SPE-172640-MS

Sodium Gluconate as a New Environmentally Friendly Iron Controlling

Agent for HP/HT Acidizing Treatments
Ahmed I. Rabie, and Hisham A. Nasr El-Din, Texas A&M University

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Middle East Oil & Gas Show and Conference held in Manama, Bahrain, 8 –11 March 2015.

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
Iron precipitation is a serious problem in acidizing treatments which can damage the formation perme-
ability by restricting the flow channels. Solutions introduced in the past included the use of buffers,
reducing agents, and chelating agents. Laboratory and field experiences concluded that chelating agents
are the most effective remedy for controlling the iron precipitation. However, substantial limitations
hinder the effectiveness and the application of several of the current chelating agents in the industry. These
limitations include poor thermal stability at elevated temperatures, higher cost, low solubility in acidic
medium, tendency of precipitating calcium products, and serious negative health and environmental
impacts.
This work introduces sodium gluconate as an efficient and environmentally friendly iron chelating
agent. The chemical exhibits an excellent sequestering property for iron over a wide range of pH values,
with a chelation power comparatively closer to those reported for EDTA and NTA. The salt is readily
dissolved in the acids with a solubility of 600 gm/l.
The objectives of this study are to: (1) investigate the ability of sodium gluconate to prevent iron
precipitation at different iron loading, (2) examine the efficiency of the new chelant in hydrochloric acid
solutions (5, 10, and 15 wt%) at a temperature of 200 and 250°F and chelant to iron molar ratios of 1:1,
2:1, and 4:1, and (3) determine the optimum chelant to iron molar ratio that results in the highest chelation
capacity. The effectiveness of the new chemical was examined by determining the percentage increase/
reduction in core permeability.
In stirred reactor experiments, iron precipitation was observed at a pH above 2 with the absence of the
chelant at iron loading at 5,000 and 10,000 ppm at 77°F. The presence of Na gluconate at an equimolar
ratio of the iron loading prevent the precipitation over the investigated range of iron load and temperature.
Coreflood results showed that at low injection rates of 0.5 cc/min, 200°F, and 5 wt% HCl with 10,000
ppm Fe3⫹ the core was damaged and the acid was not able to enter the core due to iron precipitation on
the core inlet. At a higher injection rate (2 cc/min) the presence of 5 wt% Na-gluconate enhanced the
permeability by 74% (versus 50% when no chelant was added) after injecting 0.75 PV of the acid with
a load of 5,000 ppm Fe3⫹. At a load of 10,000 ppm of iron (III), the permeability increased to 165%
compared to 70% for a controlled experiment. The results of another set of experiments at 250°F and 15
wt% HCl with a load of 10,000 ppm indicated that a 1:1 molar ratio of chelant to iron concentration is
2 SPE-172640-MS

