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Efficacy of Bisulfite Ions as an Oxygen Scavenger in Monoethylene Glycol (At

Least 20 wt%)/Water Mixtures

Article  in  SPE Journal · March 2017

DOI: 10.2118/185944-PA

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 J185944 DOI: 10.2118/185944-PA Date: 25-February-17 Stage: Page: 1 Total Pages: 11

Efficacy of Bisulfite Ions as an Oxygen

Scavenger in Monoethylene Glycol
(At Least 20 wt%)/Water Mixtures
Mobin Salasi and Thunyaluk Pojtanabuntoeng, Curtin University; Sindee Wong and Marc Lehmann, INPEX Australia

Summary oxygen concentration to less than the detrimental level (approxi-

This study investigates the oxygen-scavenging behavior of bisul- mately 20 ppb) (Braga 1987). Among the chemicals available, so-
fite ions in monoethylene glycol (MEG)/water mixtures at con- dium bisulfite (hereafter referred to as bisulfite) is widely used in
centrations commonly found in gas-transportation pipelines. seawater media because of its low cost and better stoichiometric
Temperatures and pH values were varied. The influence of transi- ratio compared with other oxygen scavengers (Kelland 2009).
tion-metal (TM) ions to catalyze the bisulfite oxygen scavenging Application of bisulfite as a chemical oxygen scavenger in water
was studied. Experimental results indicate that MEG significantly is well-documented, including its mechanism and reaction
inhibits bisulfite oxygen removal, which is hindered at low pH kinetics (Linek and Mayrhoferová 1970; Linek and Vacek 1981;
values and, to some extent, temperature. TMs can accelerate the Wilkinson et al. 1993; Mo et al. 2007; Wang et al. 2009; Karatza
oxygen-scavenging reaction in pH-unadjusted solutions, although et al. 2010; Shen et al. 2012). A comprehensive review of the
the rate was still lower than that of the pH-adjusted solutions. The mass-transfer rates has been reported by Linek and Vacek (1981),
possible mechanism for such behavior and industrial implications and a review of the kinetics of reaction is given by Ermakov
are discussed. et al. (1997).
When bisulfite is added, it dissociates to sulfite and hydrogen
ion (Eq. 1), followed by the oxidation process forming sulfate ion
Introduction (Eq. 2). This explains the pH-dependent nature of this reaction,
Hydrate formation and subsequent pipeline blockage is a common reported by Kelland (2009). Eq. 3 provides an overall reaction.
operational challenge of low-temperature and high-pressure natu-
ral-gas pipelines. MEG is one of the thermodynamic hydrate HSO 2 þ
3 () SO3 þ H ; . . . . . . . . . . . . . . . . . . . . . ð1Þ
inhibitors used to prevent hydrate formation (Brustad et al. 2005;
Carroll 2009). MEG is a preferred inhibitor over other alternatives 2SO2 2
3 þ O2 () 2SO4 ; . . . . . . . . . . . . . . . . . . . . . ð2Þ
because it provides an economic advantage of being able to be
recovered and regenerated in closed-loop systems (Son and 2HSO 2 þ
3 þ O2 ! 2SO4 þ 2H : . . . . . . . . . . . . . . . . . ð3Þ
Wallace 2000; Kelland 2009).
Although MEG can moderately inhibit carbon dioxide corro- The sulfite oxidation is a multistep process involving radical
sion of carbon steel (Gulbrandsen and Morard 1998; Dugstad and reactions (Linek and Vacek 1981). The radical reactions are com-
Seiersten 2004; Pojtanabuntoeng et al. 2014), a known issue is the plex, and factors other than pH value can also influence their
entrainment of oxygen into the MEG-regeneration process, which mechanism. For example, oxygen-containing solutions of sulfite
may lead to corrosion and operational problems (Brustad et al. have been shown to be stable even at pH value of 12 in the ab-
2005; Halvorsen et al. 2007; Joosten et al. 2007). Deleterious sence of light, radiation, or iron ions, and this is because of the
effects of trace dissolved oxygen on corrosion of carbon steels suppression of the initial generation of sulfite radicals (Ermakov
and corrosion-resistant alloys has been identified in a variety of et al. 1997; Travina et al. 1997). The overall uncatalyzed oxygen-
applications, including MEG systems (Joosten et al. 2007). Inves- scavenging reaction has been determined to be a series of com-
tigations revealed that trace levels of oxygen can facilitate flow- plex free-radical reactions (Eqs. 4 through 7), and have been the
induced corrosion of carbon steels (John et al. 2009), and enhance focus of numerous studies (Fuller and Crist 1941; Hobson et al.
their carbon dioxide corrosion rate (Martin 2001). Presence of ox- 1987; Zhang and Millero 1991; Connick et al. 1995; Ermakov
ygen at a minute quantity can impede the performance of film- et al. 1997; Snavely 2013):
forming corrosion inhibitors (Gulbrandsen et al. 2005), undermine
the protectiveness of iron carbonate film (Xiang et al. 2015), or Initiation:  SO 
3 þ O2 ! SO5 ; . . . . . . . . . . . . . . . ð4Þ
result in the pitting corrosion of corrosion-resistant alloys (Evans
Propagation:  SO 2  2
5 þ SO3 ! SO4 þ SO4 ; . . . . . ð5Þ
et al. 2004; Schofield et al. 2004; Joosten et al. 2007). Also, from
an operational point of view, oxygen should be removed from
 SO 2 2 
4 þ SO3 ! SO4 þ SO3 ; . . . . . ð6Þ
MEG circuits because it contributes to the formation of solids,
such as iron oxides, and to the formation of byproducts of MEG  SO  2
Termination: 5 þ SO5 ! S2 O8 þ O2 : . . . . . . ð7Þ
oxidation, which can both cause fouling issues commonly seen in
MEG circuits (Joosten et al. 2007; Halvorsen et al. 2009; Haque Lim et al. (1982) showed that alcohols had an inhibitory effect
2012; Latta et al. 2016). Therefore, as a common practice, the dis- at very-low concentrations. Therefore, it can then be expected that
solved-oxygen level has to be reduced and maintained at 20 ppb MEG, at concentrations commonly used for hydrate-inhibition
to avoid potential corrosion. It is also vital to remove oxygen as applications, should also show a similar inhibitory effect that can
fast as possible because prolonged exposure to minute-level oxy- significantly slow down or even stop the oxygen-removal process.
gen may lead to corrosion-pit nucleation, which may then autoca- Preliminary studies of oxygen scavenging by different commer-
talytically propagate. cial chemicals in concentrated MEG/water mixtures indicated that
In industrial applications (mostly aqueous systems), chemical significantly higher dosages of the oxygen scavengers are needed
oxygen scavenging is used to reduce and maintain the dissolved- to effectively remove oxygen in MEG than in aqueous solutions
(Salasi et al. 2013; Lehmann et al. 2014). The present study pro-
Copyright V
C 2017 Society of Petroleum Engineers vides a more-rigorous experimental study of bisulfite-oxygen-
Original SPE manuscript received for review 14 June 2016. Revised manuscript received for
scavenging kinetics without and with MEG. The focus is on the ox-
review 2 November 2016. Paper (SPE 185944) peer approved 20 December 2016. ygen scavenging of bisulfite ions in solutions containing relatively

