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Chemical Engineering Journal 451 (2023) 138789

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Chemical Engineering Journal


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Review

Up-concentration of nitrogen from domestic wastewater: A sustainable


strategy from removal to recovery
Yangjie Qin a, 1, Kaichong Wang b, 1, Qing Xia a, Siqi Yu a, Maonan Zhang a, Ying An a,
Xiaodan Zhao a, Zhen Zhou a, c, *
a
Shanghai Engineering Research Center of Energy - Saving in Heat Exchange Systems, College of Environmental and Chemical Engineering, Shanghai University of Electric
Power, Shanghai 200090, China
b
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
c
Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China

A R T I C L E I N F O A B S T R A C T

Keywords: Improving environmental quality and achieving a circular economy require developing wastewater resource
Domestic wastewater recovery facilities (WRRFs) under stringent discharge standards. As a sustainable alternative to control nitrog­
Nitrogen recovery enous pollution, nitrogen separation and recovery from wastewater is the bottleneck to break through in WRRFs
Up-concentration
and is critical to alleviating anthropogenic interference with the global nitrogen cycle. However, nitrogen from
Ion exchange
Energy
low-strength domestic wastewater (20–50 mg/L) is overlooked and requires up-concentration for adequate re­
Circular economy covery. This review overviewed the advances and significant challenges of current nitrogen removal and re­
covery methods. Then several nitrogen up-concentration technologies were summarized to clarify their working
location, technical performances, influential factors, and strategies for nitrogen recovery from concentrate. The
pretreatment and post-treatment technologies were reviewed and discussed to improve the adaptabilities of these
up-concentration technologies in WRRFs. Considering the coexistence of NH+ 4 with impurities or high salinity in
the up-concentration process, a novel workflow for nitrogen recovery by coupling up-concentration with a
targeted conversion process was proposed to reach the high up-concentration factor, satisfy stringent discharge
standards, and harvest valuable products. The results anticipated a possible effective and sustainable layout for
WRRFs via combining nitrogen up-concentration with carbon capture and phosphorus enrichment.

1. Introduction is more challenging than phosphorus [4], and nitrogen removal pro­
cesses were constantly evolving from traditional nitrification - denitri­
Wastewater treatment not only fulfills its function of effective fication to mainstream anammox and advanced treatment [5]. However,
pollutant removal, but also involves the recovery of reclaimed water, current processes for organics and nutrients removal are linear (i.e.
resources, and energy. The wastewater collection and drainage system produce-consume-dispose) and unsustainable because they convert
can be traced back to ancient Rome and the Shang Dynasty [1], and reactive compounds, which were generated using energy via natural (e.
centralizes miscellaneous substances together, making pollutant g., photosynthesis) or industrial processes (e.g., ammonia synthesis),
removal and resource recovery feasible. Organic pollutants were the first into nonreactive and nonpolluting forms [1,6]. Resource recovery from
concern of wastewater treatment. The introduction of the conventional wastewater within the constraint of discharge standards would change
activated sludge (CAS) process in 1914 impels degradation and miner­ current situation, and allow for a circular flow of nutrients, energy, and
alization of organic matters benefiting society and the environment [2]. water in the social cycle.
Since the 1970s, nitrogen and phosphorus have become primary targets Domestic wastewater contains various chemical resources [7].
of domestic wastewater treatment plants (WWTPs) because of eutro­ Methane has long been a common product for carbon recovery by
phication in waters [3]. Nitrogen in wastewater was emphasized since it anaerobic treatment, generating benefits of 0.038 $/m3 domestic

* Corresponding author at: Shanghai Engineering Research Center of Energy - Saving in Heat Exchange Systems, College of Environmental and Chemical Engi­
neering, Shanghai University of Electric Power, Shanghai 200090, China.
E-mail address: zhouzhen@shiep.edu.cn (Z. Zhou).
1
Both authors contributed equally to this manuscript.

https://doi.org/10.1016/j.cej.2022.138789
Received 6 June 2022; Received in revised form 7 August 2022; Accepted 22 August 2022
Available online 24 August 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
Y. Qin et al. Chemical Engineering Journal 451 (2023) 138789

Fig. 1. Global nitrogen cycle including wastewater treatment. The diagram shows the main exchange between N2 and Nr in water, land, and the atmosphere. Among
them, nitrogen conversion in wastewater treatment is introduced in detail from the molecular perspective. The upward arrows show re-emissions to the atmosphere
by various processes and the red color indicates the anthropogenically disturbed pathway. All the data were obtained from Bodirsky, et al. [29], MacFarlane, et al.
[30] and Zhang, et al. [31].

