barium sulfate scale. The optimum pH value for barium
sulfate scale removal was 12 (Putnis et al., 1995). At this pH, the Ba-
DTPA complex has the highest stability value. Lakatos et al. found that
among the seven evaluated chelating agents, DTPA has the best scale
removal efficiency in removing barite scale (Lakatos et al., 2002a).
Putins et al. investigated the effect of DTPA concentration on barite
removal and found that the barite dissolution in DPTA increases with
increasing concentration of DTPA until 10 mM and then starts de-
creasing (Putnis et al., 2008). Usually, some catalyst/convertors are
also added along with DTPA to enhance the dissolution of barite. Paul
et al. observed that oxalic acid at a specific concentration can be an
effective synergist for 0.5M DTPA (Paul and Fieler, 1992). Bageri et al.
used DTPA and potassium carbonate as a catalyst/convertor to dissolve
barium sulfate scale (Bageri et al., 2017). Dissolution of 95% of the
barite scale has been achieved by optimizing the concentration of DTPA
and potassium carbonate. Mixtures of chelating agents containing
DTPA and other chelating agent are less efficient in dissolving barite
compared in comparison with DTPA alone.
M.S. Kamal et al.
Fig. 6. SEM images of barite grains: a and c before dissolution in DTPA; e and g after exposure to 0.5 M DTPA solution; Others are after exposure to 0.05 M DTPA
solution (Putnis et al., 2008).
SEM images of barite grains before and after dissolution in different
concentrations of DTPA solution are given in Fig. 6. The barite grains
are clearly smooth before contacting DTPA and becomes rounded after
the dissolution in DTPA. The SEM images also showed that the DTPA at
low concentration (0.05 M) is more effective compared to high con-
centration (0.5 M) (Putnis et al., 2008). This can lower the cost of scale
removal process and make the environment less corrosive.
3.3.4. Hydroxyethyl iminodiacetic acid (HEIDA)
HEIDA is a tridentate ligand where two carboxylic acid arms are
attached to the nitrogen atom. HEIDA has better biodegradability and
solubility compared to EDTA and HEDTA. HEIDA has low dissolving
power for different scale types compared to EDTA and HEDTA chelating
agents.
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Journal of Petroleum Science and Engineering 171 (2018) 127–139
3.3.5. L-glutamic acid N,N-diacetic acid (GLDA)
GLDA has good solubility in water and acidic solutions and have
been used for iron control and stimulation of oil reservoirs. GLDA also
has better biodegradability and was used in different scale removal
applications as well. The low stability constants of GLDA for certain
scales such as barium sulfate limits its application in removing these
types of scales. At 350°F, the GLDA thermally degrades after 4 h to yield
formic acid and cyclic GLDA (LePage et al., 2009). In another study, it
was found that at the same temperature, GLDA degrades to oxote-
trahydrofuran-2 carboxylic acid, acetic acid, hydroxyglutaric acid and
monosodium glutamate monohydrate if heated for 12 h (Almubarak
et al., 2017b; Sokhanvarian et al., 2012).
3.3.6. Methylglycinediacetic acid (MGDA)
MGDA is a relatively new biodegradable chelating agent and re-
ported for some oilfield applications in recent papers. MGDA has very
M.S. Kamal et al.
low stability constants for different scales, particularly for barium sul-
fate. The MGDA has only one nitrogen atom and one chelating arm
compared to the DTPA, which is octadentate. However, MGDA is
thermally stable up to 350°F when heated for 6 h (De Wolf et al., 2014).
The results reported in the literature show that the addition of MGDA to
DTPA lowers the dissolution of barium sulfate.
3.3.7. Nitrilotriacetic acid (NTA)
NTA is a quadridentate ligand which consists of three carboxylic
acid groups attached to a central nitrogen atom. The stability constant
of NTA for most metal cations is low compared to other chelating
agents. In addition, it is carcinogenic and restricted for use in several
countries. NTA decompose at a temperature above 560 °F to N-methy-
liminodiacetic acid and trimethylamine. At lower pH, the degradation
product can be iminodiacetic acid, sarcosine, glycine, CO, CO2, and
formaldehyde (Almubarak et al., 2017b; Booy and Swaddle, 1977). The
biodegradability of NTA is higher compared to EDTA and DTPA (Means
et al., 1980).
3.3.8. Tetrakis hydroxymethyl phosphonium sulfate (THPS)
THPS is a biocide that has been used in various oilfield applications.