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(2)
(3)

(5)
(1)
(4)

(1) Sparge tube inside the solution or

retracted to provide the N2 gas cap
(2) Inlet (high-purity N2)
(3) LDO Orbisphere
(4) Headspace, purged with high purity N2
(5) Outlet (connected to Drechsel bottle)
(6) PTFE-coated magnetic bar

Enclosed vessel
containing
at least 1 L of
the solution
(6)

Fig. 1—Schematic of the experimental setup used for oxygen-scavenging studies.

high MEG concentrations, replicating conditions where MEG is solution. The flow rate of N2 was constant for all tests and was
used as a thermodynamic hydrate inhibitor. The effects of opera- at a minimum level to maintain the positive pressure inside the
tional factors such as temperature and pH value on the rate of bisul- test vessel.
fite oxygen removal in MEG/water are studied. The change of dissolved-oxygen concentration with time was
When applying oxygen scavengers to remove dissolved oxy- recorded immediately after the addition of 200 mg of AR-grade
gen from MEG solutions, it is sometimes impractical to control sodium-bisulfite salt into a 1 L solution using the Hach Orbisphere
system temperatures in actual operations, and conversely increas- sensor and controller. The measurement time was set to 60 sec-
ing the pH values of these solutions that include salts can cause onds, and data were recorded every 120 seconds. The initial and
the formation of inorganic scales that could negatively affect flow final pH values of the solution were measured by a Thermo Scien-
assurance. An attractive option is to enhance the rate of the oxy- tific Orion 5-Star Plus portable meter, attached to a Thermo Scien-
gen-scavenging reactions in MEG solutions by use of the TMs tific Orion ROSS ultraglass triode, inserted in the solution. The
that are well-known to improve the sulfite-oxidation reaction in influence of MEG on the pH measurement was taken into account
aqueous solutions (Linek and Mayrhoferová 1970; Neta and Huie according to Sandengen et al. (2007). The experiments were con-
1985). The TMs could already be present in the pipeline: for ducted in solutions without and with pH adjustment. In the pH-
instance, Fe2þ caused by corrosion of carbon steel. Alternatively, adjusted conditions, sodium bicarbonate was added.
TMs can be added as a reaction catalyst to the commercial oxygen The dissolved-oxygen concentration was recorded for 12 hours
scavenger. In this study, we looked at the effect of TMs on oxy- or until the oxygen concentration reached 20 ppb (0.6 mmolL1).
gen scavenging under very-high MEG concentrations. TM-ion Observation time longer than 12 hours implied that the bisulfite-
catalysts were evaluated for their capability to improve sulfite-ox- oxidation rate was negligible. The solution was agitated by a mag-
idation rate even at highly concentrated MEG/water solutions netic stirrer to maintain a homogeneous concentration throughout
without pH adjustment. These included Fe(II), Co(II), Mn(II), and the reaction vessel. It was also found that agitation can prevent
Ni(II) ions, added as their chloride salts. formation of bubbles over the oxygen sensor, and avoid a subse-
quent false oxygen reading (Salasi et al. 2015).
At the completion of experiments, the reduction of dissolved-
Experimental
oxygen concentration was plotted against time. The apparent reac-
Test Apparatus. An Orbisphere luminescence dissolved oxygen tion rate was calculated as
probe (Hach Orbisphere M1100 LDO sensor, 0.6–2,000
ppb, 6 0.8 ppb) was used for the dissolved-oxygen measurements. CO2 ;i  CO2 ; f
A schematic of the experimental setup is shown in Fig. 1. Details R¼ ; . . . . . . . . . . . . . . . . . . . . . . . . . . ð8Þ
t
regarding the low-level oxygen-measurement techniques in MEG
were explained elsewhere (Salasi et al. 2015). where R is apparent reaction rate in mmolL1s1 and CO2 ;i and
A helical coil, connected externally to a water bath, was placed CO2 ; f are the initial and final concentrations of dissolved oxygen
inside the test vessel to control the temperature. The mixture in mmolL1, respectively.
contained within the closed system was sparged for approximately Sulfite-oxidation reaction was shown to be a first-order reac-
30 minutes with high-purity nitrogen (N2) until a dissolved- tion, and the change in the concentration of dissolved oxygen can
oxygen concentration of approximately 1 ppm (31 mmolL1) be demonstrated as shown in Eq. 9. Therefore, natural logarithmic
was achieved. The headspace was then purged with N2 for the of dissolved-oxygen concentration was plotted against time and
remainder of the experiment to prevent oxygen ingress into the its slope corresponded to the rate constant according to Eq. 10:

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 J185944 DOI: 10.2118/185944-PA Date: 25-February-17 Stage: Page: 3 Total Pages: 11

35 40
0% MEG
30 20% MEG 35
80% MEG 30
25
[O2] (µmol.L–1)