the optimum for the maximum chelation capacity compared to the results obtained for other experiments
in which the molar ratio of sodium gluconate to iron was 2:1 and 4:1. These results were confirmed by
fluid analysis, which showed a significant increase in both ion concentrations at this molar ratio in the
effluent samples.
Introduction
Corrosion is a major challenge in any acidizing treatment. The scale of such a problem depends on the
acid type, acid concentration, temperature, and the presence of corrosion inhibitor, intensifier, or
undesirable corrosion accelerator. In cases where hydrochloric acid (HCl) is used, the impact of the
corrosion is magnified and can hinder the success of the treatment, especially at elevated temperatures and
higher acid concentrations. This is because acid corrosion does not only destroy storage and mixing tanks,
piping, fittings, coiled tubing, and wellbore tubing, but also corrosion products are carried out with the
acid flow and enter the formation. When the acid is in a live condition, these corrosion products are readily
soluble. However, when the acid reacts with the formation and the pH increases, the corrosion products
show a high tendency to precipitate and plug the pores. (Gougler et al. 1985; Dill and Fredette 1983;
Crowe 1986; Hall and Dill 1988).
Piping, fittings, and well tubular are commonly made from low carbon steel. Accordingly, iron and iron
products are the main constitutes of any corrosion materials. Some minerals are also present in oil and gas
formations and form the second source of iron such as hematite, magnetite, and pyrite. Inhibitors are often
used to mitigate the corrosion impact, and special additives such as corrosion intensifiers are required to
compensate for the degradation loss in the inhibitors at elevated temperatures, which results in a
substantial increase the treatment cost. In addition, excessive corrosion inhibitors may enter the formation,
get adsorbed on the reservoir rock, and subsequently change the wettability (Schechter 1992). Another
limitation is the low health and environmental profile of most of the current corrosion inhibitors.
Several attempts, therefore, aimed to maintain the corrosion inhibitors and intensifiers at minimum and
effectively reduce the potential of iron precipitation by using buffers, reducing agents, and chelating
agents. Laboratory and field experiences concluded that chelating agents are the most effective remedy for
controlling the iron precipitation.
In an early work, Smith et al. (1969) stated that formations with iron mineral content of 0.5% and
higher require iron sequestrating agents to be present in the acidizing fluid. The authors reported pH
values of 2.2 and 7.7 at which iron (III) and iron (II), respectively, start to precipitate. These limits,
however, were revised experimentally by Taylor et al. (1999) who showed that iron (III) precipitation may
occur at a pH value of 1.0. Because the pH of the spent acid rarely exceeds 4-5, the concentration of iron
(III) should be the basis for calculating the amount of the sequestrating agents. Smith et al. (1969) also
believed that iron sequestrating agents were overused and the reduction effect of the tubular itself on iron
(III) to iron (II) favors the two ion ratios to be between 1:5 to 1:10 and therefore, a smaller amount of
chelating agent is usually required.
In 1983, Ewing et al. performed a series of screening tests to determine the types chelating agents
required to sequestrate iron (III) in HCl solutions with different concentrations. The chemicals tested were
citric acid (CA), nitrilotriacetate (NTA), acetic acid (AA), and blends of these acids. The results, however,
showed that blends of these acids are effective only up to 185°F (85°C) and in HCl solutions with
concentrations less than 28%.
Contradicting these findings, Crow (1985) reported that these acids along with erythorbic acid were
effective chelants up to 400°F, except acetic acid which performed poorly above 125°F. Results showed
that erythorbic acid was the most effective chemical working by reducing Fe (III) to Fe (II) rather than
sequestrating Fe (III).
Walker et al. (1991) mentioned that iron sequestrating agents along with hydrogen sulfide scavengers
should be used together for sour gas wells to prevent the damage to the formation. The authors reported
SPE-172640-MS 3

four case studies for oil and sour gas wells in the Permian Basin that showed a significant increase in
production after the use of the proper iron-control-acid.
Taylor et al. (1999) introduced a procedure to examine the iron precipitation as a function of pH of the
acid solution. The work involved testing HCl with concentrations from 7.5 wt% up to 28 wt%, iron (III)
concentrations from 1000 to 10,000 ppm, and over a temperature range from 77 to 200°F. The results in
this study showed that Fe (III) starts to precipitate at pH values as low as 1.0 and completes by 2.2. Earlier
precipitation was also observed at higher temperatures (150 and 200°F) and higher acid concentrations (15
and 30 wt%). A synergistic effect was noted when citric and acetic acids were mixed in a 0.5:1 molar ratio,
respectively.
Iron controlling agents and their effectiveness were examined for sour gas wells by Taylor et al. (2001).
The focus was given to 28 wt% NTA at a temperature up to 300°F. The results showed that NTA
decomposed completely at 300°F and partially (23%) at 250°F and the authors highlighted the need to
investigate alternatives of iron chelating agents at these conditions.
Assem et al. (2013a, 2013b) examined glutamic N,N-diacetic acid or (GLDA) as an iron chelating
agents used with HCl. Acid solutions (5 - 20 wt%) with a loading of 5,000 and 10,000 ppm of Fe3⫹ were
tested at 200°F. The authors concluded that the amount of iron recovered depended on the chelate-to-iron
mole ratio and the initial permeability of the cores. An additional amount of GLDA should be added to
account for what will be consumed in sequestrating the calcium ions. However, a maximum recovery of
iron (III) in this work was as low as 12 and 30% at 5,000 and 10,000 ppm Fe (III) loading, respectively.
Gluconic acid and its sodium and calcium salts, shown in Fig. 1, exhibit attractive physical and
chemical properties, and hence are used in several applications and industries. The acid and its salts are
noncorrosive, nonvolatile, nontoxic, non-odorous, and readily biodegradable (98% at 48 hr) (Ramachan-
dran et al. 2006).