wastewater [8,9]. Nitrogen is the second abundant resource and can be 2. From removal to recovery
extracted and employed in the agricultural, explosive, food, and chem­
ical industries [10], making a potential benefit (0.018–0.086 $/m3) [11] 2.1. Nitrogen removal: Major challenges for current WWTPs
comparable to carbon recovery. Some nitrogen recovery methods, such
as ammonia stripping and struvite precipitation, have been successfully Conventionally, reactive nitrogen (Nr) in domestic wastewater was
applied in high-strength wastewater [12,13]. However, these technol­ converted into atmospheric nitrogen (N2 and N2O) through ammonifi­
ogies are only feasible at a high NH+ 4 -N level of 2–3 g/L, and have an cation, nitrification, and denitrification processes with various config­
outlet NH+ 4 -N concentration much higher than the discharge standard urations. However, it was a common phenomenon that NH+ 4 -N and TN in
[14]. Therefore, it is a challenge to meet the requirements of nitrogen the effluent of WWTPs using the nitrification - denitrification method
recovery and safe discharge simultaneously for WWTPs [4]. Addition­ exceeded the stringent standards enforced by many countries [15]
ally, recovering nitrogen directly from domestic wastewater at a low (Table S1), which will be tightened for water conservation areas and
level (20–50 mg/L) will face the hindrances of applicable technologies. sensitive areas facing eutrophication [16]. Upgrading nitrogen removal
The key points to construct wastewater nitrogen recovery systems to satisfy stringent discharge standards resulted in three significant
suitable for different scenarios include efficient nitrogen separation problems for WWTPs, including enlarged land occupancy, elevated
from wastewater, and high-factor nitrogen up-concentration for treatment cost, and increased carbon emission. The land occupancy of
economical recovery. Grounded in achieving excellent nitrogen removal WWTPs is required to prolong aerobic hydraulic retention time (HRT)
to satisfy discharge standards, a promising approach for recovering ni­ for good nitrification and to add posterior denitrification units for
trogen from domestic wastewater is to implement up-concentration in adequate nitrogen removal [4]. These measures significantly increased
the mainstream, and then recover nitrogen from the concentrate in the treatment cost because aeration for nitrification accounted for
side-stream. 50.0–60.0 % of the total process energy required [17,18], while the
The concept of up-concentration is to enrich the targeted substance external carbon sources demanded to improve denitrification accounted
from dilute solutions without unwanted pollutants accumulation by for 74.6 % of the total chemical cost [4,19]. The elevated nitrogen
specific methods. The main objective of this review is to summarize removal also has a severe impact on N2O production, with emission
nitrogen up-concentration technologies to clarify their working loca­ factors varying from 2.0 to 8.0 % of TN removed [20]. N2O, the emis­
tion, technical performances, influential factors, and strategies for ni­ sions of which comprise 14.0–26.0 % of the overall carbon footprint of
trogen recovery from concentrate. The pretreatment and post-treatment WWTPs [14], has been focused due to its high global warming potential
technologies were reviewed and discussed to improve the adaptabilities of 265 and ozone-depleting property [21].
of these up-concentration technologies. In this way, a novel workflow In recent years, newly developed nitrogen removal processes, such as
for nitrogen recovery by coupling up-concentration with a targeted simultaneous nitrification and denitrification (SND), Sharon, and
conversion process was proposed. A possible effective and sustainable anammox, have evolved as efficient and cost-effective alternatives to
layout for wastewater resource recovery was anticipated by combining conventional processes, and significantly reduced energy consumption,
nitrogen up-concentration with carbon capture and phosphorus chemical requirement, and sludge production of WWTPs [5,22]. Gran­
enrichment. ular sludge system in SND and anammox processes has gained

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popularity in wastewater treatment [23]. Mainstream anammox is Table 1


proposed as a carbon- and energy-neutral technology for domestic The Composition and Application of Nitrogen Recovery Products from
wastewater treatment [24,25], and has been successfully applied in full- Wastewater.
scale WWTPs [22]. However, the dilute and highly variable character­ Recovered product Application prospect References
istics of domestic wastewater, combined with fluctuating temperatures Wastewater irrigation Nitrogenous fertilizer [37]
and stringent discharge standards, have restrained the application of the Ammonium Ammonium Feedstock in textile, plastic, [39,40]
mainstream process [26]. Moreover, the underlying mechanism of sulfate agriculture, and food processing
conventional and novel nitrogen removal processes remains unchanged, Ammonium Feedstock in agriculture, plastics, [41,42]
bicarbonate ceramics, and printing industries
namely consuming energy to produce N2 from Nr and subsequently
Struvite An ideal slow-release fertilizer [3,43]
generating Nr from N2 by the Haber-Bosch process [14,27]. These Nitrate Ammonium Nitrogenous fertilizer, oxidizer in [27]
technologies ignore the resource value of nitrogen and don’t dovetail nitrate gas generators and propellants
with the target of wastewater resource recovery. Current nitrogen con­ N2O Excellent oxygen aid, rocket [45]
version technologies aimed at removal could be integrated into the ni­ propellant, and medication for
anesthesia
trogen recovery system by adjusting targets and regulating Microalgae Bio-oil A renewable feedstock to product [46]
transformation pathways to produce valuable products like nitrate and energy, fuels, chemical and
N2O. Recovering nitrogen from domestic wastewater would allow for a carbon materials
circular flow of the nitrogen cycle, and the nitrogen in domestic Protein Animal feed, human food, [47]
medicine, cosmetics, and other
wastewater should be reexamined as a precious resource.
industries

