Journal of Petroleum Science and Engineering 135 (2015) 723–737

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

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

A review of oilfield scale management technology for oil and gas

production
Abass A. Olajire
Industrial and Environmental Chemistry Unit, Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, P. M. B 4000, Ogbomoso,
Oyo State, Nigeria

art ic l e i nf o a b s t r a c t

Article history: The presence of formation water and the treatment methods (both water flooding and chemical treat-
Received 4 June 2015 ments) employed during exploration and production operations have great potential for mineral scale
Received in revised form formation. Scale deposition poses a lot of serious threat in field production and it is a menace to pro-
1 August 2015
duction flow assurance, which in turn reduces the production flow resulting in production losses. Al-
Accepted 9 September 2015
though oilfield scale deposit is a long standing problem, oil and gas industry are facing new challenges in
Available online 18 September 2015
managing scale deposits created during offshore exploration activities in ultra-deepwater and other
Keywords: harsh environments. Traditional onshore chemistries for scale inhibitions are not viable under HT/HP
Scale deposits conditions thereby making flow assurance a critical issue for deepwater project development. An ideal
Inhibitors
management program maximizes hydrocarbon production and minimizes the cost of scale deposits
Thermodynamics
control, thereby maintaining the economic viability of the operations. This paper reviews various types of
Kinetics
Management mineral scale deposits as well as the thermodynamics and kinetics prediction of mineral scale formation
Prediction potentials. Also, the mitigation strategies of oilfield mineral scale deposits and chemical stimulation
Ultra-deepwater wells techniques used in oil industry to improve well productivity are discussed.
& 2015 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
2. Types of oilfield mineral scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
2.1. pH independent scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
2.2. pH dependent scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
2.3. Naphthenate deposit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
3. Mechanisms of mineral scale formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
3.1. Autoscaling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
3.2. Incompatible mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 728
3.3. Evaporation-induced scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 728
3.4. Gas flood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 728
4. Thermodynamic prediction of mineral scale formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 728
5. Rate of scale precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
6. Management of scale for oil and gas production facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
6.1. Reduction of scale potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
6.2. Scale prevention methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
6.2.1. Conventional scale inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
6.2.2. Green scale inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
6.2.3. Naphthenate inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
6.3. Scale removal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
6.3.1. Mechanical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
6.3.2. Chemical treatment method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
7. Scale management and prediction in ultra-deepwater wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 734

E-mail address: olajireaa@yahoo.com

http://dx.doi.org/10.1016/j.petrol.2015.09.011
0920-4105/& 2015 Published by Elsevier B.V.
724 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737

8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735

1. Introduction 2. Types of oilfield mineral scales

Amongst the production issues in oil and gas industry is the Common oilfield scale deposits can be classified into “pH in-
scale deposition resulting from the waterflooding process and dependent” and “pH sensitive” scales. The scaling tendency of
chemical treatment operations which are applied to maintain sulfates (calcium sulfate, barite and celestite) and halite scales are
sustainable hydrocarbon production at oil, gas or gas condensate not a strong function of brine pH. The carbonates (calcite, dolomite
fields. Hydrocarbons coming out of a reservoir consist of millions and siderite) and sulfide scales are acid soluble and their scaling
of different components (N2, CO2, H2S, C1–C6, C7 þ , etc.) and may tendencies are strongly influenced by the brine pH. For pH sen-
present in a liquid (C5 þ ) or gaseous form (C1–nC5). In addition sitive scales, the scale prediction is more complicated since issues
fresh water is usually associated to hydrocarbons coming out of that control the brine pH also affect their scaling tendencies. The
reservoir, bringing within itself to the surface various dissolved most common oilfield scales are listed in Table 1 (Kelland, 2009;
compounds. The resulting composition of producing fluid may Bin Merdah, 2008). These scales are sulfates such as calcium sul-
count up to large number of different components and substances.
fate (anhydrite, gypsum), barium sulfate (barite), and strontium
These fluids will experience drop in pressure or a change in
sulfate (celestite) and calcium carbonate. Other less common
temperature, and some compounds may become more stable at
scales have also been reported such as iron oxides, iron sulfides
solid state and will start to precipitate (Time, 2011). The pre-
and iron carbonate and calcium naphthenate scale from acidic
cipitation of these solids occurs as a result of changes in the ionic
crudes (Rousseau et al., 2001).
composition, pH, pressure and temperature of the brine. When
water flooding method is applied for enhance oil recovery, then
the problem of scale deposits may occur right from water injection 2.1. pH independent scale
facilities to the producing well, and generally scale deposits can
occur during and after injection operation in the injector wellbore, These are sulfate compounds of barium, strontium, or calcium.
near the injection well bottom hole, in the reservoir between the The sulfate ion (SO42 −)normally found in the seawater reacts with
injector and producer, at the skin of producer well, in the producer Ba2 +, Sr 2 +, and/or Ca2 + ions, which are naturally found in the
wellbore, oil well casing, oil pipelines and other production facil- formation water depending on the geological history of the oil-
ities (Liu et al., 2012; Dickson et al., 2011). fields.
The composition of scale deposits samples is made up of or-
ganic, inorganic and crystal water (Jiecheng et al., 2011). A scale
deposit may occur as single mineral phases, but more commonly it
is a combination of different elements, which can occur when a
solution becomes saturated, mostly due to changes in temperature
during injection operations, changes in pH values or if two dif-
ferent chemicals that will precipitate are brought together. There
are several mineral ions usually dissolved at produced water;
these include calcium (Ca2 þ ), barium (Ba2 þ ), strontium (Sr2 þ )
cations and carbonates (CO32 −), sulfate (SO42 −) anions. Scale deposit
begins to form when the solubility limit for one or more compo-
nents is exceeded. Scale deposition products in oilfield are mainly
consisted of calcium carbonate, calcium sulfate, barium sulfate and
strontium sulfate and carbonates, iron, silicon sediment and other
insoluble solids (Jinling et al., 2009; Senthilmurugan et al., 2011;
Dickinson et al., 2012).
The effect of scale can be dramatic and immediate with a fall in
the production capacity to zero in a few hours and the treatment
cost can be massive (Al Salami and Monem, 2010). Scale deposi-
tion in the formation pores restricts the flow of fluid through the
formation of a thick layer in the wellbore tubular which reduces
the diameter of the production tubing and chokes the production
from the reservoir (Fig. 1). This can lead to a drastic increase in
pressure drop and thus a decrease in the well productivity.
Scale precipitation can also cause formation damage in the
reservoir, flow loss or blockage on flow lines and equipment, en-
ergy leak, accelerate corrosion, and severe accidents, which can
influence the safety of production and the economic benefit of
petroleum industry (El-Said et al. 2009). This paper reviews and
assesses some of the management and mitigation strategies of
oilfield mineral scale deposits in onshore and ultra-deepwater
wells, and chemical stimulation techniques applicable in oil in-
dustry to improve well productivity. Also discussed are thermo-
dynamics and kinetics models of scale prediction. Fig. 1. Scale in flow lines.
 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737 725

Table 1
Common oilfield scales.