Figure 1—The chemical structure for: a) gluconic acid, b) sodium gluconate, and c) calcium gluconate.

The US FDA (Food and Drug Administration) has assigned sodium gluconate a GRAS (generally
recognized as safe) status and its use in the food industry is permitted without limitation. Gluconic acid
and its salts are used also in pharmaceutical, hygienic products, and as mineral supplements to prevent the
deficiency of calcium and iron.
In the oil industry, a study by Barthorpe (1993) concluded that the presence of even low levels (0.1
mg/l) of chelators such as gluconic acid, EDTA, and citric acid can significantly render the use of
phosphonates, polycarboxylates, and phosphate esters as scale inhibitors.
Gluconic acid, or a derivative from this chemical, was reported as an efficient and new environmentally
friendly corrosion inhibitor (Jovancicevic and Hartwick 1996; Schmitt and Saleh 2000). Touir et al.
(2008) used the weight loss, polarisation curves, electrochemical impedance spectroscopy (EIS), and
scanning electron microscopy (SEM) techniques to investigate the effect of the sodium gluconate anion
(SG) on the corrosion and scale inhibition of ordinary steel in simulated cooling water. The results of their
work showed that sodium gluconate inhibits the corrosion of ordinary steel by adsorption on the active
4 SPE-172640-MS

sites of a metal surface suppressing the dissolution reaction. They found that the inhibition efficiency
values increase with increasing inhibitor concentration reaching a maximum at 10-2 M and that aqueous
solutions of sodium gluconate are resistant to oxidation and reduction at high temperatures.
In addition, sodium gluconate has applications as an additive to cement, controlling the setting time and
increasing the strength and water resistance of the cement. It helps in the manufacture of frost and crack
resistant concretes (Ramachandran et al. 2006). It is well suited for removing calcareous deposits from
metals and other surfaces, including milk or beer scale on galvanized iron or stainless steel.
Sodium gluconate has a high sequestering power to chelate calcium and other di- and trivalent metal
ions. It is a good chelator at an alkaline pH; its action is comparative to that reported for EDTA and NTA
(Prescott et al. 1953; Mehltretter et al. 1953). Its property of sequestering iron over a wide range of pH
values is exploited in the textile industry, where it prevents the deposition of iron and for desizing
polyester and polyamide fabrics. Sodium gluconate also used in metallurgy for alkaline de-rusting, as well
as in the washing of painted walls and removal of metal carbonate precipitates without causing corrosion.
In this study. Sodium gluconate is investigated as an environmentally friendly chelant for iron
controlling in HP/HT acidizing treatments. The proposed chelant has a strong affinity for iron over a wide
range of pH values, comparatively closer to those reported for EDTA and NTA. The salt is readily
dissolved in the acids with a solubility of 600 gm/l.
Therefore, the objectives of this work are to: (1) investigate the ability of sodium gluconate to prevent
iron precipitation at different iron loading, (2) examine the efficiency of the new chelant in hydrochloric
acid solutions (5, 10, and 15 wt%) at a temperature of 200 and 250°F and chelant to iron molar ratios of
1:1, 2:1, and 4:1, and (3) determine the optimum chelant to iron molar ratio that results in the highest
chelation capacity. The effectiveness of the new chemical was examined by determining the percentage
increase/reduction in core permeability.