[O2] (µmol.L–1)
25
20 10 ± 0.1°C
15 ± 0.1°C
20 20 ± 0.1°C
15 35 ± 0.1°C
15 40 ± 0.1°C
10
10
5 5
0 0
0.E+00 1.E+04 2.E+04 3.E+04 4.E+04 5.E+04 0.E+00 1.0E+03 2.0E+03 3.0E+03 4.0E+03 5.0E+03
Time (seconds) Time (seconds)

Fig. 2—Influence of MEG concentrations on oxygen-scaveng- Fig. 3—The influence of temperature on oxygen-scavenging
ing kinetics in pH-unadjusted solutions with various percen- kinetics of 200 mg/L of HSO2
3 in pH-unadjusted ultrapure water.
tages of MEG. The test temperature was 278C. pH value varied between 6.1 6 0.1.

ever, increasing MEG concentration from 20 to 80 wt% only mar-

CO2 ;t ¼ CO2 ;i ekt ; . . . . . . . . . . . . . . . . . . . . . . . . . . ð9Þ ginally delayed the oxidation process.
Previous studies have shown that the presence of alcohols hin-
lnðCO2 ;t Þ ¼ lnðCO2 ;i Þ  kt; . . . . . . . . . . . . . . . . . . . . ð10Þ dered the reaction kinetics of sulfite oxidation (Backstrom 1934;
Hayon et al. 1972; Deister and Warneck 1990; Wang et al. 2009).
where CO2 ;t is dissolved-oxygen concentration at time t and k is Hayon et al. (1972), by use of pulse radiolysis, showed that alco-
the rate constant in s1. hol rapidly reacts with SO  
4 but not with SO3 or SO5 . The ter-
mination reaction by an alcohol (A) can be represented by Eq. 11:
Chemicals. High-purity N2 gas was used for sparging the test  SO
4 þA !
solutions and maintaining the N2-gas blanket throughout the
experiments. The N2 gas was specified to a minimum purity of Inactive products ðsuch as organosulfates and sulfonatesÞ:
99.99% with an oxygen content of less than 10 ppm. Fiber-grade                    ð11Þ
MEG (99.8 wt%) was sourced from SPDC, Saudi Arabia. The
conductivity of high-purity water was less than 3 mScm1. Ana- Similar results were found by Wang et al. (2009), who studied
lytical-grade sodium-bisulfite powder (ACROS Organics) was the inhibition of the oxidation of sulfite ions by ethanol and
used for the investigations. hypothesized that the sulfite free radicals were absorbed by etha-
TMs were added as chloride salts: FeCl24H2O (LR grade) nol at the hydroxyl functional group. Inhibition of the sulfite-oxi-
from Chem-Supply and NiCl22H2O, MnCl24H2O, and dation reaction has also been observed for phenols (Ermakov
CoCl26H2O (AR grade) from AJAX Finechem. et al. 1997) and a range of oilfield additives (Braga 1987).
Fig. 2 shows that the critical MEG concentration expected to
inhibit the reaction between sulfite and dissolved oxygen is
Results and Discussion
much less than 20 wt%. Hence, a large drop in the oxygen-scav-
Effect of MEG Concentrations. The influence of MEG at differ- enging rate is seen in the presence of 20 wt% MEG, whereas a
ent concentrations on bisulfite oxygen scavenging, studied at further increase in MEG concentration only slightly reduces the
27 C is shown in Fig. 2. In this set of experiments, solution pH reaction rate.
value was unadjusted, and varied slightly at 6.1 6 0.1. The change In general, in aqueous systems, the rates of reaction for sulfite
in dissolved-oxygen concentration after adding 200 mg/L of so- oxidation are so fast that they are diffusion-limited (Zhang and
dium bisulfite to the solutions at different MEG concentrations is Millero 1991; Connick et al. 1995; Ermakov et al. 1997), which is
presented in Fig. 2. In the absence of MEG, the dissolved oxygen expected from reactions propagated by radicals. In the presence
was removed to less than the threshold of 20 ppb (0.6 mmolL1) of MEG, the viscosity of the solution increases significantly, espe-
within 980 seconds. The overall reaction rate was calculated to be cially when MEG is used in percent levels. However, the increase
3.09  102 mmolL1s1. By adding 20 wt% MEG, the time in viscosity of the solution with MEG is unlikely to limit the dif-
required to complete the reaction significantly increased. How- fusion rate of the reaction reactants. This is supported by Linek
and Vacek (1981), who showed that the addition of a viscosity-
35 enhancing agent such as glycerol, containing multiple alcohol
10 ± 0.1°C groups, reduced the sulfite-oxidation rate by as much as 25%,
30 15 ± 0.1°C
20 ± 0.1°C whereas the addition of carboxymethyl cellulose (another viscos-
25 35 ± 0.2°C ity-enhancing agent), where all the alcohol groups are methylated,
[O2] (µmol.L–1)

40 ± 0.2°C had only a minor effect. This indicates that the inhibition of sulfite
20 oxidation by MEG is more likely a consequence of radical-termi-
nation reactions becoming more dominant (i.e., Eq. 7) rather than
15
the reaction becoming diffusion-limited.
10
5 Effect of Temperature. Water Only. First, the effect of temper-
0 ature on bisulfite-oxygen-scavenging kinetics was studied in the
0 20 40 60 80 100 120 140 160 180 200 water-only solution. The results are depicted in Figs. 3 and 4 for
Time (seconds) solutions without pH adjustment and solutions at pH 9, respec-
tively. The calculated overall reaction rates are given in Table 1.
Fig. 4—The influence of temperature on oxygen-scavenging In pH-unadjusted solutions (Fig. 3) and at temperatures lower
kinetics of 200 mg/L of HSO2
3 in ultrapure water with pH value
than 35 C, oxygen scavenging was recorded in the beginning but
adjusted to 9.0 with NaHCO3. was observed to quickly terminate. Tests conducted from 10 to

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Temperature Rate Constant Overall Reaction

