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Adsorbent materials for ammonium and ammonia removal: A review

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F
OO
Review

Adsorbent materials for ammonium and ammonia removal: A review

Bing Han, Clayton Butterly, Wei Zhang, Ji-zheng He, Deli Chen ∗

PR
Faculty of Veterinary and Agricultural Sciences, The University of Melbourne, Parkville, VIC, 3010, Australia

ARTICLE INFO ABSTRACT

Article history: Ammonium (NH4+) and ammonia (NH3) are notorious hard-to-treat pollutants, leading to serious deterioration
Received 3 July 2020 of aquatic ecosystems and significant risks to human health. While adsorption is a promising method to tackle
Received in revised form 14 September 2020 this problem, finding suitable adsorbent materials which are abundant, low-cost and efficient remains a constant
Accepted 9 October 2020 challenge. Thus, this review summarizes recent development of important adsorbent materials implemented for

D
Available online xxx
NH3/NH4+ removal. Advantages and disadvantages of representative adsorbent materials including bentonite,
Handling editor: Prof. Jiri Jaromir Klemeš
zeolite, clay, biochar, activated carbon, metal organic framework and their modified forms are compared, and the
nature of their adsorption processes are discussed in context of adsorption sites, isotherm models (e.g. Langmuir
Keywords and Freundlich), kinetic equations (e.g. pseudo-first order, pseudo-second order and intra-particle diffusion) and
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Ammonium thermodynamic analysis. Future perspective on the utilization of inexpensive lignite is also conferred. Although
Ammonia both conventional and nanostructured materials face challenges regarding economic cost, energy consumption,
Adsorption secondary pollution and adsorption efficiency, these can be tackled by adopting various of advanced options.
Modification Current research on adsorption mechanisms forms a solid basis for the design and development of novel adsor-
Mechanism
bent materials. We speculate that the pursuit of strategies for effective surface modification of natural abundant
Kinetics
resources will lead to a bright future of removal processes suited to low NH3/NH4+ concentration conditions.
EC

© 2020

1. Introduction the atmospheric environment (Megaritis et al., 2013; Stokstad,

2014).
Over the past century, improper disposal of industrial and agricul- It has been estimated that >200 Mt of NH3/NH4+ is being gen-
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tural waste has led to significant social, economic and environmental
problems (Ravishankara et al., 2009; Stokstad, 2014). Ammonium
(NH4+) is the most frequently encountered nitrogenous (N) compound
in wastewaters. The elevated levels of N nutrients in water sources
could lead to various issues such as toxic algal blooms, fish kills and
poor drinking water quality via eutrophication (Adam et al., 2019a;
CO
erated across the world on an annual basis (DeCoste et al., 2016;
Khabzina and Farrusseng, 2018). Major anthropogenic sources in-
clude N fertilizer synthesis, intensive animal feedlots, chemical fiber
plants, agricultural wastewater, aquaculture industry and others (Busca
and Pistarino, 2003; Hao and Yan, 2016; Maia et al., 2012).
For example, intensive animal feedlots are large hotspots of NH3 emis-

Blazquez et al., 2017; Huang et al., 2018). In particular, it is toxic
to some fish even at a low level of 3 ppm (Boopathy et al., 2013); Ni-
trate (NO3−) and nitrite (NO2−) derived from NH4+ are involved in hu-
man diseases such as methemoglobinemia. This poses a significant risk
to aquatic ecosystems as well as human health. On the other hand, a
large proportion of NH4+ in aqueous streams is lost via NH3 volatiliza-
tion. As a relatively strong base and corrosive pollutant, NH3 gas could
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sions where ~60% of the N consumed in feedlot rations is wasted
as NH3 via volatilization (Chen et al., 2015). Such a loss not only
bears an environmental consequence, but also is a huge waste of an
economical resource. With a typical energy consumption of 12.1 kWh
kg−1 NH3–N (Cruz et al., 2019), industrial Haber-Bosch process of
NH3 production costs about 2% world's energy production and cause
1% CO2 annual emission (Service, 2018). Domestic wastewater an-

cause undesired odors and lead to severe burning of eyes, skin, and res-
piratory systems at a concentration as low as 50–100 ppm (Katz et al.,
2016; Katz and Leznoff, 2009; Vikrant et al., 2017). It can also
react with other air pollutants such as SOx or NOx to form ammonium
salt, contributing to fine particulate matter (PM2.5) concentration in
∗
Corresponding author.
E-mail address: delichen@unimelb.edu.au (D. Chen)
nually comprises ~20 Mt of NH3/NH4+, which is equivalent to ~19%
of the annual industrial NH3 production, and the amount is projected
to further increase to 35 Mt annually by the middle of the 21st cen-
tury (Bodirsky et al., 2014; Cruz et al., 2019). Therefore, regula-
tory agencies in many jurisdictions require the removal of NH3/NH4+
from emission hotspots before discharging to environment. According
to American Conference Governmental Industrial Hygienists (ACGIH),
only NH3 concentration < 25 ppm for time-weighted (8-h work day)
and <35 ppm for short-term (15 min) values are permitted (NIOSH,
1994; Wang et al., 2017). The National Emission Ceilings

https://doi.org/10.1016/j.jclepro.2020.124611
0959-6526/© 2020.
2 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611