Name Chemical formula Mineral

Calcium carbonate CaCO3 Calcite, aragonite, or rarely vaterite

Calcium sulfate CaSO4 Anhydrite, hemihydrate (CaSO4  5H2O) and gypsum (CaSO4  2H2O)
Calcium oxalate Beerstone

Barium sulfate BaSO4 Barite

Magnesium hydroxide Mg(OH)2 Brucite
Magnesium oxide MgO Periclase
Silicates Me(SinOx) yH2O Serpentine, acmite, gyrolite, gehlenite,amorphous silica, quartz, cristobalite, pectolite
Aluminum oxide Hydroxides AlO(OH) Boehmite, gibbsite, diaspore, corundum
Aluminosilicates AlxSiyOz Analcite, cancrinite, noselite
Copper Cu Metallic copper, cuprite (Cu2O), tenorite (CuO)
Phosphates Ca10(PO4)6(OH)2 Hydroxyapatite
Magnetite or nickel Ferrite NiFe2O4 Trevorite

Ba2 +(Sr 2 +or Ca2 +) + SO42 − → BaSO4 ↓ (SrSO4 or CaSO4 ) (1)

These compounds are also mildly soluble in water and as a
result they subsequently precipitate out and form solid solutions.
2.2. pH dependent scale
The carbonates (calcite, dolomite and siderite) and sulfide
scales are acid soluble. Their formations are as shown in the
equation below:
Ca2 +(Fe2 +) + CO32 − → CaCO3 ↓ (FeCO3 )
Fe2 +(Zn2 +or Pb2 +) + S 2 − → FeS ↓ (ZnS or PbS )
2.3. Naphthenate deposit
The heavy or slightly biodegraded crudes are "high-TAN
crudes", i.e. contains significant amounts of carboxylic (mainly
naphthenic) acids (Rousseau et al., 2001). Naphthenic acids are
mixtures of alkyl-substituted acyclic and cyclic structures with the
general chemical formula Cn H2m + z O2, where m indicates the car-
bon number and z is zero, in the case of fatty acids, or negative,
depending on the number of condensed and/or aromatic rings.
Fig. 2 displays some examples of possible monoprotic naphthenic
(2) acid structures for different z values.
Literature survey shows that certain crude oils produced from
both onshore and offshore fields in a range of places, including
(3) Angola, Congo, Cameroon and Nigeria, the North Sea (United

R (CH2)nCO2H R (CH2)nCO2H
CH3(CH2)nCO2H
(z = 0)
(z = -2) (z = -2)

R (CH2)nCO2H (CH2)nCO2H

(z = -4) R
(z = -6)

R (CH2)nCO2H
R (CH2)nCO2H
(z = -8)
(z = -10)

R (CH2)nCO2H

(z = -14)
Fig. 2. Naphthenic acid structures where z describes the hydrogen deficiency, R is an alkyl chain, and n the number of CH2 units.
726 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737
Kingdom), the Norwegian continental shelf (Norway), South East
Asia (China, Indonesia, Malaysia), South America (Venezuela and
Mexico) have naphthenate/carboxylate soap flow assurance pro-
blems (Rousseau et al., 2001; Gallup and Star 2004; Hurtevent and
Ubbels, 2006). Naphthenate formation in these fields hinders oil
production, resulting to unplanned plant shutdown, loss of pro-
duction and off-specification export oil quality control problems.
Therefore, it is important to understand the chemistry of these
crude oils and their formation waters, as well as the changes in the
physical parameters that occur during oil production to enable oil
companies address this type of flow assurance problem; and
possibly design new improved production facilities to mitigate the
naphthenate/carboxylate soap problems.
During production and processing of high-TAN crude oils, the
amphiphilic naphthenic acids may also accumulate at interfaces
and stabilize water-in-oil emulsions (Ese and Kilpatrick 2004;
Poggesi et al., 2002, Rousseau et al., 2001, Dyer et al., 2003),
causing enhanced separation problems. Pressure drop during fluid
transportation from the reservoir to the topside leads to release of
carbon dioxide from the solution during production. This increases
the pH of the co-produced water, resulting to a higher degree of
dissociation of naphthenic acids at the o/w interface as given be-
low:
RCOOH → RCOO− + H + (4)
The dissociated surface active naphthenate (RCOO ) anion at − valves or the heat exchangers/motors on pumps from operating as
the oil-brine interface reacts with either calcium or the sodium ion
in the brine to form a soft (sodium) emulsion type naphthenate
(NaN) or a hard (calcium) naphthenate (CaN) at the oil-brine in-
terface (Sarac and Civan, 2007) in accordance to the following
reaction Scheme 1:
Calcium naphthenate formation has been observed at brine pH
greater than about 6 (Goldszal et al., 2002; Rousseau et al., 2001;
Scheme 1. Reaction between naphthenic acids (RCOO–) and divalent cation (M2 þ ),
where {k1, k2} and {k–1} represent the reaction rate constants of the forward and
the reverse steps, respectively.
Turner and Smith, 2005) whilst sodium carboxylate/emulsion has
been seen at slightly higher brine pH i.e.  8.5 (Gallup et al., 2005;
Turner and Smith, 2005). The reaction and formation of these
naphthenates usually occurs at the oil–water interface and they
tend therefore to move along through the production system with
the oil and the produced fluids (Ese and Kilpatrick, 2004). Due to
low interfacial affinity and low solubility in water, especially when
multivalent cations are involved, the naphthenates will precipitate
and start to agglomerate in the oil phase. As the density of the
precipitate lies between that of oil and water, it will gradually
settle and accumulate at the o/w interface and further adhere to
process unit surfaces. The production problems associated with
the formation of metal naphthenates have been reported to occur
mostly in the surface facilities i.e. in the separators, hydrocyclones,
heat exchangers and other production equipment (Rousseau et al.,
2001; Vindstad et al., 2003).
Baugh et al. (2005) carried out the characterization of the
naphthenic acids on the derivatized acid extract from the naph-
thenate deposit, and they concluded that most of the acid species
in the calcium naphthenate sample are ARN acids. Lutnaes et al.
(2006) carried out extensive characterization of the ARN naph-
thenic acid present in the naphthenate sample from a North Sea
field and they were able to establish a more precise structure of
the ARN acid species. These authors suggested that the pre-
dominant component within the ARN acid family are composed of
six rings and also speculated that the acid is likely to be of bio-
logical archaeal bacteria origin. The proposed ARN acid structure
suggested by Lutnaes et al. (2006) is presented in Fig. 3.
3. Mechanisms of mineral scale formation
Scale formation can occur through homogeneous and hetero-
geneous nucleation mechanisms. Homogeneous nucleation occurs
in the absence of a foreign substance and is not a likely mechanism
because in nature it is not likely that environments are free from
foreign substances. Thus, homogeneously formed scale particles
do not necessarily deposit or grow onto a surface and hence, could
flow through the system without causing too many depositional
issues. Heterogeneous nucleation occurs in the presence of a for-
eign substance to trigger nucleation. The foreign substance can be
scale nuclei or corrosion products, welds/stress points on metal
surface, corrosion sites on metal surface, scratches on metal sur-
faces, or small particles of suspended solids. Therefore, hetero-
geneously formed scale particles build up on solid surfaces causing
problems such as pressure increases and restriction of fluid flow in
the formation, pipelines, surface facilities and can potentially
prevent production equipment such as downhole sub-sea safety
expected.
Mathematical models can be used to describe some scaling
processes. Advanced equations developed by some authors (Ber-
thoud, 1912; Bowen and Epstein, 1978; Ruckenstein and Prieve,
1973) have been used to describe scaling precipitation rates.
Simplified approach uses diffusion-reaction model. In this model,
growth is seen as a mass transfer process;
dm
= k m (Cb − Ce )n2
dt (5)
which can be divided into two stages, i.e
dm
diffusion = k d (Cb − Ci )
dt (6)
dm
and reaction: = k r (Ci − Ce )n1
dt (7)
where:
m is the mass of the material (per unit surface area), kg/m2; t is
time (s); Cb is the concentration of the substance in the bulk of the
fluid, kg/m3; Ci is the concentration of the substance at the inter-
face, kg/m3; Ce is the equilibrium concentration of the substance at
the conditions of the interface, kg/m3; n1, n2 are the orders of
reaction for the crystallization reaction and the mass deposition
process, respectively, (dimensionless); km, kd, kr, are the kinetic
rate constants for the mass deposition, diffusion and surface re-
action, respectively; with the dimension of m/s (when n1 and
n2 ¼ 1).
The principal mechanisms by which scales are form in both
offshore and onshore oil field system (Frenier and Ziauddin, 2008)
include:
3.1. Autoscaling
Autoscaling happens when a reservoir fluid experiences chan-
ges in temperature and pressure as it is produced, and when such
changes take the fluid composition beyond the solubility limit for
 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737 727

Fig. 3. Proposed predominant structure of ARN acid (Lutnaes et al., 2006).