Rate (µmol·L ·s )
–1 –1 –1
Solution pH (°C) (s )
–5 –4
Water Unadjusted 10 2.8×10 5.01×10
–5 –4
15 3.9×10 6.02×10
–5 –4
20 3.8×10 6.72×10
–5 –4
35 111×10 157×10
–5 –4
40 122×10 161×10
–5 –4
Water Adjusted at 9 10 1,910×10 1040×10
–5 –4
15 2,140×10 1360×10
–5 –4
20 2,290×10 1430×10
–5 –4
35 2,850×10 2220×10
–5 –4
40 4,150×10 3240×10
–5 –4
80 wt% MEG Unadjusted 10 0.8×10 1.22×10
–5 –4
20 3.03×10 5.14×10
–5 –4
35 3.26×10 5.99×10
–5 –4
40 4.76×10 5.29×10
–5 –4
Adjusted at 7 20 7.37×10 7.39×10
–5 –4
Adjusted at 9 10 5.25×10 6.80×10
–5 –4
20 8.34×10 9.26×10
–5 –4
27 12.9×10 20.6×10
–5 –4
80 wt% MEG + Unadjusted 20 730×10 717×10
1 ppm Fe2+

Table 1—Calculated apparent reaction rate and rate constants.

20 C showed poor efficiency, and the dissolved-oxygen concen- The rate of oxygen removal only gradually increased with temper-
tration remained constant. Increasing the solution temperature ature, and there was no abrupt increase as a function of tempera-
from 20 to 35 C had given rise to a two-orders-of-magnitude ture. Hence, it might be inferred that the solution pH value has a
increase in the overall reaction rate. Although the bisulfite-oxida- significant effect by controlling the rate of reaction and enhances
tion reaction at 35 and 40 C reached completion, two distinct the efficiency of bisulfite oxygen removal at temperatures lower
reaction rates were observed throughout the oxidation period. than 35 C. This is consistent with the conclusions of Ermakov
This follows the observation that the sulfite-oxidation process is et al. (1997), who highlighted that at low pH values (less than 6)
separated into two states: an oxygen-rich state where the reaction the reduced reaction rate is attributed to the significantly slower
proceeds more rapidly and an oxygen-depleted state where slow kinetics associated with the bisulfite ion vs. the sulfite ion in the
reaction rate is obtained (Wang et al. 2009). propagation step (Eqs. 5 and 6). This explains the successful
When sodium bicarbonate was added to increase the alkalinity application of bisulfite ions as an oxygen scavenger in highly buf-
and buffer the solution to pH 9, the oxygen scavenging was found fered seawater environments (Hobson et al. 1987; Hali et al.
to complete within a few minutes, even at low temperatures (Fig. 2016), where the pH is greater than 8.
4). Interestingly, under these conditions only a single state of 80 wt% MEG/Water. The temperature dependence of bisulfite
rapid oxidation was seen throughout the reaction period, and a oxidation in the 80 wt% MEG solutions was studied for a range of
second state of reduced reaction rate was absent. This indicates temperatures at solutions without pH adjustment and at pH 9, and
that the increased alkalinity facilitated a rapid oxidation reaction. the results are given in Figs. 5 and 6, respectively.
As shown in Fig. 5, each experiment starts with a sharp drop
of dissolved-oxygen concentration, which then falls off to a con-
35 siderably slower reaction rate. This feature was also observed in
10 ± 0.2°C the water-only solutions; hence, it appears to be a common char-
20 ± 0.2°C
30 35 ± 0.4°C acteristic of the pH-unadjusted solutions. Increasing the solution
40 ± 0.4°C temperature was observed to noticeably accelerate the reaction
25 kinetics. At 40 C, the scavenging rate is appreciably higher than
[O2] (µmol.L–1)

those at lower temperatures, although at this pH value the bisul-

20 fite-scavenging reaction did not reach completion within the
recorded time frame (12 hours).
15 The scavenging results shown in Fig. 6 were obtained at pH 9
with 80 wt% MEG at temperatures of 10, 20, and 27 C. It can be
10
seen that at 10 C the dissolved oxygen remained higher than the
5
20-ppb-threshold limit at the given experimental time frame.
Increasing the temperature resulted in an accelerated reaction
0 rate. At 20 and 27 C, the complete removal of dissolved oxygen
0.0E+00 1.0E+04 2.0E+04 3.0E+04 4.0E+04 5.0E+04 occurred at 9 and 4 hours, respectively. Table 1 gives the calcu-
Time (seconds) lated reaction rates showing that the kinetics of the oxygen-scav-
enging reaction in MEG increases with a rise in temperature.
Fig. 5—The influence of temperature on oxygen-scavenging These results highlight the temperature limitation of the use of
kinetics of 200 mg/L of HSO23 in pH-unadjusted 80 wt% MEG/20
uncatalyzed-bisulfite ions as an oxygen scavenger. These limita-
wt% ultrapure water. pH values varied between 4.7 and 5.1. tions would affect the application of such scavengers in cold

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35 35
10 ± 0.5°C pH value of 5.6
30 20 ± 0.1°C 30 pH value of 7
27 ± 0.3°C pH value of 9
[O2] (µmol.L–1) 25 25

[O2] (µmol.L–1)
20 20

15 15

10 10

5 5

0 0
0.0E+00 1.0E+04 2.0E+04 3.0E+04 4.0E+04 5.0E+04 0.00E+00 1.00E+04 2.00E+04 3.00E+04 4.00E+04 5.00E+04
Time (seconds) Time (seconds)

Fig. 6—The influence of temperature on oxygen-scavenging Fig. 7—The influence of pH on oxygen-scavenging kinetics of
kinetics of 200 mg/L of HSO2
3 in 80 wt% MEG/20 wt% ultrapure 200 mg/L of HSO23 in 80 wt% MEG/20 wt% ultrapure water at
water. pH value was adjusted to 9.0 with NaHCO3. 208C. NaHCO3 was used to adjust the pH value.