Directive 2016/2284/EU have required European Union (EU) countries
to decrease the NH3 emissions, in order to reduce PM2.5 concentra-
tions (Giannakis et al., 2019). In addition, the European Environment
Agency (EEA) has urged researchers to explore novel approaches for
NH3 removal (Karri et al., 2018).
To alleviate the negative impact of N pollution, various kinds of
both advantages and environmental and technological limitations. A
quantitative comparison of NH3/NH4+ removal between several es-
tablished and emerging approaches from wastewater technologies are
briefly summarized in Table 1. Among these approaches, while bio-
logical processes are very important for wastewater treatment (Ardern
and Lockett, 1914), the transformation of NH4+ into its elemental N2

F
techniques were studied, and several excellent review articles are avail- is incompatible with 21st century's goal to develop a circular economy
able (Adam et al., 2019a; Cruz et al., 2019; Gupta et al., 2015; (Cruz et al., 2019; Guest et al., 2009; Verstraete et al., 2009).
Karri et al., 2018). The current routes for NH3/NH4+ removal have Other approaches include air stripping, oxidation, precipitation, photo

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Table 1
Summary of several established and emerging approaches for removal of NH3/NH4 + from wastewater.

Outlet
concentration Removal
Technology Working conditions Advantage Challenges (mg/L NH4–N) efficiency Ref.

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Adsorption • Wide ranges of temperature and • Easy operation • Different adsorbents have different 1 43–100% This work
pH • Effectively remove removal efficiencies in Table
NH4 + 2
• Able to work in
low NH4 + concen-
trations
Air stripping • pH range: 10.8–11.5 • Widely used • High chemical demands 500–1000 50–99% Adam et
• High NH4 + concentration process for waste- • Hindered by low temperature al.

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• >15 °C water pre-treat- • Time consuming (2019)
ment Taşdemir
• High energy consuming
• Simple equipment et al.
• Scaling and fouling
• Not sensitive to (2020)
toxic substances Yin et al.
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(2018)
Zhu et
al.
(2017)
Reverse • Liquid-liquid membrane is • Low field and • Produces dilute concentrate stream, 1 60–99% Liu et al.
osmosis (RO) needed space only concentrating max 1 order of (2007)
• Easy and continu- magnitude. Talalaj
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ous operation, • Membrane fouling (2015)

• simplicity • Clean the membrane regularly Guo and
Jin
(2014)
Struvite • Require certain pH and tempera- • A valuable slow-re- • Needs phosphate to proceed 29–100 20–99% Karri et
precipitation ture lease fertilizer • Many competitors for phosphate al.
• Medium cost (calcium, magnesium phosphates) (2018)
Hakimi
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• Introduce new pollutants