Enter T, P and brine compositions

No Adjust the
Is electroneutrality satisfied concentrations
for each brine? of Cl- and Na+

Yes

Set the mixing ratio of brines and SI = 0

Calculate SI for all salts within the system

Yes
SI < 0 for all salts

No

Specify the salt(s) which meet(s) SI > 0

Solve solid-liquid equilibrium equations with

electroneutrality equation simultaneously

Calculate the precipitation of specified salt using

mass balance and adjust ions concentration of brines

No
Recalculate SI for all salts within the system

Are
Does all mixing ratio
No SI remains constant covered?
Yes
for all salts?
Yes
Are
Yes calculations for
mixture of brines?

No

Calculate SI, precipitation of each

salt and equilibrium concentration
of ions in solution

Fig. 4. Mixing of seawater with formation water (Paswan, 2008).

728 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737
a mineral, thereby leading to scale precipitation. Sulfate and car-
bonate scales can precipitate as a result of pressure changes within
the wellbore or at any restriction downhole. Sodium chloride
(halite) also forms in a similar way from highly saline brines un-
dergoing large temperature drops. Decrease in pressure and/or
increase in temperature of a brine, leads to a reduction in the
solubility of the salt, which most commonly resulting to pre-
cipitation of carbonate scales, such as CaCO3.
Ca2(aq
+ −
) + 2HCO3 (aq) → CaCO3 (s) + CO2 (aq) + H2 O(l)
In carbonate scale deposits, temperature effects often work
against pressure effects. For example, the pressure drop at the
point of entry into the wellbore can lead to matrix scale. As the
flow progresses up the tubing to surface temperatures and well-
head pressure, the resulting temperature drop may override the
pressure effect, reducing scale formation in the tubing. On the
other hand, subsequent release of pressure from the wellhead to
surface can lead to massive deposit of scale in surface equipment
and tubing.
3.2. Incompatible mixing
Scale deposits from incompatible mixing occurs when two in-
compatible waters like injected seawater into reservoir during
water flooding enhanced recovery operations and formation water
gets mixed downhole. The produced water then gets over-
saturated with scale components. This happens because seawater
has a high content of sulfate ( SO2−
4 ) and formation water is rich in
ions such as calcium (Ca2 þ ) and barium (Ba2 þ ). Mixing of these
two waters leads to precipitation of sulfate scales, such as BaSO4
(Fig. 4). The scaling tendency of the fluid mixture changes with
time depending on the ratio of seawater and formation water.
Ba (2aq
+ 2+
) (Sr , Mg
2 + or Ca2 +) + SO 2 −
4 (aq) → BaSO4 (s ) (SrSO4 , MgSO4 or CaSO4 )
Other fluid incompatibilities include sulfide scale where hy-
drogen sulfide gas mixes with iron, zinc or lead rich formation
waters:
Zn2 +(Pb2 + or Fe2 +) + H2 S → ZnS(s) (PbS(s) or FeS(s) ) + 2H2(aq
+ solution could be in equilibrium with oil and gas phases. Also
) (10)
3.3. Evaporation-induced scale
This occurs as a result of simultaneous production of hydro-
carbon gas and formation brine. A pressure drop caused by re-
duced hydrostatic pressure leads to an expansion of the hydro-
carbon gas and the hot brine phase evaporates. The salt con-
centration will then increase above the solubility limit and salt will
precipitate. Halite (NaCl) scale in high temperature, high pressure
(HT/HP) wells is the most common scale type to be formed in this
way (Frenier and Ziauddin 2008; Crabtree et al., 1999).
3.4. Gas flood
Scale deposition can occur when a formation is flooded with
CO2 gas for secondary recovery. Water containing CO2 becomes
acidic and will dissolve calcite in the formation. Subsequent
pressure drops in the formation surrounding a producing well can
cause CO2 to break out of solution and cause precipitation of car-
bonate scale in the perforations and in the formation pores near
the wellbore.
CO2 + H2 O → H2 CO3
The trioxocarbonate (V) acid then dissociates into bicarbonate
and carbonate in two steps as in (9b) and (9c)
H2 CO3 + → H + + HCO3− (12)
HCO−3 → H+ + CO23− (13)
and the overall reactions can therefore be represented as
Ca2(aq
+
) + 2HCO−3 (aq) → CaCO3 (s) + CO2 (aq) + H2 O(l) (14)
(8) Ca2(aq
+ 2−
) + CO3 → CaCO3 (s) (15)
The production of scale in the near-wellbore environment
causes further pressure drops and even more precipitation. This
self-generating process can completely seal perforations or create
an impermeable wall between the borehole and reservoir within a
few days leading to complete shutdown of the production (Frenier
and Ziauddin, 2008).
4. Thermodynamic prediction of mineral scale formation
Prediction of scaling tendency is a complex task due to many
sensitive parameters such as hydrodynamic factors, change in tem-
perature and pressure, ionic strength, pH, impurities commingling of
incompatible waters, etc. An efficient way of preventing scale forma-
tion is to use thermodynamic method for prediction of scale formation
potential in oil fields. Various methods have been used to predict
scaling phenomenon in oilfield operations. Vetter et al. (1982)
proposed a competitive model for predicting sulfate scale forming
minerals. In their predictive model, they assumed that barium sulfate
precipitates first in the brine being the most insoluble salt, followed by
strontium sulfate and lastly calcium sulfate. Yuan and Todd (1991)
improved the Vetter et al model by an iterative algorithm which used
(9) the Pitzer equation for ion activity coefficients. Haarberg et al. (1992)
used an equilibrium model for prediction of sulfate and carbonate salts
formation at reservoir temperature and pressure. The initial brine
composition consists of Ca2þ , Sr2þ , Ba2þ , CO23− and SO24−ions where
CO2 and common organic acid could dissolve in so that the aqueous
recognized in this model are the equilibrium precipitation reactions,
species mass balance and electroneutrality of brine. Yeboah et al.
(1993) developed a predictive model that could calculate the scale
formation potential and distribution in oil fields using the thermo-
dynamic and kinetic data. The input data for modeling is the com-
position of the produced water and thermochemical data for
determination of scale thermodynamic potential. When software was
used to predict the scale formation, the distribution of the salt along
the produced well was calculated based on the kinetic and well data.
Oddo and Thomson (1994) proposed scaling index (SI) for precipita-
tion of barium, strontium and calcium sulfate and calcium carbonate
salts. The proposed SI was a polynomial relation which was a function
of temperature, pressure and ionic strength. MacKay (2003) developed
a model for calculation of scale formation in producing well. The
position relevant to maximum scale precipitation and composition of
final brine in producing well were obtained by using the geometry of
reservoir, geometry of well and precipitation reaction rate. Sheikho-
leslami (2005) used scaling potential index (SPI), defined as the
difference between the measured pH and saturated pH of the brine,
for studying of the calcium carbonate scale formation. In this model,
the saturated pH was calculated using the equilibrium constants,
calcium carbonate solubility product and Pitzer activity coefficient.
(11) Garcia et al. (2005) developed an accurate thermodynamic model for
calculation of the sulfate and carbonate salts solubility under hydro-
thermal conditions, i.e. up to 300 °C and 1000 bar. They studied the
binary, ternary and quaternary systems of Ba2þ , Sr2þ and Ca2þ ion
species. The main concept of that model was based on vapor–liquid–
 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737 729

solid equilibria for carbonate salts such as CaCO3 and solid–liquid

Moghadasi et al. 2003

Sheikholeslami 2005
Yuan and Todd 1991

Haarberg et al. 1992

equilibria for sulfate salts such as CaSO4. The activity coefficient of ion

Oddo and Tomson

Yeboah et al. 1993

Garcia et al. 2005

Vetter et al. 1982
and molecular species were calculated using the extended UNIQUAC

