SPE-184514-MS

A New Approach to Combined Sulphide and Carbonate Scale Predictions

Applied to Different Field Scenarios

G. Verri, K. S. Sorbie, M. A. Singleton, and D. Silva, Heriot-Watt University; C. Hinrichsen, Chevron; Q. Wang and
F. F. Chang, Saudi Aramco

Copyright 2017, SPE International Conference on Oilfield Chemistry

This paper was prepared for presentation at the SPE International Conference on Oilfield Chemistry held in Montgomery, Texas, USA, 3–5 April 2017.

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
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Abstract
Unlike other types of inorganic scales, carbonate and sulphide scales are directly correlated to the in-situ
concentration of acid gases such as CO2 and H2S, which influence the local pH and availability of reactive
species. The common approach to sulphide and carbonate scale prediction often does not account for three
phase CO2 and H2S partitioning at different temperatures and pressures along the system. This leads to the
use of inaccurate compositions and pH values for the mineral scaling calculations.
In this paper, we apply a rigorous workflow (step-by-step procedure) based on a compositional PVT
model to calculate molecular CO2 and H2S distribution, three phase relative volume changes, compositional
changes and scale precipitation trends from the reservoir to the wellhead separation stage using commonly
available surface field data, a full PVT software and a scale prediction software of user's choice.
A simplified version of the workflow was previously applied to high CO2 and H2S gas/condensate wells
with production of condensed water only (Verri et al., 2016).
This paper focuses on the field application of our general workflow to North Sea oil wells with high water
cut and medium H2S levels (≈2200 ppmv in the separator gas phase). By following this rigorous procedure
and applying the concept of Maximum Dissolved Iron (MDI) we were able to provide accurate sulphide
and carbonate scale prediction profiles from reservoir to separator.
The combination of reservoir, production and chemical engineering models using specific iterative
processes (within the workflow) has provided a new and reliable step-by-step procedure for the prediction
of combined sulphide and carbonate scales in oil and gas wells which can be implemented by anyone using
any PVT and scale prediction software. However, in our ongoing work, we are building a model which
incorporates all of this workflow by coupling together PVT/VLE models with our aqueous scale prediction
software.

Introduction
To accurately predict carbonate and sulphide scale precipitation we must correctly model the three phase
CO2 and H2S partitioning and obtain in-situ values for aqueous molecular carbonate and sulphide species.
2 SPE-184514-MS

These values are closely coupled with the water pH and directly impact the formation of scale such as
CaCO3, FeCO3 and FeS as shown schematically in Figure 1.

Figure 1—Schematic representation of carbonates and sulphides partitioning, speciation and precipitation.

Although some software models integrate PVT and scale prediction models, these packages are usually
more targeted to aqueous systems and have limited hydrocarbon capabilities. Likewise, full PVT software
packages do not normally model pH, speciation and scale prediction in the aqueous phase. In addition, little
has been published on the correct use and manipulation of commonly available field data and there is no
widely available comprehensive step-by-step procedure to predict scale profiles from reservoir to separator
(Verri et al., 2016).
The Flow Assurance and Scale Team (FAST) at Heriot-Watt University have been trying to close this gap
by developing and applying a general scale prediction workflow based on a compositional PVT model to
rigorously quantify carbonate and sulphide scale precipitation from reservoir to first separation stage using
commonly available field data analysed using full PVT and scale prediction software.
It is important to highlight that this is not a new software but a methodology which can be applied using
any PVT and scale prediction code of user's choice. Nevertheless, when running these types of calculations
we must be aware of the main issues which can be associated with each software package. An upcoming
publication will include a full list of measurement, procedural and model errors associated with carbonate
and sulphide scale predictions but some will also be discussed as part of this work.

The Workflow
The workflow developed by Heriot-Watt University is divided in two parts:
– Part1: From separator to reservoir. These first calculations steps are aimed at reconstructing the
reservoir water chemistry from separator water chemistry and are based on Equation (1). The
concentrations are expressed in mol/l and the derivation of this equation will be included in an
upcoming publication.

