SPE-202267-MS

Systematic Calcium Carbonate Scale Risk Evaluation from Downhole to

Topside Flowline

Norah Aljeban, Bader Al-Harbi, Tao Chen, and Salem Balharth, Saudi Aramco

Copyright 2020, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Asia Pacific Oil & Gas Conference and Exhibition originally scheduled to be held in Perth, Australia, 20 - 22
October 2020. Due to COVID-19 the physical event was postponed until 17 - 19 November 2020 and was changed to a virtual event. The official proceedings were
published online on 12 November 2020.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
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Abstract
The formation of CaCO3 mineral scale is a persistent flow assurance problem in the oil and gas industry. It
deposits at various locations with different levels from reservoir to topside flowline. It could restrict well
intervention, block flowline and reduce production. To make an effective mitigation strategy, it is essential
to understand the location and severity of scaling, and the performance of scale inhibitor under specific
operation conditions.
In the work reported herein, the dynamic scale loop tests were performed to evaluate the severity of scale
deposition at different locations from the reservoir to transport flowline in the absence and in the presence
of scale inhibitors under dynamic conditions. The tests are carried out at various temperatures (20-130°C)
and pH (6.0-8.3), which are major factors contributing to calcium carbonate formation and representative
of the operating conditions at different locations from reservoir to topside flowline.
The results showed low calcium carbonate risk from reservoir to wellhead under tested conditions.
Although the high reservoir temperature favors calcium carbonate formation in downhole, the low pH
reduces the risk of calcium carbonate formation at downhole conditions. Harsher calcium carbonate
deposition is evaluated at the conditions of phase separator/degasser units due to the higher pH of produced
water after released CO2 from fluid. Calcium carbonate scale can also deposit in transport flowline,
especially at high temperature during summer in the desert area, along with higher pH of the produced water.
Calcium carbonate scale prevention and mitigation treatments are required to inhibit scale deposition. The
tested phosphonate scale inhibitor provides low dose rate to effectively inhibit calcium carbonate formation
at high temperature. The corrosion inhibitor could have a negative impact on the performance of scale
inhibitor, and this must be considered when designing the scale inhibitor treatment.
This paper gives a comprehensive study of scaling risk evaluation from downhole to topside flowline in
the absence and in the presence of scale inhibitor. It contributes to the understanding of calcium carbonate
formation and inhibition in the whole production system and recommends effective scale mitigation
strategies.
2 SPE-202267-MS

Introduction
The formation of mineral scales, CaCO3, BaSO4, and CaSO4, etc., is one of the major flow assurance
problems experience in the oil and gas industry. It can deposit from the reservoir to transport flowline, which
affects well deliverability, interferes with well surveillance, restricts well intervention and blocks flowline
(Yang, 2001; Zhang, 2001; Shen, 2008).
The precipitation of calcium carbonate (CaCO3) deposit is controlled by the equilibrium shown in
Equation 1. Calcium ions react with bicarbonate ions, and form calcium carbonate deposit under a certain
condition.
(1)
The two major driving forces causing CaCO3 deposition in the oil and gas industry are reduction in
pressure and high temperature during production (Alkhaldi, 2009; Proctor, 2000). Pressure drop leads to
the loss of carbon dioxide (CO2) as gas-phase forms from the aqueous solution. The continuous released
CO2(g) from fluid due to pressure drop disturbs the equilibrium of the system and increases the chemical
driving force of the forward reaction of Equation (1). Consequently, the reaction moves towards the right-
side of Equation 1 and facilitates the increased precipitation of CaCO3. The solubility of CaCO3 decreases
with temperature increase; hence CaCO3 crystallization frequently occurs at high temperature (Kjellin,
2001). In addition, the kinetics of CaCO3 scale formation is a function of temperature, i.e., slow kinetics
at low temperature. As the temperature increases, the formation of calcium carbonate will accelerate, and
precipitation may occur at an earlier stage (Oddo, 1982). The risk of CaCO3 scale is various from the
reservoir to topside facilities due to the change of the temperature and pressure at different locations.
One of the most common methods to mitigate calcium carbonate scale in the oil and gas industry is to
apply scale inhibitor treatment through continuous injection or squeeze treatment. The principal inhibitor
types used in order to control deposition in the oil and gas industry are polyphosphates, phosphonates,
polycarboxylic acid and polyelectrolytes. The key characteristics of the inhibitors are summarized in
Table 1. The inhibitors can work on different conditions against specific scales. The selection of scale
should be according to the type of scale and detailed operation conditions. For example, Diethylene
triaminepenta(methyl enephosphonic acid) (DETPMP) has very good inhibition performance against
CaCO3 scale at high temperature of 150 °C (Chen, 2012) but poor inhibition performance at low temperature
of 20 °C compared to polymeric scale inhibitor (Chen, 2004).

