Mechanistic M

icrobiologically influenced
corrosion (MIC) is increas-
ingly becoming a significant
problem in the oil and gas

Modeling of
industry because of enhanced recovery
and aging equipment. Apart from pigging
of pipelines, mitigation of MIC relies
mostly on biocides. Seawater, used regu-
larly for seawater injection in production,

Anaerobic
is also routinely used for hydrotesting.
The water used for hydrotesting is usually
treated, typically with biocides. Even
treated seawater, however, can be a

Thps Biocide
source of sulfate-reducing bacteria (SRB)
inoculum, according to Sanders.1 THPS
(tetrakis hydroxymethyl phosphonium
sulfate) is a popular biocide used in oil-
field operations because it is environmen-

Degradation
tally green and relatively easy to handle.
THPS vendors recommend acidic pH for
its use.2 Corrosion engineers, however,
prefer not to accept pH <7, especially for

Under Akaline
hydrotesting.
THPS can easily degrade to THPO
(trishydroxymethyl phosphine oxide), a
process facilitated by hydrolysis, oxida-
tion, photo-degradation, and biodegrada-

Conditions
tion. Equation (1) shows the THPS
chemical structure and its two major
degradation products.3-4

Kaili Zhao, Jie Wen, and Tingyue Gu, Ohio University, Athens, Ohio
Ardjan Kopliku, BP America, Inc., Houston, Texas
Ivan Cruz, Saudi Aramco, Dhahran, Saudi Arabia

This article presents a mechanistic model based on

experimental data to predict THPS
(tetrakis hydroxymethyl phosphonium sulfate)
degradation in seawater as a function of
time, temperature, and pH. (1)

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 C H E M I C A L T R E AT M E N T

table 1
Test matrix for THPS degradation investigation in the
presence of mild steel
Test Conditions
THPS degradation has been studied     Test Media (All Sterilized) Initial pH after THPS was Added
by several researchers.3,5-8 Unfortunately, 1. Persian Gulf seawater 8.12
almost all the THPS degradation data in 2. pH-adjusted Persian Gulf seawater at low pH 6.06
the literature are for acidic or neutral pH.
3. pH-adjusted Persian Gulf seawater at high pH 9.33
Usually, a minimum of 50 or 100 ppm
Notes: Initial THPS concentration was 160 ppm. Media were tested at 4, 23, 31, and 37 °C.
THPS is needed to prevent planktonic
bacterial growth and biofilm establish-
ment. A much higher concentration is
needed to treat established biofilms.
Because of THPS degradability, it is
important to predict residual THPS FIGURE 1
concentration to ensure a desired mini-
mum after a certain period of time with-
out an excessively high initial concentra-
tion. This article presents a mechanistic
model based on experimental data to
predict THPS degradation as a function
of time, temperature, and pH. The
model is aimed at alkaline pH under
which THPS degrades much faster than
under acidic pH.

Experimental Methods
All tests were carried out using 100-
mL serum bottles. Test media were
deoxygenated by N2 sparging before use
and sterilized in an autoclave. Each bottle
contained an X65 pipeline steel coupon THPS degradation at pH 8.1 and the change of specific reaction rate kT(T) with
with dimensions of 1.87 by 0.43 by 0.06 temperature in Persian Gulf seawater.
in (47.5 by 10.92 by 1.52 mm). The cou-
pon surface area to liquid volume ratio
was set close to that in 12-in (0.3-m) inside THPS degradation was found to follow are surprisingly straight and parallel to
diameter (ID) pipes. Natural seawater was the first-order kinetics and the relation- each other. This suggests a linear rela-
used together with artificial seawater. ship between the specific reaction rate tionship of lnk ∝ pH with a slope that is
Hydrochloric acid (HCl) and sodium kT(T) and temperature follows the Ar- independent of temperature. Based on
hydroxide (NaOH) solutions were used rhenius equation. the definition pH= –log10[H+], the lnk vs.
for pH adjustment. An assay kit (CODE The effect of pH on THPS degrada- pH relationship now translates to a pro-
8776†) from the LaMotte Co. was used to tion initially appeared to be quite com- portional relationship of k ∝ [H+]–n, in
measure THPS concentration. plicated. During the first two or three which the parameter n (that is equal to
days after the introduction of THPS into slope 2.303 in Figure 2) is positive. Be-
Results and Discussion seawater, pH shifted but it then became cause n is independent of temperature,
Table 1 shows a test matrix using quite stable.9 This could be due to the we may use k(T, pH)=kT(T){[H+]–n, where
Persian Gulf seawater with different ini- slow-acting buffering power of the sea­ kT(T) is the rate constant with a fixed pH.
tial pH values at different test tempera- water. When the stable pH values were The first-order kinetics equation for
tures. When pH was fixed as shown in used to explore the pH impact on THPS THPS concentration can be modified to
Figure 1 using pH 8.1 as an example, degradation, a definitive trend was re- include [H+] as shown in Equation (2).
vealed. Figure 2 shows the pH effect on
dC
†
Trade name. k at different temperatures. All the lines - = k (T, ph) # C = k T (T) # [h + ] - n # C (2)
dt