Mackay 2003
model (Thomsen and Rasmussen, 1999). A summary of the past works
references

done in modeling of thermodynamic scale formation in porous and

non-porous medium is given in Table 2.

1994
The basis for scale model is the thermodynamic solubility
product of mineral salt which is defined for a simple salt MX as;
Minimization of Gibbs free energy
Simultaneous precipitation of sul-

to obtain solid–liquid equilibrium

Developing OSPMod software o 2

Salt precipitation sequence is

K sp (MX (s) ) = mMX . γ M +. γ X − (16)

BaSO4, SrSO4 and CaSO4

o
where K sp is the crystal solubility product, m and γ denotes con-
centrations (mol/kg solvent) and activity coefficients respectively.
m is measured at saturation and γ found from the Pitzer ion in-
Descriptions

teraction model developed by Pitzer and co-workers (Pitzer, 1975,

fate salts

1973; Wang et al., 1997; Phutela et al. 1987; Pitzer et al., 1985,
point

1984; Rogers and Pitzer, 1981).

–

Solubility product, equilibrium relation –

–
For hydrated salt of the form MX  yH2O, the water activity must
bye–Huckel–Brønsted– Guggenheim—
Gibbs free energy of system with De-

be introduced for phases including crystal water and the solubility

Solubility product and extended UN-
Mass balance, solubility product and
Mass balance and solubility product

Position of maximum scale formation and Equilibrium equation and fluid flow

product expression is given as

and Pitzer activity coefficient
Semi empirical scaling index

Semi empirical scaling index

o
K sp 2
(MX . yH2 O(s) ) = mMX . γ M +. γ X −. a Hy2 O (17)
IQUAC activity coefficient
Pitzer activity coefficient

where y denotes the number of moles of crystal water.

The main equations

Scale formation potential and distribution Solubility product

For a mineral/water reaction, based on the classic Gibbs ther-

UNIQUAC model

modynamic theory, a general solubility equation at a constant

temperature and pressure can be described by:

o
⎛ ΔG o ⎞
K sp = ∏ γiυi = exp ⎜ − ⎟
i
⎝ RT ⎠ (18)
Salt solubility/salt precipitation amount

Solubility of sulfate and carbonate salts

Salt precipitation amount and salt type
Salt supersaturation ratio (SR) and salt

composition of final brine in produced

Sulfate and carbonate scale index

Carbonate scaling potential index

o −ΔG o
In K sp =
RT (19)
Salt precipitation amount

where γi is the activity coefficient of the ith species, υi is the

precipitation amount

stoichiometric coefficient of the ith species in the solid phase, ΔGo

Output of model

is the change in standard state Gibbs energy for equilibrium at the

temperature T (K), and R is the gas constant.
Thermodynamic solubility product of electrolytes in solution
well

substantially depends on
A summary of previous thermodynamic modeling of scale formation in oilfields.

temperature. The temperature dependence of equilibrium

Temperature, pressure and composition of

species in aqueous phase and geometry of

Temperature, pressure, ionic strength and
produced brine and thermochemical data
pressure, composition of species in aqu-

constants at a pressure of 1 bar for temperatures expressed in K

Salt supersaturation ratio (SR) and salt

Temperature, pressure, composition of

Temperature, pressure, composition of

Temperature, pressure, composition of

Temperature, pressure, composition of

can be described as,

species in aqueous phase and CO2
species in aqueous phase and pH

K2 K
Temperature, pressure and pH

o
In K sp , MX (T ) = K1 + + K3 In T + K4 T + 25
T T (20)
eous, oil and gas phases
precipitation amount

where coefficients K1–K5 are given in Table 3 for BaSO4 and SrSO4
Input of the model

CO2 concentration

scaling minerals.
concentration

This equation can be deduced from the Gibbs’ energy change

for the dissolution reaction. Using the relationship between the
change in Gibbs free energy ( ΔGo ) for a reaction and the enthalpy
brine

well

ΔH o and the entropy ΔS o at a specific temperature, Eq. (19) at some

temperature and Po (a reference pressure) can be rearranged to Eq.
Calculation of sulfate and car-

Calculation of sulfate and car-

Calculation of scale formation

Calculation of carbonate scale

Prediction of sulfate and car-
distribution along the well

(14) as follows:
Prediction of sulfate scale

Prediction of sulfate scale

Prediction of sulfate scale

Prediction of sulfate scale

bonate scale formation

bonate scale formation

bonate scale formation

Table 3
Coefficients of Eq. (20) for temperature dependence of equilibrium constant
(Pedersen et al. 2006).
formation

formation

formation

formation

formation

Salt K1 K2 K3 K4  103 K5
Modeling
Table 2

BaSO4 208.839  13084.5  32.4716  9.58 2.58594

SrSO4 89.6687  4033.9  16.0305  1.35 31402.1
730 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737

−ΔG To, Po −ΔHTo, Po ΔSTo, Po precipitation of barium sulfate in porous medium using the solu-
In (Ksp )T , Po = = +
RT RT R bility product, temperature, pressure and brine composition. Mi-
K2 neral supersaturation is probably the most important factor re-
= K1 +
T (21) lated to kinetics of scale nucleation and growth and can be ex-
pressed by the scaling index (SI). For salt MyXz it is defined as;
where K1 and K2, corresponds to enthalpy and entropy respec-
tively. If ΔH° and ΔS° are regarded as constants, the right hand side ⎧ ⎫
⎪ [M Z +]. [X y −]. γ Z +γ y − ⎪
will equal the first two terms in Eq. (20) as shown in Eq. (21) SIMy Xz = log ⎨ M X
⎬
⎪ M y X z ⎪
above. The temperature dependence of the enthalpy and entropy ⎩ K sp ⎭ (28)
is given from the heat capacity where T denotes the temperature
in question and T° corresponds to the reference temperature, Or rewritten as;
usually 298 K;
T
SIMy Xz = log [M Z +][X y −] γ M Z +γ X y − + pKst (29)
ΔHTo, Po = ΔHToo + ∫T o
ΔCp dT
(22)
where Kst is the stability constant, defining the ratio of paired ions
to the free metal and sulfate product and is given by Eq. (29)
T ΔCp
ΔSTo, Po = ΔSToo + ∫T o
T
dT
(23)
[My X z ]0
Kst =
[M Z +][X y −] (30)
If the change in heat capacity is regarded as constant i.e. not a
temperature function,this will give a ln T term from the entropy When SI equals zero, the solution is at equilibrium with the
relation in Eq. (23). Thus Eq. (21) becomes; solid scale; negative values of SI meaning nonscaling conditions of
the solution with respect to the particular scale; if saturation index
−[ΔHToo + ΔCp (T − To )] is greater than zero, it indicates a supersaturated or scaling con-
In (Ksp )T , Po =
RT dition. Thus, the saturation index (SI) is also commonly used to
⎡ o T ⎤ express scaling tendency.
⎣ To ΔCp In
ΔS + To ⎦
+ Several models have also been proposed to describe rate of
R (24)
calcite precipitation based on affinity models of surface-controlled
crystallization (Ramstad et al., 2005). A general equation for de-
When the heat capacity, Cp, is a polynomial linear in tem- scribing the rate of calcite precipitation is given as (Statoil 2011):
perature, which appears to be sufficient to represent the proper-
⎡⎛ m ⎤n
ties of aqueous species up to high temperatures (Pitzer, 1982; ⎡ m ΔG ⎤n ⎢ IAP ⎞ n
Tanger and Pitzer, 1989a and 1989b; Holland and Powell, 1998), Eq. Rppt = k ⎢ e RT − 1⎥ = k ⎜ ⎟ − 1⎥ = k ( Ω m − 1)
⎣ ⎦ ⎢⎣ ⎝ Ksp ⎠ ⎥⎦
(24) leads upon substitution and integration to Eq. (20) as: (31)