Table 1—Summary of the characteristics of scale inhibitors (Chen, 2005)

Inhibitor Temperature Scale Existing conditions

CaCO3; CaSO4;
phosphate Stable up to 90 °C Soluble in and compatible with high calcium brines
SrSO4; BaSO4

Stable up to 170
Against the various In acid form or with any portion of the acidity neutralized by ammonia, amines or
Phosphonates °C depending on
types of scales alkaline hydroxides.
chemistry

Polycarboxylic acid CaCO3; CaSO4; Crystal distorters or dispersive, often blended with other types of scale inhibitors to
200 °C or higher.
or polyelectrolytes BaSO4 obtain at low dosage rates.

The mechanism of inhibition of scale is mainly categorized as three types, nucleation and growth, crystal
distortion and dispersion. Scale inhibitors can act as a nucleation center to chelate the calcium/barium/
strontium cations, which results in a decrease of activity of free cations and causes a lower supersaturation. It
can prevent the formation of scale ion pair and nuclei, and further hinders the growth of scale crystals through
adsorption at active growth sites on the crystal surfaces. The scale inhibitor is able to be adsorbed on specific
crystal surfaces and hinders growth there (Nancollas, 1975). Crystal distortion is another mechanism where
SPE-202267-MS 3

the inhibitor adsorption onto the nuclei can change the crystal structure during growth and the change often
involves a loss of adhesion on the solid surface and easier dispersion. The dispersion mechanism is an
indirect inhibition mechanism, where the ability of chemicals are to reduce the agglomeration and settling
of suspended particles. With the inclusion of a relatively large, irregularly shaped polymer in the crystalline
lattice, scale can often be prevented from developing or adhering to surfaces where it could cause problems
(Sohenel, 1982; Gill, 1980).
The inhibition mechanism are different depending on the specific inhibitor chemistry. The combined
scale inhibitors with varying mechanisms of inhibition could perform better than a single scale inhibitor
component. Chen et al, (Chen, 2012) studied a combined polymer and phosphoric based scale inhibitor.
The polymer based inhibitor showed the inhibition effect on induction time and nucleation and growth
stage. The phosphoric based scale inhibitor showed dispersion effect on scale inhibition. The combined
scale inhibitor at a certain mixing ratio showed a synergistic effect on BaSO4 inhibition with much
better inhibition performance than either single component. Ko et al., (Ko, 2020) studied the combined
carboxymethylcellulose (CMC) and phosphonate scale inhibitors. CMC can effectively inhibit BaSO4,
CaSO4 and CaCO3 through dispersive mechanism. When it is combined with a phosphonate scale inhibitor, a
nucleation and crystal growth inhibitor, the inhibition performance against the sulfate scale was significantly
improved.
This paper gives a laboratory evaluation of scaling risk from downhole to topside flowline under different
conditions. The combined phosphonate and polymer inhibitor was introduced to mitigate scale formation
under worse scaling condition at transport flowline.

Experiment procedures
The dynamic tube blocking test has been carried out in this study to evaluate the risk of calcium carbonate
deposition at different test conditions. A schematic of the dynamic tube blocking system is shown in Figure
1. The test consists of the single injection of two scaling test brines, anion and cation, at equal rates into the
apparatus. Both brines pass into heating coils within the oven set at the test temperature. At a T-junction,
the brines mix and pass into the scaling coil. The differential pressure (DP) is measured across this scaling
coil and rises once scale formation and adhesion to the coil walls causes a blockage. Differential pressure
(DP) is recorded as a function of time.
4 SPE-202267-MS

Figure 1—Flow diagram of the dynamic tube blocking system (Xu, 2014)

All tests were performed under the conditions given below.