Experimental Studies

Materials
Low permeability Indiana limestone cores (1.5 inch diameter and 6 inch length) were used for the
coreflood experiments. Table 1 shows the XRF results for the chemical composition of the three samples
cut from different locations of the main block that the coreflood plugs were drilled from. Table 2 shows
the initial permeability, porosity, and pore volume of the coreflood plugs. Concentrated hydrochloric acid
solutions were obtained from Sigma Aldrich and titrated using 1 N sodium hydroxide solution and
phenolphthalein as an indicator. A concentration of 35.64 wt% ⫾ 0.35 was reported with a density of 1.18
gm/cm3 measured by an Anton Paar DMA 35 density meter. Acid solutions of 5, 10, and 15 20 wt% of
HCl were prepared from this concentrated solution and a corrosion inhibitor was added with a concen-
tration of 1 vol%. Ferric chloride was used as a source of iron (III). Sodium gluconate salt was obtained
from Sigma Aldrich and was used as received. The iron concentration of the liquid samples was measured
using an induced coupled plasma spectrometer (ICP).
SPE-172640-MS 5

Table 1—Chemical composition (wt%) of three samples of the

Indiana limestone used in the current work measured by XRF
technique.
Composition, wt%

Element Sample-1 Sample-2 Sample-3 Avg.

CaO 97.3 97.3 94.1 96.233

MgO 1.15 1.01 0.865 1.008
Al2O3 0.345 0.412 0.885 0.547
SiO2 0.494 0.651 3.49 1.545
SO3 0.0911 0.0582 0.0521 0.067
Cl 0.0539 0.0236 0.0163 0.031
TiO2 NA NA 0.0989 0.033
Cr2O3 NA NA 0.0206 0.007
MnO 0.0115 NA 0.0238 0.012
Fe2O3 0.232 0.249 0.333 0.271
SrO 0.0555 0.0547 0.0531 0.054
SnO2 0.0293 0.0275 0.028 0.028
K2O NA 0.161 NA 0.054

Table 2—Initial permeability, porosity, and pore volume of the cores used in the coreflood experiments.
Experiment Core Number Initial Permeability, md Porosity, % Pore Volume, cm3

CF-19 20 7.5 15.9 27.7

CF-23 23 6.48 15.8 27.3
CF-25 25 9.28 15.3 26.7
CF-26 26 10.4 14.1 24.6
CF-27 27 5.45 15.8 27.5
CF-29 31 9.15 15.5 26.9
CF-30 32 6.10 15.1 26.2
CF-31 30 6.89 14.8 25.7
CF-32 28 9.00 14.9 25.8

Procedure
Precipitation of iron (III) in HCl solutions of 5 and 10 wt% was investigated at iron (III) loading of
5,000 and 10,000 ppm in the presence and the absence of sodium gluconate. The following procedure was
followed. A 100 ml sample of the acid solution was prepared with a predetermined amount of ferric
chloride and sodium gluconate in a 200 ml three-neck reactor shown in Fig. 2. A pH meter was inserted
into the solution from one neck, while the other two openings were used to hold a thermometer and to take
samples. A solution of 2 M Na2CO3 was prepared to neutralize the acid. At room temperature,
experiments started with the addition of the neutralizing Na2CO3 solution in very small increments. Upon
the addition of each increment, enough time was given to reach stabilization and then a pH reading and
a 3 ml sample were taken. All samples above the pH value of 2 were subjected to 15 minutes of
centrifugation at a speed of 3000 rpm followed by the separation of the precipitate, if found. The liquid
volume was diluted for Fe concentration measurements using ICP. All experiments were conducted at a
stirring speed of 200 rpm.
6 SPE-172640-MS

Figure 2—Setup used to study iron precipitation in the presence and the absence of sodium gluconate.

Equipment
A coreflood setup, demonstrated in Fig. 3, was used to simulate the matrix stimulation treatment. A
pressure gauge was used to apply a back pressure of 1,100 psi on the outlet of the core. This pressure is
enough to maintain the CO2 dissolved in the spent fluid. A pressure transducer was connected to a
computer to monitor and record the pressure drop during the experiments every five seconds. A hand
pump was used to provide an overburden pressure of 1,600 psi. A new core was used in each experiment
and the cores were imaged using a CT scan technique after each run. A heat jacket was placed around the
core holder and was used to heat up the sample to the desired temperature. Samples from the effluent were
collected throughout the experiment, diluted, and subjected to Ca and Fe concentration measurements
using Induced Coupled Plasma (ICP).
SPE-172640-MS 7

Figure 3—Coreflood setup.

