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Nitrogen oxide removal using seawater electrolysis

in an undivided cell for ocean-going vessels
Cite this: RSC Adv., 2016, 6, 114623
Shaolong Yang, Zhitao Han, Xinxiang Pan,* Zhijun Yan and Jingqi Yu

As massive nitrogen oxide (NOx) emissions from marine slow speed diesel engines have caused serious
Published on 21 November 2016. Downloaded on 5/31/2019 7:40:24 AM.

Received 2nd October 2016
Accepted 19th November 2016
DOI: 10.1039/c6ra24537d
www.rsc.org/advances
health and environmental problems, NOx removal using electro-generated chlorine under seawater
electrolysis was studied in a lab-scale scrubbing reactor. Electro-generated chlorine was prepared by
seawater electrolysis in an undivided cell. Results showed that active chlorine concentration increased
linearly with the increase of current density and electrolysis time. Energy consumption decreased from
83 to 6.1 kW h per (kg [Cl2]) with the salinity varying from 3.2 to 37.8 ppt after 5 min of electrolysis.
Onsite generation of active chlorine using concentrated seawater from desalination plants operated on
a ship was suggested to be a cost-effective solution with less energy consumption. Then, effects of
dilution ratio (seawater/electrolyte), inlet NO and SO2 concentration, and initial pH value of scrubbing
solution on NOx removal efficiency were further investigated. NOx removal efficiency of electro-
generated chlorine at pH value of 7 decreased from 98.9% to 20.2% with the dilution ratio increasing
from 2.4 to 96. The NO absorption rate by HOCl was proved to be higher than that by OCl
. NO
absorption rate increased linearly as inlet NO concentration increased. When SO2 concentration
increased from 207 to 814 ppm, NOx removal efficiency decreased slightly, but SO2 removal efficiency
was almost kept at 100%. The possible reaction mechanism and pathways were discussed by evaluating
the pH-dependant NOx removal efficiency using electro-generated chlorine. The proposed method of
wet scrubbing using electro-generated chlorine was demonstrated to be a potential after treatment
strategy to control NOx emissions from large marine diesel engines.

been successfully applied to four-stroke medium speed engines.

1. Introduction
With over 90% of world trade carried by sea, international ship-
ping has caused an increasingly serious impact on air pollution
over the past few decades.1,2 Worldwide, from 2007 to 2012,
shipping is estimated to produce approximately 18.6 million tons
of NOx annually, which accounts for approximately 15% of global
NOx emissions from anthropogenic sources.2,3 NOx plays an
important role in the formation of acid rain, photochemical
smog, aerosol warming, and toxic haze, which inuence human
lives and activities at regional scales.4 Currently, the International
Maritime Organization (IMO) and some environmental protec-
tion agencies from developed countries implement more strin-
gent regulations5 to limit NOx emissions from shipping.
Various technologies have been proposed to meet these regu-
lations on ship NOx emissions,6,7 including exhaust gas recircula-
tion (EGR), selective catalytic reduction (SCR), non-thermal
plasmas (NTP), electrochemical catalysis, wet scrubbing. Among
these technologies, NH3 SCR is the best-known technology, which
is currently commercial available to achieve compliance with Tier
III NOx standards for marine engines.8 Until now, SCR systems have
Marine Engineering College, Dalian Maritime University, Dalian 116026, China.
E-mail: dmu.slyang@gmail.com; panxx@dlmu.edu.cn; Tel: +86-411-84725200
However, only a few slow speed crosshead engines have been
equipped with SCR. This is mainly because emissions of slow speed
diesel engines burning low-quality fuels contain a high concen-
tration of sulfur oxide (SOx) and a low exhaust temperature
(<300  C),9 which deteriorate the catalyst performance in SCR
systems. Therefore, wet scrubbing method, which uses chemical
reagents to absorb NOx gas via gas–liquid reactions, becomes
a potentially attractive technique. Moreover, wet scrubbing tech-
nique can be coupled with the existing desulfurization technique,
so that the investment cost for removing multiple pollutants can be
saved.
More than 90% of ship NOx emissions is in the form of nitric
oxide (NO). For wet scrubbing systems, chemical additives are
usually added into the scrubbing liquid to rst convert relatively
inert NO into more soluble NO2, which is then removed by
alkaline absorbents. A number of chemical oxidants10 have been
investigated to determine their effectiveness in NOx removal,
including KMnO4, H2O2, NaOCl, NaClO2, O3. However, the
storage space required for most of the chemical oxidants is
expected to be extremely large. This is mainly attributable to two
reasons: (1) two-stroke slow speed diesel engines emit a high
concentration of NOx (typically 10 g kW
1 h
1), and (2) the
replenishment interval of ocean-going vessels can be up to three

