GLS-14 PAPER CODE

INDIAN INSTITUTE OF TECHNOLOGY ROORKEE

2019 222

Electrochemical Denitrification of Highly Contaminated

Actual Nitrate Wastewater by Ti/RuO2 Electrode
Rohit Chauhan1, Vimal Chandra Srivastava2*
1&2 Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee
247667, Uttarakhand, India
1rohitchn18@gmail.com, 2vimalcsr@yahoo.co.in, vimalfch@iitr.ac.in

14th International Conference on Gas-Liquid and Gas-Liquid-Solid Reactor Engineering

(GLS-14)
May 30-June 3 2019, Guilin, China

Organized by: Institute of Process Engineering of Chinese Academy of Sciences (CAS)

Co-organized by: Chinese Society of Particuology
CONTENT
• Introduction
• Wastewater Treatment Technologies
• Electrochemical Treatment
• Literature review
• Parameters
• Research gap
• Research objective
• References

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3
 GLS-14
INTRODUCTION 2019

 After carbon, hydrogen, and oxygen, nitrogen is the next most abundant element in
the environment.

 Inorganic and organic compounds of nitrogen feature prominently in many biological

and environmental, as well as industrial, processes.

 Nitrogen can be found mainly in three forms in water bodies i.e. ammonium ion
(NH4+), nitrite (NO2-) and nitrate (NO3-).

 Source of nitrate as pollutant: nuclear & explosive

waste, production of some valuable and relatively
expensive compounds and Comprehensive utilization of
nitrogen based fertilizers etc.

 In nature, the inorganic compounds of nitrogen are

controlled by a reaction cycle called the nitrogen cycle.
(Fig.1. Nitrogen cycle)

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 GLS-14
INTRODUCTION 2019

 The mechanisms for electrochemical conversion of nitrate to nitrogen gas are highly
complex, involving numerous reactions, products and stable intermediates (e.g.,
ammonia, nitrite, hydrazine, hydroxylamine, nitric oxide, nitrous oxide) spanning the
many nitrogen oxidation states (from -III up to +V).

 The Frost-Ebsworth representation is shown in Fig. (2) in which all the nitrogen species
are shown according to their oxidation numbers.

 The maximum acceptable concentration of nitrate

ion (NO3-) in drinking water supply 45 mg/L set by
the Bureau of Indian Standards (isBIS).

Fig. (2) Frost-Ebsworth representation of nitrogen

species in alkaline (pH=14) and acidic medium (pH=0).

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 GLS-14
TREATMENT PROCESS 2019

 Treatment technologies available for nitrate contaminant wastewaters are:

• Physical
• Chemical
• Biological
• Electrochemical Processes
 Electrochemical technology offers ideal tools for addressing environmental
problems. The main reagent used here is electron, which is a clean reagent and
therefore there is no need for adding extra reagent.

 Nitrate belongs to the second group anions (NO3-, BrO3-, BrO4-, IO4- etc.) and these
are reduced by transfer of electron and proton simultaneously by proton donor
through elementary step of EC reduction shown by following eq.:

A z A  HBz D  e -  HA z A  Bz D -1
where AzA=target anion for reduction with charge zA, HBzD= proton donor with charge zD,
HAzA=resulting products by attachment of electron and proton to the initial anion, B=
conjugate base to the proton donor.

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 GLS-14
ELECTROCHEMICAL REDUCTION 2019

 Electrochemical reduction generates different types of intermediates as well as by

products which are necessary to oxidize into N2 gas.

 For oxidizing in-situ generated intermediates and by products like NO2─ and NH4+
into N2, dimensionally stable anodes (DSA) were used previously.

 Several types of dimensionally stable electrode have been researched in the

literature for the treatment of bitrate contaminated wastewaters like-
 Boron doped diamond
 Titanium coated with metal oxides (e.g. PbO2, TiO2 and SnO2)
 Iron coated with RuO2
 TiO2 – IrO2 coated with RuO2

 There are many transition metals which can be use for electrode i.e. Ruthenium,
Tantalum, Titanium, Iridium, Tin, Antimony etc.

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 GLS-14
ELECTROCHEMICAL REDUCTION
2019

 Metal Oxides like RuO2, PbO2, TiO2 ,SnO2 etc. used for coating of transition
metals for dimensionally stable anode (DSA).

 Compared to other metal oxides, RuO2 is highly stable and has high
mechanical and chemical resistance even under strong acid conditions.