et al.
(2020)
Zhao et
al.
(2019)
Peng et
al.
(2017)
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Biological • Growth of heterotrophic or pho- • Free of chemical • Produces biomass, not NH4 + – not <5 70–99.9% Adam et
treatment tosynthetic (or phototrophic) al- reagents readily useable. al.
gae or bacteria • No need for com- • Only operates at low input/output (2019)
• Sensitive to temperature plicated configura- concentrations Lin et al.
tion • Long start-up time (2020)
Moondra
et al.
(2020)
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Miao et
al.
(2020)
Photocatalysis • In both liquid and gas phase • Solar energy is free • Efficient photocatalysts are still un- 35–100% Yao et
• No secondary pol- der development al.
lution • Efficiency depends on light source (2020)
Vikrant
et al.
(2020)
Bahmani
et al.
(2020)
Ren et
al.
(2020)
 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
catalysis and chemical coagulation (Dong et al., 2019a; Gupta et
al., 2015; Kinidi et al., 2018; Ma et al., 2020; Rada-Ariza et al.,
2017; Tao et al., 2020; Ye et al., 2018)Ma et al., 2020. These
processes, however, required complicated configuration, high NH4+ lev-
els (>2 g L−1 NH4–N) and pose difficulties for maintenance (Boopa-
thy et al., 2013; Cruz et al., 2019). Adsorption to solid media has
many favourable characteristics including a high removal efficiency,
ease of operation and low energy consumption. It is suitable especially
for dilute NH4+ concentration in domestic wastewater (40–60 mg L−1
NH4–N) (Cruz et al., 2019; Henze et al., 2008), landfill leachate
(100–1000 mg L−1 NH4–N) (Karadag et al., 2008), rainfall runoff
(20–49 mg L−1 NH4–N) (Wang et al., 2016), municipal secondary ef-
fluent (~50 mg L−1 NH4–N) (Zhang et al., 2016) and fish pond water
(~10 mg L−1 NH4–N) (Soetardji et al., 2015). These significant advan-
tages make it a promising method to be applied on a commercial scale.
Nevertheless, the success of the technique greatly relies on finding suit-
able adsorbent materials. So far, the representative adsorbent materials
widely used in NH3/NH4+ removal in both lab- and pilot-scale studies
include bentonite, zeolite, clay, biochar, activated carbon, metal organic
frameworks (MOFs) and other nanostructured materials, which will be
discussed below.
Recent review articles about NH4+ adsorption have emphasised the
importance of operation parameters like adsorbent material dosage, pH,
contact time and coexisting ions (Wang and Peng, 2010). Huang
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et al. (2018) compared a range of cost-effective adsorbent materials
in context of cost, efficiency and preparation. However, very little at-
tention has been paid to mechanistic/kinetic pathways and thermody-
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namic insights. Furthermore, despite intensive efforts to enhance NH4+
removal by surface modifications, comprehensive reviews on this are
scarce. Therefore, the goal of the present review is to summarize our
current understanding of representative adsorbent materials as well as
their modified forms for the removal of NH4+ (aqueous) and NH3 (in
the gas phase), by using published studies mainly in last 3 years as ex-
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amples. Specifically, this review will (i) compare different classes of ad-
sorbent materials, (ii) illustrate the promising modification approaches,
and (iii) discuss the adsorption mechanisms, kinetics and thermodynam-
ics involved.
2. Methods
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The methods applied in this literature review included identification
of the relevant studies and preparing set of questions to be addressed
to selected literature relevant to the scope of this review. Identifica-
tion of relevant literature was performed by searching in Science Di-
rect, Scopus and Google Scholar databases using following keywords:
“ammonia”, “ammonium”, “removal”, “adsorption”. After that the gen-
CO
erated literature list was checked manually (reading materials and meth-
ods and results) in order to exclude studies, in which (i) adsorbent ma-
terials were not used; (ii) removal efficiency of NH3/NH4+ before and
after adsorption was not conducted. Moreover, literature reviews were
not considered. It should be noted that mainly relevant articles pub
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Fig. 1. The advantages and disadvantages of conventional and nanostructured adsorbent materials.
3
lished during the period 2016–2020 were included to this review. More-
over, relevant studies found during screening other studies were in-
cluded to the list during literature identification. The literature search
was limited to articles published in peer-reviewed journals in English
language. Reports published in other languages as well as books were
excluded from the literature search.
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Prepared list of scientific articles was critically analysed through ex-