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months. As the engine room space for a ship is limited, the
storage of abundant chemical oxidants will probably reduce the
transport capacity and increase the potential risk of safety for
the crew. Therefore, the interest in NaOCl wet scrubbing tech-
nique has increased in recent years because of its onsite
production character by an electrochemical process.
Elena Ghibaudi et al.11 studied the reaction between NO and
NaOCl aqueous solution over a pH range of 6–12. They pointed
that NO absorption rate by HOCl was much faster than that by
OCl
. Luke Chen et al.12 investigated NO absorption using
NaOCl reagent and developed a mass transfer model for
a packed-bed scrubbing system. Ruitang Guo et al.13 analyzed
NO absorption kinetics with weak acidic NaOCl solution in
a stirred tank reactor. Results showed that the absorption
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reaction was rst-order with respect to both NO and NaOCl.
Monoj Kumar Mondal and Chelluboyana Vaishnava Raghu-
nath14,15 studied optimal conditions for simultaneous absorp-
tion of NO and SO2 into NaOCl freshwater solution. They found
that NO removal efficiency could be inuenced by several
parameters, such as absorbent concentration, initial NO and
SO2 concentration, initial pH value of NaOCl solution.
Although many experiments have been conducted with
NaOCl wet scrubbing technique, only a few studies have been
done on NO removal using NaOCl solution generated under
seawater electrolysis. Sukheon An and Osami Nishida16,17
proposed a two-stage wet scrubbing system to control exhaust
emissions from large marine diesel engines. They used
a divided electrochemical cell to produce both acidic seawater
and alkaline seawater, which are applied to oxidize NO to NO2
and absorb NO2 and CO2, respectively. Nevertheless, a high
concentration of total dissolved solids in seawater would
accelerate the fouling of diaphragm in the divided cell. Thus,
a short lifetime of ionic membrane could add extra operational
cost of this method. In addition, Tae-Woo Kim18 investigated
NO oxidation characteristic of seawater treated by undivided
electrolysis in a bubbling reactor. Although some operational
conditions (e.g., active chlorine concentration and temperature)
were discussed, energy consumption and reaction mechanism
of the NO absorption process remained unclear.
Therefore, the main objective of this study is to (1) determine
effective operational conditions for onsite generation of active
chlorine onboard with less energy consumption; (2) investigate
NOx removal performance of electro-generated chlorine. Effects
of current density and seawater salinity on the production of
active chlorine and energy consumption were studied in an
undivided cell. Aer that, some parameters, such as dilution
ratio, inlet NO and SO2 concentration, and initial pH value of
scrubbing liquid were investigated on NOx removal efficiency.
The possible reaction mechanism and pathways between NO
and active chlorine species were discussed.
2. Materials and methods
2.1 Experiment apparatus and materials
A schematic diagram of the experimental apparatus is shown in
Fig. 1. The experimental apparatus was composed of a simulated
ue gas system, a spray scrubber, and a ue gas analysis system.
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Fig. 1 Schematic diagram of experimental apparatus.
The ue gas of a diesel engine was simulated by mixing
different gas species: NO (9.8% NO with 90.2% N2 as balance gas),
SO2 (9.9% SO2 with 90.1% N2 as balance gas) and N2 (99.9%). The
ow rate of each material gas was regulated by a mass ow
controller (MFC, D07-19B, Sevenstar Electronics, China). The NO
and SO2 concentration of the simulated ue gas were adjusted by
the proportional ratio. All pipes, valves, regulators, and ttings
were made up of stainless steel 316 grade or Teon.
The spray scrubber (height 30 cm; internal diameter 6 cm)
was a custom-made lucite spray column. The spray nozzle (B1/
4TT-SS+TG-SS0.4, Spraying System Co., America) orice was
0.04 cm. The feed pump was a peristaltic pump (YZ1115, Longer
Precision Pump, China). The scrubbing liquid in the feeding
tank (1.3 L) was mixed by a magnetic stirrer (750 rpm). In order
to reduce the interference of photochemical decomposition by
sunlight, the outside of the feeding tank was covered with
aluminum foil.
The ue gas analysis system consisted of an electronic
condenser and a gas analyzer (MGA 5, MRU, Germany). The
MGA 5 gas analyzer was an infrared multigas analyzer with
a detection range up to 2000 ppm at a resolution of 1 ppm,
which was used for online measurement of inlet and outlet
concentrations of NO, NO2, NOx, and SO2.
The articial seawater (salinity of 23.3 ppt) was prepared
according to the ASTM D1141 standard as described previ-
ously.19 All chemicals used in our experiments were analytical
reagent grade. The deionized water (15 MU cm) was prepared in
a two-stage ELGA PURELAB Option R15 purication system.
The undivided cell for seawater electrolysis was a cylindrical
lucite tank (2.2 L) with two plate electrodes (10  10  0.2 cm,
Baoji Ruicheng Titanium Industry Co., Ltd., China). The anode
material and cathode material were IrO2–RuO2/Ti and Ti,
respectively. They were placed vertically in parallel with an inter-
electrode gap of 2 cm. The electrolysis was performed using
a DC power supply (GuDeng Electric GD-80V-25A, China) with
a constant current control mode.
2.2 Experimental procedure
First, onsite generation performance of active chlorine by
seawater electrolysis was investigated in the undivided cell.
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Before each operation, the cell was sonicated to completely
desorb any remaining materials. During each run, the electro-
lyte was mixed by a magnetic stirrer, and a sample (5 mL) was
withdrawn for measuring TOS concentration at an interval of
5 min. Then these samples were diluted when necessary and
stored in a 4  C water bath. Active chlorine concentrations of
samples were determined by N,N-diethyl-p-phenylenediamine
(DPD) colorimetric method (ASTM 4500 G), using a spectro-
photometer (Shimadzu UV1800, Japan) at 515 nm.
Then, further experiments were performed to study NOx
removal characteristics by electro-generated chlorine in the
custom-made spray scrubber. The active chlorine solution