(1)
– Part 2: From reservoir to separator. This second set of calculations allows us to obtain a scale
precipitation profile in the wellbore and at separator conditions use the calculated reservoir water
composition.
The workflow steps are shown in Figure 2.
SPE-184514-MS 3

Figure 2—HWU Workflow for determining scale prediction profiles

from reservoir to separator using commonly available field data.
4 SPE-184514-MS

The entire workflow will be described in details in a forthcoming publication from the Heriot-Watt
University FAST (Flow Assurance and Scale Team) laboratories.
In the current paper, we focus specifically on the application of the workflow to real field data and show
the results obtained from a North Sea reservoir.
Before moving to the field application, it is important to note that by "reservoir water composition" we
refer to the near wellbore reservoir brines that are "just produced" i.e. he composition of the water which
is just about to enter the wellbore. Note that, since produced water compositions are known to change over
time, then the currently produced brine is likely to be different from deep reservoir conditions depending
on the geochemical and microbial reactions which occur in the reservoir.
In addition, due to the uncertainty associated with water soluble iron measurement in sour systems
(NACE, 2012) we applied the Maximum Dissolved Iron (MDI) concept (upcoming conference paper,
(Verri and Sorbie, 2017)) and investigated iron sulphide formation after running the carbonate and sulphide
equilibrium calculations.

North Sea Oil Well Example

A number of water flooded North Sea oil wells producing 19°API oil were investigated as part of this project
and in this paper we show example results for well "O". The field data available for well "O" is shown in
Table 1 and original PVT reports for this reservoir hydrocarbon were also available.

Table 1—Well "O" field data.

T(°C) p (bar) BFPD Water Gas CO2 Gas H2S Ca2+ (ppm Alkalinity Salinity
cut (%) (%) (ppmv = = mg/kg) (eq. HCO3– (mol NaCl/
vol/vol) mg/l) l solution)

Separator 65 8 12,830 95 0.45 2200 370 740 0.58

Reservoir 77.78 221 – – – – – – –

While applying the HWU general scale prediction workflow, we identified some key challenges
associated with this type of produced fluids:
– The deviation between measured and simulated parameters in the hydrocarbon Equation of State
(EOS) can be significant when pseudo components are used (i.e. C7+, C10+) (Pedersen and Christensen,
2007). The pseudo component fraction of a 19°API oil is significant and for this reason we run PVT
experimental data regression.
– Although water is an integral part of the reservoir and produced fluids, the hydrocarbon composition
and PVT experimental data only refer to the hydrocarbon fraction. The phase behaviour of water-
hydrocarbon mixtures is more complicated because water is a polar molecule and can associate with
other water molecules (Danesh, 1998). Hence, we need to account for this water-water interaction
in the choice of EOS and mixing rule. Numerous alternatives have been proposed but we are
restricted to the equations implemented in the available PVT software. In our case we used Winprop
(CMG, 2014) which only runs Soave-Redlich-Kwong (SRK) and Peng-Robinson (PR) EOS, both not
recommended for water-hydrocarbon interaction. In our future work we will compare these results
with others obtained using a different PVT software and mixing rule choice. At this stage we believe
that although the final values may be different, the scale prediction trends will remain the same.
Nevertheless, we must prove this assertion as part of our future work.
– The wells investigated produce a medium/low H2S concentration (500-2200ppmv in the separator
gas phase). At these lower concentrations the relative H2S solubility error will be higher than for the
high H2S gas condensate wells discussed in a previous publication (Verri et al., 2016). A possible
SPE-184514-MS 5

way to address this problem would be to obtain reliable three phase H2S field measurements and use
these values to tune the solubility parameters. Although Winprop has the capability to do this type
of data fitting, the experimental data was not available.
For this work we used Winprop PVT software (CMG, 2014) despite some issues associated with
modelling water-containing systems. As part of our future work we will be comparing results obtained using
different PVT software but ultimately it is the user's choice and decision to establish which commercially
available software best suits the calculations to be performed.
For the scale prediction/water phase model we used our in-house HWU code (Silva et al., 2016) but
different software can also be chosen to run the same calculations.