 It can produce powerful oxidants such as chlorine, ozone, and free radicals,
which are responsible for the oxidization of organic pollutants.

 These DSA produces negligible amount of sludge or scum in the EC reactor.

 Therefore, there is need of that Electrochemical denitrification process which

can perform both type of process i.e. reduction of the nitrate on cathode and
simultaneously oxidation of the nitrite and ammonia at anode.

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LITERATURE REVIEW GLS-14
(Synthetic wastewater) 2019
Wastewater Source Electrode Operating Conditions Results Reference
Synthetic Cu, Pt/Cu, Ti, Pt/Ti I=0.7-2.5 A; W×L=7.5×170 mm; ≈ 75% Nitrate Kim et al.,
wastewater d=7.5 mm; t=20 min removal 2017
Synthetic Anode=S.S.; I=0.2-1 A; A=11 cm×6 cm; 2 g ≈ 70% Nitrate Kalaruban
wastewater Cathode=Cu adsorbent; d=0.5-3 cm;; pH=3-11; removal et al., 2017
t=200 min
Synthetic Bipolar Si/BDD cell j=35.7 mAcm-2; t=2 h; RSM ≈ 91% Nitrate Ghazouani
wastewater Methodology; A=70 cm2; pH=5.5 removal et al., 2016
Synthetic wastewater Anode= Ti/TiO2 j=15 mA cm−2; t= 4h; A= 72 cm2; d=8 ≈ 91% Nitrate Li et al.,
nanotube array; mm; Na2SO4= 0.5 g/L removal in dual 2016
Cathode= Fe chamber cell
Synthetic Conductive −2 2
j= 150–1400 A m ; A=78 cm ; d=9 ≈ 90% Nitrate Lacasa et
wastewater diamond, stainless mm; Q= 1.5 dm3min-1 removal al., 2012(a)
steel, silicon carbide,
graphite or lead
Synthetic wastewater IrO2 &RuO2 and BDD j= 30 mAcm−2; A=78 cm2; d=9 mm; BDD≈90 % Removal; Lacasa et
NaCl= 0.51-51.3 mM; pH=2; Q= 1.5 IrO2 &RuO2≈75 % al., 2012(b)
3
dm min -1 Removal
Synthetic wastewater Anode=Ti/IrO2–Pt; j=20 mAcm-2; A=75 cm2; d=8 mm; ≈ 87% Nitrate Li et al.,
Cathode= Fe , Cu, Ti t=3 h; Na2SO4= 0.5 g/L removal 2009(a)
Synthetic wastewater Ti/IrO2–Pt j=10-60 mAcm-2; A=75 cm2; d=8 mm; ≈ 90% Nitrate Li et al.,
t=5 h; NaCl= 0.5 g/L; pH=6.5 removal 2009(b)

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LITERATURE REVIEW GLS-14
(Actual wastewater) 2019

Wastewater Electrode Operating Conditions Results Reference

Source
Actual textile Co3O4/Ti j=10 mAcm-2; A=16 cm2; d=1.5 cm; 80% Nitrate Su et al.,
wastewater pH=7; NO3˗-N=50-100 mg/L; t=3 h removal 2017
Actual BDD electrode j=35.7 mAcm-2; A=70 cm2; ≈ 85% Total Ghazouani
wastewater Conductivity= 2.6 and 5.2 mS cm−1; Kjeldhal et al., 2017
t=3 h Nitrogen
Wet scrubber Al & Fe electrode j=180 Am-2; A=55 cm2; d=5-15 cm; 60.6% Nitrate Jo et al.,
wastewater t=1 h removal 2016
Metal- Anode= Pt; j= 25–100 A m−2; L×W×H=10 ≈ 90% Nitrate Sim et al.,
finishing Cathode=Ti, Ni, Fe, cm×10 cm×20 cm; d=10 mm; NO3- removal 2012
wastewater Cu, Zn N=100 mg/L; pH=2; HRT=10-60
min; Zn : sulfamic acid : nitrate=1 :
1:1
Agro-industrial BDD electrodes j=450–2500 A m−2; A= 68 cm2; ≈ 89% Nitrate Georgeaud
wastewater d=10 mm; pH=2.5 removal et al., 2011

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 GLS-14
RESEARCH OBJECTIVES 2019

 Following aims and objective were set after the literature survey –

 Reduction of highly contaminated NO3─ wastewater and oxidation of in-situ

generated by products like NH4+ and NO2─ by using Ti/RuO2 (DSA) as anode and Al as
a cathode.