(2400 mg L
1 [Cl2]) was prepared by articial seawater elec-
trolysis under conditions of seawater salinity 23.3 ppt and
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current density 150 mA cm
2. During each set of scrubbing
experiments, the active chlorine solution was stored under seal
in 20  C water bath shielded from light, so that the decay of
active chlorine was less than 2% in 10 h. Aer that, the scrub-
bing liquid was prepared by freshly mixing the electro-
generated chlorine with articial seawater. The initial pH
value of scrubbing liquid was adjusted to the desired value by
adding HCl solution (1 mol L
1) or NaOH solution (1 mol L
1).
The pH value and oxidation–reduction potential (ORP) of the
scrubbing liquid were measured by a pH/ORP meter (Mettler-
Toledo S210, Switzerland).
As shown in Fig. 1, during each run, the simulated ue gas
went through the main line (V1 open, V2 closed). When the inlet
gas concentrations were stable, the scrubbing liquid was
introduced into the main scrubber. The gas absorption reac-
tions occurred at room temperature (25  C). The outlet
concentrations of NO, NO2, NOx and SO2 were measured by the
gas analyzer at an interval of 10 s during each run. The scrub-
bing liquid was supplied without recirculation, and the effluent
liquid was collected in the bottom tank. Aer scrubbing, the
simulated ue gas was discharged into atmosphere. Under all
experiments, liquid ow rate and gas ow rate were set to 0.25 L
min
1 and 1.25 L min
1, respectively.
2.3 Data processing
When the simulated ue gas reacted with the electro-generated
chlorine in the counterow scrubber, NOx and SO2 were
removed. The removal efficiency (hi, %) was dened as
Ci;inlet
Ci;outlet
hi ¼  100% (1)
Ci;inlet
where i stands for NO, NOx or SO2; Ci,inlet is the inlet gas i
concentration (ppm); Ci,outlet is the outlet gas i concentration
(ppm). The NOx is the sum of the NO and NO2. The outlet
concentrations of NO, NO2 and SO2 were obtained by taking
averages aer 2 min.
For the kinetic calculation, NO absorption rate (NNO, mol
(m
2 s
1)) was calculated by
Qg  ðCNO;inlet
CNO;outlet Þ
NNO ¼  10
7 (2)
6  Ai  MNO
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where Qg is the gas ow rate (L min
1); Ai is the gas–liquid
interfacial mass transfer area (m2); MNO is the molecular weight
of NO (MNO ¼ 30 g mol
1).
3. Results and discussion
3.1 Production of active chlorine
Although seawater electrolysis is well known as an onsite active
chlorine generation technology, its high energy consumption
limits the application in marine equipment industry. To
determine the feasibility of onsite generation of active chlorine
on the ship with less energy consumption, we investigated
effects of current density and seawater salinity on the produc-
tion of active chlorine and energy consumption in an undivided
cell.
3.1.1 Current density. Fig. 2 shows the effect of current
density on the production of active chlorine as a function of
electrolysis time (main graph) and the slope of active chlorine
regression line as a function of current density (inset graph).
Experiments were carried out in an undivided cell under
condition of seawater salinity of 23.3 ppt. At all current densi-
ties, the active chlorine concentration increased linearly with
increase of electrolysis time. The linear relationship between
the active chlorine formation rate (i.e. the slope of active chlo-
rine regression line) and the current density is presented in the
inset graph in Fig. 2, which was similar to the results reported
by Byung Soo Oh.20 According to the Faraday's law, the active
chlorine formation rate (mg (L
1 min
1) [Cl2]) can be expressed
as
dACC MCl2  Ae  CE
¼  i  60 (3)
dt nF V
where ACC is the active chlorine concentration (mg L
1 [Cl2]); t is
the electrolysis time (s); MCl2 is the molecular weight of chlorine
(M ¼ 71 g mol
1); Ae is the area of the electrode (Ae ¼ 100 cm2);
Fig. 2 Active chlorine concentration as a function of electrolysis time
at different current densities (main graph), and slope of active chlorine
regression line as a function of current density (inset graph). Experi-
mental condition: seawater salinity 23.3 ppt.
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n is the number of electrons transferred in the reaction at the
anode (n ¼ 2); F is the Faraday constant (F ¼ 96 500 C mol
1
electrons); V is the volume of the electrolyte solution (V ¼ 2.2 L);
CE is the current efficiency of the anode (%); i is the current
density (mA cm
2).
As the CE of electrolysis of highly concentrated electrolytes
was almost constant under different current densities,21 the eqn
(3) proved the linear relationship, which is shown in the inset
graph in Fig. 2. This linear model implies that quantitative
prediction of active chlorine is possible during seawater elec-
trolysis using constant current mode. Moreover, this simple
linear relationship also contributed to the easy control of
seawater electrolysis cells onboard.
3.1.2 Seawater salinity. Considering that the salinity of
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seawater drawn through the sea chest of a ship varies from place
to place, the effect of seawater salinity on active chlorine
concentration and energy consumption are shown in Fig. 3 and 4,
respectively. As seen in Fig. 3, active chlorine increased logarith-
mically as electrolysis time increased at all salinities, which was
similar to those reported by Husam D. Al-Hamaiedeh.22 However,
the active chlorine curves at salinities of no more than 7.2 ppt and
no less than 13.2 ppt diverged aer 20 min, which might be due to
the temperature variation of electrolyte. When the seawater
salinity was no more than 7.2 ppt, the resistive heating caused by
the high cell resistance resulted in a sharp rise in the temperature
of electrolyte. This rise in temperature promoted the conversion
of active chlorine to chlorate and accelerated the dissolved chlo-
rine to escape into the atmosphere, which resulted in the drop of
the active chlorine formation rate aer 20 min (Fig. 3). In
contrast, the resistive heating caused by the cell resistance at
salinity of no less than 13.2 ppt only resulted in a limited rise of
the temperature of electrolyte. Consequently, the active chlorine
formation rate at salinity of no less than 13.2 ppt decreased
slightly with the electrolysis time varying from 20 to 30 min.