2.2. Nitrogen resource: Domestic wastewater should be emphasized


resource-limited environments, the system for nitrogen recovery from
Nature is an abundant nitrogen reservoir, with many natural trans­ domestic wastewater can reduce energy consumption and CO2 emission
mission pathways to form a systematic nitrogen cycle (Fig. 1). Nitrogen and offset the cost of nitrogen fertilizer production [3], contributing to
plays a central role in human society, including in food, agriculture, mitigating global warming and protecting natural biogeochemical cy­
metallurgical industry, etc. [10,27]. Many natural pathways are cles [30].
anthropogenically disturbed, and the mass of anthropogenic nitrogen
fixation (210 Tg/a) is now equivalent to the natural process (203 Tg/a). 2.3. Nitrogen recovery: Potential products considered in WWTPs
Therefore, the massive increase in anthropogenic Nr flows and its
associated emissions to the environment are profoundly altering the Wastewater irrigation is a traditional nitrogen recovery method that
global biogeochemical nitrogen cycle. Among all global environmental contributes to soil accumulation of nitrogen to improve crop growth and
impacts, Nr is most severely exceeding the carrying capacity of the earth restore the function of desert sandy soil [37]. However, wastewater also
(around 3 times), in which fertilizer use, livestock wastes and domestic contains pathogens, heavy metals, and organic contaminants, and its
wastewater have primary responsibility for this [28]. A majority of the direct use in agriculture will cause severe environmental pollution [38].
Nr entering biosphere is in the form of ammonium produced by dint of On the other hand, the receiving capacity of farmland is dwarfed by the
Haber-Bosch process, which is the predominant industrial way ac­ abundance of domestic wastewater. Wastewater transportation is also a
counting for about 1/3 of the global Nr production [28] and consumes critical limitation because large-scale WWTPs are usually located in
1–2 % of global energy [14]. cities short of cropland. Therefore, recovering nitrogen from wastewater
The nitrogen contained in domestic wastewater is expected to in­ in the form of nitrogenous resources attracted more attention.
crease from 20 Tg/a in 2010 to 35 Tg/a in 2050 [29,30]. However, the Recovering nitrogen from domestic wastewater varies widely in its
energy consumption of the “destructive” biological nitrogen removal technique, fundamental process, and product. Table 1 summarizes the
(12.2 kWh/kg N) is higher than the average energy for the Haber-Bosch application and product characteristics of these nitrogen recovery
process dissipated (10.3 kWh/kg N) [14,18,27], and will continue to technologies. Nitrogen recovery as ammonium sulfate is the common
increase along with the growing stringent discharge standards. There­ technology practically feasible for high-strength wastewater with
fore, the dissipative nitrogen removal in WWTPs is not a sustainable increased temperature [39,40]. Although effectively increasing plant
pathway, and society with a nitrogen circular economy is needed for yield, ammonium sulfate only made up a minor portion of global fer­
promoting the sustainability of production and consumption patterns tilizers [27]. Farmers and engineers prefer to use ammonium bicar­
[32]. Moreover, the Haber-Bosch process itself is optimized and is bonate with higher cost performance in the actual market [41,42].
reaching near thermodynamic process efficiencies, but its energy cost Struvite is an ideal slow-release fertilizer precipitated by equimolar
has a huge surge owing to dramatic increases in energy price [28]. Thus, magnesium, phosphorus, and nitrogen [43]. Still, it is usually utilized for
for decreasing the social cost of Nr, the development of environmentally phosphorus recovery instead because of the shortage of alkaline mag­
and economically sustainable alternative to Nr removal and Haber- nesium and a high molar ratio of nitrogen to phosphorus in domestic
Bosch Nr synthesis is urgent. Nitrogen recovery from domestic waste­ wastewater [7,44].
water is nothing new [33], but a fundamental challenge in the years Nitrate [48] and N2O [49] are also potential forms of recovered ni­
ahead will re-envision the role of nitrogenous resources embedded trogen in addition to ammonium. Nitrate is the principal nitrogenous
within the circular economy [34]. The circular economy argues for a species in the effluent of WWTPs, and thus its recovery is crucial in
resource-product-renewable resource paradigm that strives to maximize meeting the stringent standards [50]. However, the proportion of ni­
resource recycling and to connect economic growth to finite resources. trogen recovery here is relatively low (about 30.0 %) [4]. Additionally,
Nitrogen has emerged as a particularly urgent case in the element- further testing is required for nitrate separation, operation stability, and
specific circular economies that convert water pollutants into valuable product acceptability in the market. As a sustainable energy source and a
products [32]. Globally, nitrogen in domestic wastewater can provide powerful oxidant in hybrid rocket motors in the aerospace industry
20.0–30.0 % of the ammonia currently produced by the Haber-Bosch [45,51], N2O is a product recovered by incomplete denitrification [52]
process [6]. The design of nitrogen recovery processes does not only in a coupled aerobic-anoxic nitrous decomposition operation [49].
rely on the techno-economic feasibility and the environmental benefits. However, its systematic complexity and strict operational conditions
Besides sharply increased requirements of nitrogen in some industries, would lead to instability in N2O production and obstruct its wide
such as agriculture, the decisive aspects also include production mass/ application in WWTPs [53].
volume, market value, product strengths, and purity [35,36]. In Microalgae can be cultivated through wastewater by absorbing

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Fig. 2. Different nitrogen up-concentration technologies for domestic wastewater. The advantages of wastewater pretreatment, the influential factors of nitrogen up-
concentration, and the product of recovery are summarized in this diagram.

ammonium to biosynthesize amino acids and proteins [13] and is but not least, microalgal biomass can absorb certain pollutants and
extensively utilized as feedstock in many industries [46,54–56]. heavy metals, and the recovered biomass must be further refined to
Microalgae-based processes (1.5–8.0 × 10− 3 kWh/m3) are energy- ensure consistent and safe quality [27]. Orienting nitrogen recovery
saving compared with CAS processes (0.5 kWh/m3), but are recom­ towards high-value products will promote the construction of waste­
mended as the secondary and tertiary wastewater treatment for their water resource recovery systems and improve nitrogen cycle load under
commendable organic removal but ineffective nutrients removal [55]. the social scale.
Moreover, the high HRT applied in microalgae-based processes is usu­
ally more than one week, which requires vast land occupancy [54]. Last

Table 2
Summary of Nitrogen Up-Concentration Technologies for Domestic Wastewater.
Process Material or technology Scale Ci UCF NRE Ce References
(mg/L) (%) (mg/L)

EAS concentration AM-AAO Full 27.2a – 14.9 8.0 [57]


Oxidation ditch Full 21.0a – 29.0 2.2 [58]
AAO Pilot 35.3a 3.0–8.1 – 14.2 [59]
Ion exchange and adsorption Resin Lab 16.5 8.5 37.5 – [33]
ZSM-5 Lab 38.4 – 90.0 3.5 [60]
Zeolite Pilot 26.7 20.0 93.7 1.2 [4]
Resin Lab 11.5 18.7 65.0 – [12]
Resin Lab 25.7 17.3–22.6 97.0 – [61]
33.4 5.6–11.0 96.5 –
Pressure-driven membrane RO Lab 40.0 3.8 95.0 0.5 [62]
RO Lab 32.5 3.8 97.0 0.8 [63]
RO Pilot 40.0 – 87.0 0.1 [64]
FO Lab 40.0 4.5–5.3 93.3 2.8 [65]
RO Lab 35.0 5.9 – – [66]
Electrodialysis ED Lab 100.0* 19.2 90.0 10.0 [48]
EDI Lab 15.0 12.0 90.0 – [67]
Capacitive deionization CDI Lab 18.2 – 49.8 6.7 [68]
CDI Lab 26.0 1.9 – – [69]
MCDI Lab 13.2 4.2 89.4 – [70]
FCDI Lab 20.0 20.0 81.9 2.6 [71]
FCDI Lab 42.5 3.5 62.5 10.5 [72]
FCDI Lab 43.0 6.1 – – [10]
Bio-electrochemical process MEC Lab 30.0 – 66.0 5.9 [73]
MEC Lab 50.0 2.4 36.5 16.0 [74]
MEC Lab 96.0 8.2 65.0 37.0 [75]
MEC Lab 84.0 5.8 26.3 – [76]
a
Note: 1) The “Ci” is calculated in NH+
4 -N except for the “*” for NO3-N and the “ ” for TN.

