1 Available online at www.sciencedirect.

com

ScienceDirect
Availableonline
Available onlineatatwww.sciencedirect.com
www.sciencedirect.com
Energy Procedia 00 (2017) 000–000

ScienceDirect
ScienceDirect
www.elsevier.com/locate/procedia

Energy
EnergyProcedia 142
Procedia 00(2017)
(2017)1421–1426
000–000
www.elsevier.com/locate/procedia

9th International Conference on Applied Energy, ICAE2017, 21-24 August 2017, Cardiff, UK

Concentration of nitrogen as new energy source from wastewater

The 15th International Symposium on District Heating and Cooling
by electrodeionization
Haoyue Assessing
Zhenga, Xiao theGong feasibility
a
, Yang Yang of using
a
, JingbotheYang heata
, Xudemand-outdoor
Yanga, Zucheng Wua,*
a temperature function for a long-term district heat demand forecast
Department of Environmental Engineering, Laboratory for Electrochemistry & Energy Storage, Zhejiang University, Hangzhou 310058, P.R.
China
I. Andrića,b,c*, A. Pinaa, P. Ferrãoa, J. Fournierb., B. Lacarrièrec, O. Le Correc
a
IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal
b
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
c
Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France
Abstract

With the popularity of ammonia fuel cell, nitrogen-containing compounds are becoming an alternative energy sources. However,
Abstract
most of those nitrogen compounds, especially ammonia, are dispersed in domestic wastewater and their treatment is often energy
consumption. Therefore, the nitrogen retrieval from wastewater is becoming urgently needed of development. Adopting a new
District heating networks
five-compartment are commonly
electrodeionization addressed
technology, thisinpaper
the literature as one
demonstrates theofpossibility
the most effective solutions
to concentrate for decreasing
ammonia nitrogen inthe
greenhouse
synthetic gas emissions
wastewater. fromindicates
The result the building
that sector. These current
the optimum systemsisrequire
0.18 A high investments
in artificial which
domestic are returned
sewage with lowthrough the heat
concentration
sales. Dueions
ammonium to the changed
among climate
15 mg/L. conditions
The nitrogen and building
concentration canrenovation
be enrichedpolicies,
for aboutheat demand
12 times in thestage.
in single futureThe
could decrease,
removal rate
ofprolonging the reach
nitrogen can investment return
over 90% period.
with energy consumption of 19.104 g/kW·h. It explores a feasibility of recovering the ammonia
The main
nitrogen in scope of this paper is to assess the feasibility of using the heat demand – outdoor temperature function for heat demand
wastewater.
forecast. The district of Alvalade, located in Lisbon (Portugal), was used as a case study. The district is consisted of 665
©buildings
2017 Thethat
Authors.
vary inPublished by Elsevierperiod
both construction Ltd. and typology. Three weather scenarios (low, medium, high) and three district
Peer-review
renovation under responsibility
scenarios of the scientific
were developed (shallow,committee of the
intermediate, 9th International
deep). To estimate Conference on Applied
the error, obtained heatEnergy.
demand values were
compared with results from a dynamic heat demand model, previously developed and validated by the authors.
The results
Keywords: showed that when
electrodeionization; only weather
wastewater; change isions;
urea; ammonium considered, the margin of error could be acceptable for some applications
energy; concentration
(the error in annual demand was lower than 20% for all weather scenarios considered). However, after introducing renovation
scenarios, the error value increased up to 59.5% (depending on the weather and renovation scenarios combination considered).
1.The
Introduction
value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the
decrease in the number of heating hours of 22-139h during the heating season (depending on the combination of weather and
renovation scenarios considered).
Energy shortage is one of the On biggest
the otherenvironmental
hand, function intercept
challengesincreased
today.forIt 7.8-12.7%
is the mostper decade
important(depending
task foronall
the
coupled scenarios). The values suggested could be used to modify the function parameters
mankind to change the energy structure and search for new energy sources. As we all know, the energy density of for the scenarios considered, and
improve
urea the accuracy
is higher of heat
compared demand
with estimations.
compressed or liquid hydrogen which makes it a potential energy[1,2]. In 2009, S.
W.Tao’s research group had already proposed the direct urine fuel cell which can generate electricity from urea
© 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and
* Corresponding author. Tel.: +86-0571-85660839 .
Cooling.
E-mail address: wuzc@zju.edu.cn
Keywords: Heat demand; Forecast; Climate change
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.