As an energy-intensive process, the energy consumption of
production of active chlorine was calculated as a function of
Fig. 3 Active chlorine concentration as a function of electrolysis time
at different salinities. Experimental condition: current density 150 mA
cm
2.
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Fig. 4 Energy consumption as a function of electrolysis time at different
salinities. Experimental condition: current density 150 mA cm
2.
seawater salinity at different electrolysis time under condition
of current density of 150 mA cm
2 (Fig. 4). The energy
consumption decreased rapidly with an increase in the salinity,
which was consistent with results reported by Hilary Nath
et al.23 The power type energy consumption prole was almost
irrespective of electrolysis time.
The ohmic resistance of the electrolyte (R, U) is dened as
l 1 l 1
R¼  ¼  (4)
Ae k Ae  B S
where k is the conductivity of the electrolyte (1/(U cm)); B is the
conversion coefficient from salinity to conductivity (B z 1560
(ref. 24)); l is the distance of the inter-electrode gap (cm); S is the
salinity of the electrolyte (ppt).
According to the literature,25 the applied cell voltage (U, V)
can be given bellow
U ¼ Ure + Ue + UR + Ut (5)
where Ure is the thermodynamic (equilibrium) potential difference
for the given electrode reactions (V); Ue is the sum of the anodic and
cathodic overpotentials (V); UR is the ohmic drop of the electrolyte
(V); Ut is the dri of DU with electrolysis time due to degradation of
the electrode performance, for fresh electrodes DU ¼ 0 V.
For the specic undivided electrolysis cell in our experi-
ments, we can simplify the eqn (5) into the following eqn (6), in
which the applied cell voltage keeps a power function with the
salinity of electrolyte.
i  Ae  R
U ¼ U 0 þ UR ¼ U 0 þ ¼ U 0 þ k0  S
1 (6)
1000
where U0 and k0 are constant,
U0 ¼ Ure + Ue, k0 ¼ (i  l)/(1000  B).
For seawater electrolysis process, heat dissipation at elec-
trodes caused extra thermal energy loss, which resulted in
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a high energy consumption. According to the model proposed
by Øystein Ulleberg,26 thermal energy generated due to the
energy inefficiency was linear to the difference between the
applied cell voltage and the theoretical thermoneutral voltage.
Therefore, from energy balance perspective, the energy
consumption was expected to have a power function with the
salinity, which was in agreement with nonlinear trends shown
in Fig. 4.
Considering the actual situation of seawater on a ship,
concentrated seawater can be obtained from desalination
plants (e.g. vacuum boiling evaporator) operated on the ship,
which is usually 1.5 to 2 times higher than the salinity of
ambient seawater.27 Therefore, onsite generation of active
chlorine using concentrated seawater electrolysis was demon-
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strated to be a cost-effective solution with less energy
consumption for ocean-going vessels.
3.2 NOx removal by electro-generated chlorine
3.2.1 Dilution ratio of seawater to electrolyte. A set of
experiments was performed to assess NOx removal performance
by electro-generated chlorine in a lab-scale scrubber. The effect
of the dilution ratio of seawater to electrolyte on removal effi-
ciencies is shown in Fig. 5.
When the initial pH value of scrubbing solution was
uncontrolled (above 8), the NOx removal efficiency dropped
from 62.2% to 6.57% with the dilution ratio varying from 1 to
32, which was due to the reduction of the electro-generated
chlorine.15 By comparison, when the initial pH value of scrub-
bing solution was adjusted to 7, the NOx removal efficiency by
the electro-generated chlorine solution was more efficient than
that without pH control at all range of the dilution ratio. Thus,
the NO absorption rate by the active chlorine at pH value of
7 was higher than that at pH value of above 8.2. This result
might suggest that HOCl was the more active than OCl
in
Fig. 5 Removal efficiencies as a function of dilution ratio (seawater/
electrolyte). Experimental conditions: pH 7 (solid points), uncontrolled
pH (open points), inlet NO concentration 1000 ppm.
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terms of NO absorption, even though its equilibrium concen-
tration was much lower than the concentration of OCl
in
alkaline solution.
When the pH value of the electro-generated chlorine solu-
tion is above 7, the hypochlorite exists in equilibrium with the
hypochlorous acid (i.e. dissociation of hypochlorous acid),
depending on the pH value.28
HOCl 4 H+ + OCl
, pKa ¼ 7.54 (25  C) (7)
Cl
+ 2OH
/ ClO
+ H2O + 2e
, E0 ¼
0.89 V (8)
Cl
+ H2O / HOCl + H+ + 2e
, E0 ¼
1.482 V (9)
According to the literature,29 the NO removal efficiency was
described as a function of the standard redox potentials of half
reactions in which the reagents take part. As the standard
oxidation potential of HOCl (E0 ¼
1.482 V) was lower than that
of OCl
(E0 ¼
0.89 V), NO removal efficiency was expected to
decrease with the pH value of above 7. Moreover, these results
might also be explained by the ORP of electro-generated chlo-
rine solution as a function of pH (data not shown). The ORP was
observed to decrease with the increasing pH value, which was
consistent with the results reported by Cheryl N. James et al.30
According to the dissociation of hypochlorous acid (reaction
(7)), the concentration of HOCl at pH value of 7 is higher than
that under pH value of above 8. Thus, the ORP of active chlorine
solution decreased with the increasing pH value in weak alka-
line solution, which eventually resulted in a reduction of NOx
removal efficiency.
3.2.2 Inlet NO concentration. Fig. 6 displays the effect of
inlet NO concentration on NO and NOx removal efficiencies.
The NO removal efficiency increased from 14.2% to 75.9% with
inlet NO concentration varying from 250 to 1250 ppm. Likewise,
the NOx removal efficiency increased from 10.2% to 59% with
inlet NO concentration varying from 250 to 1250 ppm. In
addition, as the gas and liquid ow rate were unchanged under
Fig. 6 Removal efficiencies as a function of inlet NO concentration.
Experimental conditions: dilution ratio (seawater/electrolyte) 7, pH 7.
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all experiments, the gas–liquid interfacial mass transfer area of