Workflow Part 1
Step 1: Define PVT Total Feed. For oil wells, this step is divided into two.
Step 1a. PVT experimental data regression.
The original field hydrocarbon PVT experimental data is used to adjust the oil and gas EOS. The gas-
oil-ratio (GOR) and relative oil volume (ROV) before and after data regression are shown in Figure 3.

Figure 3—GOR and ROV trends before and after PVT experimental data regression.

Step 1b. Adjust CO2 and add H2S and H2O to the original hydrocarbon composition.
We need to obtain the PVT total feed which gives the correct measured gas CO2 and H2S at separator
temperature (T) and pressure (p) as well as the correct relative fluid rates. The original hydrocarbon
composition does not contain any water or H2S (the latter produced over time from reservoir souring)
and the CO2 concentration is not related to this specific well. Hence, we must add H2S and H2O to the
original hydrocarbon feed and adjust CO2 until the flash calculations at separator conditions give the correct
measured values. This new PVT feed represents the specific well total feed at given conditions. The original
hydrocarbon feed and the calculated total PVT feed for well "O" are shown in Table 2.
6 SPE-184514-MS

Table 2—Original hydrocarbon feed and calculated well "O" total feed to include H2S and H2O.

Well "O"
Original hydrocarbon
calculated total feed

Mol % Mol %

H2S 0.00000 0.00193

CO2 0.16000 0.00171

N2 0.11000 0.00046

CH4 39.87000 0.16591

C2H6 1.42000 0.00591

C3H8 0.30000 0.00125

IC4 0.07000 0.00029

NC4 0.11000 0.00046

IC5 0.06000 0.00025

NC5 0.04000 0.00017

FC6 0.28000 0.00117

C7+ 57.58000 0.2396

H20 0.00000 99.58091

Total 100 100

Field changes such as increased water cut and reservoir souring can affect the total PVT feed. Hence,
this calculated composition is unique to well "O" and is likely to change over time.

Table 3—PVT results for well "O" at separator T (65°C) and pressure (8 bar). *=matched to measured field data.

Mole % Feed Water Oil Gas

H2S 0.00193 0.00146 0.04759 0.22459*

CO2 0.00171 0.00087 0.05108 0.45393*

N2 0.00046 0.00002 0.0053 0.27222

CH4 0.16591 0.01045 2.91408 93.9617

C2H6 0.00591 0.00308 0.16228 1.53679

C3H8 0.00125 0.00086 0.04823 0.16932

IC4 0.00029 0.00018 0.0221 0.03585

NC4 0.00046 0.00027 0.04143 0.05384

IC5 0.00025 0.00011 0.0391 0.02318

NC5 0.00017 0.00007 0.02909 0.01428

FC6 0.00117 0.00031 0.29175 0.06511

C7+ 0.23960 0.00000 92.63998 0.00007

H20 99.58091 99.98233 3.70799 3.18913

Total 100 100 100 100

Phase volume % 74.01* 3.8953* 22.0947

Phase mole % 99.5839 0.2586 0.1575

SPE-184514-MS 7

Step 2: Run PVT at Separator Conditions. After calculating the total PVT feed, we run the oil/gas/water
flash calculations at separator T and p using the selected PVT software (Winprop) to obtain three phase
relative volumes (which should match field data) and three phase CO2 and H2S distribution. The results for
Well "O" are shown in Table 3.
Step 3: Calculate Separator Water Composition. We now have the separator aqueous molecular CO2 and
H2S (from PVT), the measured Ca2+ and separator alkalinity. Please note that all these values represent the
"final" water composition when running scale predictions.
CO2, H2S, Ca2+ and alkalinity are used in an aqueous scale prediction model to calculate the water pH,
HCO3–, HS– and CO32–.
Most people working with scale predictions are aware that field data is not always accurate because
of challenges related to sampling and sample preservation. This is particularly true for pH and alkalinity
measurements. Hence, it is important to know which field measurements can be trusted when calculating
the separator water chemistry.
For well "O" we noticed that the combination of measured alkalinity and Ca2+ with the calculated
molecular CO2 and H2S concentration would produce additional CaCO3 precipitation. We have identified
4 possible causes for this behaviour:
1. The measured gas phase CO2 and H2S are incorrect and give the wrong aqueous molecular CO2 and
H2S concentrations.
2. The solubility of CO2 and H2S in the water phase calculated with Winprop is incorrect. This can be
due to the mixing rule problems mentioned above and parameter selection.
3. The separator fluids are not in equilibrium because there is not sufficient retention time.
4. The measured Ca2+ or alkalinity are too high.