2) “AM-AAO” represents Anoxic Moving bed biofilm AAO reactor.

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3. Nitrogen up-concentration technologies in domestic 3.2. Ion exchange and adsorption


wastewater treatment
Ion exchange and adsorption refers to the separation of substances
Nitrogen up-concentration from domestic wastewater is crucial for through electrostatic attraction and other chemical bonds between ions,
effective and economic recovery. Nitrogen up-concentration technolo­ which is suitable for and effective in swapping NH+ 4 from domestic
gies in wastewater treatment can be categorized as excess activated wastewater [61]. NH+ 4 is exchanged with cations between wastewater
sludge (EAS) concentration, ion exchange and adsorption, pressure- and ion exchangers, and then concentrated in a small side-stream with
driven membrane, electrically-driven, and bio-electrochemical pro­ high UCF by suitable regeneration methods [33,93]. Based on a similar
cesses. The wastewater pretreatment method is usually required to theory, NO–3 can also be selectively enriched [94].
ensure effectiveness, stability, and economic viability of the up- Various ion exchangers, including natural zeolite and its modifica­
concentration technology. Besides, the methods for nitrogen recovery tion [60,95], resins, and other materials [96,97] were popularly
from the concentrate are divided into direct use, precipitation, crystal­ researched in domestic wastewater treatment. Lahav and Green [98]
lization, stripping, and extraction [27]. The compatibilities of different concentrated 40 mg/L NH+ 4 -N using zeolite, achieving a removal effi­
up-concentration technologies with recovery methods are illustrated in ciency of over 95.0 % and a UCF of 7.1 through sodium chloride
Fig. 2. regeneration. Malekian, et al. [95] enriched NH+ 4 -N on natural Iranian
By the up-concentration technology, nitrogen in the wastewater is zeolite and found that the nitrogen-loaded zeolite had potential as a
enriched into the concentrate (or regenerant for ion exchange). Some controlled release fertilizer because NH+ 4 release was nearly complete
technical parameters related should be defined first to exhibit the per­ within 200 min. Resin is inferior to zeolite for NH+ 4 exchange because it
formance of different technologies. The up-concentration factor (UCF) is prefers high-valence ions while zeolite has the opposite preference
defined as Eq. (1). [93,97]. The adsorption effect is also related to the reaction time and
temperature [14], and decreased temperature increases the spontaneous
UCF = Cu /Ci (1)
and exothermic process for NH+ 4 -N exchange [4]. The presence of metal
The nitrogen-enriched in the concentrate can be recovered as cations will compete with NH+ 4 for the available exchange sites and
nitrogenous products with nitrogen recovery efficiency (NRE) defined as lower its removal efficiency [33], which may need to increase the
Eq. (2). regeneration frequency [14], add pretreatment processes [12], or apply
chemical strategies [99] for mitigating inhibition.
NRE = mN /Qi Ci (2)
The regeneration of loaded ion exchangers usually obtained a
where mN is the mass of the up-concentrated nitrogenous product, g/ regenerant with 400–600 mg/L NH+ 4 , which is 8–20 times that of do­
d; Qi is the volume of the influent, m3/d. Table 2 summarizes the UCF, mestic wastewater (Table 2), making ammonia stripping and crystalli­
characteristics of influent and effluent, and NRE of various up- zation adaptable [4]. NH+ 4 -N in regenerant can be recovered with
concentration technologies. products varied depending on the used regenerant of salt, acids [100], or
lye [94]. If sulfuric acid is the regenerant, ammonium sulfate can be
3.1. Excess activated sludge concentration directly produced [100]; if magnesium or phosphorus is present, struvite
recycling is an ideal option [4]; if N, P, and K are rich, ammonium po­
In CAS processes, nitrogen in wastewater will partly be accumulated tassium phosphate fertilizer can be synthesized [94]. The result of life
by activated sludge apart from being removed [77]. The nitrogen con­ cycle assessments revealed that ion exchange with nitrogen recovery is
tent in sludge was 40.8–60.3 g/kg dry matter [78,79], and ammonium an efficient and environmentally benign technology for WWTPs because
assimilation could be enhanced by integrating organic adsorption unit it can reduce 25.0 % of energy demand, 66.0 % of global warming po­
with the anaerobic/anoxic/aerobic (AAO) process [80]. However, tential, and 62.0 % of marine eutrophication compared to CAS [101].
limited by the biological assimilation, the captured nitrogen in EAS is
usually not high (14.9–29.0 %, Table 2). Direct utilization of sludge or 3.3. Pressure-driven membrane processes
its digestive on land enables efficient utilization of nutrients for fertil­
ization and soil improvement [81]. However, land utilization of sludge Reverse osmosis (RO) and forward osmosis (FO) are typical pressure-
was not widely popularized due to the potential environmental damage, driven membrane technologies for nitrogen up-concentration from do­
the lack of social recognition, and the high transportation cost. mestic wastewater [62,65]. The membrane efficiency critically depends
Generally, the discharged EAS is transported to post-treatment, on permeability and selectivity [44], and the trapped nitrogen is stored
where anaerobic digestion (AD) is one of the commonly applied pro­ in the concentrate for recovery. Bilstad [102] proved that RO concen­
cesses for sludge stabilization [82]. During AD, nitrogen is significantly trate for coagulated domestic wastewater was rich in NH+ 4 -N and could
re-solubilized through protein hydrolysis and fermentation, resulting in be recovered as ammonium sulfate in a 10-month pilot test. Despite the
a high UCF reject water with the NH+ 4 -N concentration up to 1 g/L when potential for nutrient recovery, there are still many limitations in current
the digested sludge is dewatered [83]. Some pretreatment methods, pressure-driven membrane processes. The concentrations of Ca2+ and
including thermal hydrolysis [84] or freezing/thawing disintegration bicarbonate significantly affect the cost of RO since these parameters
[85], were applied to improve AD and synchronously increase NH+ 4 -N directly influence water hardness [103]. Feed solution pH resulted in
release from sludge. Unfortunately, NH+ 4 -N is also one of the inhibitory changes in salt rejection [104] because it was related to membrane
compounds in suppressing methanogenesis [86]. Therefore, these stra­ scaling and salt diffusion coefficients. Thus, acid is added together with
tegies were probably more suitable for post-treatment of digested sludge the coagulant to reduce the feed water pH, enhancing the coagulation
than pretreatment. Sludge reject water, accounting for 10.0–30.0 % of and preventing scaling formation [105]. In addition, the use of large
the nitrogen load to WWTPs [59,87], is generally recircled and mixed pore (>0.2 μm) membranes to reject multiple contaminants simulta­
with the influent for treatment, requiring a high energy consumption neously has become technically and economically feasible in recent
(~12.5 kWh/kg N) for its low readily biodegradable organic matters and decades [105].
C/N ratio [88,89]. Therefore, many efforts, including struvite precipi­ Currently, RO for domestic wastewater can concentrate pollutants
tation [90], stripping [91], bio-electrochemical system [83], and with a UCF of 2.0–7.0 [62], while FO obtained a similar nitrogen UCF of
3–
membrane distillation [92], were intensively studied for recovering ni­ 4.7–5.3 [65]. The rich NH+ 4 and PO4 in the concentrate are indispens­
trogen from reject water. able materials for struvite generation, and their simultaneous recovery
can be realized by adding accessible and low-cost magnesium precipi­
tant [64] (Fig. 2). A more common treatment method is to pass