THPS has been reported to be used as a scale removal for different types
of iron sulfide scale including pyrrhotite, Mackinawite, pyrite, marca-
site, calcite, and anhydrite (Wang et al., 2015). THPS dissolves iron
sulfide scale through chelation and its dissolution increase in the pre-
sence of ammonium salt or phosphonate. Several studies showed that
under similar conditions, the performance of the THPS was comparable
and even better compared to HCl (Gilbert et al., 2002; Wylde, 2014;
Wylde and Winning, 2004). The effectiveness of THPS reduces at high
pressure. It also causes a high corrosion on mild steel (Wang et al.,
2013b). Two major problems were reported with THPS are; its high
corrosion rate at temperatures above 100 °C, and the precipitation of
calcium sulfate scale in the presence of calcium source such as calcium
carbonate. THPS has a sulfate group that can react with the calcium and
precipitate calcium carbonate. THPS is recommended for low tem-
peratures and if calcium source is present, it has to be combined with
one of the chelating agents to prevent the calcium sulfate scale pre-
cipitation (Mahmoud et al., 2017c).
3.4. Chelating agent-acid mixtures
The mixtures of chelating agent and acids have been used in several
studies to effectively remove the different types of scales. However, this
approach is complicated due to several factors. Most of the chelating
agents have low solubility in acidic media at low pH (< 4) (Frenier,
2001). Chelating agents and metal-chelate degrade at temperatures
above 121 °C and this degradation is catalyzed in the presence of some
strong acid (Gambardella et al., 2005). Mahmoud et al. found out that
the maximum soluble concentration of EDTA was 20 wt% at pH 6; at
lower pH values, the maximum soluble concentration decreases
(Mahmoud and Elkatatny, 2017). EDTA is not soluble in HCl compared
to HEDTA, GLDA, and DTPA. Summary of scale dissolution of different
chemical dissolvers is displayed in Table 5.
The recent literature reported different polymer-based dissolvers.
However, the exact chemical structure for most of the dissolvers is not
mentioned. Wang et al. developed polymer-based dissolvers with a
neutral pH value (Wang et al., 2013b). The results showed that the
developed dissolver can dissolve up to 96% for a field sample con-
taining 40% pyrite. Other scale removers such as tetrakis hydroxy
phosphonium sulfate (THPS), crown ethers are used to remove oilfield
scales. The problem with THPS is its corrosion rate, it is very corrosive
and causes lots of environmental and health issues. Other acids such as
sulfuric, nitric, sulfamic acids are not easy to handle. We focused on the
common scale removers that are used currently in the oilfield
(Mahmoud et al., 2018).
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Journal of Petroleum Science and Engineering 171 (2018) 127–139
4. Conclusions and future perspectives
This paper provides a detailed review of different oil field scales,
their sources, formation, and chemical scale removal strategies. The
paper summarized different oil field scales that are commonly en-
countered in oil and gas production operation. The scales are mainly
sulfide (iron, zinc, and lead), sulfate (barium, calcium, and strontium),
and carbonate (calcium and iron) scales. The review also discussed and
compared different scale dissolvers that are used in industry and in
laboratories. Due to the complex nature of scales and variation of the
chemistry of scales within the same well, a single scale dissolver che-
mical may not be sufficient to remove scales from the same well.
Hydrochloric acid is the conventional acid that has been used to remove
oilfield scales since decades. However, due to high corrosion, genera-
tion of H2S gas, limited solubility for selected scales and handling issues
new chemical formulations are developed. Organic acids are proposed
as an alternative due to lower corrosion; however, they are expensive
and not effective to dissolve certain scales such as carbonates. Chelating
agents appeared to be the most attractive choices for dissolution of
different types of scales owing to low corrosion and ability to dissolve a
wide range of oilfield scales.
There are three main factors that need to be considered in paving
the way to proffer future solutions in dealing with oilfield scales. These
factors are the dissolution chemistry, the equilibrium effect on iron
complexations with chelating agents and the pH sensitivity. Firstly, the
chemistry of dissolution of the scales needs to be well understood. This
will enable the designing of proper formulations. A combined approach
of applying both computational and experimental tools would make
this achievable. This article focused on the amine derivates of acetic
acid. Nevertheless, other organic acids would need to be considered.
The use of weak organic acids would reduce corrosion as they would
have high solubility. Moreover, the role of what is called a ‘catalyst’ or
converter such as K2CO3 is still vague. It is not known whether it reacts
with iron sulfide and sulfate scales or it only affects the pH. The pH
plays a dominant role in the rate of different scales dissolution (car-
bonate, sulfate, and sulfides) as proved by experimental findings. Other
possible chemicals that can act as converters would need to be con-
sidered. Therefore, understanding of the dissolution of iron sulfide
scales would aid the development of green formulations that can re-
place inorganic acids. Hence, more work needs to be done in this area.
On the other hand, more research should be focused on preventing the
scale formation such as finding how to reduce the sulfide formation in
the well. This could reduce the need for resources required to remove
sulfide scales.
Carbonate scales are very common and occur in different locations
in the well. HCl is the most effective acid in removing carbonate scales
but it represents lots of challenges especially in HPHT wells. HCl can be
combined with organic acids to reduce its impact on the tubular's
corrosion. HCl may cause damage during scales removal such as the
formation of iron hydroxide and asphaltene precipitations, therefore,
numerous additives should be included when using HCl. These ad-
ditives such as iron control agents, corrosion inhibitors, anti-sludge
agents, etc.