Results and Discussion

Iron Control in the Presence of Sodium Gluconate

Using the setup shown in Fig. 2 and the procedure outlined previously, two experiments were conducted
using 5 wt% HCl loaded with 5,000 ppm Fe (III). In one experiment, no chelant was added and the
samples collected were shown in Fig. 4. The color of the samples changed from light green as in the first
sample to a dark brown towards the last sample. After the centrifugation, a precipitate was found in all
samples above pH 2. The change of the sample color to dark brown is most likely due to the precipitation
of ferric hydroxide. In the second experiment, sodium gluconate was added in a 1:1 molar ratio to the iron
load in the solution. Fig. 5 shows an image for all samples collected during this experiment. The image
was taken after centrifuging all samples above pH 2 for the same period as in the previous experiment.
No precipitate was observed in any sample, however a reduction in the initial Fe (III) concentration was
observed. This is believed to be a result of the dilution effect when the neutralizing volumes were added.
A comparison between the samples collected from both experiments at fairly close pH values is shown
in Fig. 6, while the iron concentration as a function of pH of solution is shown in Fig. 7. The results also
reflect the effectiveness of using sodium gluconate as a chelating agent at elevated pH.
8 SPE-172640-MS

Figure 4 —Samples collected while neutralizing 5 wt% HCl with 5,000 ppm Fe (III).

Figure 5—Samples collected while neutralizing 5 wt% HCl loaded with 5,000 ppm Fe(III) in the presence of 1:1 molar ratio of sodium
gluconate.
SPE-172640-MS 9

Figure 6 —A comparison between samples collected while neutralizing 5 wt% HCl loaded with 5,000 ppm Fe (III): (a) in the presence of
1:1 molar ratio of sodium gluconate and (b) without adding the chelant.

Figure 7—Fe concentration in the samples collected while neutralizing 5 and 10 wt% HCl loaded with 5,000 and 10,000 ppm Fe (III),
respectively in the presence and the absence of 1:1 molar ratio of sodium gluconate.
10 SPE-172640-MS

A following set of experiments were performed using 10 wt% HCl with an iron load of 10,000 ppm
with and without the chelant. The results are shown in Fig. 7 and confirm the ability of sodium gluconate
to prevent iron precipitation at higher iron loads. The selected iron to chelant ratio in this set was also a
1:1 molar ratio.
Coreflood Studies
Coreflood experiments were performed using the setup shown in Fig. 3. Each experiment involved an
initial stabilization period with the injection of deionized water in a preflush stage followed by the main
stage of acid injection. The cumulative injected acid pore volume is selected to avoid breakthrough in
order to examine effectively the impact of using the proposed chelant. After this stage, flow is switched
back to deionized water for a postflush stage and a final stabilization pressure drop across the core was
recorded.
Fig. 8 shows the pressure drop across the core as a function of the cumulative pore volume for
coreflood experiment CF-19, in which a 0.6 PV of 5 wt% HCl loaded with 10,000 ppm of Fe (III) was
injected into the core at 200°F and an injection rate of 0.5 cc/min. No chelating agent was added in this
run. As shown in the figure, the pressure drop at final stabilization is significantly higher than the pressure
drop at the initial stabilization. This indicates that iron had precipitated and that the core was damaged.

Figure 8 —Pressure drop of coreflood CF-19 as a function of the cumulative pore volume during the injection of 0.6 PV of 5 wt% HCl
with a loading of 10,000 ppm of iron (III) at 200°F and 0.5 cc/min.

Fig 9 illustrates an image of the core inlet before and after injection of the acid, and the images show
a clear dark green color at the core inlet after the experiment, which indicates the precipitation of iron (III).
Fig. 10 is a 3D CT-scan image of the core after the treatment and interestingly shows no wormhole at any
length of the core after the injection of 0.6 PV of the acid. The final permeability of this core was
measured at room temperature as the initial permeability and the data indicates a 31% reduction. This
SPE-172640-MS 11

reveals that at this acid concentration and the injection rate, the acid was not able to penetrate the core due
to the damage that a load of 10,000 ppm of ferric ions caused.

