Indian Journal of Chemical Technology

Vol. 17, July 2010, pp. 291-295

Corrosion inhibition of carbon steel in open recirculating cooling water

system of petroleum refinery by a multi-component blend containing
zinc (II) diethyldithiocarbamate
P K Gogoi* & B Barhai
Department of Chemistry, Dibrugarh University, Dibrugarh 786 004, India
Email: dr_pradip@yahoo.com

Received 27 January 2010; revised 3 May 2010

A multi-component blend of inhibitors containing sodium salt of diethyldithiocarbamate (DEDTC) (50 to 100 ppm),
Zn2+as ZnSO4.7H2O (50 to 70 ppm) and 1-hydroxy ethyledene-1,1-diphosphonic acid (HEDP) (50 to 150 ppm) was
formulated as corrosion and fouling inhibitor for carbon steel in open recirculating cooling water system of Numaligarh
Refinery Limited (NRL), Golaghat, Assam and evaluated by weight loss and potentiodynamic polarization methods. The
results showed that each of NaDEDTC, HEDP and ZnSO4.7H2O in 1.0:1.4:1.0 ratios can significantly decrease corrosion,
scale build-up and microbial growth under the test condition. Potentiodynamic polarization curves indicate both cathodic
and anodic corrosion inhibition. SEM and EDS studies indicate the formation of an adsorbed protective film containing of
Fe2+-HEDP, Zn2+-HEDP, Zn2+-DEDTC complexes on the metal surface.
Keywords: Corrosion, Scale inhibitors, Open recirculating cooling system, Zinc (II), Sodium diethyldithiocarbamate, SEM,
EDS

Open recirculating cooling water system (ORCS) is
one of the most vital units of a petroleum refinery.
The most common problems affecting the
performance of this system are corrosion, scale
formation and biofouling, which directly have an
impact on the productivity. A substantial quantity of
utility water of a petroleum refinery is used in cooling
system. In this system, cooling water is pumped
through various heat exchangers to cool the hot
process fluid such as high speed diesel (HSD),
aviation turbine fuel (ATF) etc. A heat exchanger is
an important part of the ORCS in which the
recirculated cooling water is separated from hot
process fluid by a thin heat conducting CS or brass
surfaces. As a result of this process, heat moves from
the hot process fluid through the exchanger surface,
raising the temperature of cooling water. The hot
cooling water is then allowed to pass through the
cooling tower to cool the water. Due to the presence
of total dissolved solids (TDS), total suspended solids
(TSS), total hardness, microorganism, dissolved gases
such as O2 and CO2 in cooling water there is frequent
occurrence of fouling, scaling, under deposit and
microbiological corrosion in heat exchanger surfaces.
Fouling decreases its heat transfer efficiency. Beside,
chlorine is used as biocide in ORCS along with other
chemicals. The pH of open recirculating cooling
water system is kept towards the alkaline side. In this
high pH or ammonical level, Cl2 causes metal
corrosion as well as increases TDS in cooling water.
On the other hand, many water treatment chemicals,
such as ethylenediaminetetraacetic acid (EDTA),
nitrilo triacetic acid and trisodium salt (NTA) and
adenosine monophosphate (AMP) are attacked by
Cl21. In present study, a multi-component blend of Zn
(as ZnSO4.7H2O), HEDP and sodium salt of DEDTC
has been formulated as fouling, scaling and corrosion
inhibitors to solve most of the problems of ORCS
simultaneously. In the formulated blend, HEDP
works as an anticorrosion as well as antiscalent
agent. Zn2+ acts as cathodic inhibitor. Normally,
HEDP controls the anodic corrosion reaction (Fe→
Fe2+ +2e-) by forming Fe2+-HEDP complex on the
metal surface. This film is easily broken in presence
of chloride ions and Fe2+-HEDP complex dissolves in
cooling water. Zn2+ in presence of HEDP forms Zn2+-
HEDP complex (in solution) which diffuses in the
bulk of the solution and gets deposited on the metal
surface as thin protective film. As the anodic reaction
is controlled by HEDP, the cathodic reaction (2H2O +
292 INDIAN J. CHEM. TECHNOL., JULY 2010

O2 + 4e- → 4 OH-) is controlled by formation of where CR is expressed in mm/year, weight loss in