subsea applications or when the pipeline is wet-parked at the solutions tested. In solutions without pH adjustment (both MEG/
seabed conditions; the pipeline temperature can reach as low as water mixtures and water only), there was an initial sharp drop in
4 C, lower than the minimum temperature in this study. dissolved-oxygen concentration, followed by a reduction in the
slope. The bisulfite-oxygen-scavenging reaction in the water-only
and MEG/water solutions is described by a first-order reaction, as
Effect of pH. Fig. 7 displays the effect of pH on oxygen-removal
observed by the constant slope in all conditions studied. Table 1
rate at 20 C. As previously observed without pH adjustment, the
summarizes the determined rate constants for the reactions. As
bisulfite ions are unable to remove oxygen within the 12-hour
anticipated, the rate constants determined for the sulfite oxidation
time frame. By adjusting the solution pH at values of 7 and 9, the
in water are significantly higher than for solutions containing
dissolved-oxygen concentration was decreased to less than 20 ppb
MEG. The rate constants were found to increase with temperature,
after 12 and 9 hours, respectively. The trends of dissolved-oxygen
according to the Arrhenius equation, as shown in Eq. 12:
levels against time for the solutions at pH values of 7 and 9 over-
lap in the beginning, but thereafter the oxidation process with pH  
Ea 1
value of 9 tends to progress faster. The higher reaction rate in the lnk ¼  þ lnA: . . . . . . . . . . . . . . . . . . . . . ð12Þ
R T
slightly alkaline solutions (pH value of 9) can be attributed to the
corresponding increase in sulfite-ion concentration. It has been The natural logarithms of the rate constants given in Table 1
established for water systems that the bisulfite dissociation is a were plotted against inverse temperature (in K) and are shown in
preceding step to the more-rapid oxidation reaction described by Fig. 10. The observed linear relationships allow for calculation of
Eq. 4. The concentration of sulfite ions available for oxidation the activation energies, where the pre-exponential factors were
increases with pH as can be seen in the normalized speciation dis- taken from the slope and intercepts.
tribution in Fig. 8. Table 2 displays the activation energies and pre-exponential
Despite the gradual increase in reaction rate with pH, the over- factors calculated from Fig. 10. As expected, there appears to be
all reaction rate in MEG solutions is still three orders of magni- no linear relationship for sulfite ions in water. This is attributed to
tude smaller than that of water at the same pH value. This the fact that when solution pH is unadjusted, the final solution pH
confirms the inhibitory effect of MEG, as described previously by value is related to the pH induced by the addition of the bisulfite
Eq. 8. salts. The pH shift gives rise to a continuous change of reaction
rate depending on the sulfite concentration, which results in a non-
Determination of Rate Constant and Activation Energy. Figs. linear relationship.
9a through 9d illustrate the linear relationship between natural A significant difference exists in the activation energies of sul-
logarithm of oxygen concentration—ln[O2]—against time for the fite oxidation in water-only and MEG/water solutions. The activa-
tion energy doubles in the presence of MEG, which explains its
inhibitory effect. Interestingly, despite a marked increase in the
reaction rate at pH value of 9, the activation energy is similar to
100 that of a pH-unadjusted condition. This suggests that the overall
90 mechanisms of sulfite oxidation are the same regardless of the so-
80 lution pH value, and that the enhanced rates observed at pH value
Species Formation (%)

70 of 9 are merely because of a higher concentration of sulfite radi-

cals available in the propagation-reaction step (Eq. 5).
60
50 H2SO3
HSO3– Effect of TM Catalysts. The effect of TMs on oxygen-scaveng-
40
SO3
2– ing rate in concentrated MEG/water mixtures are illustrated in Fig.
30 11. When the sulfite oxidation was catalyzed by Co(II), Mn(II),
20 and Ni(II) ions, two distinct stages in the reaction kinetics were
10 observed, consistent with the characteristics of the scavenging
reactions observed in solutions without pH adjustment (Figs. 3 and
0
0 1 2 3 4 5 6 7 8 9 10 5). The differences in the rate constants between the rapid and slow
pH Value states in the presence of TM catalysts are listed in Table 3.
Although the initial rates appear sensitive to the presence of the
Fig. 8—Speciation distribution of sulfite species as a function catalysts, the second oxygen-depleted state appears to have no de-
of pH value. pendency on the presence of the selected catalysts. The initial rate

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4 4
3.5 3.5
3 3
In (106 × [O2])

In (106 × [O2])
2.5 2.5
2 2
1.5 1.5
10 ± 0.2°C
1 1 20 ± 0.2°C
35 ± 0.4°C
0.5 10 ± 0.2°C 15 ± 0.3°C 20 ± 0.1°C 0.5 40 ± 0.4°C
35 ± 0.2°C 40 ± 0.3°C
0 0
0.0E+00 1.0E+04 2.0E+04 3.0E+04 4.0E+04 5.0E+04 0.0E+00 1.0E+04 2.0E+04 3.0E+04 4.0E+04 5.0E+04
Time (seconds) Time (seconds)
(a) (c)

4 10 ± 0.1°C
3.5
15 ± 0.1°C 10 ± 0.5°C
3 20 ± 0.1°C 20 ± 0.1°C
35 ± 0.2°C
2 40 ± 0.2°C 3 27 ± 0.3°C
In (106 × [O2])

In (106 × [O2])
1 y = –5.251E–05x + 3.412
2.5
0

–1 2
y = –1.290E–04x + 3.45
y = –8.337E–05x + 3.432
–2
–3 1.5
0 20 40 60 80 100 120 140 160 0 5,000 10,000 15,000 20,000 25,000 30,000
Time (seconds) Time (seconds)
(b) (d)

Fig. 9—Oxygen-scavenging kinetics of 200 mg/L of HSO2 3 in (a) pH-unadjusted water solutions, (b) water solution pH adjusted at 9,
(c) 80 wt% MEG in ultrapure pH-unadjusted water, and (d) 80 wt% MEG in ultrapure water adjusted at pH 9. Temperature was varied
as indicated. Data are presented in a natural logarithmic scale. Linear relationship of ln(106 3 [O2]/lmol/L) vs. time is characteristic
of first-order reaction.