Figure 9 —Inlet face of the core used in coreflood CF-19: a) before and b) after the injection of the acid.

Figure 10 —3D image for the core used in coreflood CF-19 showing no evidence of wormhole or that the acid penetrated the core.

In another set of experiments, the iron concentration was reduced to 5,000 ppm and an injection of 0.75
PV of the acid was used at a rate of 2 cc/min at 200°F. In the first run, labeled coreflood CF-27, no sodium
gluconate was added to the acid solution. Fig. 11 illustrates the pressure profile across the core and shows
a reduction in the pressure drop from an initial value of 57 psi to a final stabilization drop of 40 psi. This
reveals an overall improvement in the permeability which was determined by measuring the final
permeability again at room temperature. The results are listed in Table 3 and show a 50% increase in the
permeability.
12 SPE-172640-MS

Figure 11—Pressure drop of coreflood CF-27 as a function of the cumulative pore volume during the injection of 0.75 PV of 5 wt% HCl
with a loading of 5,000 ppm of iron (III) at 200°F and 2 cc/min.

Table 3—Initial, final, and folds of increase (I) or reduction (R)

in permeability for the coreflood experiments CF-19 through
CF-27.
Initial Final
Run # Permeability, md Permeability, md kf/ki

CF-19 7.5 5.20 0.69

CF-27 5.45 8.2 1.50
CF-23 6.48 11.29 1.74
CF-26 10.40 17.7 1.72
CF-25 9.28 24.6 2.65

Injection of the same acid pore volume (0.75 PV) at the same conditions of temperature and injection
rate was repeated with the presence of 5 wt% of sodium gluconate in solution. The pressure drop for this
run (CF-23) is depicted in Fig. 12 and shows that the final pressure drop stabilized at a value of 28 psi,
while the initial pressure drop before acid injection was 54 psi. This is a significant reduction in the
pressure drop which was corresponding to an enhancement in permeability with a value of 74.2%.
SPE-172640-MS 13

Figure 12—Pressure drop of coreflood CF-23 as a function of the cumulative pore volume during the injection of 0.75 PV of 5 wt% HCl
with a loading of 5,000 ppm of iron (III) and 5 wt% sodium gluconate at 200°F and 2 cc/min.

Fig. 13 illustrates the 3D CT-scan images for the two cores used in these two experiments and confirms
the observation of the permeability enhancements by comparing the length of the two wormholes that
resulted from the injection of the same acid pore volume. The figure shows that for coreflood CF-27, with
no chelant added, the wormhole was 1.92 inch (32% of the total length of the core), while a wormhole
with a length of 2.78 inch (46% of the total length of the core) was determined for the coreflood CF-23
in which sodium gluconate was used as 5 wt% of the acid solution.
14 SPE-172640-MS

Figure 13—3D images for the cores used in coreflood experiments CF-27 and CF-23: a) CF-27 with no chelant added and b) CF-23 in
the presence of 5 wt% sodium gluconate.

These results were further confirmed by analyzing the iron concentration in the fluid samples collected
during and after the acid injection in each of these two experiments. A sample was taken every 5 minutes
starting from the moment the flow was switched to the acid. Fig. 14 shows these results and indicates that
a higher iron concentration with a maximum ppm was observed in coreflood CF-23 compared to the ppm
collected from the coreflood CF-27. The presence of sodium gluconate succeeded to chelate more iron and
prevent its precipitation, and hence, a higher concentration was observed in the effluent. The data shows
that in case of using sodium gluconate the maximum iron recovery was 47% vs. 37% when no chelant was
used.
SPE-172640-MS 15

Figure 14 —Iron concentration in the effluent samples as a function of the injected acid pore volume during coreflood experiments
CF-27 (no chelant) and CF-23 (5 wt% sodium gluconate).