o
In K sp = K1 + K2 T−1 + K3 In T + K4 T (25)
IAP = γCa2 +γCO 2 − (32)
where K1 and K2, corresponds to enthalpy and entropy respec- 3

tively, and K3 and K4 are the heat capacity polynomial (Prausnitz

where k is the rate constant (mol m  2 s  1), ΔG is the Gibbs free
et al., 1999; Hillert, 2008).
It can be seen from the above expression that increasing tem- energy change of the overall reaction (J mol  1), Ω the saturation
perature will increase scale tendency in the oil and gas production index (Ω¼IAP/Ksp), Ksp is the solubility of calcite, IAP the ion ac-
facilities and such facilities will be under threat of scale forming. tivity product defined as above eq. (31), γCa2 + and γCO 2 − are the
3
activities of Ca2 + and CO32 −respectively, R is the gas constant
(J K  1 mol  1) and T the absolute temperature (K).
5. Rate of scale precipitation The value of n and m are semi-empirical constants that depend
on the kinetic behavior involved in the chemical reaction, although
When a crystalline salt precipitates onto rock surface, the fol- m can be interpreted as the Temkin coefficient (Temkin and Pyz-
lowing reaction may take place between the cation and anion hev, 1940) relating the reaction stoichiometry in the rate limiting
contributing to scale formation:
step to the reaction stoichiometry of the overall reaction (Graham
M z + + X y − → My X z (26) and Collins, 2004; Westgarth, 2013). For instance, a first order
reaction (n ¼1) has been attributed to crystallization limited by
adsorption of lattice ion (Ramstad et al., 1999, Nielsen, 1984), al-
Many rate laws have been proposed in the literature (Bed-
though it may also be ascribed to a rate controlled by diffusion
rikovistsky et al., 2003, 2004), but we shall use the rate law of the
(Fleming, 2010; Pokrovsky et al., 2005) and in some cases to a
form:
multi-source spiral growth mechanism (Teng et al., 2000; Patter-
d [M z +] k [M z +][X y −] k [M z +][X y −] γ M z +. γ X y − son et al., 2013). Theoretical models have also been used to argue
r= − = =
dt Ksp (My X z ) Ksp (My X z ) (27) that second order equations (n ¼2) may be used to describe
where [Mz þ ]and [Xy  ] and γ M Z + and γ X y − refer to concentration growth at screw dislocations by the spiral mechanism while
(molality) and activity coefficients of Mz þ and Xy  ions, respec- higher order ones (n ¼2–3) can be applied to growth at both screw
tively; r is the rate of MyXz precipitation reaction (m. min  1); Ksp is and edge dislocations (Romer et al., 2007) or growth by 2D nu-
the solubility product of MyXz in solution under the reaction cleation. The kinetics of calcite precipitation has been fitted to
conditions. second order expressions at ambient (Vetter, 1973) and elevated
Bin Merdhah et al. (2010) developed a simple kinetic model for temperatures (Vetter, 1976).
 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737
6. Management of scale for oil and gas production facilities
6.1. Reduction of scale potential
Effective scale management is an important issue for field de-
velopment planning and can have a direct impact on production
viability (Graham and Collins, 2004). Seawater with a high content
of sulfate ions is a convenient source for offshore production fa-
cilities and thus increases the risk of forming different sulfate
scales in the well. Therefore, some changes have to be made to
remove these sulfate ions from the water in order to reduce the
sulfate content and thus minimizing and/or mitigating against
sulfate scale. To achieve the above objective, a sulfate removal
plant (SRP) can be used to desulfate seawater before it is injected
into a well. Desulfation of injected seawater will only prevent
sulfate and sulfide scales while leaving other salts substantially
unaffected (Westgarth, 2013). Again, not all the sulfate ions can be
removed in the SRP, but substantial amounts is removed to reduce
sulfate and sulfide scale problems considerably. The sulfate con-
centration in seawater has been reported to be reduced from ap-
proximately 2700 ppm to 40–100 ppm in the SRP (Kelland, 2009).
The use of SRP is considerably a high capital investment but is the
best option for large fields with severe predicted sulfate scale
formation.
Aquifer water and produced water are other water types that can
be injected to avoid the risk of sulfate scaling. The sulfate contents of
both waters are negligible (o20 mg/L) in terms of sulfate scale for-
mation potential (Ramstad et al., 1999, Fleming, 2010, Patterson et al.,
2013). A risk of carbonate scale formation may occur if the injected
aquifer water has a high content of calcium ions (Ca2þ ), while the
formation water has a high content of bicarbonate (HCO3−).
Another method that may reduce the scale potential is a good
well production strategy. This involves careful production of the
well to avoid large pressure drops, or by choking back wells that
produce water which may lead to mixing of incompatible waters
(Kelland, 2009; Westgarth, 2013; Ramstad et al., 2005).
6.2. Scale prevention methods
Scale prevention can be achieved by performing squeeze
treatments in which chemical scale inhibitors are injected in the
producers near wellbore (Romero et al., 2007). Scale inhibition is a
chemical treatment used to control, delay or reduce scale from
forming in a producing well. In all the cases considered below,
however, the term “prevention” really refers to a reduction in
scaling rates rather than a complete elimination of scale-forming
pathways. Adding chemical antiscalant is an economical and
simple effective route for the prevention of scaling (Dickson et al.,
2011). Scale inhibitors (SI) have, for many years, been the preferred
downhole treatment for the prevention or control of scale for-
mation and its subsequent deposition, by application in a ‘squeeze’
treatment (Vetter 1973, 1976; Sorbie et al., 1992). They can reduce
the rate of scale formation to almost zero. A good scale inhibitor
must (Oilfield-Wiki., 2010):
 be sufficiently stable under the conditions imposed.
 must not interfere with the action of other oilfield chemicals,
nor be affected itself by them. It must be compatible with the
chemical injection system under operating conditions.
 hibitors (Kumar et al., 2010). Some chemistries were also proposed
be able to inhibit the scale in question, irrespective of the me-
chanisms operating.
Inhibitory action of the chemical can best be achieved by
choosing the right inhibitor and the right dosage of it, testing the
water in the well to find the type and concentration of scale
731
forming compounds present in the water and ability to place the
chemical properly. Most of the modern scale inhibitors used in the
oilfield functions by one or both of the following mechanisms
(Connell, 1983):
 When scale first begins to form, very tiny crystals precipitate
from the water. At this point, the scale inhibitor absorbs onto
the crystal surface thus preventing further growth.
 In some cases, scale inhibitors prevent the scale crystals from
adhering to solid surfaces such as piping or vessels.
6.2.1. Conventional scale inhibitors
Conventional scale inhibitors are hydrophilic, that is, they dis-
solve in water. In the case of down-hole squeezing, it is desirable
that the scale inhibitor is adsorbed on the rock to avoid washing out
the chemical before acting as desired (Fink, 2009). The most com-
mon inhibitor chemicals are inorganic phosphates, organopho-
sphorous compounds, and organic polymers. PPCA (Poly phospho-
no carboxylic acid) and DETPMP (diethylenetriaminepenta (me-
thylene phosphonic acid)) are the two common commercial scale
inhibitors used in the oil and gas industry (Kelland, 2009; Frenier
and Ziauddin, 2008; Oilfield-Wiki, 2010; Bezemer and Bauer, 1969;
Browning and Fogler, 1996). By inhibition mechanism, PPCA is said
to inhibit by nucleation while DETPMP operates by inhibiting
crystal growth (Chen et al., 2004).
6.2.2. Green scale inhibitors
The oil industry is facing severe restrictions concerning the
discharge of oilfield chemicals into the environment. More and
more severe environmental constraints have prompted users to
assume a rational management of industrial waters and brines
and to take more restrictive steps concerning its disposal. Green
chemistry, or pollution prevention at molecular level is the
chemistry designed to minimize or eliminate the use or re-
generation of hazardous materials associated with manufacture
and application of chemicals. It combines critical elements of en-
vironmental improvement, economic performance and social re-
sponsibility (Taj et al., 2006; Frenier and Wilson, 2000). The
number of chemicals allowed to be used as inhibitors has thus
been limited mainly to three criteria-tier level of biodegradability,
bioaccumulation and toxicity. According to the PARCOM (Paris
Commission), an ideal green inhibitor should be non-toxic, readily
biodegradable and shows no bioaccumulation (Taj et al., 2006).
Though the use of green scale inhibitors to inhibit scale in oil and
gas wells is relatively an unexplored area (Kumar et al., 2010),
there have been several works on this promising alternative
(Kohler et al., 2004). The inherent and consequent environmental
hazards of using these toxic and non-biodegradable scale in-
hibitors, has hindered the use of phosphonates due to their poor
ecotoxicity and many polymers, due to their failure to meet
minimum biodegradation requirements (Holt et al., 2009). Many
of the organic phosphates and phosphonates that are widely in use
as scale inhibitors are quite toxic to the environment. These have
been replaced by some organic phosphorus compounds which are
less toxic such as dibutylphosphorodithoic acid and carboxyhy-
dromethylphosphonic acids. All these inhibitors are based on
phosphorus chemistry, but environmental regulatory bodies
worldwide are encouraging operators to use greener chemicals,
hence the popularity of phosphorous free and non-toxic scale in-
including natural compounds and carboxylated plant poly-
saccharides such as carboxylated inulins (Putilova et al., 1960).
Among the “greenest “scale inhibitors are the biodegradable As-
partate and Inulin derivatives (Gupta, 2004; Miksic et al., 2005).
The biodegradation data of commonly used scale inhibitors are
given in Table 4. Fig. 5.
732 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737