tracting relevant information using the list of questions shown below:
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• Which type of adsorbent material was used?
• Was the regeneration of NH3/NH4+ materials studied?
• Which type of modification approach was used?
• Was the recycling or reuse of the adsorbent materials studied?
• Which type of wastewater was used?
• What was the scale of performed experiments?
• Was the modification approach realistic, applicable in real world
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cases?
• Were the adsorption efficiencies of adsorbent materials compared?
• Was the concentration of NH4+ in the solution identified?
• Were the mechanisms underlying adsorption process addressed?
3. Adsorbent materials
Due to the impact of NH3/NH4+ emission, numerous adsorbent ma-
terials have been studied. Those materials were roughly categorized
into conventional (e.g. clay, carbonaceous materials) and nanostruc-
tured (e.g. MOFs) materials based on their structures and properties.
Both have advantages and disadvantages (Fig. 1). Bentonite, zeolite,
other clay materials and biochar were mainly used for NH4+ removal
from aqueous phase, whereas activated carbon and MOFs were mainly
employed for NH3 removal from gas phase. Generally, conventional ma-
terials are relatively abundant and low-cost, but their binding affinities
with NH3/NH4+ are usually weak. On the other hand, nanostructured
materials could show high adsorption capacity and rapid adsorption ki-
netics in many cases. However, most of those materials were only pre-
pared from laboratory with tedious preparation procedures using expen-
sive precursors. Hence the yield is low and material properties vary a
lot. In this sense, modifying conventional materials to enhance their in-
teraction with NH3/NH4+ is a promising approach for real world ap-
plication. The modification methods can be roughly divided into phys-
ical modification including sonication, calcination (to increase surface
area) and pelletization (to avoid pressure drop), and chemical modifica-
tion (e.g. acid/base treatment, oxidation and coating) to promote bind-
ing affinity (Fig. 2). Following the order of cost of adsorbent materi-
als, here we firstly discuss natural abundant bentonite, zeolite and other
clay materials both in their natural and modified form, and then move
to biochar and activated carbon which need manufacturing but are po-
tentially low-cost. In the end, we briefly summarize novel materials that
are still under laboratory testing including MOFs and other nanostruc-
tured materials.
4 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
Fig. 2. Common modification methods to enhance NH3/NH4+ removal.
3.1. Bentonite
Bentonite is frequently utilized as an adsorbent material because of
its cost-effectiveness and availability throughout the world. It is an alu-
minosilicate material composed of one layer of aluminum oxygen octa-
hedron and two layers of silicon oxygen tetrahedron inclusions clamped
together in a ratio of 1:2 (Cheng et al., 2019). Strong NH4+ adsorp-
tion capacity of bentonite originated from the high negative charge on
surface, and high cation exchange capacity (CEC), which is generally
40–130 cmol kg−1. In 2017, Angar et al. (2017) found that raw ben-
tonite exhibited an NH4+ adsorption capacity of 19.01 mg g−1 corre-
sponding to a removal efficiency of 53.4% (pH = 7, 30 °C) and this per-
centage could be improved to 81.2% by increasing adsorbent material
dosage to 40 g L−1.
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Organic and metal oxide materials have been combined with ben-
tonite by mixing in solution and heating at elevated temperature, in or-
der to enhance adsorption performance of NH4+. On one hand, coat-
ing bentonite with functional materials can increase the number of ac-
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tive sites for chemical adsorption. As a result, the hybrid samples usu-
ally show superior adsorption capacity. On the other hand, bentonite
can act as a binder to create composites in a pelletized form with con-
trolled particle size, and thus be suitable for dynamic conditions in
comparison with powder adsorbent materials considering pressure drop
(Seredych et al., 2016). In 2015, Seredych et al. (2016) reported
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that on phenolic-formaldehyde resin/bentonite the adsorption capacity
of NH3 reached 38.0 mg g−1 and 12.4 mg g−1 in dry and moist condi-
tions, respectively. Yadi et al. (2016) found that a bentonite/chitosan
composite shows a maximum NH4+ adsorption capacity of 11.6 mg g−1,
whereas natural bentonite showed NH4+ adsorption capacities of only
0.75 mg g−1, respectively. Recently, Cheng et al. (2019) first modi-
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fied bentonite with aluminum via cross-linking reaction and then adding
concentrated tannic acid to further enhance its functional capacity. The
product showed a high removal rate of >70% while that of natural ben-
tonite is only ~30%.
3.2. Zeolite