In the following set of experiments (CF-26 and CF-25), the load of the iron concentration was
increased to 10,000 ppm, while the other conditions of acid concentration, temperature, and injection rate
were kept the same as 5 wt% HCl, 200°F, and 2 cc/min, respectively. Due to the higher load of iron (III)
in the inlet fluid, the injected cumulative acid pore was increased to 1 PV. Figs. 15 and 16 show the
pressure drop during coreflood CF-26, when no chelant was added, and coreflood CF-25 in the presence
of 5 wt% sodium gluconate, respectively. An increase in the permeability in both experiments was
observed, however, with a significant increase in CF-25 (165% vs. 70%). These values were determined
by measuring the initial and final permeability of the tested cores at room temperatures as listed in Table
3.
16 SPE-172640-MS

Figure 15—Pressure drop of coreflood CF-26 as a function of the cumulative pore volume during the injection of 1 PV of 5 wt% HCl with
a loading of 10,000 ppm of iron (III) at 200°F and 2 cc/min.

Figure 16 —Pressure drop of coreflood CF-25 as a function of the cumulative pore volume during the injection of 1 PV of 5 wt% HCl with
a loading of 10,000 ppm of iron (III) and 5 wt% sodium gluconate at 200°F and 2 cc/min.
SPE-172640-MS 17

Fig. 17 illustrates the 3D images of the scanned cores after the experiments, while Fig. 18 compares
the iron concentration in the effluent samples. The significant difference in the percentage of permeability
enhancement with the close measurements of the resulting wormholes in both cores reveals a different
condition of cleanness inside both channels and indicates that more iron precipitated in the wormhole of
coreflood CF-26. Iron concentration measurements in the effluent samples confirms this result and shows
that 80% (8000 ppm out of 10,000) was the maximum recovery of iron during experiment. This value was
60% when no chelant was used.

Figure 17—3D images for the cores used in coreflood experiments CF-26 and CF-25: a) CF-26 with no chelant added and b) CF-25 in
the presence of 5 wt% sodium gluconate.
18 SPE-172640-MS

Figure 18 —Iron concentration in the effluent samples as a function of the injected acid pore volume during coreflood experiments
CF-27 (no chelant) and CF-23 (5 wt% sodium gluconate).

Another important observation is that in both coreflood experiments, CF-23 and CF-25, sodium
gluconate was used as 5 wt% of the acid solution with 5,000 and 10,000 ppm of iron load, respectively.
However, by comparing the results of the iron concentration in the effluent, it is noted that a higher
percentage of recovery was obtained in the second case (CF-25). This indicates that the ratio of the iron
to the chelant in solution is critical for the maximum iron recovery, and hence, the success of the
treatment.
In order to investigate this idea in more detail, the following set of experiments were conducted. Acid
solutions of 15 wt% HCl and a fixed load of 10,000 ppm of iron (III) were tested in four corefloods, CF-29
through CF-32, by injecting 1.5 PV of the acid at a rate of 2 cc/min at 250°F. The pore volume of all the
cores was sufficiently close that the same volume of acid on absolute basis was injected in all cases. In
these runs and after the acid injection, the post flush stage with deionized water was performed as a
reverse flow in the opposite direction to the flow in the preflush and acid injection stages. This was an
attempt to investigate the effect of the flow back on the precipitated iron in these treatments.
No chelant was added in coreflood run CF-29, while sodium gluconate was added to the iron in molar ratios
of 1:1, 1:2, and 1:4 in CF-30, CF-31, and CF-32, respectively. Figs. 19 through 22 show the pressure drop across the
cores used in the four experiments. The pressure drop in the flow back stage stabilized at a significantly low value
of 13 psi only in CF-30 in which the molar ratio of iron (III) to sodium gluconate was 1:1 as shown in Fig. 20. Higher
values of 27.5 and 30 psi were reported for CF-29 and CF-31 together with CF-32. The percentage increase with
permeability for these experiments is listed in Table 4. The data shows that 75% was the maximum percentage of
increase in permeability for the case when the molar ratio of sodium gluconate to iron used in the solution was 1:1.
In cases when the iron to chelant molar ratios were 1:2 and 1:4, a reduction in the percentage of permeability
enhancement of 56 and 30% were reported, respectively. The corresponding wormhole formed in these experiments
are shown in Fig. 23 which illustrates a longer wormhole in coreflood CF-30 compared to other experiments.
SPE-172640-MS 19

Figure 19 —Pressure drop of coreflood CF-29 as a function of the cumulative pore volume during the injection of 1.5 PV of 5 wt% HCl
with a loading of 10,000 ppm of iron (III) at 250°F and 2 cc/min.