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 C H E M I C A L T R E AT M E N T Mechanistic Modeling of Anaerobic THPS Biocide Degradation
Under Alkaline Conditions

FIGURE 2

presence very well. This demonstrates

the robustness of the mechanistic model.
The presence of mild steel accelerated
THPS degradation as demonstrated by
the slower THPS degradation at pH 8.1
without coupon presence (Table 3). The
acceleration was most likely the result of
THPS reactivity with mild steel as indi-
cated by the pitting pattern in Figure 3
that was not observed in a control with-
out THPS.
In our lab tests using the borosilica
glass serum bottles, no appreciable ultra-
The relation of k(T, pH) with pH at four different temperatures in Persian Gulf violet degradation was observed under
seawater.
normal fluorescent lighting conditions.
Persian Gulf seawater (that has salinity
This shows that the effect of pH can MATLAB† Version 7 software quickly 1.6 times than that of the Gulf of Mexico
be viewed as proton inhibition of THPS yielded A = 3.10 × 107, E = 8.448 x 104 seawater) and fresh water were used as
degradation. In terms of reaction kinet- J{mol–1, and n = 0.76. The R2 value of test media to study the effect of salts on
ics, [H+] appears in the rate expression the multi-linear regression is 0.998. With THPS degradation at 31 and 37 °C with
as a negative order (–n) of reaction. the lnk(T, pH) function known, Equation a fixed stable pH of 6.3. After 10 days, it
Equation (2) can be reformulated using (2) can be solved with the initial THPS was found that the THPS degradation
a linearized Arrhenius equation to obtain condition C = C0 at t = 0 to give THPS rate remained almost the same in sea­
Equation (3). concentration as a function of tempera- water and fresh water at the same tem-
ture (in °C) and pH and time (in days) as perature and pH. The results showed that
ln k (T, ph) = ln k T (T) - n # ln [h + ]= shown in Equation (4). salts may have very little intrinsic effect
(3)
ln A -
E
+ 2.303n # ph on THPS degradation after pH is fixed.
R # (T + 273.15)
ln cm =- k (T, ph) # t =
C Salts may only affect THPS degradation
C0
by pH buffering, but such an effect is not
- 3.10 # 10 7 # exp ; E
- 10, 161 (4)
where E and A are activation energy and intrinsic.
T + 273.15
frequency factor, respectively. The uni- # exp (1.75 # ph) # t
versal gas constant R=8.314 J{mol–1{K–1. Conclusions
Equation (2) shows a linear relationship Table 3 compares the model predic- • THPS degradation follows the first-
of lnk vs. 1/T and pH with A, E, and n tion with experimental data at 31 °C with order kinetics. Our mechanistic
as correlation parameters. three different pH values. Table 3 also model shows that it is strongly de-
Table 2 lists k(T, pH) data obtained shows experimental data of THPS deg- pendent on temperature and pH.
from Table 1 at different pH values and radation in another two test media, Gulf THPS degradation increases with
different temperatures in Persian Gulf of Mexico seawater and artificial sea­ the increase of temperature and pH
seawater. The pH values in Table 2 were water, which were also used to test the as well as the presence of mild steel,
stabilized pH values. Multi-linear re­ model. The results show that the model while salts have almost no intrinsic
gression of the data in Table 2 using fit the experimental data with coupon effect on THPS degradation.

table 2
Data for multi-linear regression
Temperature (°C) 4 4 4 23 23 23 31 31 31 37 37 37
pH 7.8 8.2 9.5 7.72 8.14 9.04 7.6 8.1 8.8 7.56 8.03 8.6
–lnk(T, pH) 5.81 4.96 2.78 3.54 2.92 1.25 2.78 2.04 0.71 2.27 1.39 0.45

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 C H E M I C A L T R E AT M E N T

table 3
Comparison of THPS degradation model predictions with experimental data
(all model and experimental data involved coupon unless specifically indicated)
Input Parameters
T (°C) Time (Days) C0 (ppm) pH Symbol
31 10 100 8.1 (In Persian Gulf seawater without coupon presence) Black circle
7.9 (In artificial seawater) Red square
7.9 (In pH-adjusted Persian Gulf seawater) Green triangle
8.1 (In Persian Gulf seawater) Purple square
8.4 (In pH-adjusted Gulf of Mexico seawater) Blue diamond
8.4 (In pH-adjusted Persian Gulf seawater) Brown circle

• pH effect can be decoupled from

FIGURE 3
temperature. Experimental data
indicated that proton acted as
an inhibitor of THPS degradation
in the form of a negative order
reaction.
The proposed THPS degradation
model is applicable to alkaline pH in the
presence of mild steel with the fixed cou-
pon size ratio to medium volume. It is
recommended that future work should
include the quantitative effects of mild
steel, and other factors, like microbes and
the presence of other treatment chemicals
such as oxygen scavenger and corrosion
inhibitor also need to be studied.