1876-6102 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.
10.1016/j.egypro.2017.12.529
1422 Haoyue Zheng et al. / Energy Procedia 142 (2017) 1421–1426
2 Haoyue Zheng / Energy Procedia 00 (2017) 000-000

directly. Since the emergence of ammonia fuel cell, nitrogen as a kind of new energy has been noticed. However,
the source of nitrogen is a tricky issue. Unfortunately, most of nitrogen compounds, especially ammonia, are
dispersed in domestic sewage as a waste. About 77% of the energy consumption of sewage treatment is in the
activated sludge process of nitrification which consumes energy as high as 45 WJ to remove nitrogen per
kilogram[3,4]. Why not will people have retrieved those compounds as useful chemicals? If it would be recovered
from wastewater, the nitrogen energy sources can be gained instead of its disposal as a waste.
We are herein concerning about their retrieval methodological development. However, the exiting technologies
of nitrogen recovery mainly depend on chemical and biochemical methods, such as struvite recovery process[5],
which often exist different defects like the application of the precipitation agent or coagulant aids bringing high cost
and secondary pollution and are hard to recover ammonia nitrogen from low-concentration nitrogenous wastewater.
The “electro-dynamic inspissation (EDI)” technology applied in this experiment is a combining process based on
the technology of ion exchange and electrodialysis[6,7]. It is not only used to “de-ionize” water to purify it but also
is a novel desalination technology for gathering or recovering ions under electro-forces. It overcomes the
concentration polarization and chemical regeneration existed in original single process and can treat low
concentration solution efficiently. In our previous work, we employed this technology to recover some metal ions as
well as carbon dioxide instead of discarding them[8,9]. In this study, a new electrochemical deionization apparatus
of five compartments was designed to achieve the continuous regeneration of resin on line without addition of
chemicals aiming at recycling the resources of nitrogen. The object of this study was to demonstrate the utilization of
the apparatus to recover nitrogen from wastewater, to examine its recovery performance and to evaluate its power
consumption.

2. Method

2.1. Materials

Synthetic domestic sewage: its formula is shown in Table 1[10].

Table 1 Formula of synthetic domestic sewage water

Formula glucose NH4Cl NaCl MgSO4 CaCl2 NaHCO3 NaOH K2HPO4 trace elements

Quality(g/mL) 0.2 0.11 0.1 0.003 0.004 0.02 0.1 0.028 0.4
Constant volume to 1000mL

Ion exchange resin: the anion exchange resin is D201 macroporous-type strong base and the cation exchange
resin is D001 macroporous-type strong acid, which all produced by Hangzhou glory resin Co., ltd.
Ion exchange membrane: anion membrane and cation membrane, produced by Shandong Tianwei membrane
technology Ltd.
Equipment: Vertical pressure steam sterilizer, produced by Shanghai Boxun Industrial Co., Ltd. medical
equipment factory; Magnetic driven circulating pump MP-6R, produced by Shanghai Xishan Industrial Co., Ltd;
2802 UV-VIS spectrophotometer, etc.

2.2. Experimental apparatus

The five-compartment EDI apparatus is shown in Figure 1. Based on the traditional electrodeionization
technology, the anion and cation resin are filled into different compartments and separated by corresponding ion
exchange membranes. Under the electric field force, the H+ migrate faster than OH-, resulting the pH in concentrated
chamber maintain acidic so that the divalent ions in solution will not be precipitated[11]. The chambers of anion and
cation resin are connected together. The influent goes through the anion resin chamber in which anions migrate to
the concentrated chamber, and then passes through the cation resin so the cations can migrate to it as well. Finally,
the concentrated ammonia in concentrating chamber and freshwater in diluting chamber are obtained, respectively.
 Haoyue Zheng et al. / Energy Procedia 142 (2017) 1421–1426 1423
3 Haoyue Zheng / Energy Procedia 00 (2017) 000-000

Figure1. The five-compartment EDI apparatus. AEM: anion exchange membrane; CEM: cation exchange membrane; AR: anion exchange resin;
CR: cation exchange resin; A-: anion; B+: cation; Effective volume of compartment: 19.4 cm × 2.0 cm × 0.7 cm.