Figure 20 —Pressure drop of coreflood CF-30 as a function of the cumulative pore volume during the injection of 1.5 PV of 15 wt% HCl
with a loading of 10,000 ppm of iron (III) and sodium gluconate to iron as 1:1 molar ratio at 250°F and 2 cc/min.
20 SPE-172640-MS

Figure 21—Pressure drop of coreflood CF-31 as a function of the cumulative pore volume during the injection of 1.5 PV of 15 wt% HCl
with a loading of 10,000 ppm of iron (III) and sodium gluconate to iron as 1:2 molar ratio at 250°F and 2 cc/min.

Figure 22—Pressure drop of coreflood CF-32 as a function of the cumulative pore volume during the injection of 1.5 PV of 15 wt% HCl
with a loading of 10,000 ppm of iron (III) and sodium gluconate to iron as 1:4 molar ratio at 250°F and 2 cc/min.
SPE-172640-MS 21

Table 4 —Initial, final, and folds of increase (I) or reduction (R) in permeability for the coreflood experiments CF-19 through CF-27.
Run # Initial Permeability, md Final Permeability, md kf/ki

CF-29 9.15 10.37 1.13

CF-30 6.10 24.53 4.02
CF-31 6.89 21.81 3.17
CF-32 9.00 17.35 1.93

Figure 23—3D images for the cores used in coreflood experiments CF-29 through CF-32 with different iron to sodium gluconate molar
ratio: a) CF-29 (no chelant), b) CF-30 (1:1), c) CF-31 (1:2), and d) CF-32 (1:4).

In addition, Fig. 24 shows the iron concentration in the effluent samples collected during these runs
every 5 minutes. The maximum recovery or iron was observed in coreflood CF-30 with a value of 7840
ppm out of the total injected iron of 10,000 (i.e. 78%). The maximum iron concentration recovered in the
effluent samples during CF-29 with no chelant added was 744 ppm, while 5560 and 1886 ppm was
measured for the iron concentrations in the effluent samples from CF-31 and CF-32 in which the iron to
sodium gluconate molar ratio was 1:2 and 1:4, respectively.
22 SPE-172640-MS

Figure 24 —Iron concentration in the effluent samples as a function of the injected acid pore volume during coreflood experiments
CF-29 through CF-32 with different iron to sodium gluconate molar ratio: CF-29 (no chelant), CF-30 (1:1), CF-31 (1:2), and CF-32 (1:4).

The results from these measurements support the pressure drop data and confirm what was observed
in coreflood CF-23 and CF-25. Revising the iron to sodium gluconate in these two runs gives a ratio of
1:2.6 for CF-23 (47% recovery) and 1:1.3 for CF-25 (80% recovery). This means that a ratio of iron to
chelant near 1:1 is the optimum for maximizing iron recovery and minimizing precipitation.

Conclusions
In this work, the use of sodium gluconate as an environmentally friendly chelating agent for sequestrating
the iron in the acidizing fluids was investigated. The results of the coreflood analysis at different iron loads
and iron to sodium gluconate molar ratios can be summarized as follows:
1. Iron precipitation during an acidizing treatment can cause severe damage to the formation and
impair the permeability, especially at low acid concentrations or acid injection rates.
2. An injection of 0.75 PV of 5 wt% HCl acid solution with 5 wt% sodium gluconate was able to
increase the permeability by 74% versus 50% with no chelant added at a load of 5000 ppm Fe (III).
3. At a load of 10,000 ppm Fe (III) and 5 wt% HCl acid solution, the presence of 5 wt% sodium
gluconate increased the efficiency of the acidizing experiment to 165% versus 70% when no
chelant was added.
4. The iron to chelant molar ratio is an important factor for the success of the acidizing treated. The
results in this study showed that the iron to chelant molar ration of 1:1 was the optimum ratio for
maximizing iron recovery and preventing acid precipitation.
SPE-172640-MS 23

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