To address the first option, we tried to double the aqueous CO2 concentration but the final calculated
alkalinity was still too low. The error in gas measurements would have to be >100% to be the main reason
for this inconsistency and since we have comparable values from pressurised commingled gas samples, we
believe the gas readings are sufficiently accurate.
The second option is highly likely to play a role in these calculations. As mentioned above, we need to use
different mixing rules in the presence of water and Winprop does not give us this flexibility. Nevertheless,
as per option 1, even doubling the water phase CO2 still produces additional CaCO3 precipitation at the
given Ca2+ concentration.
The third option is possible but if the water in the separator is oversaturated, CaCO3 may precipitate after
collecting the sample (the samples are not immediately analysed but it takes 1-5 days to run them on the
ICP). Hence, the final water chemistry values would be closer to equilibrium.
Calcium ICP measurements for these fluids are rather accurate and when we looked at Ca2+ trends for
well "O" over the years we noticed very good consistency. On the other hand, the water alkalinity in these
samples is measured on a "dead" sample, often days after sampling has occurred. This can have a great
impact on the final values and give unreliable alkalinity results. The presence of weak acids can also change
the alkalinity value but it has been confirmed that the equivalent acetic acid concentration in these samples
is negligible.
Hence, we conclude that the alkalinity value is far less reliable than all other values and we adjust it
accordingly to the other given and calculated concentrations.
The final calculated separator water chemistry is shown in Table 4.
8 SPE-184514-MS

Table 4—Separator water chemistry for well "O". *=matched to measured field data or calculated PVT value.

pH 6.7

CO2 (ppm = mg/kg) 21*

HCO3– (ppm = mg/kg) 180

2–
CO3 (ppm = mg/kg) 0.7

H2S (ppm = mg/kg) 27*

–
HS (ppm = mg/kg) 67

Ca2+ (ppm = mg/kg) 370*

–
Alkalinity (ppm eq. HCO3 ) 305

Step 4: Run PVT at Reservoir Conditions. As for the separator, this calculation will give us three phase
relative volumes and three phase CO2 and H2S distribution. The results for well "O" are shown in Table 5.

Table 5—PVT results for well "O" at reservoir T (77.78°C) and pressure (221 bar).

Mole % Feed Water Oil

H2S 0.00193 0.00183 0.03055

CO2 0.00171 0.00148 0.07292

N2 0.00046 0.00023 0.06965

CH4 0.16591 0.09263 22.40901

C2H6 0.00591 0.00524 0.20833

C3H8 0.00125 0.00107 0.05474

IC4 0.00029 0.00021 0.02378

NC4 0.00046 0.00032 0.04349

IC5 0.00025 0.00013 0.03796

NC5 0.00017 0.00008 0.02763

FC6 0.00117 0.00032 0.25656

C7+ 0.23960 0.00000 72.97377

H20 99.58091 99.89646 3.79160

Total 100 100 100

Phase volume % 94.8803 5.1197

Phase mole % 99.6717 0.3283

Step 5: Calculate Reservoir Equilibrium Water Composition (with separator Ca2+). We start by fixing the
reservoir aqueous molecular CO2 and H2S (from PVT) and the CaCO3 equilibrium conditions (saturation
ratio (SR) =1). At this stage, we do not know the reservoir Ca2+ composition because if CaCO3 precipitated
somewhere between the reservoir and separator, this concentration would be higher than that measured
at the separator. In this first calculation, we fix the reservoir Ca2+ to the separator value and calculate the
final reservoir alkalinity. If these values satisfy Equation (1) (for the non-precipitation scenario the equation
result is zero), we have no precipitation in the well and we have found the final reservoir equilibrium water
composition. If not, we move to Step 6.
For well "O", the results of this calculation do not satisfy Equation (1). Hence, we proceed to Step 6.
SPE-184514-MS 9