Table 4
Commonly used scale inhibitors and their biodegradation data. O
H
Inhibitor type Acronym Inherent biodegradability result H N
N
Phosphonates PBTC 17% in 28 days
ATMP 23% in 28 days O O
HEDP 33% in 28 days O OH
Polyacrylic acid PAA 10% in 35 days
Phosphino polyacrylates PPCA 0% in 35 days n m
Polymaleic acid PMA 18% in 35 days
Maleic acid terpolymer MAT 35% in 35 days
alpha beta
Sulfonic acid co-polymers SPOCA 7% in 28 days (OECD 306)
Polyaspartate PASP 83-87% in 28 days Fig. 6. Molecular structure of poly-alpha, beta-D, L-aspartate (or polyaspartate
Carboxy methyl inulin CMI 4 20% (OECD 306) (PASP)).
Poly carboxylic acid PCA 68.6% in 28 days (OECD 306)
Maleic acid polymer MAP 54.9% in 35 days acetate as reagent in alkaline medium (Verraest et al., 1996). Inulin
has an excellent calcium tolerance thus allowing its application in
various oilfield conditions. It is an inherently biodegradable scale
6.2.2.1. Polyaspartate (PASP). Polyaspartates are prepared from L-
aspartic acid through three different synthetic routes that are inhibitor with an excellent ecotoxicity profile for fresh and sea-
based on intermolecular dehydration: thermal polycondensations water species. CMI is particularly effective in sequestration of hard
without or with an acid catalyst and bulk polycondensations with water cations, and thus serves as an anti-scalant which could find
catalyst (Collins, 1999). The structural formula of PASP is given in uses in food processing (Johannsen, 2003). The structural formula
Fig. 6. Laboratory studies using the jar tests and the tube blocking of carboxy methyl inulin is given in Fig. 7.
tests demonstrated that polyaspartate can inhibit both carbonate
and sulfate based scale deposits (Inches et al., 2006), and has a 6.2.3. Naphthenate inhibition
dual functionality, acting as both a scale and corrosion inhibitor Naphthenate inhibition is very crucial in oil production where
under oil field conditions (Collins, 1999; Inches et al., 2007). the crude oil and the water properties are prone to either calcium
Polyaspartate is readily biodegradable. naphthenate or sodium carboxylate/emulsion formation. In order
to reduce the extent of naphthenate formation, chemical mixtures
6.2.2.2. Carboxy methyl inulin (CMI). The carboxy methyl inulins of various compositions can be injected into the well production
(CMI) are derivatives from inulin which is a natural ß (2-1) poly- stream. Naphthenate deposition is a problem only if the aqueous
fructoside with a glucose unit at the reducing end, extracted from pH exceeds the pKa of the naphthenic acids in the oil phase.
chicory roots. Carboxylate groups are introduced into the poly- Therefore, injection of short-chain organic acids will keep the pH
saccharide by carboxy methylation with sodium monochloro low and may thus hinder formation of naphthenates scale deposits

PO3H2 PO3H2
H2O3P H2O3P
N
N N N PO3H2
N
PO3H2 H2O3P
H2O3P
H2O3P

Hexamethylenediamine Diethylenetriamine penta (methyl phosphonic acid)

tetramethylene phosphonic acid (HMDP) (DETPMP)

PO3H2
H2O3P PO3H2
N
N N

PO3H2 PO3H2

Bis (hexamethylene) triamine penta bis (methylene phosphonic acid) (HMTPMP)

PO3H2 PO3H2 PO3H2

H2O3P
N N N
N N N
PO3H2
H2O3P H2O3P H2O3P

Pentaethylene hexaamine octa kis-(methylene phosphonic acid) (PEHOMP)

O OH O OH
HO OH
O
P O
O N P
P
OH H
HO HO H m n
P
HO O OH
Nitrilotris (methylene) triphosphonic acid (NTP)
Poly phosphino carboxylic acid (PPCA)