Zn(OH)2 2. This accounts for the improved inhibition grams, corrosion period (T) in days and coupon area
efficiency of Zn2+-HEDP system. Organo sulphur in cm2.
compound, DEDTC works as a good biocide as well
IE% =R0 – R × 100 / R0 … (2)
as an anodic corrosion inhibitor effectively over a pH
range of 7 to 14 due to its sulphur donor1,3,4,5. The Here R0 and R are the corrosion rates in absence and
pronounced inhibition action of DEDTC is attributed in presence of inhibitors respectively.
to metal-sulphur bond formation. On the other hand,
Electrochemical studies
Zn2+ reacts with DEDTC to form Zn2+-DEDTC
The electrochemical studies were carried out in a
complex which also acts as corrosion inhibitor as well
three electrode cell assembly at room temperature
as good biocide in cooling water system for carbon
(30○C) using a potentiostate of model 600C of CH
steel6. Thus the inhibition efficiency of various blends
instrument. Carbon steel specimen in the form of a
is due to the formation of protective films of Fe2+-
rod of same composition as taken in weight loss
HEDP, Zn2+-HEDP, Zn2+-DEDTC complexes along
studies of exposed area 0.05 cm2 (remaining area was
with Zn(OH) 2.
insulated by covering with teflon) was used as a
working electrode. Platinum was used as counter
Experimental Procedure
electrode and the reference electrode was a silver-
For performing the various experiments, blends of silver chloride electrode. The studies were made at
diethyldithiocarbamate (DEDTC) (50 to 100 ppm), the scan rate of 0.01 V/s. Before starting the
Zn2+ as ZnSO4.7H2O (50 to 70 ppm) and 1-hydroxy polarization scan, minimum 30 min was given to
ethyledene-1,1-diphosphonic acid (HEDP) (50 to stable the open circuit potential (OCP) within
150 ppm) of different concentrations were prepared ±10 mV. The plot of E (potential) versus log I was
separately. Table 1 gives the details of these blends. drawn and from this the corrosion kinetic parameters
Tests were carried out by weight loss and such as corrosion potential (Ecorr) and corrosion
potentiodynamic polarization methods. current (Icorr) were evaluated.
The percentage of inhibition efficiency (%IE) can
Weight loss method
be calculated from the Eq. (3)10.
Carbon steel coupons of known composition
(S, 0.05; P, 0.04; Mn, 0.306, C; 0.08-0.13; Al, 0.03; % IE = (Icorr –Io corr) × 100 / Icorr … (3)
Si, 0.21 and Fe remainder) and size (1.0×1.0×0.15 cm)
Table 1— Composition of various inhibitors
were used for weight loss study. Test were carried out
in a constant temperature bath of cooling water used Blend Zn (ppm) HEDP (ppm) DEDTC (ppm)
in NRL, Golaghat, Assam, in absence and in presence
of various blends of inhibitors separately for 15 days A-50 50 70 50
at temperature of 30±1○C. The cooling water was A-70 50 70 70
analyzed for various parameters by using standard A-100 50 70 100
method7 (Table 2). All these coupons were washed A-150 50 70 150
with double distilled water, degreased with acetone D-50 50 50 100
and finally dried in an oven at 105○C before and after D-70 50 70 100
each experiment. Coupons were then kept in a D-100 50 100 100
moisture free desicator for conditioning. After D-150 50 150 100
conditioning, coupons were weighed. From the T-50 50 50 70
weight difference the corrosion rate (CR) and A-II-70 70 50 50
percentage of inhibition efficiency (%IE) were Table 2— Parameters of cooling water used
calculated by using the Eqs (1)8 and (2)9 respectively.
pH Turbi- Conduc- TDS Total Ca
3,650 × Weight loss (g) dity tivity (ppm) hardness hardness
CR = (NTU) (µs/cm2 ) (ppm) (ppm)
Metal density (g/cm 3 ) × Coupon area × Time (T)
… (1) 7.5 <0.10 148.0 97.68 22.0 16.0
 GOGOI & BARHAI: CORROSION INHIBITION OF CARBON STEEL BY MULTI-COMPONENT BLEND 293

where Icorr and Io corr are corrosion current densities of

the bare and coated CS specimen respectively.
Scanning electron micrograph
Scanning electron micrographs of carbon steel
surfaces were recorded after treatment in cooling
water in absence and in presence of inhibitors (blend
A-50 was taken) for 5 days separately at CIF, IIT,
Guwahati.