the scrubber was kept constant. According to the eqn (2), NO
absorption rate was dependent on the difference between
CNO,inlet and CNO,outlet. As shown in Fig. 7, this difference
increased linearly as inlet NO concentration increased. There-
fore, the NO absorption rate increased linearly as inlet NO
concentration increased, which was in accordance with the NO
absorption model proposed by Yangxian Liu et al.31 According to
the two-lm theory, an increase in inlet NO concentration
would increase mass transfer driving force of NO gas in gas–
liquid two phase and reaction rate of electro-generated chlorine
with NO, which eventually improved NO absorption rate.
3.2.3 Inlet SO2 concentration. In general, SO2 is one kind of
harmful gaseous species from exhaust emissions of marine
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diesel engines. This acid gas also has a potential to affect NO

removal. Therefore, experiments were performed to investigate
SO2 concentration on NO, NOx and SO2 removal efficiencies,
and results are shown in Fig. 8. The SO2 removal efficiency was Fig. 8 Removal efficiencies as a function of inlet SO2 concentration.
almost kept at 100% under all SO2 concentrations, which might Experimental conditions: dilution ratio (seawater/electrolyte) 7, pH 7,
inlet NO concentration 1000 ppm.
suggest that SO2 removal was controlled by liquid mass transfer.
The NO and NOx removal efficiencies decreased slightly as SO2
concentration increased from 207 to 814 ppm, which might be
resulted from a competition reaction between SO2 and NO.
These results implied that SOx and NOx could be simulta-
neously removed by sufficient amount of electro-generated
chlorine. Therefore, the proposed method could have the
potential to meet requirements of emission control regulations
for ocean-going vessels using low-quality marine fuel oil.