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Up to 4 Mt of natural zeolites are mined every year across the
world. Different from bentonite which has 2D layered structure, zeo-
lites composed Al3+ and Si4+ form tetrahedral with O bridge to form
3D porous framework with negatively charged lattice. These negative
charges, balanced by exchangeable cations, make zeolite one of the most
common ion-exchangers and have been widely applied to NH4+ ad-
sorption since 1970's (Liu et al., 2018). However, the removal effi-
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ciency depends on the physiochemical properties of zeolite. In 2017,
Martins et al. (2017) first evaluated NH4+ adsorption capacity of
natural zeolite, which was 10.8 mg g−1 and then biological regenera-
tion was carried out with nitrifying bacteria suspension. It was found
that the adsorption capacity decreased by only 4.55% after regenera-
tion. Zeolites can also be produced synthetically. Compared with nat-
ural zeolite, synthetic zeolites possess favourable properties towards
adsorption like uniform porosity and high surface area. In 2018, Liu
et al. (2018) synthesized zeolite from fluidized bed fly ash, which
showed a maximum NH4+ adsorption capacity of 22.9 mg g−1 in
40 min at pH of 6, which is 2 times greater than the that of nat-
ural zeolite reported by Martins et al. (2017). Based on the review
by Wang and Peng, 2010, NH4+ adsorption on natural zeolite is
2.7–30.6 mg g−1.
Modification to zeolite was done to enhance NH4+ adsorption by i)
acid/base treatment, ii) physical modification through increasing sur-
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face areas, iii) incorporation of functional coatings that decreases con-
centrations of competing adsorbates and strengthen binding affinity of
NH4+, and iv) embedding zeolite particles in a framework to reduce dif-
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fusion resistance. Generally acid treatment of zeolite decreased removal
efficiency of NH4+, while base treatment improves it by e.g. convert-
ing zeolite's exchange sites to the Na form, where NH4+ has high affin-
ity over Na+ (Wang and Peng, 2010). Physical modification by ultra-
sound with a power density of ~5 W cm2 was employed by Zielinski
et al., 2016 who increased NH4+ removal rate by ca. 30%. Zhang et
al. (2016) showed that coating Na-modified zeolite with an anion ex-
change resin improved NH4+ removal efficiency from 78% to 95%, due
PR
to the resin's ability to reduce dissolved organic matter in effluent. In
2015, Kang et al. (2015) showed that coating of hydrophilic zeolite
with microporous organic polymer materials improves NH3 adsorption
capacity from 1.8 to 5.6 mg g−1 under 43% relative humidity. Putra
and Lee, 2020 proved that the entrapment of zeolite particles in porous
hydrogels had a high NH4+ adsorption capacity of 28.17 mg g−1, which
was 4.3 times higher than those of zeolite beads. Additional benefits of
this strategy include minimal agglomeration and good settle ability. Pu-
tra and Lee, 2020 also summarized the maximum NH4+ adsorption
capacities of both natural and synthesized zeolite-type adsorbent mate-
rials as a function of particle sizes in the literatures, which are presented
in Fig. 3. Nevertheless, although zeolite is a low-cost material, some
modification processes could be energy intensive and requires expensive
chemical reagent, which may prohibit its large-scale application.
3.3. Other clay materials
Abundant natural clay materials (NCM), geopolymers and discarded
concrete, which are inexpensive and non-toxic are also promising adsor-
bent materials for NH4+. It was reported that NCM is about 20 times
cheaper than activated carbon (Alshameri et al., 2018). Therefore,
investigation on adsorption capacities of different types of NCM is of
high importance. Alshameri et al. (2018) compared six natural clay
minerals for NH4+ removal from aqueous solution including kaolin-
ite, halloysite, montmorillonite, vermiculite, palygorskite and sepiolite
Fig. 3. Comparison of the maximum NH4+ adsorption capacities of zeolite-type adsor-
bent materials as a function of particle sizes (ZP: zeolite particles, PAZ: polyvinyl alcohol
(PVA)-alginate-ZPs, ZB: zeolite bead) (Putra and Lee, 2020).
 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
(Fig. 4). The Langmuir isotherms indicated that the highest NH4+ ad-
sorption capacities were achieved by vermiculite (50.06 mg g−1) and
montmorillonite (40.84 mg g−1). Jing et al. (2017) also found that hal-
loysite showed a NH4+ adsorption capacity of 1.66 mg g−1 (pH = 5.6,
303 K) with initial NH4+ concentration of 600 mg L−1, and it increased
with increasing initial concentration of NH4+, pH values and tempera-
tures (288 K–313 K).
Artificial clay materials have also been produced and tested, but
many of their NH4+ adsorption capacities are comparable or even
lower than that of NCM. Cheng et al. (2017) synthesized Na-rich
birnessite, which showed NH4+ adsorption capacity of 22.61 mg g−1.
In 2016, Luukkonen et al. (2016) synthesized a geopolymer from