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Fig. 3. Schematic representations of nitrogen up-concentration by (a) electrodialysis, (b) capacitive deionization, (c) microbial fuel cell and (d) microbial elec­
trolytic cell.

concentrate into the subsequent processes, such as ion exchange [33], of recovered products is improved [3,115].
ED [106], or microalgae adsorption [107], for further up-concentration. Concentration polarization and membrane fouling are the main
reasons for the degradation of ED performance for wastewater treat­
ment. Optimizing the process or changing the structure of ED is a
3.4. Electrically-driven processes feasible improvement [113,116]. van Linden, et al. [115] applied dy­
namic current density to allow ions to diffuse on the surface of IEMs, but
Nitrogen, which is usually in the cationic ammonium form in concentration polarization still contributed to the NH+ 4 current effi­
wastewater [108], is more easily transferred and up-concentrated under ciency decreasing from 69.0 % to 54.0 %. anti-scaling or chemical
the electric drive. Electrically-driven processes can mitigate membrane cleaning measures were usually employed to avoid membrane fouling;
fouling compared to pressure-driven membrane processes because the moreover, changing the structure of ED is also a better strategy with the
passive flow water, which is not filtered through the membranes, advantage of economical and uninterruptible operation [116]. Rodri­
elevated the tolerance of electrical processes to organic matters and gues, et al. [117] developed cell pairs with only bipolar membranes and
turbidities [109,110], and the representatives include electrodialysis cation exchange membranes for ammonium recovery, which could
(ED), capacitive deionization (CDI), and bio-electrochemical processes. reduce the use of anion exchange membranes and alleviate biological
fouling. An additional cell for Donnan dialysis introduced in ED could
3.4.1. Electrodialysis delay calcium carbonate precipitation and extend the operation time
In ED, the nitrogen up-concentration is achieved by voltage-driven without interruption for cleaning, resulting in a high NRE of 83.0 % from
transportation of charged NH+ 4 or NO3 through ion exchange mem­

high-strength wastewater (1.0 g/L) with 9.7 kWh/kg N energy input
branes (Fig. 3a) [48,111]. Nitrate can be concentrated with UCF of [116].
16–24 and NRE of about 80.0 % by ED [48]. The practice of ED in NH+ 4
up-concentration from domestic wastewater is hampered by the accu­ 3.4.2. Capacitive deionization
mulation of calcium and magnesium scale on the IEMs [24]. However, In a typical CDI cell (Fig. 3b), ions in the solution are adsorbed and
ED is widely applied in high-strength ammonium wastewater, such as immobilized in the porous electrode by charging, and then the captured
urine [112], digested swine manure [113], and reject water [114]. ED ions are desorbed from the electrodes and released into the concentrate
concentrates, due to their high concentration and purity, can be stripped by discharging [72,118]. The main advantage of CDI to ED is the robust
or evaporated to obtain desired nitrogenous products. For example, the performance and low energy consumption resulting from low cell volt­
dissolved NH3 concentrated in the cathode solution can be stripped and ages [119], which makes it more economical for the up-concentration of
absorbed by sulfuric acid to produce ammonium sulfate [112]. Bipolar nitrogen at low concentrations. However, the nitrogen removal effi­
membrane ED, producing H+ and OH− by dissociating water when an ciency of CDI is much lower than other electrically-driven processes
electric current is applied, does not require additional salts, so the purity