Fig. 5. Typical phosphonate scale inhibitors to treat carbonate and sulfate scale (Dyer et al., 2003).
 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737
OH
O
OH
HO
HO
O removal (Johnson et al., 1998).
HO
O 6.3.1. Mechanical methods
HO
HO CH2
x last option (Fleming, 2010; Sho-Wei et al. 2011). It is very expensive,
(x = 1 - 50)
HO O does not remove the scale deposits from the formation i.e from
O outside the wellbore, thus ignoring all the formation damage. An
HO
CH2
HO
OH
Fig. 7. Molecular structure of carboxy methyl inulin (CMI).
(Goldszal et al., 2002). The formation of calcium naphthenate can
also be contolled by using acid injection approach (Hurtevent and
Ubbels, 2006; Turner and Smith, 2005; Vinstad et al., 2003). Acetic
acid is the most commonly used chemical for the inhibition of
naphthenate formation worldwide (Ese and Kilpatrick, 2004;
Brocart et al., 2005; Lutnaes et al., 2005). The application of this
acid to lower the water pH to r 6 has been reported to produce
the minimum level of naphthenate deposits (Rousseau et al., 2001;
Ese and Kilpatrick, 2004; Shepherd et al., 2005). Acid demulsifiers
consisting of acetic acid in an aromatic solvent mixture, and
non-acid demulsifiers consisting of ethoxylates and alcohol, have
shown to reduce naphthenate scale deposition significantly
(Gallup and Star, 2004). The main mechanism behind naphthenate
inhibition by using non-ionic surfactants is a competitive process
which takes place at the interface. Ethoxylates are highly inter-
facially active and have much higher affinity towards the o/w in-
terface than naphthenic acids. Consequently, they may occupy the
interface and thus hinder the naphthenic acids to reach it and to
further react with the cations.
Phosphoric acids and phosphoric based products, rather than
acetic acid, have also been reported to be effective on sodium car-
boxylate emulsions (Gallup et al., 2005). Other types of acids and
their products, such as sulfonic and hydrochloric acids, have been
used in the past to inhibit naphthenate formation (Vinstad et al.,
2003; Turner and Smith, 2005). The use of inhibitors rather than
acid is becoming common in the petroleum industry due to the vast
logistics involved in deploying large volumes of acid solutions. Re-
cently, Gallup et al. (2010) reported the use of some naphthenate
inhibitors that were able to inhibit the formation of sodium soap
emulsion in a South East Asian field. These inhibitors were tested
733
on sodium soap emulsion that could not be inhibited using
the acidic demulsifier. These inhibitors were suggested to work via
complexation.
6.3. Scale removal
Calcium sulfate (CaSO4) and strontium sulfate (SrSO4) scale
deposits that are formed in sandstone formations are difficult
to remove chemically and impossible to remove mechanically
whereas scale deposits form from incompatible water mixing oc-
curring in tubing are accessible to both chemical and mechanical
Mechanical removal has been used in the past for removing
scales (Amjad and Zuhl, 2008). Use of mechanical method (drilling
or reaming) is quite easy to understand and has been used to re-
move different kinds of scale depositions. However, it is not without
several limitations and therefore should only be considered as the
a drilling rig has to be moved in and, particularly in deep well, with
a lot of complications associated with the drilling process. Also the
method is not very effective for re-stimulating a well because it
impermeable skin may also remain inside the wellbore caused by
the drilling cuttings squeezed into the perforation holes or pro-
duction slots in the tubing or liner; and this can cause the pro-
ductivity to drop to zero. Therefore chemical procedures of re-
moving scale are preferred over mechanical methods (Vetter, 1976).
6.3.2. Chemical treatment method
Chemical scale removal is often the lowest cost approach,
especially when scale is not easily accessible or exists where con-
ventional mechanical removal methods are ineffective or expensive
to deploy. The role and the impact of the different reactants used for
the chemical treatments (hydrochloric acid (HCl), hydrofluoric acid
(HF), chelatants and mixed compounds) will be discussed.
6.3.2.1. Acid stimulation (acidizing). Acidizing is the most widely
used stimulation practice in the oil industry. The rate of flow of oil
or gas out of production wells or the rate of flow of oil-displacing
fluids into injection wells may be increased by dissolving all acid
soluble components within underground rock formations, or re-
moving material at the wellbore face. Different carbonates scales
like calcium carbonate (calcite; CaCO3) and iron carbonate (side-
rite; FeCO3) as well as iron sulfide, and iron oxide (Fe2O3) are so-
luble in acid. Carbonate scale can be dissolved in both organic acid
(e.g. citric, formic or sulfamic acid) and in inorganic acids (e.g.
hydrochloric acid). Hydrochloric acid (HCl) is the cheapest and
easiest acid to use, but the disadvantage is that the acid is very
corrosive. This means that a corrosion inhibitor must often be
added to the acid solution when being used (Kelland, 2009;
Ramstad et al., 2005). Most of the reaction products of HCl and
carbonates are water soluble and are easily removed (eq. (32)).
2HCl(aq) + CaCO3 (s) → CaCl2 (aq) + CO2 (g ) + H2 O(l) (33)
Although hydrochloric acid is considered to be the best oilfield acid
for most applications, the system can be very costly, particularly in
high-temperature environments that require additives to control re-
action rates. Hydrochloric acid reacts so quickly with carbonates and
thus may require chemical retardants to extend the reaction time and
allow the acid to dissolve the carbonate formation completely as un-
dissolved impurities in the limestone can plug the formation if they
are allowed to settle after a matrix treatment.
734 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737
Table 5
Relative solubility of calcium carbonate in various acids.
Acid Dissociation constant, Relative solubility of carbonate
Ka at 77 °F (Ib/1000 gal. of acid)
HCl 10 3500
Formic 1.77  10  4 700
Acetic 1.75  10  5 400
Again, prolonged contact of hydrochloric acid with steel pipe at
high-temperature can cause severe corrosion. In high-temperature
wells, effective inhibition can be difficult and costly with HCl.
Consequently, organic acid with their slower reaction rates can be
more effective. They have lower corrosion potential and are easier
to inhibit at high temperatures than hydrochloric acid. Organic
acids such as acetic, formic or citric are less commonly used in
carbonate stimulation because of their high cost and relatively
poor performance in dissolving carbonate scales at low tempera-
tures. Table 5 shows a comparison of the solubility of calcium
carbonate in different acids (Al Kaabi 2003). Other possible
treatment fluid includes combinations of hydrochloric acid with
one or more organic acids to balance the limitations of each of the
classes, especially for high-temperature carbonate formations.
These combinations are sometimes used for acidizing high-tem-
perature carbonate formations. They combine the fracture-face
etching power of hydrochloric acid with the deeper formation
penetration of organic acids.
Optimization of acid reaction rates is a key factor in obtaining
the desired effects on the formation at downhole conditions.
Sufficient acidization must be achieved without overtreatment,
which could cause the collapse of pore structures, and may reduce
well productivity (Al Kaabi, 2003). Acid strength, temperature,
pressure, pumping rate, leak-off control and rock composition are
among the important factors that influence reaction rates.
Hydrochloric acid is not a good solvent for CaSO4. The max-
imum solubility of calcium sulfate in HCl is only 1.8 wt% at 25 °C
and atmospheric pressure (Al Kaabi, 2003). Gypsum can be con-
verted to acid soluble compounds by using converters such as
(NH4)2CO3, Na2CO3, NaOH and KOH. The following reactions il-
lustrate the mechanism of converter performance.
CaSO4 + (NH4 )2 CO3 → (NH4 )2 SO4 + CaCO3 (soluble)
The calcium carbonate is then dissolved with HCl:
CaCO3 + 2HCl → H2 O + CO2 ↑ + CaCl2
Scales are frequently coated with hydrocarbons, thus making it
difficult for acid to contact and dissolve the scales. Surfactants can
be added to all types of acid solutions to develop a better acid-to-
scale contact. Surfactant selection for this use should be tested to
ensure that the surfactant prevents acid-crude oil emulsion and