metakaolin and found that the NH4+ adsorption capacity of the geopoly-
mer (21.07 mg g−1) was 46% greater than that of clinoptilolite-heulan-
dite zeolite (14.42 mg g−1) as a reference. Later on, they found that the
optimal performance was achieved, when hydroxide and silicate maxi-
mized, metakaolin minimized, and Na-based reagents used (Luukkonen
et al., 2017). Reutilization of discarded concrete as a kind of industrial
construction wastes was also investigated. Zhang et al. (2019) found
that tricalcium aluminate, a mineral phase in Portland cement, showed
maximum removal capacity of 155.4 mg g−1 at 298 K with dosage of
6.5 g L−1. Additional advantages of such approach include saving land
resources by reducing secondary pollution to the landfill.
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3.4. Biochar
Biochar obtained from carbonization of biomass feedstocks under
oxygen-limited conditions has the potential to be a cost-effective and
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highly efficient adsorbent material but in general exhibits relatively
lower NH4+ adsorption capacity. Fidel et al. (2018) found that only
0.84 mg g−1 NH4+ was adsorbed at around pH = 7 on biochar pre-
pared at low pyrolysis temperature (400 °C). However, Yu et al. (2016)
prepared two types of biochar using pig manure and straw biogas
residues, which both exhibited good NH4+ adsorption capacities of
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13.66 mg g−1 and 11.36 mg g−1, respectively. Yang et al., 2018 syn-
thesized biochar by pyrolyzing pine sawdust at 300 °C which exhib-
ited higher NH4+ adsorption capacity (5.38 mg g−1) than that at 550 °C
(3.37 mg g−1), and ascribe it to higher H/C and O/C ratios of former
one (0.78 and 0.32) than the latter one (0.35 and 0.10). This suggests
that existence of oxygen-containing functional groups on biochar sur-
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face is important. However, contribution of high surface area generated
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Fig. 4. Influence of agitation time on the NH4+ adsorption by kaolinite (Kaol), halloysite
(Hal), montmorillonite (Mt), vermiculite (Ver), palygorskite (Pal) and sepiolite (Sep) (Al-
shameri et al., 2018).
5
at high pyrolysis temperature can't be neglected. Zheng et al. (2018)
prepared biochar from distillers' grains residue at 300–800 °C and found
biochar produced at 700 °C exhibited the highest NH4+ adsorption ca-
pacity of 5.86 mg g−1. Furthermore, the pH value of NH4+ solution also
influenced NH4+ adsorption on biochar. Fan et al. (2019) found that
adsorption capacity of bamboo biochar increased with increasing pH
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values at pH range of 2–7 and then decreased at pH range of 7–8, ex-
hibiting an optimal 114.84 mg g−1 at pH = 7.
Biochar has been modified by subsequent treatment in order to pro-
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mote NH4+ adsorption. A range of oxidative reagents such as HNO3
and H2O2 have been employed to increase amount of oxygen-containing
functional groups. Furthermore, NH4+ adsorption capacity could also
be enhanced by neutralizing surface acidity, because affinity of alka-
line metal ions to functional groups are generally lower than that of
H+, and thus can be replaced by NH4+ more easily. In 2015, Wang et
al. (2015) showed that NH4+ adsorption of modified wood biochar in-
PR
creased to 5.44 mg g−1 by 3 folds after neutralizing biochar pH from 3.7
to 7. However, others have shown that coating metal oxide on biochar
surface can be used for simultaneous removal of other pollutants in ad-
dition to NH4+ capture. For example, Li et al. (2017) showed that 20%
MgO-coated biochar materials produced by an integrated adsorption-py-
rolysis approach can adsorb 22 mg g−1, 398 mg g−1 and 247 mg g−1 for
NH4+, PO43+, and humate through electrostatic attraction, struvite pre-
cipitation, and π–π interactions mechanisms, respectively. Xu et al.
(2018) also demonstrated Mg-biochar has high removal capacity of
47.5 mg g−1 for NH4+ and 116.4 mg g−1 for PO43+ and the product ob-
tained after adsorption can be used as a nutrient-enriched fertilizer. The
last but not the least, incorporation of additives during pyrolysis process
can further improve the product structures. A bentonite hydrochar com-
posite prepared by Ismadji et al. (2016) at 500 °C under CO2 shows
NH4+ adsorption capacity of 23.67 mg g−1, which was greater than ei-
ther sole bentonite (12.37 mg g−1) or biochar (9.49 mg g−1). This is as-
cribed to the higher surface area and pore volume in the composite
which can capture more NH4+ from aqueous phase via van der Waals
force.
3.5. Activated carbon
Activated carbon is usually produced from coal or polymer at rela-
tively high temperature (700–1000 °C) under atmospheric control with
addition of chemical reagents (Quach et al., 2017). It is well known as
a versatile adsorbent materials because of the high surface area, porous