Results and Discussion

In the weight loss experiment after treatment of the
C-1010 test coupons in cooling water in absence and
in presence of various blends, layered deposition on
the coupon surfaces were observed, which could be a
mixture of hematite (Fe2O3), magnetite (Fe3O4) and Fig. 1— SEM micrograph of carbon steel after testing for 5 days
goethite[FeO(OH)] as usually found to form on in absence of inhibitor
iron11,12. In absence of inhibitors some random pits
were also observed on the C-1010 surfaces. Thus in
normal experimental condition, besides general
corrosion, pitting and under deposit corrosions were
also observed due to feed water quality.
In absence of inhibitor the SEM (Fig. 1) of the test
carbon steel coupon shows a rough surface
morphology with some pits, indicating severe
corrosion, while the SEM (Fig. 2) of test coupon
immersed in presence of A-50 blend inhibitor showed
a comparatively uniform surface. This indicates the
formation of a passive film on the carbon steel
surfaces. The corresponding EDS patterns also
corroborate the same. The EDS analysis of the
specimen surface (Fig. 3) showed presence of carbon,
oxygen, phosphorus, sulphur, zinc and iron after
immersion in the solution containing the blended
Fig. 2— SEM micrograph of carbon steel after testing for 5 days
mixture, which indicates the formation of a adsorbed in presence of inhibitor
layer containing Fe2+-HEDP, Zn2+-HEDP,
Zn2+-DEDTC complexes on the metal surface.
Besides the above, the presence of aluminium is due
to pretreatment of makeup water with alum for
controlling TDS and TSS, while silica is already
present in the feed water, which appears in the EDS
together with aluminium.
From the weight loss study it is found that the
inhibitors of blend D-50 and blend A-50 showed
satisfactory corrosion inhibition results (91.42% and
93.67%) compared to other blends. In case of blend D
(blend D includes blend D-50, blend D-70, blend
D-100 and blend D-150), on increasing the HEDP Fig. 3—EDS analyses of carbon steel after testing for 5 days in
concentration from 50 to 150 ppm, keeping DEDTC presence of inhibitor
294 INDIAN J. CHEM. TECHNOL., JULY 2010