 Current density (J), time (t) and pH were optimized for EC denitrification of actual
wastewater. Specific energy consumption (SEC) and current efficiency (CE) was
examined on the basis of lab scale experiments.

 A reduction as well as oxidation mechanism and pathway has been proposed for the
treatment of highly contaminated nitrate wastewater.

 Field emission scanning electron microscope (FE-SEM) coupled with energy

dispersed X-ray (EDX) was utilized for the characterization of electrodes before and
after the all the EC treatment process.

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 GLS-14
ANALYSIS PROCEDURES 2019

 CE:- Current efficiency (CE) which is defined as the ratio of the charge used for oxidation of compound to the
total charge passed during electrolysis will be calculated using the following relationship [Panniza and
Cerisola 2006] :
([NO 3- ]i - [NO 3- ]t )  n  F  Vr
CE (%)   100
I t

 SEC:- Specific Energy Consumption (SEC) defined as the energy consumed in kWh for removal of per kg of
COD removed will be calculated using the following equation [Mohan et al. 2001] :

I  Vap  Δt
SEC 
(C NO - )  Vr
3

 KINETICS:- First order rate constant (k) for COD and CP degradation was calculated by constructing graph
between ln(C0/Ct) versus time (min) at different current densities (j) [Chauhan et al., 2016]:

- d([NO 3- ]) [NO 3- ]o
1 order kinetic model :
st
 k([NO 3 ])  ln
-
 kt
dt [NO 3- ]t

where, [NO3-], [NO2-] and [NH4+] are the concentration of nitrate, nitrite and ammonium ion (mol/L), respectively and i and t
represents concentration initially and at time t, respectively, n is the stoichiometric coefficient (n=5, 2, 8 if N2, NO2- and NH4+ are
the final product respectively), F is the Faraday constant (=96,485 C/mol), Vr is working cell volume (L), I is the applied current (A),
Δt is electrolysis time (s).

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RESULTS & DISCUSSION GLS-14
(EFFECT OF CURRENT DENSITY (J)) 2019

3500 300 3500 300

(a) Nitrate (b) Nitrate
3000 Ammonia 250 3000 Ammonia 250
Nitrite Nitrite

Concentration (mg/L)
Concentration (mg/L)

Concentration (mg/L)
Concentration (mg/L)
2500 2500
200 200
2000 2000
150 150
1500 1500
100 100
1000 1000

50 500 50
500

0 0 0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Time (min) Time (min)

J=142.86 A/m2 J=285.71 A/m2

Nitrate reduction efficiency ≈45% Nitrate reduction efficiency ≈51%

Fig. Concentration profile of nitrate, ammonia and nitrite in aqueous solution at current density (J)
of (a) 142.86 A/m2; (b) 285.71 A/m2.
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RESULTS & DISCUSSION GLS-14
(SEC & CE) 2019

40
(a) 50 (b)
35

30
40
SEC (kwh/kgΔNO3-)

25
30

CE (%)
20

15 20

10 142.86
J (A/m2) 10
285.71
5
0
0
142.86 285.71
0 30 60 90 120 150 180
Time (min) J (A/m2)

Fig. Effect of current density (J) (A/m2) on the (a) SEC (kWh/kg NO3- reduced) and (b) CE for nitrate
ion reduction at pH= 7.95.

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RESULTS & DISCUSSION GLS-14
(REDUCTION KINETICS) 2019

4 60
(a) (b) nth order kinetics
1st order kinetics
50
3
([NO3-]t-[NO3-]i) × 10-4

Concentration (NO3-)
40

2 30
Solid line=Actual concentration

20 Dotted line=Fitted concentration

y = 0.0134x + 0.8541
1 142.86 R² = 0.8352
J (A/m2) J=142.86 (n=2.12) R2=0.982
285.71 10
y = 0.0103x + 0.7868 J (A/m2)
R² = 0.7751 J=285.71 (n=2.54) R2=0.988
0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Time (min) Time (min)

Fig. (a) First order kinetics and (b) nth order kinetics at J= 142.86 and 285.71 A/m2.