structure and rich surface chemistry (Bandosz, 2006). Mochizuki et
al. (2016) prepared activated carbon from petroleum coke and KOH
and ascribed the adsorbed NH3 to surface hydroxyl and carboxyl groups.
However, most common activated carbon lacks sufficient surface acid-
ity, and thus only adsorbs NH3 through H bonding or Lewis acid-base in-
teractions, which were relatively weak (Seredych et al., 2009). More-
over, given that the average pore size of common activated carbon
(1–2 nm) is much larger than that of NH3 molecules (0.3 nm), the mol-
ecular trapping of NH3 within porous activated carbon is suppressed.
Therefore, activated carbon is generally regarded as a less efficient NH3
adsorptive material.
Much effort has been dedicated to modifying or functionalizing the
activated carbon surface to enhance interaction between surface and
NH3 molecules. Main approaches include i) chemical or aerobic oxida-
tion to generate acidic functional groups that can capture alkaline NH3
and ii) combination of activated carbon with metals, oxides and chlo-
rides, which facilitates complexation reactions. In 2015, work of Qajar
et al. (2015) showed that adsorbed NH3 of synthesized nonporous car-
bon material increased from 180 to 306 mg g−1 under 1 bar at 25 °C af-
ter HNO3 treatment. Zheng et al. (2016) prepared carbon fiber com-
posites from phenolic precursor, which showed increased NH3 adsorp-
tion capacity from 10 to 50 mg g−1 after oxidation by concentrated
6 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
HNO3. In 2017, Travlou and Bandosz, 2017 prepared N-containing
polymeric resin-derived carbons substrate that adsorb 73 mg g−1 NH3 at
1000 ppm after oxidation in air at 350 °C, which is about 45% higher
than that before oxidation. In the same year, Wang et al. (2017)
prepared mesoporous carbon beads for NH3 capture from atmosphere.
They found that the type and loading amount of transition metal chlo-
ride play important role. For example, impregnated mesoporous carbon
beads displayed increased breakthrough capacity of 111.4 mg g−1 from
6.1 mg g−1 after NiCl2 loading for NH3 adsorption at 30 °C with a rela-
tive humidity of 80%.
3.6. Metal organic frameworks (MOF)
MOFs are novel porous materials that provide immense possibilities
for design of NH3 adsorbent materials, but current study was mostly
limited at laboratory scale due to the high cost (Rieth et al., 2019a;
Vikrant et al., 2017). Jasuja et al. (2015) investigated six func-
tionalized variations of UiO-66 (a type of Zr-based MOF) towards NH3
removal from air and found that UiO-66-OH has the highest adsorp-
tion capacity of ~96.9 mg g−1 under dry conditions. DeCoste et al.
(2016) prepared HKUST-1 membranes from polyvinylidene difluoride
for NH3 gas removal and found they exhibited outstanding structural
stability in comparison with original powdered HKUST-1. Recently,
Moribe et al. (2019) compared three isoreticular porphyrin-based
D
MOFs containing Brønsted acidic bridging hydroxyl groups and FTIR
analysis suggested that the strength of the Brønsted acidic –OH sites
was determined by the identity of the metal center. In 2018, Chen
et al. (2018) synthesized a series of M(NA)2 (M = Zn, Co, Cu, Cd;
TE
NA = nicotinate) flexible MOFs and among them Co(NA)2 had the high-
est NH3 uptake of 297.5 mg g−1. Rieth et al. (2016) designed a se-
ries MOFs prepared from extended bisbenzenetriazolate linkers, which
possess coordinatively unsaturated metal sites that contribute to high
and reversible uptake of NH3 and found that isostructural Mn, Co,
and Ni materials adsorbed 263.0, 204.0, and 204.3 mg g−1 NH3 respec
EC
RR
CO
UN
Fig. 5. NH3 uptake vs water uptake at 40% relative humidity measured and 20 °C by breakthrough experiments for a NH3 concentration of 1200 ppm (yellow), 1294 ppm (purple) and
1431 ppm (blue). The yellow line indicates dissolved NH3 based on Henry's law with k°H = 70 mol kg−1bar−1 at 25 °C (Khabzina and Farrusseng, 2018). (For interpretation of the
references to colour in this figure legend, the reader is referred to the Web version of this article.)
tively. Khabzina and Farrusseng, 2018 have summarized NH3 ad-
sorption capacity of many MOF materials as shown in Fig. 5.
3.7. Other nanostructured materials
Recently, there are emerging efforts on synthesizing novel nanos-
F
tructured materials towards adsorption of NH3, which can be roughly
divided into inorganic and organic materials. Inorganic nanostructured
adsorbent materials mainly include metal particles, metal complex and
OO
graphene-like nanosheets. Li et al. (2019) showed that the density of
NH3 molecules adsorbed on the inner wall surface of AgI-coated hol-
low waveguides was 1015 molecules cm−2. In 2016, Takahashi et al.
(2016) found that Prussian blue, first synthesized at the beginning of
18th century, showed 212.5 mg g−1 of NH3 capacity under 0.1 MPa.
Recently, Silva et al. (2019) showed the dinuclear FeIII metallacy-
cle complex had excellent capacity of 192.1 mg g−1 at 25 °C to selec-
tively adsorb NH3 in comparison with amines, alcohols and hydrocar-
PR