and Zn2+concentration constant, the inhibition Table 3—Corrosion parameters obtained from weight loss
efficiency gradually decreases from 91.42 to 68.46%. measurements for carbon steel at various concentrations of
inhibitors at 30oC
At low concentration of HEDP (up to 60 ppm) the
inhibition efficiency increases due to the adsorption Blend Weight Corrosion rate Inhibition pH
of HEDP onto the oxide layer, which prevents the loss (mmpy) efficiency
breakdown of oxide layer13. In presence of Zn2+ ion (g) (%)
the inhibition efficiency increases abruptly, because A-50 0.0011 0.062 93.67 6.0
Zn2+ ion facilitates the transport of HEDP towards the A-70 0.0033 0.185 81.12 6.2
metal surface by forming Zn2+ -HEDP complex (in A-100 0.0044 0.247 74.79 6.5
solution) which diffuses from the bulk of the solution A-150 0.0051 0.286 70.81 7.0
to the metal surface. On the other hand above this low D-50 0.0015 0.084 91.42 7.2
concentration level, HEDP become aggressive to D-70 0.0020 0.112 88.57 6.5
form soluble Fe2+-HEDP complex rather than a D-100 0.0031 0.174 82.24 5.5
passive oxide layer, as a result of which the
D-150 0.0055 0.309 68.46 4.5
dissolution of iron oxide layer take place. This may
A -II-70 0.0041 0.230 76.53 6.5
account for the decrease of inhibition efficiency even
T-50 0.0050 0.281 71.32 6.0
on increasing the HEDP concentration from 50 to
Blank 0.0174 0.980 - 7.2
150 ppm while keeping Zn2+ and DEDTC
concentration constant. The pH value decreases from Table 4 —Inhibition efficiency of various blends of inhibitors by
potentiodynamic polarization method
7.2 to 4.5 as the concentration of HEDP increases
from 50 to 150 ppm in various D-blends (Table 3). Blend -E corr I corr IE
This decrease in the pH factor could be also one of (mV) (µA/cm2 ) (%)
the reasons for decreasing inhibition efficiency. This
— 984.0 5.75 —
is also supported by potentiodynamic polarization
D-50 1038.1 0.55 90.43
studies (Icorr values shifted from 0.55 to 1.95 µA/cm2
D-70 822.5 0.93 83.79
as given in Table 4). Thus, blend D prevents the
D-100 978.1 1.04 81.91
metal dissolution more effectively in slightly alkaline
D-150 1032.8 1.95 66.00
condition. Similarly in case of inhibitors of blend A
(blend A includes blend A-50, blend A-70, blend A-50 940.9 0.40 93.04
A-100 and blend A-150) on increasing the DEDTC A-70 1011.3 1.48 74.26
concentration from 50 to 150 ppm, keeping Zn2+ and A-100 1059.3 2.38 58.60
HEDP concentration constant, the inhibition A-150 1016.6 2.67 53.56
efficiency decreases from 93.67 to 70.81%, which is A-II70 995.0 1.73 69.91
also supported by potentiodynamic polarization T-50 989.7 2.22 61.32
studies (Icorr values shifted from 0.40 to 2.67 µA/cm2
as given in Table 4). This is due to the precipitation
of Zn2+-DEDTC as white colloidal particles. In case
of blends A-II-70 and T-50, it is found that on
increasing the Zn concentration from 50 to 70 ppm
(keeping HEDP concentration constant and
minimizing DEDTC concentration) the inhibition
efficiency decreases from 76.53 to 71.32%, which is
also supported by potentiodynamic polarization study
(the Icorr value increases from 1.73 to 2.22 µA/cm2)
(Table 4). The Ecorr values (Table 4) do not change
significantly in presence of inhibitors as compared to
the solution without inhibitors (Figs 4, 5 and 6). This
indicates that both cathodic as well as anodic
corrosion reactions are influenced simultaneously to Fig. 4— Potentiodynamic polarisation curves for blends D
 GOGOI & BARHAI: CORROSION INHIBITION OF CARBON STEEL BY MULTI-COMPONENT BLEND
Fig. 5— Potentiodynamic polarisation curves for blends A
Fig. 6— Potentiodynamic polarisation curves for blends A-II-70
and T-50
the same extent by the inhibitors, showing a mixed
nature of the inhibitors in cooling water environment.
Conclusion
(1) The present study shows that NaDEDTC, HEDP
and ZnSO4.7H2O in respective ratio of
1.0:1.4:1.0 gives the most effective blend of
inhibitors for corrosion, scale as well as
microbiological problem.
(2) From the polarization study it is seen that this
blends dominates anodic as well as cathodic
corrosion current equally, indicating mixed
nature of inhibitors.
295
(3) SEM and EDS study confirm the formation of
an adsorbed passive film on the metal surface.
Acknowledgements
The authors are grateful to the authorities of
Numaligarh Refinery Limited, Golaghat, Assam for
allowing us to use the cooling water and providing
other facilities connected in this study.
References
1 The treatment of cooling water with chlorine
dioxide,technical data sheet,technical services 800-7333-
1165, OxyChem.
2 Rajendran S, Maria Joany R, Apparao B V & Palaniswamy
N, Indian J Chem Technol, 9 (2002) 197.
3 Gogoi Pradip K, Phukan Deba P & Sharma Neelotpal,
Indian J Chem Technol, 2 (1995) 46.
4 Gogoi Pradip K & Sonowal Juthika, Indian J Chem Technol,
12 (2005) 50.
5 Awadh S & Turgoose S, Br Corros J, 37 (2002) 147.
6 Rathore H S, Ishratullah K, Varshney C, Varshney G &
Mojumdar S C, J Thermal Anal Calorimetry, 94 (2008) 1,
75.
7 Andrew D Eaton, Lenore S Clescer & Arnold E Greenberg,
Standard method for the examination of water and
wastewater, 19th edn (American Public Health Association,
Water works association and Water environment federation,
New York), 1995.
8 Corrosion rate calculations from coupons, AN 116, Rohrback
Cossack Systems 11841 E, Smith Avenue, Santa Fe Springs,
CA 90670 USA.
9 Quraishi M A & Khan S, Indian J Chem Technol, 12 (2005)
576.
10 Taha K K, Sheshadri B S, Ahmed M F & Muralidharan V S,
Indian J Chem Technol, 13 (2006) 128.
11 Sang-Hea Shim, Donald A Johnson & Barbara E Moriaty,
Nalco Chemical Company, Presented at the National
Association of Corrosion Engineers, Corrosion’88 meeting,
St. Louis. Missouri, March 21-25, 1988.
12 Herro H M, Nalco Chemical Company, Presented at the
National Association of Corrosion Engineers, Corrosion ‘89
meeting, New Orleans, Louisiana, April 17-21, 1989.
13 Awad H S & Turgoose, Corros Eng, 60(12) (2004) 1168.
14 Vishwanatham S & Haldar Nilesh, Indian J Chem Technol,
14 (2007) 501.
15 Sanbhag A V, Prabhu R A, Kulkarni G M, Kalkhambkar R
G & Venkatesha T V, Indian J Chem Technol, 14 (2007)
584.
16 Timothy Keister, Cooling Water Management, ProChem
Tech International, Inc. Brockway, Pennsylvania. Issue 08-
03-01 and revised on 01/05.
17 Enrique A Castro, Kinetics and mechanisms of reactions of
Thiol, Thiono and Dithio Analogs with Nucleophiles, ACS
Publication, American Chemical Society, 5th Nov. 1999.
18 Choi Dong- Jin, You Seung-Jae & Kim Jung-Gu, Mater Sci
Eng, A335 (2002) 228.