improvement was greatest for the following order of catalyst ions: potential of corrosion at lower pH values is often a concern.
Fe(II)>Mn(II)>Co(II)>Ni(II). Therefore, at the early stages of gas production, when only con-
There have been numerous laboratory studies undertaken to densed water is present, the pH value could be increased (pH neu-
understand the role that metal-ion catalysts play in the oxidation tralization) as a corrosion-mitigation technique, which would
of sulfite ions in aqueous solutions. It is now understood that TM enhance sulfite-oxygen-scavenger effectiveness. However, when
ions catalyze the sulfite oxidation and consequent oxygen removal formation water is present, the pH value of production fluids is
by providing a cycling-redox couple for initial oxidation and the generally kept as low as possible to avoid unwanted scale forma-
continued propagation of sulfite ions. Table 4 shows the key reac- tion. Under these circumstances, the performance of uncatalyzed
tions involved when ferrous ions are used to catalyze oxygen re- oxygen scavengers is often challenged.
moval. In the presence of oxygen, a small amount of ferric ions Recent studies have proposed that the first and key step of sul-
will be present in solution, and in the pH range of 2–5 are thermo- fite oxidation in the presence of catalysts is the formation of a
dynamically stable as FeOH2þ (Hem and Cropper 1959). Carbon metal-sulfite complex—½MSO3 a2 —shown by Eq. 13 (Grgić and
dioxide is always present as a dissolved gas, making the solution Berčič 2001):
acidic depending on the partial pressure of the gas and the water
a2
chemistry. Thus, it is not uncommon for the pH value of produc- Maþ þ SO2
3 () ½MSO3  : . . . . . . . . . . . . . . . . ð13Þ
tion fluids in gas-flow lines to be in the range of 4–5, but the
The binding or association constant (Ka) for the associated
ions in the complex described by Eq. 9 is given by Eq. 14, and is
–2 the inverse of the dissociation constant:
y = –1991.3x + 3.0475

–4 Water, pH value of 9
Rate of association ½MSO3 a2
Ka ¼ ¼ aþ : . . . . . . . . ð14Þ
Rate of dissociation ½M ½SO23 
–6 Table 5 shows the association constants for a range of TM/sul-
Ink

fite and metal/sulfate complexes in aqueous solutions. Iron and

–8 80 wt% MEG, pH value of 9
80 wt% MEG,
y = –4544.1x + 6.1585 Ea Pre-Exponential
pH unadjusted –1
Factor A (s )
–1
Reaction (kJ·mol )
–10
y = –4519.9x + 4.5285
Water, pH = 9 16.6 21.1
–12 MEG, pH = unadjusted 37.5 92.6
0.0031 0.0032 0.0033 0.0034 0.0035 0.0036 MEG, pH = 9 37.8 472.7
Inverse Temperature (K–1)
Table 2—Calculated apparent activation energies of pH-unadjusted
Fig. 10—Arrhenius plots for the sulfite oxidation in three differ- and -adjusted (pH 9) solutions of 80 wt% MEG and 20 wt% ultrapure
ent solutions in accordance with Eq. 12. water extracted from Fig. 10.

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40
Co2+ 40
35 Fast reaction
35 Ni2+ Slow reaction

[O2] (×106 mol.L–1)

30 rate
rate
Mn2+
30 25
Fe2+ 20

[O2] (×106 mol.L–1)

Blank 15
25
10
20 5
0
0 200 400 600 800 1,000
15 Reaction Time (seconds)

10

0
0 5,000 10,000 15,000 20,000
Reaction Time (seconds)

Fig. 11—The influence of TMs added as their chloride salts on the improvement of oxygen-scavenging kinetics of 200 mg/L of
HSO 3 in 80 wt% MEG at 278C. pH-unadjusted solutions have pH values varying between 4.7 and 5.1. The inset illustrates the abrupt
decrease in the reaction rate.

Rate Constant (s )
–1 manganese have been shown as the most-effective catalysts in the
oxidation of sulfites in aqueous solution (van Eldik et al. 1992;
Solution Rapid State Slow State Brandt et al. 1994; Brandt and van Eldik 1995; Novič et al. 1996;
2+ –4
1 ppm Fe 127×10 – Grgić and Berčič 2001; Podkrajšek et al. 2004). Interestingly, the
1 ppm Mn
2+
36×10–4 6.59×10
–5 iron and manganese sulfite complexes have been reported in a va-
2+ –5
riety of studies to have higher association constants with sulfite
1 ppm Co 21×10–4 8.14×10 than other TMs. The overall reaction rate for catalyzed reactions
2+ –5
1 ppm Ni 17×10–4 6.39×10 has been shown to be proportional to the concentration of the
No catalyst 2.78×10
–4
7.09×10
–5 metal/sulfite complex in the initial step of a radical-chain mecha-
nism. Thus, the stability of the metal/sulfite complex has been
Table 3—Rate constants of sulfite oxidation in 80 wt% MEG 1 20 proposed as the key reason why iron and manganese ions show
wt% water without pH adjustment in the presence of different TM consistently better performance than other metals (Grgić and
catalysts at 20º C. Berčič 2001). These observations are in agreement with the order

Rate
Equation Constant k
–1 –1
No. Reaction (mol ·L·s ) Reference
4 ⋅SO3− + O 2 → ⋅SO5− 2.5×10
9
Warneck and Ziajka (1995)
9
1.0×10 Ziajka et al. (1994)
15 Fe2+ +⋅SO5− + H2O → FeOH2+ + HSO5−
4.3×10
7 Herrmann et al. (1996)
Podkrajšek et al. (2004)
− 2+ +
Carlyle (1971)
16 HSO + FeOH ⇔ [FeOHSO3 H ]
3
270
Brandt et al. (1994)
Grgić and Berčič (2001)
17 [FeOHSO3H]+ → ⋅SO3− + Fe2+ + H 2O 39 Warneck and Ziajka (1995)

6 Grgić and Berčič (2001);

3.2×10
Buxton et al. (1992)

18 [FeOHSO3H]+ + ⋅SO3− → 2SO32− + Fe2+ + H 2O 3.9×10

6 Brandt and Eldik (1995);
Eriksen (1974)
Brandt and Eldik (1995);
Warneck et al. 1993)
19 Fe 2 + + HSO5− → FeOH 2+ + ⋅SO −4 3.6×10
4
Warneck et al. (1996)
8
3.0×10 Warneck et al. (1996)
2+ − 2+ 2− +
20 Fe + ⋅SO + H 2O → FeOH + SO + H
4 4 8
9.9×10 Brandt and Eldik (1995);
Heckel et al. (1966)
Table 4—Key reactions in the iron catalysis of oxygen scavenging by sulfite ions.