also leaves rock surfaces waterwet.
6.3.2.2. Chemical stimulation with chelating agents. An alternative to
acid treatment is the use of chelating agents such as ethylenediami-
netetraacetic acid (EDTA) or nitrilotriacetic acid (NTA). Chelating
agents have the ability to chelate, or bind, metals such as calcium ion
in the scale deposits (Nergaard and Grimholdt, 2010). Through the
process of chelation, a calcium ion would be solvated by the chelating
agent, allowing the calcite to be transported either to the surface by
flowing the well or further into the formation by injecting into the
well. The rate of calcite dissolution using chelating agents is not as fast
as the rate of calcite dissolution using strong mineral acids. The lower
dissolution rate allows the chelating agent to take a more balanced
path and more evenly dissolve calcite along the wellbore and in all
available fractures, rather than following the first fluid entry zone and
leaving the rest of the wellbore relatively untouched. The chelatants
are mainly used in oil and gas wells with the advantage of having very
low corrosion rates, much lower than that of HCl solutions, in the
same conditions. As a consequence, the use of chelatants needs small
amounts of inhibitor to protect the casings. Among the chelatants, the
most commonly used are compounds of the EDTA family Ethylene-
diaminetetraacetic acid (EDTA), Hydroxyethylenediaminetriacetic acid
(HEDTA), Hydroxyethyliminodiacetic acid (HEIDA), Nitrilotriacetic acid
(NTA)). The disadvantages of using chelatants are their high cost
compared to acids and for some of them, their impact on the
environment.
There are some commercially available chemicals such as EDTA
and diethylene triamine penta acetic acid (DTPA), which can re-
move gypsum scale without conversion. Calcium sulfates are so-
luble in many chelate dissolvers and is therefore the easiest sulfate
scale to handle. In contrast, barium sulfate is more difficult to
handle, being very hard (Al Salami and Monem, 2010; Kelland,
2009; Ramstad et al., 2005). The dissolution mechanism is differ-
ent from conventional acids in that hydrogen ions are not re-
quired. However, the rate of dissolution is enhanced at low pH as a
result of the combined influence of hydrogen ion attack and che-
lation. The rate of calcium sulfate dissolution varies considerably
with pH and the type of chelating agent because of changes in the
ionic form of the chelating agent and the influence of hydrogen ion
attack. In general, the rate of calcium sulfate dissolution increases
as the number of hydrogen ions associated with the chelating
agent increases. Based on the chelation behavior of EDTA, one
molecule of fully ionized EDTA (EDTA-4) is required to chelate
each dissolved calcium ion in accordance with the following
equation
2Ca2 + + EDTA−4 ⇔ EDTA Ca2 (36)
It has also been found that a mixture of 2% citric acid and 2%
EDTA is extremely effective in dissolving iron oxide deposits and
deposits containing copper oxides (Palma and Mecozzi, 2007;
Argañaraz MBQ et al., 2010). According to the authors, sulfate-
containing deposits will even be dissolved when this mixture of
chelating agents is employed.
(34)
7. Scale management and prediction in ultra-deepwater wells
The ultra-high temperature (150–250 °C), pressure (1000–
(35)
2000 bar, 15,000 to 30,000 psi) and TDS ( 4300,000 mg/L) in
deepwater oil and gas production pose significant challenges to
scaling control due to limited knowledge of mineral solubility,
kinetics and inhibitor efficiency at these extreme conditions. Pre-
diction of thermodynamic properties of common minerals is lim-
ited by lack of experimental data and inadequate understanding of
modeling parameters. Shi et al. (2012) evaluated predictions by a
thermodynamic model based on Pitzer's ion interaction theory
using experimental data. They examined the dependence of Pit-
zer's coefficients (Pitzer, 1975, 1973; Pitzer et al., 1985, 1984; Ro-
gers and Pitzer, 1981) for ion activity coefficients on temperature
and pressure and incorporated them into the scale prediction
model. Their prediction is consistent with both experimental and
literature data at all conditions tested. Fan et al. (2012) examined
the accuracy of the saturation index (SI) predicted by the scale-
prediction software, ScaleSoftPitzer™ (SSP) at HT/HP. Their results
indicate that in an ultra-deepwater production, well conditions
such as temperatures, pressures, TDS, and alkalinity are often
difficult to measure accurately. A small error in the measurement
can cause a totally different scale prediction at these HT/HP
 A.A. Olajire / Journal of Petroleum Science and Engineering 135 (2015) 723–737
conditions and therefore concluded that more caution is needed in
scale prediction at harsh conditions for any field application.
Deepwater oil and gas production involves hydrocarbons,
produced water (brine), carbon dioxide (CO2), hydrogen sulfde
(H2S), and other chemicals. Under high pressures and tempera-
tures, brine can form acidic mixtures that cause general corrosion
and pitting of pipes and solid mineral deposits (scale) that inhibit
flow in a well. Another unforeseen situation is that the tempera-
ture of ultra-deepwater is high enough for water to dissolve sand
(SiO2) forming volatile orthosilicic acid (eq. (36)), which in itself is
an interesting problem.
SiO2 + 2H2 O → H4 SiO4
Silicic acid
The pressure drop experience by the fluid during transporta-
tion from reservoir to topside, with subsequent increase in pH, can
lead to dissociation of orthosilicic acid at the o/w interface as
shown below:
H4 SiO4 → SiO44 − + 4H+
The dissociated orthosilicate anion, SiO4−
4 at the oil-brine in-
terface reacts with either Ca2 þ or Na þ cation or both in the brine
to form stable silicate mineral deposits of different classes (eqs.
38–40), thereby causing flow assurance issues at the surface fa-
cilities.
SiO44 − + 2Ca2 + → Ca2 SiO4
SiO44 − + 4Na+ → Na 4 SiO4
SiO44 − + 2Na+ + Ca2 + → Na2 CaSiO4
Although production companies take steps to mitigate scale
formation, such as the use of scale inhibitors which are primarily
meant for onshore or shallow water offshore and were not re-
quired to withstand high-temperature/high-pressure (HT/HP) and
salinity conditions found in ultra-deepwater reservoirs. Now,
deepwater operations are changing the game of oilfield production
chemicals, requiring significant innovation, as well as modifica-
tions to the existing technology, to be effective.
More deepwater projects are also using seawater flooding that
will result in potential scale formation and require sophisticated
scale inhibitor treatment programs to prevent flow assurance is-
sues. Recent innovations in scale monitoring use a quartz-based
crystal that is sensitive to microscopic inorganic deposition to
predict the potential for scale formation. This real-time process
allows scaling problems to be predicted and controlled on site by
determining brine stability as well as other crucial scaling ten-
dency parameters. The scale treatment cost and the potential well
remediation cost are reduced by continually optimizing the scale
inhibitor treatment program. Remotely located deepwater projects
can realize substantial savings from these two benefits alone.
8. Conclusion
Many oilfields are under threat of scale formations in produc-
tion facilities. When scale deposits are held onto the production
equipment surface, it reduces its diameter and subsequently grows
continuously until it blocks the tubing as well as the surface
equipment. This leads to production stoppage, and results in losses
to the production company. Therefore, scale formation should be
given a priority treatment because of its threat to flow assurance.
A good management strategy must be put in place to prevent it
from building up or having further occurrence. Just as it has been
735
acknowledged over the years that scale prevention is better than
waiting until it forms and then taking remedial action. Many dif-
ferent technologies that could potentially be deployed by the oil-
field operators to reduce the risk of scale formation, control scale
formation and to remove it if formed within downhole and topside
oil/gas facilities are critically reviewed. With the significant ad-
vancement and improvements in chemistry and fluid finish for
effective scale inhibitions, oilfield scale can be removed from in-
side the tubular without risk to the steel tubing.
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