Sulfate scales usually precipitates in seawater injection wells.
Calcium, barium, and strontium sulfate are very common in oil, gas,
and water wells. Sulfate scales are stable in low pH, therefore, high pH
fluids should be used to remove sulfate scales. Chelating agents are very
effective in removing sulfate scales. Barium sulfate scale has low to
moderate solubility in different chelating agents. Recently, the concept
of scale conversion was introduced in which sulfate scales are converted
to carbonate scales by using a potassium carbonate converting agent.
Scale conversion process has improved the sulfate scale removal effi-
ciency from 60 to more than 90%.
M.S. Kamal et al. Journal of Petroleum Science and Engineering 171 (2018) 127–139

Table 5
Scale dissolution of different chemical dissolvers reported in literature.
Formulation Concentration Temp. Scale Type pH Time, hrs Dissolution, % Ref

DTPA 20% 158 °F Pyrite 11 48 85 (Mahmoud et al., 2015)

DTPA 20% 125 °C Iron sulfide 11.50 24 24 (Elkatatny, 2017)
DTPA 20% 125 °C Iron sulfide 7.95 24 29 (Elkatatny, 2017)
DTPA 25% 125 °C Iron sulfide 11.50 24 27 (Elkatatny, 2017)
DTPA 25% 125 °C Iron sulfide 7.95 24 36 (Elkatatny, 2017)
DTPA 25% 125 °C Iron sulfide 6.02 24 41 (Elkatatny, 2017)
DTPA 30% 125 °C Iron sulfide 6.02 24 42 (Elkatatny, 2017)
DTPA 0.5 M 80 °C Barite 11 24 70 (Bageri et al., 2017)
DTPA 0.5 M 132 °C Barite 11 24 75 (Bageri et al., 2017)
DTPA 20% 200 °F Barite 11.5 24 68 (Mahmoud et al., 2017a)
DTPA 20% 270 °F Barite 11.5 24 70 (Mahmoud et al., 2017a)
DTPA + K2CO3 0.5 M + 6% 80 °C Barite 11 24 95 (Bageri et al., 2017)
DTPA + K2CO3 20% + 6% 200 °F Barite 11.5 24 86 (Mahmoud et al., 2017a)
DTPA + K2CO3 20% + 6% 270 °F Barite 11.5 24 97 (Mahmoud et al., 2017a)
DTPA + KCL 20% + 6% 200 °F Barite 11.5 24 75 (Mahmoud et al., 2017a)
DTPA + KCL 20% + 6% 270 °F Barite 11.5 24 85 (Mahmoud et al., 2017a)
DTPA + CHKO2 20% + 6% 200 °F Barite 11.5 24 75 (Mahmoud et al., 2017a)
DTPA + CHKO2 20% + 6% 270 °F Barite 11.5 24 84 (Mahmoud et al., 2017a)
EDTA 18 200 °F Barite 12 24 27 (Geri et al., 2017)
EDTA 20 125 °C Iron sulfide 11.10 24 21 (Elkatatny, 2017)
EDTA 20 125 °C Iron sulfide 8.70 24 25 (Elkatatny, 2017)
EDTA 25 125 °C Iron sulfide 11.10 24 24 (Elkatatny, 2017)
EDTA 25 125 °C Iron sulfide 8.80 24 34 (Elkatatny, 2017)
EDTA 25 125 °C Iron sulfide 6.52 24 39 (Elkatatny, 2017)
EDTA 30 125 °C Iron sulfide 6.52 24 39 (Elkatatny, 2017)
HEDTA 18 200 °F Barite 12 24 18 (Geri et al., 2017)
Gluconic Acid + DTPA 20 + 20 125 °C Iron sulfide 10.5 24 20 (Elkatatny, 2017)
Gluconic Acid + DTPA 20 + 20 125 °C Iron sulfide 13.6 24 29 (Elkatatny, 2017)
Gluconic Acid + DTPA + succinic acid 20 + 20+10 125 °C Iron sulfide 10.3 24 28 (Elkatatny, 2017)
Gluconic Acid + DTPA + Maleic Acid 20 + 20+10 125 °C Iron sulfide 10.8 24 28 (Elkatatny, 2017)
Gluconic Acid + EDTA + Maleic Acid 20 + 20+20 125 °C Iron sulfide 9.8 24 6 (Elkatatny, 2017)
Gluconic Acid + DTPA + Maleic Acid 20 + 20+20 125 °C Iron sulfide 9.9 24 16 (Elkatatny, 2017)

Acknowledgements
This publication was made possible by NPRP Grant # 9-084-2-041
from Qatar National Research Fund (a member of Qatar Foundation).
The findings achieved herein are solely the responsibility of the authors.
Authors would also like to acknowledge the support of KFUPM.
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