Acknowledgments
The authors would like to thank BP
America and Saudi Aramco for their fi-
nancial support of this work as part of a
project and for their permission to present Scanning electron microscopy image of X65 coupon surface after acid cleaning
the results. (five-month test in Gulf of Mexico seawater with initial THPS 50 ppm at 4 ºC).

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 C H E M I C A L T R E AT M E N T Mechanistic Modeling of Anaerobic THPS Biocide Degradation
Under Alkaline Conditions

References 5 G.R. Lloyd, “UV Degradation of Kaili Zhao obtained a Ph.D. in chemical engineering
THPS,” Albright & Wilson U.K. Ltd., at Ohio University, Stocker Center, Athens, OH 45701.
1 P.F. Sanders, “Overview of Souring, 1994, Specialties Technical Laboratory, He also holds an M.S. degree in chemical engineer-
Corrosion and Plugging Due to Reser- Oldbury, U.K. ing from Tianjin University, China. His corrosion
voir Organisms,” U.K. Corrosion 98,
6 J. O’Connor, “THPS: Determination of research experience includes MIC in hydrotests
paper no. 15 (Sheffield, U.K., Oct.
Hydrolysis as a Function of pH,” Eye, using seawater, biocides and biocide enhancers for
20-21, 1998).
1992, Life Science Research Ltd., U.K. MIC mitigation, and MIC modeling. He has been a
2 Rhodia, Product Technical Data on NACE International member for four years.
TOLCIDE®PS75, Issue No. 6, October 7 M. Gorman, “Anaerobic Aquatic Me-
2004. tabolism of 14C-tetrakishhydroxylmethyl Jie Wen is a Ph.D. candidate in the Department of
Phosphonium Sulfate (THPS): Final Chemical and Biomolecular Engineering at Ohio
3 WHO, “Flame Retardants: Tris(2-Bu- report,” 1997. University, e-mail: [email protected]. He earned
toxyethyl) Phosphate, Tris(2-Ethylhexyl)
8 P. McWilliam, “Tolcide PS355A: an M.S. degree in chemical engineering from
Phosphate and Tetrakis(Hydroxymethyl)
Biodegradability in Seawater-Closed Louisiana Tech University. He is a four-year member
Phosphonium Salts,” Environmental Health
Bottle Test,” 1994. of NACE.
Criteria 218, 2000, World Health Organi-
zation, Geneva, http://www.inchem. 9 K. Zhao, J. Wen, T. Gu, A. Kopliku, I. Tingyue Gu is an associate professor of chemical
org/documents/ehc/ehc/ehc218.htm. Cruz, “Mechanistic Modeling of Anaer- and biomolecular engineering and assistant director
4 “ACG Phase I—Supplementary Lenders obic THPS Degradation in Seawater of the Institute for Corrosion and Multiphase
Information Package, Executive Sum- Under Various Conditions,” CORRO- Technology at Ohio University, e-mail: [email protected].
mary,” April 2003, http://www.bp.com/ SION 2008, paper no. 512 (Houston, He has a Ph.D. in chemical engineering from Purdue
liveassets/bp_internet/bp_caspian_en/ TX: NACE, 2008). University. He has published approximately 40
STAGING/local_assets/downloads_ articles in 20 different peer-reviewed journals as
pdfs/t/ACG_English_SLIP_Content_ This article is based on CORROSION 2008 well as one book, two encyclopedia articles, two
ACG_Phase_1_SLIP.pdf. paper no. 08512, presented in New Orleans, Louisiana. handbook articles, and three book chapters. He is a
member of the Bioprocess & Biosystems Engineering
journal editorial board and is the primary creator of
a MIC pitting progression prediction software based
on a new mechanistic model. He is a five-year
member of NACE.

Ardjan Kopliku is a senior materials and corrosion

engineer at BP America, Inc., 501 Westlake Park
Blvd., Westlake 1, Houston, TX 77079, e-mail:
[email protected]. His primary areas of
expertise are corrosion management, material
selection and testing, failure analysis, risk
assessment, and corrosion control. He is a company
trainer in the area of material selection for well
completions, subsea equipment, and surface
(topside) facilities. Before joining BP in 2004, he
served as a materials and corrosion engineer at
ENI–E&P Division (formerly Agip) in Italy. He has a
degree in physics from the University of Tirana,
Albania, and a Ph.D. in materials engineering from
the Polytechnic of Milan, Italy. He has published 26
papers, mainly on materials and corrosion in the oil
and gas industry. A nine-year member of NACE, he is
a member of ASM International and ASME.

Ivan Cruz is a senior engineering consultant at

Saudi Aramco, PO Box 6891, Dhahran, 31311, Saudi
Arabia. Prior to joining the company in 1992, he was
senior engineering advisor at the Mobil Exploration
& Producing Technical Center in Dallas, Texas. He
has extensive corrosion engineering experience in
the oil and gas industry. He has a B.S. degree in
www.CortecVCI.com chemical engineering and is a NACE-certified
Corrosion Specialist, Materials Selection and Design
[email protected] Specialist, and NACE instructor. He received a 2007
NACE Distinguished Service Award. He has been a
member of NACE for 32 years.

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