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Sulfite-Binding Sulfate-Binding
Metal Ion Coefficient (M) Respective References Coefficient (M) Respective References
Bhatti and Lark (1981)
Conklin and Hoffmann
Matthews (2010)
2+ (1988a, b)
Mn 0.48, 3.00, 5.00 2.14, 2.22, 2.86 Matthews and Naidoo (2010)
Roy et al. (1991)
Mattoo (1959)
Grgić and Berčič (2001)
Izatt et al. (1969b)
Izatt et al. (1969a)
Conklin and Hoffmann Matthews (2010)
2+
Fe 0.77, 3.75 (1988a, b); Grgić and 2.20, 2.26, 2.20 Matthews and Naidoo (2010);
Berčič (2001) Mattoo (1959)
Izatt et al. (1969b)

3+ Conklin and Hoffmann Mattoo (1959)

Fe 6.6 2.42
(1988a, b) Izatt et al. (1969b)
Chen et al. (2005)
Matthews (2010)
2+ Conklin and Hoffmann
Ni 1.33, 2.88 2.29, 2.31, 2.81 Matthews and Naidoo (2010)
(1988a, b); Roy et al. (1991)
Mattoo (1959)
Izatt et al. (1969b)
Bhatti and Lark (1981)
Chen et al. (2005)
2+ Conklin and Hoffmann Matthews (2010)
CO 1.28, 3.08 2.52, 2.46, 2.69
(1988a, b); Roy et al. (1991) Matthews and Naidoo (2010)
Mattoo (1959)
Izatt et al. (1969)

Table 5—Association constants (molar scale) for M21 and SO2

x ion pairs.

of rate improvement of oxygen scavenging, observed in this study (Nurmi et al. 1982; Brandt and van Eldik 1995). Similarly, at pH
at relatively concentrated MEG solution, when iron and manga- values greater than 5, ferric ions become insoluble and are ther-
nese were added. modynamically stable as Fe(OH)3, thus limiting the applicable pH
Adding iron into the aqueous solution leads to the formation of range for practical use. In contrast, Mn(II) ions are soluble up to
ferric/sulfite complex (Eqs. 15 and 16), which subsequently leads an approximate pH value of 8 (Hem 1963).
to the self-oxidation reactions described by Eqs. 17 and 18 in Ta- Therefore, it should be noted that in practice (i.e., gas-trans-
ble 4. The generated sulfite radical ions, ðSO 3 Þ, react with the mission pipelines and MEG-regeneration cycles), when dealing
dissolved oxygen to generate SO 5 radicals by means of the reac- with radical-chain reactions, the actual rates and dominant path-
tion described by Eq. 4. The SO 5 radical can react with ferrous way of the chain mechanism are particularly sensitive to the con-
ions to regenerate the ferric ion, and ultimately the associated sul- centration of the active species, oxidation state of the metal ions,
fite complexes described by Eqs. 15 and 19. Eq. 19 can generate pH value of the reaction solution, and temperature. Furthermore,
SO 4 radicals that are scavenged by ferrous ions to again regen- the reaction can be influenced by the presence of different impur-
erate ferric ions (Eq. 20). This is a key change in the radical-chain ities and extraneous substances (van Eldik et al. 1992; Brandt
mechanism compared with the uncatalyzed reaction where reac- et al. 1994; Brandt and van Eldik 1995; Novič et al. 1996; Grgić
tion of SO 4 in the presence of alcohols such as MEG would and Berčič 2001; Podkrajšek et al. 2004). Another observation of
have resulted in chain termination (Eq. 7). The second slow-state interest was found in the experimental practice of deoxygenating
rates shown in Table 3 are attributed to oxygen depletion, which MEG. The time to deoxygenate MEG solutions with N2 took sig-
affects the viability of the reaction described by Eq. 4 in Table 4. nificantly longer than with water (Salasi et al. 2015). This leads to
Therefore, in relatively concentrated MEG solutions, the chain- a speculation that dissolved oxygen may not just exist as a molec-
termination reactions are possibly prevented by the anticipated ular solute but could form a potential adduct with MEG. If this
complexation reactions of the SO 4 radical with ferrous ions. were true, the initial rates of reaction of dissolved oxygen and sul-
This is supported by the relatively strong binding constants of fite may be associated with an even-more-complicated mecha-
iron with sulfate ions, as shown in Table 5, and very-fast reaction nism, and would be worthy of additional work.
rates for those reactions, as shown in Table 4. As the MEG con-
centration in water is increased, the binding constants of the com-
plexes shown in Table 5 are expected to also progressively Conclusions
increase, based on analogous studies (Niazi and Hussain 1994; This study focused on the oxygen-scavenging reaction by bisulfite
Tsierkezos and Molinou 2002, 2006; El-Dossoki et al. 2011; in relatively concentrated solutions of MEG at levels normally
Masood et al. 2013), and will up to a point compensate for the used in oilfield operations for hydrate inhibition. On the basis of
additional MEG available for chain termination. the results, the following conclusions can be drawn.
Manganese ions catalyze sulfite oxidation in a similar fashion 1. The inhibitory effect of MEG on bisulfite-oxygen scaveng-
as iron ions, though by means of a slightly more-complex chain ing has been demonstrated by the observed increase in the
mechanism, and consequently are less effective. In addition, man- activation energy of the sulfite oxidation, and the conse-
ganese ions have been shown to be synergetic to the iron-cata- quential decrease in the overall reaction rate in the presence
lyzed reactions by providing an alternative redox couple for both of MEG.
sulfite and ferrous oxidation (Grgić and Berčič 2001; Podkrajšek 2. The pH value of the MEG solution was shown to be the pri-
et al. 2004). However, the necessary availability of the metal ions mary factor for determining the creation of sulfite oxida-
to catalyze the sulfite oxidation in MEG leads to the expectation tion. The oxygen-removal rate proceeds faster in both
that the reaction will likely be impeded if the metal ions are com- water and MEG solutions at higher pH values, and is attrib-
petitively sequestered in complexes with greater stability than the uted to an increase in the level of available sulfite ions
metal/sulfite complex. For example, organic acids such as suc- and the respective levels of sulfite radicals available for
cinic acid have been shown to hinder the catalysis reaction chain propagation.