3. Results and discussion

3.1 Effect of flow rate

It’s generally believed that the decrease of flow rate can increase the residence time of influent and improve the
quality of effluent[12]. On the other side, excessive flow rate is able to enhance the exchange among water,
membrane and resin. And the changes in liquid flow will affect the transfer of mass and heat[13]. In this paper, the
migration of nitrogen in EDI system was observed in the condition of 3 L/h and 6 L/h with current of 0.15 A. The
results can be seen from Figure 2(a) that the EDI system can effectively remove NH4+ at different cyclic flow rates,
and the migration terminus are both about 270 min. It may be that the circulation of the solution can continuously
supplement the ions in dilute chamber at the same current density, and when the amounts of added ions is more than
that of migration, the total number of migrating ions will not change. However, in the event the flow rate is too large,
the ion migration would be interfered, the energy consumption of the pump is increased at the same time, which is
detrimental to the operation of the EDI system. The Figure 2(b) shows the relationship between voltage and flow
velocity, which infers that the enhancement of liquid circulation can speed up the ion supplement, reduce the
resistance of the weak chamber as well as the voltage.

(a) (b)

Figure 2. different flow rate (a) NH4+ concentration in dilute effluent (b) voltage

3.2 Effect of applied current

The migration of nitrogen in the EDI system was investigated at 20, 30, 40, 50 mA/cm 2 (0.08 A, 0.12 A, 0.15 A,
0.19 A, respectively). Figure 3 (a) shows that the removal efficiency of NH4+ improved with the increase of current
1424 Haoyue Zheng et al. / Energy Procedia 142 (2017) 1421–1426
4 Haoyue Zheng / Energy Procedia 00 (2017) 000-000

density, and the best current density is 40 mA/cm2. Yet illimitably increasing current density will not change the
treatment efficiency without limit. When the current varies from 20 mA/cm 2(0.08 A) to 40 mA/cm2(0.15 A), the
removal efficiency increased obviously. But from 40 mA/cm2 (0.15 A)to 50 mA/cm2(0.19A) , the ion concentration
changes little and even the concentration curve is overlapped. This may be due to the enhancement of the current
density along with the rise of the voltage leading to the water dissociation reaction directly. Low voltage is not
conducive to ion migration and resin regeneration[14], while the high voltage will cause severe water dissociation
reaction producing a large amount of H+, OH- which migrate to the concentrated chamber to compete with NH 4+.
Obviously, the current density of 40 mA/cm2 is already the best state for ion migration and the resin regeneration.
Besides, the lower current density is more favorable to prolong the service life of ion exchange membrane. From
Figure 3 (b), the voltage increases continuously and there is no stable process in 0.08A and 0.12A, which shows that
ionic conductance is dominant in the system. However, When the current is 0.15A and 0.19A, there is a voltage
stability process, which means that the resin replaces the ion and becomes the main mode of conduction after the ion
is exhausted.
By comparison, it is found that the effect of current density on the migration of ammonium ions is more
significant, which indirectly shows that electromigration is dominant in the influence factors of diffusion,
electromigration and convection.

(a) (b)

Figure 3. different current (a)NH4+ concentration in dilute effluent (b) voltage

3.3 The concentration of ammonium ions in synthetic domestic sewage

From the previous experiments, it has been proved that the current has a greater influence on the migration of
ammonium ions, so the effect of currents on the recovery of nitrogen in simulated domestic sewage was inspected
emphatically to determine the best conditions for the recovery of nitrogen. The results are shown in Figure 4. It
shows the concentration of nitrogen ions in the concentrated chamber under different currents. Although the current
grows in proportion, it takes a disproportionate amount of time to reach the same concentration. The concentration
factor reduces under high current, while the concentration time is greatly shortened. It is confirmed that the water
dissociation reaction of high current can promote the resin regeneration and enhance its ion exchange capacity, thus
speeding up the process of ion migration. For this reason, 0.18 A is the optimum current of ammonium ion
concentration for this apparatus and the removal rate of nitrogen can reach more than 90% in this condition, the
nitrogen concentration can be enriched for about 12 times in single stage at the same time.
5 Haoyue Zheng
Haoyue / Energy
Zheng et al. /Procedia 00 (2017)142
Energy Procedia 000-000
(2017) 1421–1426 1425

Figure 4. NH4+ concentration in dilute effluent.

3.4 The energy consumption

The corresponding voltage is about 6.0 V under the current of 0.18 A, and the nitrogen migration flux is 19.104
mg/h with an energy consumption of 1 kW·h. It means that 1 kW·h can recycle N element 19.104 g. Since the
experiment uses a single deionization system in which the cathode and anode consume most of the electricity. If it’s
multistage, the ratio of electricity consumption at the poles will be reduced, meanwhile the unit energy consumption
of nitrogen recovery will be less[15].