3.3 Reaction mechanism

To determine the reaction mechanism between NOx and active
chlorine solution, experiments were carried out to investigate
the effect of initial pH value of scrubbing solution on the NO
and NOx removal efficiencies, under conditions of dilution ratio
7 and inlet NO concentration 1000 ppm. The results are
summarized in Fig. 9.

Fig. 9 Effect of initial pH value of scrubbing solution on NO and NOx

removal efficiencies. Experimental conditions: dilution ratio (seawater/
electrolyte) 7, inlet NO concentration 1000 ppm.

When the initial pH value of scrubbing solution increased

Fig. 7 Difference between CNO,inlet and CNO,outlet as a function of inlet
NO concentration. Experimental conditions: dilution ratio (seawater/
electrolyte) 7, pH 7.
from 3 to 5, the NO removal efficiency maintained 100%, while
the NOx removal efficiency decreased gradually. However, when
the initial pH value of scrubbing solution was in the range of 6–
8, the NO and NOx removal efficiencies at pH value of 7 reached
the peak value of 80.7% and 60.9%, respectively. Then, the NO
and NOx removal efficiencies decreased sharply with the pH
value further increasing to 9. The effect of initial pH value on
NO and NOx removal efficiencies by the electro-generated
chlorine solution can be explained by the impacts of pH on
the distribution of active chlorine species. With pH changing,
there may be four kinds of oxidizing agents in the scrubber,
which can be represented by:

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The reactions of dissolution and hydrolysis of chlorine in

acid seawater solution are shown as follow:

Cl2(aq) + H2O 4 HOCl + H+ + Cl
(10)

Cl2(aq) + Cl
4 Cl3
(11)

pCl2(aq) ¼ KH[Cl2(aq)] (12)

[ACC]T ¼ [Cl2(aq)] + [Cl3
] + [HOCl] + [OCl
] (13)

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where KH is the Henry's constant (16.1 atm L mol
1 (25  C)); [ACC]T Fig. 10 Distribution of active chlorine species as a function of pH in
is the total concentration of chlorine in solution (mg L
1 [Cl2]). seawater. Experimental condition: dilution ratio (seawater/electrolyte) 7.
Considering the ionic strength effect of scrubbing solution
(ionic strength I z 0.49 M), the corrected equilibrium constants
for dissociation of hypochlorous acid and hydrolysis of chlorine fHOClg
% HOCl ¼
reactions are represented by:32 fACCgT