Step 6: Increase Ca2+ and Recalculate Reservoir Equilibrium Water Composition. We fix the same
molecular CO2 and H2S (from PVT) and CaCO3 SR=1 but increase the Ca2+ concentration until the final
alkalinity value gives the correct result for Equation (1).
The results are shown in Table 6 for well "O" and the recalculated reservoir Ca2+ is 394 mg/l.
2+
Table 6—Calculated reservoir alkalinity and Equation (1)) results for different Ca concentration.

Reservoir pH Reservoir alkalinity Result of

Reservoir Ca2+ mg/l (fixed)
(calculated) (calculated eq. HCO3- mg/l) Equation (1))

400 6.5 377 1.55

396 6.5 378 1.82

394 6.5 381 2.04

At the end of Part 1 of the workflow we have fully characterised the separator and reservoir water
composition which are summarised in Table 7 for well "O".

Table 7—Calculated separator and reservoir water chemistry for well "O".

Separator Reservoir

pH 6.7 6.5

CO2 (ppm = mg/kg) 21 35.4

HCO3– (ppm = mg/kg) 180 238

CO32– (ppm = mg/kg) 0.7 0.9

H2S (ppm = mg/kg) 27 33.5

HS– (ppm = mg/kg) 67 76

Ca2+ (ppm = mg/kg) 370 394

Alkalinity (ppm eq. HCO3–) 305 381

Workflow Part 2
After calculating the equilibrated reservoir water chemistry corresponding to the measured separator values,
we use this composition to obtain scale prediction trends.
Step 7: Calculate Reservoir Total 2 Phase Carbonates and Sulphides. We use the reservoir water
composition and oil/water mole fractions to calculate the total 2 phase carbonates (CO2 (oil), CO2(aq),
HCO3–, CO32–) and sulphides (H2S (oil), H2S (aq), HS–). To do this we need to fix the total number of moles
of produced water, oil and gas equal at separator and reservoir.
Carbonates and sulphides will re-partition and re-speciate in the wellbore and separator as a consequence
of temperature and pressure changes. However, the total moles of carbonates and sulphides (including any
precipitated carbonate and sulphide scale) will remain constant. Hence, we use these calculated values as
a constraint in the following calculations. Well "O" mole distribution, total carbonates and total sulphides
are shown in Table 8.
10 SPE-184514-MS

Table 8—Well "O" three phase mole distribution, total sulphides and carbonates at separator and reservoir conditions.

Separator Reservoir

Oil (mol) 273,741 347,414

Gas (mol) 166,670 0

Water (mol) 105,381,811 105,474,807

Total carbonates (mol) 9,444 9,444

Total sulphides (mol) 6,510 6,510

Step 8: Run PVT at Selected Temperature and Pressure. For this second part of the workflow, the PVT
calculations provide two/three phase relative mole % and the gas/water and oil/water CO2 and H2S partition
coefficients which will be used to recalculate total carbonates and sulphides. This is discussed in more
details in Step 9. The pressure and temperature steps selected for well "O" are shown in Table 9.

Table 9—well "O" selected T and p steps and calculated partition coefficients (mol fraction/mol fraction) and relative phase mole %.

T(°C) p(bar) KOW (CO2) KGW (CO2) KOW (H2S) KGW (H2S) Water Gas Oil (mole
(mole %) (mole %) %)

Reservoir 77.78 221 49 – 17 – 99.6717 – 0.3283

Step 1 77.01 188 51 – 19 – 99.6702 – 0.3298

Step 2 71.54 69 57 81 27 23 99.6573 0.0174 0.3253

Step 3 69.96 42 58 120 29 34 99.6301 0.0744 0.2955

Separator 65 8 59 525 33 154 99.5841 0.1574 0.2584

NOTE: the partition coefficients are expressed as (mole fraction/mole fraction).