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 GLS-14
ELECTRODE MORPHOLOGY 2019

Ti/RuO2 (Anode)

Al (Cathode)

Before Treatment After Treatment

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 GLS-14
CONCLUSIONS 2019

 The ultimate NO3- reduction efficiency of ≈45% and ≈51% was observed at J=142.86
A/m2 J=285.71 A/m2 respectively at pH=7.69 and after 180 min.

 SEC and CE calculated to be 30 kWh/kgNO3-reduced and ≈44% respectively for ultimate

nitrate reduction efficiency.

 The proposed mechanism concluded that nitrate ion was reduced into N2, N2O and
NH4+ at cathode as final products and simultaneously available and produced NH4+ and
NO2- were oxidized at anode into N2 as the final product by Fe and Ti/RuO2 electrode.

 The characterization of electrodes before and after all The EC experiments done by FE-
SEM suggests that Ti/RuO2 as anode and Fe as cathode had not changed their surface
and molecular structure at high applied potentials.

 The advantages for using EC reduction and oxidation with DSA like Ti/RuO2 was that it
produced negligible amount of sludge and scum and for this study there was no
amount of sludge and scum was produced.

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REFERENCES GLS-14
2019

• S. Garcia-Segura, M. Lanzarini-Lopes, K. Hristovski, P. Westerhoff, Electrocatalytic reduction of nitrate: Fundamentals to full-scale

water treatment applications, Appl. Catal. B Environ. 236 (2018) 546–568.
• J.F. Su, I. Ruzybayev, I. Shah, C.P. Huang, The electrochemical reduction of nitrate over micro-architectured metal electrodes with
stainless steel scaffold. Appl. Catal., B 180 (2016) 199-209.
• I. Standard, Bureau of Indian Standards drinking water specifications, BIS 10500 (2012).
• J. Ma, Q. Yang, S. Wang, L. Wang, A. Takigawa, Y. Peng, Effect of free nitrous acid as inhibitors on nitrate reduction by a biological
nutrient removal sludge, J. Hazard. Mater. 175 (2010) 518–523.
• J. Shi, C. Long, A. Li, Selective reduction of nitrate into nitrogen using Fe-Pd bimetallic nanoparticle supported on chelating resin at
near-neutral pH, Chem. Eng. J. 286 (2016) 408–415.
• Z. Zhang, Y. Xu, W. Shi, W. Wang, R. Zhang, X. Bao, B. Zhang, L. Li, F. Cui, Electrochemical-catalytic reduction of nitrate over Pd-
Cu/γAl2O3 catalyst in cathode chamber: Enhanced removal efficiency and N2 selectivity, Chem. Eng. J. 290 (2016) 201–208.
• L. Su, K. Li, H. Zhang, M. Fan, D. Ying, T. Sun, Y. Wang, J. Jia, Electrochemical nitrate reduction by using a novel Co3O4/Ti cathode,
Water Res. 120 (2017) 1–11.
• B.P. Dash, S. Chaudhari, Electrochemical denitrificaton of simulated ground water, Water Res. 39 (2005) 4065–4072.
• V. Georgeaud, A. Diamand, D. Borrut, D. Grange, M. Coste, Electrochemical treatment of wastewater polluted by nitrate: selective
reduction to N2 on boron-doped diamond cathode., Water Sci. Technol. 63 (2011) 206–12.
• I. Kalaruban, P. Loganathan, J. Kandasamy, R. Naidu, S. Vigneswaran, Enhanced removal of nitrate in an integrated electrochemical-
adsorption system, Sep. Purif. Technol. 189 (2017) 260–266.
• J. Sim, H. Seo, J. Kim, Electrochemical denitrification of metal-finishing wastewater: Influence of operational parameters, Korean J.
Chem. Eng. 29 (2012) 483–488.
• J.O. Bockris, Electrochemical Reductions of Hg(II), Ruthenium-Nitrosyl Complex, Chromate, and Nitrate in a Strong Alkaline Solution,
J. Electrochem. Soc. 143 (1996) 3801.
• G.E. Dima, A.C.A. De Vooys, M.T.M. Koper, Electrocatalytic reduction of nitrate at low concentration on coinage and transition-metal
electrodes in acid solutions, J. Electroanal. Chem. 554–555 (2003) 15–23.
• A.C.A. De Vooys, R.A. Van Santen, J.A.R. Van Veen, Electrocatalytic reduction of NO3- on palladium/copper 3 electrodes, J. Mol. Catal.
A Chem. 154 (2000) 203–215.

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THANK
YOU

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