½Hþ ½OCl
 Kd c ½Hþ 

c
c
K1 ¼ ¼ 3:95  108 M ð25  CÞ ¼ c ½Hþ 2c ½Cl
 þ c K c ½Hþ  þ c K c K þ c ½Hþ 2c K c ½Cl
2
½HOCl 4 1 4 5

(16)

½HOCl½Hþ ½Cl
 fOCl
g

c
K4 ¼ ¼ 5:35  104 M2 ð25  CÞ % OCl
¼
½Cl2 ðaqÞ fACCgT
c
K1 c K4
¼ c ½Hþ 2c ½Cl
 þ c K c ½Hþ 
4 þ c K 1 c K 4 þ c ½Hþ 2c K 5 c ½Cl
2
 
Cl3
(17)
c
K5 ¼ ¼ 0:191 M
1 ð25  CÞ
½Cl2 ðaqÞ½Cl

pCl2 ðaqÞ ¼ KH fACCgT  % Cl2 ðaqÞ
½Hþ 2c ½Cl
KH ½ACCT  106
c
Then the relative molar percentage of Cl2(aq), HOCl and ¼ c ½Hþ c ½Cl

(18)
OCl
, as well as the partial pressure of gaseous chlorine Cl2(g) þ c K 4 c ½Hþ  þ c K 1 c K 4 þ K5 c ½Hþ 2c ½Cl
2
can be expressed in eqn (14)–(18).
As the seawater has a high concentration of Cl
ion, we When the pH value was below 5, NOx gas was mainly
proposed the hypothesis that the Cl
ion concentration removed by HOCl, Cl2(aq) and Cl2(g) in both liquid and
unchanged during the experiments. Therefore, the pH- gas phase. HOCl and Cl2(aq) were strong oxidants, which
dependant active chlorine species and gaseous chlorine were
calculated and plotted in Fig. 10.
According to the literature,12,13,18,33,34 reaction pathways of NO
absorption by electro-generated chlorine solution were
proposed based on the pH-dependant active chlorine species
and gaseous chlorine (Fig. 11).
fCl2 ðaqÞg
% Cl2 ðaqÞ ¼
fACCgT
½Hþ 2c ½Cl

c
¼ c ½Hþ 2c ½Cl
 þ c K c ½Hþ  þ c K c K þ c ½Hþ 2c K c ½Cl
2
(14)
4 1 4 5


Cl3

% Cl3
¼
fACCgT
c
K 5 c ½Hþ 2c ½Cl
2
¼ c ½Hþ 2c ½Cl
 þ c K 4 c ½Hþ  þ c K 1 c K 4 þ c ½Hþ 2c K 5 c ½Cl
2
(15) Fig. 11 Proposed reaction pathways of NO and active chlorine reac-
tion system.

This journal is © The Royal Society of Chemistry 2016 RSC Adv., 2016, 6, 114623–114631 | 114629

RSC Advances
contributed to a high removal efficiency of NO gas (reactions
(19)–(21), (24) and (27)). Moreover, some of the aqueous
molecular chlorine escaped into the gas phase in the scrubber,
and then reacted directly with NO gas (reactions (28) and (29)).
However, when the pH value increased from 3 to 5, the
concentrations of Cl2(aq) and Cl2(g) decreased, while the
concentration of HOCl increased. In this case, the concentra-
tion of NO2(aq) produced by HOCl (reaction (21)) increased,
which caused the reduction of NOx removal efficiency.
However, when the pH value was greater than or equal to 6,
NOx gas was mainly absorbed by HOCl and OCl
ion. The
concentration of HOCl decreased, whereas the concentration of
OCl
increased when the pH value changed from 6 to 9. As the
standard redox potential of HOCl was lower than that of OCl
,
Published on 21 November 2016. Downloaded on 5/31/2019 7:40:24 AM.
NO removal efficiency was expected to decrease with the
increase of pH value of scrubbing solution. However, it was
interesting to note that both NO and NOx removal efficiencies
reached a peak value at pH value of 7 of scrubbing solution. This
might be attributed to two reasons. On the one hand, the NO2
absorption efficiency by HOCl/OCl
was not as efficient as the
NO oxidation efficiency by HOCl/OCl
.29 Thus, although HOCl
was strong oxidants which converted NO(aq) into NO2(aq), the
high concentration of NO2(aq) might inhibit NO absorption by
electro-generated chlorine solution and escape into the gas
phase. Nevertheless, it was worth noting that an increase of
OH
ion concentration was believed to promote the production
of NO2
and NO3
by NO2(aq) absorption reactions (22)–(23)
and (25)–(26). Then, this NO2
further converted to NO3
by an
excessive amount of HOCl in solution through reactions (24),
which in turn accelerated NO2(aq) absorption. Therefore, when
the pH value changed from 6 to 7, NO and NOx removal effi-
ciencies increased from 76% and 55.3% to 80.8% and 60.9%,
respectively. On the other hand, according to results of hypo-
chlorous acid decomposition reported by Luke C. Adam et al.,35
the HOCl had a maximum decomposition rate at about 7. The
intermediates, such as ClO2
and Cl2O$H2O, might react with
NO(aq), and then enhance NO and NOx removal efficiencies at
pH value of 7.
When the pH value reached 9, the molar percentage of OCl