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3. Higher temperatures were observed to enhance the reaction Deister, U. and Warneck, P. 1990. Photooxidation of Sulfite (SO2 3 ) in
kinetics, hence increasing the rate of oxygen removal from Aqueous Solution. J. Phys. Chem. 94 (20): 2191–98. http://dx.doi.org/
both water and MEG solutions. 10.1021/j100368a084.
4. Suitable TMs that can be used as a catalyst for oxygen re- Dugstad, A. and Seiersten, M. 2004. pH-Stabilisation, a Reliable Method
moval include iron and manganese ions, although at higher for Corrosion Control of Wet Gas Pipelines. Presented at the SPE
pH values, manganese ions are preferred because of solubil- International Symposium on Oilfield Corrosion, Aberdeen, 28 May.
ity issues with iron. SPE-87560-MS. http://dx.doi.org/10.2118/87560-MS.
5. Other TMs extend the rapid oxidation state but are ineffec- El-Dossoki, F. I., Abdallh, N. E. Y., and Elmasly, S. E. T. 2011. The
tive in complete removal of dissolved oxygen. Transport Properties and the Association Behavior of Some 1:1 and
2:1 Electrolytes in Some Binary Alcoholic–aqueous Mixtures. J. Mol.
Liq. 163 (3): 135–140. http://dx.doi.org/10.1016/j.molliq.2011.08.009.
Nomenclature Eriksen, T. E. 1974. pH Effects on the Pulse Radiolysis of Deoxygenated
A ¼ pre-exponential factor, s1 Aqueous Solutions of Sulphur Dioxide. J. Chem. Soc. Farad. T. 1 70:
Ea ¼ activation energy, Jmol1 208–215. http://dx.doi.org/10.1039/F19747000208.
k ¼ rate constant, s1 Ermakov, A. N., Poskrebyshev, G. A., and Purmal, A. P. 1997. Sulfite Oxida-
R ¼ gas constant, 8.314 Jmol1K1 tion: The State-of-the-Art of the Problem. Kinet. Catal. 38 (3): 295–308.
Fuller, E. C. and Crist, R. H. 1941. The Rate of Oxidation of Sulfite Ions
by Oxygen. J. Am. Chem. Soc. 63 (6): 1644–1650. http://dx.doi.org/
Acknowledgment 10.1021/ja01851a041.
The authors would like to express their appreciation to Stuart Bai- Grgić, I. and Berčič, G. 2001. A Simple Kinetic Model for Autoxidation
ley for his support and to Timothy Nicholls for conducting some of S(IV) Oxides Catalyzed by Iron And/or Manganese Ions. J. Atmos.
experimental work. Chem. 39 (2): 155–170. http://dx.doi.org/10.1023/A:1010638902653.
Gulbrandsen, E. and Morard, J. H. 1998. Why Does Glycol Inhibit CO2
Corrosion? Presented at CORROSION 98, San Diego, California,
22–27 March. NACE-98221.
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 J185944 DOI: 10.2118/185944-PA Date: 25-February-17 Stage: Page: 11 Total Pages: 11

Xiang, Y., Choi, Y. S., Yang, Y. et al. 2015. Corrosion of Carbon Steel in Thunyaluk Pojtanabuntoeng is a research and teaching fellow
MDEA-Based CO2 Capture Plant under Regenerator Condition: Effect at the Curtin Corrosion Engineering Industry Centre at Curtin
of O2 and HSS. Corrosion 71 (1): 30–37. http://dx.doi.org/10.5006/1354. University. Her collective research and industry experience
Zhang, J.-Z. and Millero, F. J. 1991. The Rate of Sulfite Oxidation in Sea- during the past 10 years focuses on internal corrosion in the oil
water. Geochim. Cosmochim. Ac. 55 (3): 677–85. http://dx.doi.org/ and gas industry. Pojtanabuntoeng holds a PhD degree from
the Department of Chemical Engineering at Ohio University.
10.1016/0016-7037(91)90333-Z.
Ziajka, J., Beer, F., and Warneck, P. 1994. Iron-Catalysed Oxidation of Sindee Wong is a graduate process engineer working at Inpex
Bisulphite Aqueous Solution: Evidence for a Free Radical Chain Australia, an oil and gas company. She holds bachelor’s
Mechanism. Atmos. Environ 28 (15): 2549–2552. http://dx.doi.org/ degrees in chemical engineering and chemistry from Curtin
10.1016/1352-2310(94)90405-7. University.
Marc Lehmann is principal production chemist with Inpex Aus-
tralia in Perth. He is a production chemist with more than 20
Mobin Salasi is a research fellow at the Department of Me- years of experience in the chemical industry, with the last 12
chanical Engineering at Curtin University, Australia. He is a years focused on upstream oil and gas operations for both
materials scientist with 10 years of academic and industrial ex- onshore and offshore. Lehmann is a member of the American
perience. Salasi holds a PhD degree from the School of Me- Institute of Chemical Engineers and SPE. He holds a PhD
chanical Engineering at the University of Western Australia. degree in physical chemistry.

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