For example, KOW= (mol fraction H2S in oil) / (mol fraction H2S in water).
Step 9: Run Scale Prediction at Selected Temperature and Pressure Using Equilibrated Reservoir Water
Composition. We take the equilibrated reservoir water (or the equilibrated water from the previous wellbore
step) as initial conditions and change temperature and pressure to the new values. Knowing that the total
number of moles of water + oil + gas is the same throughout the system and using the calculated final
aqueous molecular CO2 and H2S, the gas/water and oil/water partition coefficients (from PVT) and the phase
mole % of water, oil and gas, we calculate total two/three phase carbonates and sulphides.
If carbonate and sulphide scales precipitate they need to be included in the calculations. If these final
carbonate and sulphide values do not match the reservoir carbonates and sulphides, we move to Step 10.
An example for well "O" is shown in Table 10 where the reservoir water is taken to Separator temperature
and pressure and the total sulphides and carbonates recalculated using the partition coefficient from PVT.
The new calculated total moles are higher than the original reservoir values because this process has not
accounted for the loss of molecular CO2 and H2S to the oil and gas phase due to the pressure drop. This
is accounted for in Step 10.

Table 10—Reservoir and separator total carbonates and sulphides if only

T and p are changed and CO2 and H2S re-partitioning is not accounted for.

Total carbonates
Total sulphides (mol)
(mol)

Reservoir 9,444 6,510

Separator (only change reservoir water T and p) 10,709 7,117

SPE-184514-MS 11

Step 10: Change Initial Molecular CO2 and H2S and Re-calculate Final Water Composition and
Total Carbonates and Sulphides. Adjust (reduce) the initial aqueous molecular CO2 and H2S from
the equilibrated reservoir water, recalculate the final water compositions and the total two/three phase
carbonates and sulphides at the selected T and p step (as described in Step 9). This iteration is repeated until
the final total carbonates and sulphides match the reservoir values. Results for well "O" (Table 11) show
that CaCO3 is expected to precipitate at all selected points but particularly at separator conditions where the
saturation ratio (SR) and mass of scale precipitated are the highest. This is also shown in Figure 4.

Table 11—Well "O" reservoir to separator water chemistry and carbonate scale predictions. (*) these
recalculated values slightly differ from the values shown in Table 7 (see explanation in paragraph below).

pH Ca2+ (ppm) CO2 HCO3– CO32– (ppm) H2S HS– (ppm) CaCO3 (SR) CaCO3
(ppm)
(aq) (ppm) (ppm)
(aq) (mg/l)

Reservoir 6.5 394 35 238 0.9 34 76 1 0

Step 1 6.5 392 36 235 0.8 34 75 1.06 4.8

Step 2 6.5 388 37 228 0.7 37 73 1.19 13.1

Step 3 6.5 386 35 221 0.7 36 72 1.06 4.2

Separator* 6.6 380 26 199 0.7 32 70 1.35 20.0

Figure 4—Well "O" reservoir to separator CaCO3 scale prediction.

Reducing aqueous molecular CO2 and H2S is a way to account for the repartitioning of CO2 and H2S
to the oil and gas phase without impacting the initial alkalinity. The final alkalinity value will obviously
depend on the carbonate and sulphide speciation and scale precipitation at the new conditions.
By using this method of adjusting the initial aqueous CO2 and H2S concentration, the final calculated
water phase molecular CO2 and H2S are slightly different from the values given by the PVT calculations.
This is due to the fact that the concentration of CO2 and H2S in the total feed may change from reservoir
to separator due to carbonate and sulphide reactions and re-partitioning in the water phase. However, this
change is very small for the given example and the partition coefficients do not change because they are
mostly dependent on temperature and pressure. Hence, in practical terms we can use the same PVT total
feed from reservoir to separator and simply use the partition coefficients to calculate the total aqueous
carbonates and sulphides. The small changes in total PVT feed also slightly affects the final separator Ca2+
12 SPE-184514-MS

concentration (calculated 380 mg/l vs measured 370 mg/l) and pH (calculated 6.7 vs original calculation
result of 6.6) but in this scenario the difference is < 3%.
If other scenarios show a larger discrepancy between reservoir and separator PVT total feed, it is
necessary to adjust the reservoir total feed until we obtain the correct one at separator (which is derived
from real field data).
Finally, the same separator results can be obtained by running multiple steps in the wellbore or by going
directly from reservoir to separator. The former type of multi-step procedure is often applied in our workflow
since it gives the wellbore profile of where carbonate scales are deposited. Moreover, if scale precipitates
along the wellbore but not in the separator, it is necessary to run multiple wellbore steps or we would obtain
the wrong separator water composition.