4. Conclusion

This experiment demonstrated the possibility of retrieving ammonium ions from waste water directly. It is
concluded that the optimum current of recovering ammonium ions is 0.18 A in simulated domestic sewage and the
concentration of ammonium ions can reach about 12 times under this current. The removal rate of ammonium ions
in dilute chamber can reach more than 90%. It greatly relieves the energy consumption and operation cost of the
urban sewage treatment for denitrification process. The operation process uses the electric energy only without
chemical reagent and secondary pollution. And 1kW·h electric energy may recycle nitrogen element of 19.104 g,
which is energy efficient. This novel EDI technology of five compartments can realize the low concentration of
nitrogen to higher concentration in wastewater and it would be better if running multi membrane stack. It can
effectively extract the energy from the waste water, and provide a cheap and easily available raw material for
ammonia fuel cell with a good development prospects.

Acknowledgements

The authors are grateful for the financial support of the National Natural Science Foundation of China (Grant No.
21173188 and 21473158.)

References

[1] Lan R, Tao S, Irvine JTS. A direct urea fuel cell - power from fertiliser and waste. Energ Environ Sci. 2010;3:438-41.
[2] Lan R, Tao S. Preparation of nano-sized nickel as anode catalyst for direct urea and urine fuel cells. J Power Sources. 2011;196:5021-6.
[3] Cano R, Perez-Elvira SI, Fdz-Polanco F. Energy feasibility study of sludge pretreatments: A review. Appl Energ. 2015;149:176-85.
[4] Maachou R, Lefkir A, Bermad A, Djaoui T, Khouider A. Statistical analysis of pollution parameters in activated sludge process. Desalin
Water Treat. 2017;72:85-91.
[5] Zou S, Qin M, Moreau Y, He Z. Nutrient-energy-water recovery from synthetic sidestream centrate using a microbial electrolysis cell -
forward osmosis hybrid system. J Clean Prod. 2017;154:16-25.
1426 Haoyue Zheng et al. / Energy Procedia 142 (2017) 1421–1426
6 Haoyue Zheng / Energy Procedia 00 (2017) 000-000

[6] Mahmoud A, Hoadley AFA. An evaluation of a hybrid ion exchange electrodialysis process in the recovery of heavy metals from simulated
dilute industrial wastewater. Water Res. 2012;46:3364-76.
[7] Strathmann H. Electrodialysis, a mature technology with a multitude of new applications. Desalination. 2010;264:268-88.
[8] Willauer HD, DiMascio F, Hardy DR, Lewis MK, Williams FW. Development of an electrochemical acidification cell for the recovery of
CO2 and h-2 from seawater II. Evaluation of the cell by natural seawater. Ind Eng Chem Res. 2012;51:11254-60.
[9] Yang Y, Tian Y, Wu Z. Retrieval of CO2 from a carbonate solution for its sequestration by a novel electrochemical decarbonizing and
ingathering method. Rsc Adv. 2015;5:103534-40.
[10] Zhang F, Li J, He Z. A new method for nutrients removal and recovery from wastewater using a bioelectrochemical system. Bioresource
Technol. 2014;166:630-4.
[11] Feng X, Gao J, Wu Z. Removal of copper ions from electroplating rinse water using electrodeionization. J Zhejiang Univ-Sc a. 2008;9:1283-
7.
[12] Zarnetske JP, Haggerty R, Wondzell SM, Baker MA. Dynamics of nitrate production and removal as a function of residence time in the
hyporheic zone. JOURNAL OF GEOPHYSICAL RESEARCH-BIOGEOSCIENCES. 2011;116.
[13] Bassani CL, Barbuto FAA, Sum AK, Morales REM. Modeling the effects of hydrate wall deposition on slug flow hydrodynamics and heat
transfer. Appl Therm Eng. 2017;114:245-54.
[14] Spoor PB, Ter Veen WR, Janssen L. Electrodeionization 2: The migration of nickel ions absorbed in a flexible ion-exchange resin. J Appl
Electrochem. 2001;31:1071-7.
[15] Zhang Y, Desmidt E, Van Looveren A, Pinoy L, Meesschaert B, Van der Bruggen B. Phosphate Separation and Recovery from Wastewater
by Novel Electrodialysis. Environ Sci Technol. 2013;47:5888-95.