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(Table 2) because the CDI process does not have high selectivity for 4. Discussions
targeted ions [68]. The selectivity of IEMs can prevent co-ions adsorbing
onto the electrodes and prohibit the mobility of unwanted ions [120]. 4.1. Biological nitrogen up-concentration processes are ineffective
Then, membrane capacitive deionization (MCDI) was proposed by
introducing IEMs in front of the electrode [118] to enhance ions capture When talking about nitrogen recovery, its efficiency should be dis­
efficiency. MCDI could increase the nitrogen removal efficiency to 89.7 cussed together with nitrogen removal efficiency because the first and
% at a low NH+ 4 -N concentration of 13.2 mg/L with a UCF of 4.17 [70]. foremost role of WWTPs is to protect the environment and public health.
Nevertheless, CDI and MCDI face the problem of limited total adsorption Nitrogen could be captured and assimilated via activated sludge [80],
capacity of the fixed electrode, requiring regeneration once electrodes but most are still converted to N2 biologically. Increasing sludge yield
are saturated. Furthermore, their non-continuous operation requires from 0.23 to 0.33 g MLVSS/g COD promoted microbial anabolism with
complicated control design and leads to the loss of solution in the pro­ the nitrogen assimilation rate rising from 30.0 % to 38.0 % [80]. But
cess of charge/discharge conversion [108,121]. only 11.8 % of the nitrogen in sludge was ionized ammonium recover­
The introduction of flow-electrode capacitive deionization (FCDI) able by stripping [77]. In some carbon capture processes, organics were
overcomes the limitations because of its infinite adsorption capacity due separated for energy recovery by AD [17], where reject water rich in
to the continuous electrode regeneration [108]. Zhang, et al. [72] firstly NH+ 4 -N through ammonification can be obtained [130]. Owing to most
applied FCDI for nitrogen recovery because NH+ 4 was efficiently of the nitrogenous pollutants in wastewater being soluble [38], the
enriched by electro-adsorption and then recovered by concomitant pH harvested nitrogen by carbon capture or biological assimilation is
increase. The selectivity for NH+ 4 toward other cations reached 11.4 in negligible, and a substantial fraction of nitrogen is still lost. Thus, for
this system [121]. By inserting a gas-permeable membrane into an FCDI raising NRE, the treatment processes of WWTPs require redesign. Given
unit, the NRE reached 62.5 % for synthetic domestic wastewater [122]. that the nitrogen conversion based on activated sludge is more mature
Fang, et al. [71] also confirmed that FCDI could be employed to pre- and effective, the coupling of abiotic nitrogen capture and biotic tar­
concentrate NH+ 4 from domestic wastewater with a UCF up to 20 geted conversion is a prospective orientation deserving further research.
(Table 2). The energy consumption of FCDI for ammonium recovery Microalgae is an economically sustainable and environmentally
from domestic wastewaters is 25.4 kWh/kg N, which is comparable to friendly eco-technology for its bioeconomy in nutrients recovery and
other electrically-driven systems [122]. To obtain better NRE and lower CO2 capture [55]; however, it is hard to meet discharge standards for
energy consumption, suitable electrode materials with good electrical current WWTPs [131]. Meanwhile, microalgae growth is inhibited by
conductivity and desorption capacity should be developed [108]. For high organic loading [55] or low temperature, which also decreases the
commercialized applications, FCDI should be implemented on a larger selectivity of microalgae to nitrate [13]. The major limitations of
scale to assess their durability and cost-effectiveness for nitrogen microalgae technology remain the land requirement and its availability
recovery. [54]. The intensification of urban land use is a common global trend
[132], and microalgae are advantageous for treating wastewater in rural
3.4.3. Bio-electrochemical processes areas with low population density, which can provide plenty of cheap
Bio-electrochemical processes, including microbial fuel cell (MFC) lands for large-scale cultivation [133]. Extracting nitrogen in the bio-oil
and microbial electrolytic cell (MEC), use the catalysis of microorgan­ to produce protein or amino acid concentrate has a good development
isms attached to an anode and/or a cathode to promote NH+ 4 migration prospect [46,56,134].
under the current (Fig. 3c and 3d) [13,123,124]. MFC is a galvanic cell
system usually applied in nitrogen removal rather than recovery because 4.2. Suitable pretreatment and post-treatment processes for nitrogen up-
of its low UCF. Kuntke, et al. [125] showed that 31.0 % of NH+ 4 in urine concentration
could be recovered at the highest current density. MEC applies the
electrochemical active biofilm to achieve simultaneous and effective Important challenges in using nitrogen up-concentration strategies
recovery of ammonium and energy [126]. As the accumulation of NH+ 4 are nontarget adsorption and biofouling, and the pretreatment tech­
in the cathode is up to 10 times that of the anode [127], MEC can pro­ nologies shown in Fig. 2, such as high rate activated sludge (HRAS),
vide higher UCF than MFC [75,93]. Because of the low strength, the chemically enhanced primary treatment (CEPT), and membrane-based
nitrogen in the concentrate of MEC should be further up-concentrated by pretreatment processes, are required for the removal of colloids and
other technologies firstly, and then recovered as ammonium bicarbonate suspended solids [4]. Low aeration requirement and short HRT to sub­
[42] or ammonium sulfate [128] by evaporation due to its excellent stantially remove organic matters through adsorption rather than
purity. mineralization is the vital feature of HRAS systems, which usually pro­
Except for current density, there are many factors affecting MEC duces an organically rich EAS for AD and preserves ammonium [17].
performance, including applied voltage, pH in cathode electrolyte, dis­ Qiang, et al. [135] placed ammonium ion exchange posterior to an
solved oxygen, and activity of electroactive bacteria. With the increase HRAS process, achieving stable and efficient nitrogen capture from
of applied voltage, NRE of NH+ 4 increases from 21.4 % to 29.0 % for domestic wastewater. CEPT is an efficient and sustainable technology to
domestic wastewater [73]. Sotres, et al. [129] found that under addi­ enrich non-soluble fractions and phosphorus into sludge with reduced
tional voltage and sodium chloride, 94.3 % of the nitrogen in pig slurry CO2 emissions [17,33]. Wang, et al. [136] proposed an emerging
could be concentrated by MEC. The increase of pH in the cathode wastewater treatment system by using CEPT as the pretreatment to
electrolyte promotes the conversion of NH+ 4 to NH3, improving the maintain the stability of the downstream nitrogen up-concentration
mobility of NH+ 4 [127]. In gas recovery systems, pH can be adjusted to unit. Membrane-based pretreatment can be divided into direct mem­
12.0 and 6.7 for NH3 and N2, respectively [123]. In addition, slightly brane filtration (microfiltration or ultrafiltration) and anaerobic mem­
higher dissolved oxygen (1–2 mg/L) could be reduced in the cathode brane bioreactors (MBR), which are recommended to recover organic
and result in an unstable biological anode potential, which greatly matters from domestic wastewater [62,137]. The membrane-based
hindered and even destroyed the performance of MEC [128]. The elec­ pretreatment can efficiently separate organic matters from domestic
troactive bacteria and their metabolic characteristics are revealed to be wastewater, ensuring good permeate quality for further treatment by
critical factors determining the conversion of oxidized nitrogen into nitrogen up-concentration [33]. Lim, et al. [8] used an anaerobic MBR
NH+ 4 , and the occurrence of the transformation is linked to the low and a coagulation-sedimentation unit as the pretreatment of ammonium
cathodic coulombic efficiency [127]. ion exchange, achieving holistic wastewater treatment and resources
recovery. The sludge separated by CEPT or direct membrane filtration
was further treated by AD to produce biogas containing methane [17].