Maximum Dissolved Iron (MDI) and FeS Scale Predictions

Measuring total and dissolved iron in sour waters can be highly inaccurate for a number of reasons (NACE,
2012). One important reason is due to the presence of colloidal FeS particles and interference with other
corrosion products from the sample point. Nevertheless, "dissolved Fe2+" has been measured for well "O"
and the concentration in produced water seems to have gone up just before the H2S concentration increased
rapidly (Figure 5). This may be due to additional corrosion caused by H2S but there is no other available
data to support this idea yet.

2+
Figure 5—Well "O" Fe and H2S trends.

The water samples used to measure Fe2+ were acidized after being collected and particles of FeS may
have re-solubilised increasing the "dissolved Fe2+" concentration.
To evaluate the maximum concentration of dissolved iron potentially present in these fluids, we applied
the Maximum Dissolved Iron (MDI) concept (Verri and Sorbie, 2017) and calculated MDI from reservoir to
separator. In practical terms, the water composition obtained from Workflow steps 1 through 10 (including
pH and aqueous H2S, HS– and S2–) is used as initial conditions in a scale prediction model and Fe2+ added
until any FeS forms (FeCO3 may precipitate first in other scenarios). This Fe2+ concentration represents the
maximum dissolved iron concentration potentially present in the water phase at the given conditions.
SPE-184514-MS 13

For well "O" the MDI is <0.1 mg/l from the reservoir to the separator. This allows us to draw two
important conclusions:
– If Fe2+ is found in the produced fluids, it must be coming from an external source such as corrosion
mechanisms or from colloidal FeS precipitated in the reservoir and transported into the wellbore.
– Wherever corrosion occurs, the free Fe2+ will precipitate as FeS because the iron sulphide solubility
at these conditions is extremely low.
Iron sulphide scale has been found in well "O" water samples and throughout the production system
in wellhead samples, hydrocyclone filters and water treatment vessels. However, it is has been difficult to
quantify the problem and to pinpoint the exact locations where corrosion is occurring.

Conclusions
In this work we have applied the HWU general scale prediction workflow to a North Sea oil well to
determine the carbonate and sulphide scale precipitation profile from reservoir to wellhead separation stage.
Based on the separator water equilibrium we concluded that the measured alkalinity was too high and
calculated a new value consistent with more reliable field data.
We reconstructed the separator and reservoir water chemistry and the latter was used to determine the well
scaling profile which shows CaCO3 precipitation at all selected steps but particularly at separator conditions.
Iron sulphide was studied separately using the maximum dissolved iron (MDI) approach (Verri and
Sorbie, 2017). This shows that Fe2+ is not stable at any given condition for well "O" and any available iron
(likely to be from corrosion) will precipitate as FeS.
Precipitation kinetics are not included in these calculations but are part of our future work as well as
the study of carbonate and sulphide scale precipitation in other field scenarios and using different EOS and
mixing rules.

Acknowledgments
The authors would like to thank the management of both Chevron and Saudi Aramco for funding this work
and for agreeing to its publication. Thanks also to CMG for the use of Winprop for PVT calculations.

References
Computer Modelling Group (CMG). 2014. Winprop - Phase Behaviour & Reservoir Fluid Property, http://www.cmgl.ca/
software/.
DANESH, A. 1998. PVT and Phase Behaviour of Petroleum Reservoir Fluids, Elsevier.
NACE. Monitoring Corrosion in Oil and Gas Production with Iron Counts, SP0192-2012, 2012,
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