Scaling coil length: 1m

Scaling coil internal diameter: ~1mm
Coil: Stainless steel coils
Total brine flow rate: 10ml/min
Back pressure: 300 psi
Pass criteria: < 1psi pressure rise in DP over a set time
Temperature: 25-130°C

The chemistry of tested water is shown in Table 2.

Table 2—Formation water chemistry for calcium carbonate scaling tests

Formation Water (ppm)

Na+ 19000

Ca2+ 6000

Mg 2+ 50

Cl
- 40000

HCO3 -
450

pH 6.0 - 8.2
SPE-202267-MS 5

The generic chemical components of tested scale and corrosion inhibitors are listed in Table 3, including
phosphonate and polyacrylic scale inhibitors and a propyn/methyloxirane corrosion inhibitor.

Table 3—Basic chemical component of tested scale inhibitors

Inhibitor Inhibitor Chemistry

Scale inhibitor (SI-1) Phosphonate based inhibitor

Scale inhibitor (SI-2) Polyacrylic based polymer

Corrosion inhibitor (CI) Propyn/methyloxirane

Results and Discussion

The first set of experiments was conducted to investigate the calcium carbonate formation tendency over
a wide range of parameters corresponding to reservoirs, wellhead, and flowline conditions. Calcium brine
and bicarbonate brine were injected at 5 ml/min each.
To evaluate calcium carbonate scale risk at the downhole condition, the test temperature and pH of scaling
water were set at 130 °C and 6.0, respectively. As shown in Figure 2, the pressure across the coil increased
by 1 psi within 10 minutes and then it took around 2 minutes to increase from 1 psi to 5 psi. The passing
criteria of scaling test is < 1psi pressure rise in DP over a set time. So, the scaling time under downhole
condition is about 10 minutes. A similar trend was obtained when the test was repeated, indicating good
reproducibility.

Figure 2—Calcium carbonate formation at 130 °C and pH 6, i.e., downhole conditions

Another experiment was conducted to examine the CaCO3 scaling tendency at wellhead conditions, i.e.,
T=50 °C and pH=6.6. It is clear from Figure 3, and there is no scale up to 30 minutes at wellhead conditions.
6 SPE-202267-MS

Figure 3—Calcium carbonate formation at 50 °C and pH 6.7 i.e. wellhead condition

Similarly, when the scale tendency was tested at 25°C and pH of 8.2, representing for scaling in transport
flowline during winter in the region, there was no scale formation in the first hour, then there was a slight
increase in the pressure indicating CaCO3 scale formation. In the oil and gas production region in this study,
the temperature could drop to about 10°C during the winter, where the calcium carbonate scaling risk should
be even lower due to the lower calcium carbonate supersaturation at low temperature.
Another test was repeated under the similar conditions as test shown in Figure 4, except at a temperature
of 50 °C instead of 25 °C, which represents the worse scaling scenario of transport flowline during summer
in the region. It is interesting to note the difference in the scaling tendency due to the slight increase in the
temperature as shown in Figure 5. The differential pressure increased gradually by 1 psi within 40 minutes
as a consequence of the scale formation. It indicates a harsher calcium carbonate scale could deposit during
summer time in the transport flowline, and the tendency of scaling is harsher than in winter (Figure 4).

Figure 4—Calcium carbonate formation at 25 °C and pH 8.2, i.e., transport flowline in winter
SPE-202267-MS 7

Figure 5—Calcium carbonate formation at 50 °C and pH 8.2, i.e., transport flowline in summer