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Y. Qin et al. Chemical Engineering Journal 451 (2023) 138789

25 100 4.3. Is a multi-stage strategy effective for high-factor nitrogen up-


UCF NRE concentration?

20 80 For nitrogen up-concentration from domestic wastewater, three as­


pects need to be considered, namely, low effluent concentration to
achieve stringent discharge and elevate the economy of nitrogen re­

NRE (%)
15 60 covery, high UCF to ensure the applicability of nitrogen recovery tech­
UCF

nologies, and robust performance to adapt to complex wastewater


characteristics. As shown in Table 2, ion exchange and pressure-driven
10 40 membrane processes achieved good effluent quality with nitrogen
level below 5 mg/L, while electrically-driven processes usually obtained
effluent nitrogen level above 6 mg/L. The UCF and NRE of these tech­
5 20 nologies are summarized in Fig. 4. For the ion exchange and adsorption
process, the UCF has a large and unstable span, depending upon various
factors, including regenerant volume, nitrogen release performance of
EAS IEA RO ED CDI MEC
the materials, and the applied regeneration strategy. The ion exchange
Fig. 4. The range of UCF and NRE of different nitrogen up-concentration used zeolites and pressure-driven membrane processes both kept the
technologies (IEA: ion exchange and adsorption). NRE steadily more than 90.0 %. In contrast, for the electrically-driven
processes, only ED and the advanced CDI obtained NRE above 80.0 %.
At the same time, anaerobic pretreatment for domestic wastewater Unfortunately, the direct up-concentration of nitrogen from domestic
could capture more than 90.0 % of organics [9], rendering a promising wastewater is hard to satisfy the nitrogen concentration needed for re­
vision toward carbon neutrality in WWTPs. Future investigations should covery [14].
be conducted to explore the performance change of ammonium sepa­ Theoretically, multi-stage nitrogen up-concentration processes are
ration and up-concentration system for pretreated wastewater during expected to overcome the defects of different technologies. Fig. 4 visu­
long-term operation and to clarify the interaction mechanism between ally provides the basis for the assumption of multi-stage processes,
wastewater components and ammonium separation materials. Appro­ which will be integrated into two or more units to improve nitrogen up-
priate fouling control strategies, such as microfiltration to remove fine concentration performance limited by the characteristics of domestic
particles, ultrafiltration to control organic fouling, and softening to wastewater. A possible treatment is to use ion exchange, RO or FCDI
prevent scaling [62,97], should be advanced to propel the application of firstly, and then convey the ammonium-rich concentrate into subse­
ammonium separation and up-concentration technology for actual quent units such as ED [106] for further up-concentration. The strategy
wastewater treatment. of multi-stage up-concentration will enable first-stage technology to
The post-treatment for nitrogen up-concentration should be consid­ achieve stringent discharge standards and high NRE, and overcome the
ered to satisfy relevant discharge standards. CEPT coupled ammonium drawback of low conductivity in domestic wastewater [143]. The
ion exchange could remove particulate, phosphorus, and nitrogenous second-stage technology should have good UCF and low energy con­
pollutants effectively; however, the soluble COD must be removed by sumption to elevate nitrogen concentration further. For ammonium-rich
biological units, such as biological aerated filter [136] or MBR [138]. As wastewater with high conductivity, ED can theoretically concentrate
for HRAS and membrane-based pretreatment [139], phosphorus could NH+ 4 -N to about 56000 mg/L [24]. However, the technically feasible
be captured via coagulation-sedimentation or ion exchange before or multi-stage up-concentration process is not economically viable because
after nitrogen up-concentration units [8,140]. Ion exchange can achieve NH+ 4 in the first-stage concentrate usually coexisted with impurities (for
the selective nitrogen up-concentration, making a concentrate with RO) or high salinity (for ion exchange), which dissipates massive energy
relatively homogeneous ions [135]; however, the concentrate compo­ for their up-concentration or removal. Therefore, energy should be a
sitions generated from pressure-driven and electrically-driven processes focus for nitrogen up-concentration from wastewater beyond nitrogen
are more complex [141,142]. Especially, the RO concentrate contains itself.
high concentrations of nutrients, heavy metals, and harmful organic
compounds, and such technologies as advanced oxidation and biological
processes should be applied after nitrogen recovery to allow its 4.4. Cost-benefit analysis for nitrogen up-concentration and recovery
discharge into the water bodies [141].
The conventional social cycle of nitrogen via ammonia synthesis and
wastewater nitrogen removal by nitrification - denitrification is
employed as a reference standard to estimate the economic feasibility of
nitrogen up-concentration and recovery. The global average energy
requirement for the Haber-Bosch process is 10.3 kWh/kg N [27], and the

Table 3
Energy Consumption and Product value for Ammonia Synthesis (Including Wastewater Nitrogen Removal) and Proposed Nitrogen Recovery from Wastewater.
Process Product Energy consumption Product value Net profit References
(kWh/kg N) (kWh/kg N) (kWh/kg N)

Ammonia synthesis + Nitrification - denitrification NH3 22.5 13.1 − 9.4 [14,18,27]


nitrogen removal Sharon - anammox NH3 11.7 13.1 +1.4

Nitrogen recovery from IE - ED - Stripping - MVR - (NH4)2SO4 44.1 13.8 − 30.3 [4,18,112,145,147,150]
wastewater Crystallization
IE - Nitrification - ED - MVR - NaNO3 22.5 37.7 +15.2
Crystallization

Note: 1. IE - ion exchange; MVR - mechanical vapor recompression.