in electro-generated chlorine solution was over 90%. NOx gas
was mainly absorbed by OCl
through reactions (30) and (31).
As the NO absorption rate by OCl
was lower than that by HOCl,
the NO and NOx removal efficiencies decreased as pH value
increased. The NO2(aq) generated by oxidation of NO gas was
completely absorbed in this alkaline solution.
NO(g) 4 NO(aq) (19)
NO(aq) + Cl2(aq) + H2O 4 NO2(aq) + 2H+ + 2Cl
(20)
NO(aq) + HOCl 4 NO2(aq) + H+ + Cl
(21)
3NO2(aq) + H2O 4 2H+ + 2NO3
+ NO(aq) (22)
2NO2(aq) + H2O 4 HNO2 + H+ + NO3
(23)
NO2
+ HOCl / NO3
+ H+ + Cl
(24)
114630 | RSC Adv., 2016, 6, 114623–114631
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Paper
HNO2 4 H+ + NO2
(25)
3HNO2 4 H+ + NO3
+ 2NO(aq) + H2O (26)
NO2(aq) 4 NO2(g) (27)
2NO(g) + Cl2(g) / 2NOCl(g) (28)
NOCl(g) + H2O / H+ + Cl
+ HNO2 (29)
NO(aq) + OCl
4 NO2(aq) + Cl
(30)
NO2
+ OCl
/ NO3
+ Cl
(31)
4. Conclusions
In this study, a method of NOx removal by seawater electrolysis
with less energy consumption was proposed. The following
conclusions can be drawn:
(1) The active chlorine concentration increased linearly with
the increase of current density and electrolysis time. The active
chlorine formation rate kept a linear model with current
density, which contributed to quantitative prediction and
automatic control of active chlorine production onboard. The
energy consumption decreased from 83 to 6.1 kW h per (kg
[Cl2]) with the salinity varying from 3.2 to 37.8 ppt aer 5 min of
electrolysis. Electrolysis using concentrated seawater from
desalination plants operated on a ship was suggested to be
a cost-effective solution.
(2) The effect of pH value had a substantial impact on NOx
removal performance by electro-generated chlorine, followed by
the effect of dilution ratio (seawater/electrolyte) and inlet NO
concentration. Results showed that the NOx removal efficiency
at pH value of 7 decreased from 98.9% to 20.2% with the dilu-
tion ratio varying from 2.4 to 96. In contrast, the NOx removal
efficiency without pH control reduced from 62.2% to 6.57%
with the dilution ratio varying from 1 to 32. These pH-
dependent results suggested that HOCl was the more active
than OCl
in terms of NO absorption. Compared with the inlet
SO2 concentration, the NO absorption process was more
sensitive to inlet NO concentration. The reaction mechanism
and pathways of NOx removal by electro-generated chlorine
were speculated by discussing the pH-dependant distribution of
active chlorine species.
Further experiments are suggested to calculate the kinetics
and model the absorption process, so that more engineering
valuable information can be obtained to design and optimize
the exhaust gas cleaning system for NOx emission control
onboard.
Acknowledgements
This paper was supported by Science and Technology Plan
Project of China's Ministry of Transport (2015328225150) and
the Fundamental Research Funds for the Central Universities
(3132016018), and the Scientic Research Fund of Liaoning
Provincial Education Department of China (No. L2014198).
This journal is © The Royal Society of Chemistry 2016

Paper
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