As shown in the previous figures, the calcium carbonate scale can form and be expected harsh deposition
in the downhole conditions where the temperature is 130°C. Thus, two scale inhibitor chemistries were
examined at 130°C. In this set of experiments, the pH was increased from 6 to 6.75, which is a worse scaling
condition used to evaluate the performance of scale inhibitors in this study. The results are plotted in Figure
6 and Figure 7 for the phosphonate (SI-1) and polymeric (SI-2) scale inhibitors, respectively. In the absence
of scale inhibitors, the scaling time is about 8 minutes. In the presence of 15 ppm SI-1, it took more than 30
minutes for the differential pressure increase up to 1 psi. The inhibition test was carried out with different
concentrations of SI-1. The inhibition results clearly show that 1.875 ppm SI-1 was not sufficient to delay
the calcium carbonate inhibition as the scaling time (1 psi increase) was 9 minutes while it was 8 minutes in
the blank solution. Increasing the scale inhibitor concentration to 3.75 ppm and 7.5 ppm resulted in better
inhibition efficiency suggested by the delay in the increase in the pressure difference. In 3.75 ppm and 7.5
ppm inhibitor solutions, the pressure increased by 1 psi after 20 minutes and 30 minutes compared to that
of 8 minutes in the blank solutions. It is interesting to note the difference in the trend of pressure increase
between 15 ppm SI-1 solution and the rest of the solutions. In the presence of 15 ppm SI-1, the pressure
increased gradually to 1 psi, and then it took around 20 minutes to increase to 5 psi. The rest of solutions,
e.g., 7.5 ppm SI-1, the pressure increased to 1 psi after 30 minutes followed by sharp increase to 5 psi in
almost 2 minutes. In this study, the passing criterial of scale inhibitor efficiency is the scaling time in the
presence of a certain concentration of scale inhibitor up to 30 minutes (when 2.5-3 times of blank is less
than 30 minutes). Therefore, the Minimum Inhibitor Concentration (MIC) is 7.5 ppm for SI-1.
8 SPE-202267-MS

Figure 6—Calcium carbonate inhibition at 130 °C and pH 6.75 using phosphonate scale inhibitor

Figure 7—Calcium carbonate inhibition at 130 °C and pH 6.75 using polymeric scale inhibitor

Another polymer-based scale inhibitor (SI-2) was examined for calcium carbonate inhibition to examine
the inhibition efficiency of the tested polymeric scale inhibitor, and compare the results with the tested
phosphonate inhibitor. As shown in Figure 7, up to 30 ppm of SI-2 did not show promising inhibition
efficiency, as the scaling time was less than 12 minutes. According to the pass criteria, i.e., <1 psi increase
in pressure over 30 minutes (when 2.5-3 times of blank is less than 30 minutes), 15 ppm and 30 ppm SI-2
failed to prevent calcium carbonate scaling under tested conditions.
In the oil and gas industry, scale inhibitor and corrosion inhibitors are commonly used to prevent scale
and corrosion from the downhole to topside facilities. Scale and corrosion inhibitors could inject in the same
produced water to inhibit both scale and corrosion simultaneously. Scale inhibitor and corrosion inhibitor
have different chemistry, and could interfere with each other and impact on the inhibition performance.
To investigate the impact of corrosion inhibitor on the inhibition efficiency, 0.1 ppm corrosion inhibitor
was added to 7.5 ppm SI-1, and results are plotted in Figure 8. It is clear from this set of experiments, the
corrosion inhibitor had a negative impact on the performance of SI-1 as the scaling time decreased from 30
minutes (see Figure 6) to 10 minutes (see Figure 8) as a consequence of the addition of 0.1 ppm corrosion
inhibitor.
SPE-202267-MS 9

Figure 8—Calcium carbonate inhibition at 130 °C and pH 6.75. Impact of corrosion inhibitor on the inhibition efficiency.

Conclusions
The formation and the inhibition of calcium carbonate scale have been investigated using dynamic apparatus
over a wide range of parameters. The main conclusions are
– The calcium carbonate scaling tendency and risk are different from the reservoir to the topside
flowline. In this study, it showed the calcium carbonate scale is problematic at downhole conditions,
i.e., high temperature; however, it can form downstream as a result of the increase in the temperature
in the summer.
– The tested phosphonate scale inhibitor managed to delay the formation of calcium carbonate scale
while the tested polymeric scale inhibitor did not show promising inhibition results.
– The tested corrosion inhibitor had a negative impact on the performance of the tested phosphonate
scale inhibitor, and this must be considered when designing the scale inhibitor treatment.

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