2. The detailed calculation procedure of energy consumption refers to Text S2 and Table S2.
3. The product values of NH3, (NH4)2SO4 and NaNO3 were obtained from the https://www.made-in-china.com/, and converted into the unit “kWh/kg N”.

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Y. Qin et al. Chemical Engineering Journal 451 (2023) 138789

Fig. 5. A process layout for full resources recovery in domestic WWTPs.

development of sustainable alternatives is expected to decrease the re­ ammonium product. Thus, an ion exchange - side-stream nitrification -
quirements to 9.1 kWh/kg N [144]. For nitrogen removal from domestic ED process can be designed to recover nitrogen from wastewater as
wastewater, the average power requirement for the conventional nitri­ sodium nitrate, with energy consumption comparable to the reference
fication - denitrification process is typically 5.6 kWh/kg N [18]. Equally standard considering the electricity and sodium carbonate (as alkalinity)
important, organic carbon consumed in denitrification is equivalent to requirement for nitrification (Table S2). Considering the price variance
11.0 kWh/kg N, and the dissipative energy is about 6.6 kWh/kg N between sodium nitrate and ammonia, the proposed process is profitable
considering the realistic energy recovery from organic carbon of 59 % in (+15.2 kWh/kg N) with solid sodium nitrate as the final product. During
the form of biomethane [14]. Therefore, the sum of energy requirements long-term operation, membrane fouling of ED may increase energy
for the Haber-Bosch process and dissipative energy for nitrification - consumption to 1.6–2.8 times [148]. Considering this additional energy
denitrification is 22.5 kWh/kg N, and the conventional social cycle is not consumption, the profit of the proposed process decreased to +
cost-effective (-9.4 kWh/kg N) considering the product value of NH3 (13.2–14.5) kWh/kg N, still much higher than the Haber-Bosch process.
(Table 3). Wastewater nitrogen removal via Sharon - anammox is ex­ In addition, the solid recovered product is convenient to transport;
pected to turn a profit (+1.4 kWh/kg N), but its adaptation and stability therefore, the transportation energy accounts for a small portion of the
in domestic wastewater require further study. total energy consumption because half of the recoverable nitrogen is co-
Recovering nitrogen from wastewater consumes energy and chem­ located with cropland-dominant areas globally [149]. Therefore,
icals for up-concentration and harvest from concentrate to produce coupling nitrogen targeted conversion with up-concentration is a
nitrogenous products, the benefits of which should be considered in the promising strategy for energy-efficient nitrogen recovery from waste­
cost-benefit analysis. Taking the proposed two-stage process above as an water, and has the potential to put forward the transition of wastewater
example, first-stage up-concentration by ion exchange can concentrate systems from pollutants removal to resource recovery.
NH+ 4 -N to ~600 mg/L (regenerate by NaCl of 20 g/L), and second-stage
up-concentration by ED achieves a concentration of ~1300 mg/L, 5. Conclusions and future perspectives
requiring energy of 3.8 and 30.6 kWh/kg N, respectively (Table S2)
[4,145]. If NH+ 4 in the concentrate from ED is recovered as ammonium Nowadays, the traditional WWTPs are turning to wastewater
sulfate by air stripping, the total energy consumption is more than twice resource recovery facilities, which will awake the revolution of the
the reference standard (Table 3), suggesting that direct up-concentration whole wastewater treatment industry. Nitrogen recovery is essential for
and recovery of nitrogen is infeasible (− 30.3 kWh/kg N) compared to lessening nitrogenous pollutants discharge, reducing energy consump­
conventional social cycle. It is because most of the energy consumed by tion in nitrogen removal and Nr synthesis, and providing various
ED is dissipated since the concentration of Na+ in the feed solution is products for industrial or agricultural applications. However, nitrogen
much higher than that of NH+ 4 . Besides, the homocharge of Na and NH4
+ +
recovery methods successfully applied in high-strength wastewater
impeded the sustained regeneration of ion exchangers. faced many challenges when directly applied to domestic wastewater. In
Converting NH+ 4 in the first-stage concentrate to free state (NH3), this study, we have highlighted the nitrogen up-concentration technol­
gaseous form (N2O or even N2), or negative charge (NO–3 or NO–2) is a ogies in domestic wastewater, which bridged the gap between removal
problem-solving strategy, and it is also hopeful of achieving cyclic up- and recovery. For these approaches to become attractive and viable al­
concentration via coupling regeneration with nitrogen conversion. An, ternatives, a crucial factor will be the development and coupling of
et al. [146] reported that coupling ion exchange with side-stream pretreatment and post-treatment technologies to construct more robust
nitrification, Na+ below 10 g/L had less significant adverse effects on and reliable processes than current practice or other emerging biotic
the ammonium conversion efficiency, and De Paepe, et al. [147] ob­ nitrogen removal technologies. Although the technologies for nitrogen
tained a concentrate with NO–3-N accumulation of 1477 mg/L from a 40 up-concentration have improved in recent years, future endeavors are
% urine solution. Recovering nitrogen as nitrate is probably more highly desired in the following aspects.
profitable because of its high economic value compared to ammonia or

9
Y. Qin et al. Chemical Engineering Journal 451 (2023) 138789

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