bons. In 2017, Yang et al. (2017) reported boron doped graphene ox-
ide showed an increase of NH3 adsorption with increasing concentration
of boron to as high as 16.30 mol kg−1. In 2018, Yang et al. (2018) pre-
pared boron nitride nanosheets that has NH3 adsorption up to 91 mg g−1
at 1 bar.
Organic nanostructured adsorbent materials include polymer, ionic
liquid and hydrogel. (i) NH3 removal: Lee et al. (2017) compared
NH3 removal performance of porous polycyclic imide (PI) and porous
poly(amic acid) (PAA) and found that PAA (27.2 mg g−1) is higher than
PI (6.8 mg g−1) under 1 mbar, which is ascribed to the presence of
amic acid functionality on PAA. In 2016, Ruckart et al. (2016) syn-
thesized a series of ionic liquid composites which exhibit NH3 load-
ing as high as 26.01 mg g−1 at a low pressure of 0.01 kPa and outper-
form many known materials such as MOF and activated materials. (ii)
NH4+ removal: NH4+ removal from aqueous phase has also been in-
vestigated. Wang et al. (2016) showed that amphoteric straw cellu-
lose had a high NH4+ adsorption capacity of 68.4 mg g−1 at pH = ~7.0.
Recently Cruz et al. (2018) reported on the rapid removal of NH4+
 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
on polymer hydrogels from domestic wastewater. The maximized ad-
sorption capacity is 32.2 mg g−1, which corresponded to removal effi-
ciency of 80%. It is worth mentioning that porous 3D framework of hy-
drogels with high water content can decrease mass transfer resistance
of diffusion process and efficient regeneration can be obtained by mild
acid washing.
3.8. Comparison of adsorbent materials and modification methods
Considering the perspective of economy, naturally abundant re-
sources such as clay rather than artificial product (e.g. activated carbon,
nanostructured materials) were preferred for low concentration NH4+
wastewater treatment. For example, the reported price of MOFs (~70 k
USD kg−1), biochar (0.35–1.2 USD kg−1) and activated carbon (1.8–2.1
USD kg−1) are much higher than that of clay materials (0.04 USD kg−1)
(Burakov et al., 2018; Thompson et al., 2016; Vikrant et al.,
2017). Hence application of MOFs is hindered by production cost that
is higher than other commercial products, although MOFs display out-
standing performance for the removal of NH3 (Chen et al., 2018; De-
Coste et al., 2016; Mounfield et al., 2016; Rieth et al., 2016). Fur-
thermore, since nanostructured materials are generally expensive, they
must be regenerated by chemicals such as acid once exhausted, which
is a source of secondary pollution (Cruz et al., 2019). The poor sta-
bility also holds back deployment of MOFs because the empty voids
D
of porous materials tend to collapse during adsorption process (Rieth
et al., 2019a). Those facts are detrimental to practical applications of
MOFs and many other nanomaterials.
NH4+ adsorption capacities of biochar and activated carbon are com-
TE
parable or even lower than that of clay materials in many cases (Table
1). This is because performance of carbonaceous materials varies dra-
matically depending on their feedstock and treatment conditions. It is
reported that lower treatment temperature (<300 °C) leads to higher
density of oxygen-containing functionalities with strong bonding with
NH3/NH4+ (Yang et al., 2018). Nevertheless, the use of clay materi-
EC
als such as zeolite have some serious drawbacks that limited the adsorp-
tion of clay as a full-scale technology. For example, powdered forms of
clay materials require conduction in conventional packed-bed columns
which is not suitable for continuous operation within existing waste-
water treatment plant (WWTP) (Cooney et al., 1999). Furthermore,
biofouling which causes a significant drop in adsorption capacity over
RR
time (Damayanti et al., 2011; Lu et al., 2010) and high chemical re-
quirement for regeneration (Wang and Peng, 2010; Weatherley and
Miladinovic, 2004) were also considered as major drawbacks for ze-
olite. While seawater can be potentially used as a cheap regeneration
chemical, it is only cost-effective at coastal area and scaling could be a
concern (Cruz et al., 2019).
Various modification methods have been demonstrated effective to
CO
enhance capacity of adsorbent materials, but the cost of chemical ad-
ditives and consumed energy must be considered for practical applica-
tion. Functional coating could be a promising approach for modifica-
tion of natural abundant clay materials if coating materials are low-cost
and eco-friendly. Potential candidates include resin (Seredych et al.,
2016; Zhang et al., 2016), chitosan (Yadi et al., 2016) and tannic
acid (Cheng et al., 2019). By contrast, acid/base treatment, calcina-
UN
tion or sonication either consume energy or generate secondary pollu-
tion (Cheng et al., 2017; Luukkonen et al., 2017). In those cases,
chemical modification is not economically viable at a large scale. Car-
bonaceous materials are amenable to modification for varying surface
chemistry, but utilization of high temperature (Ismadji et al., 2016)
or chemical reagent such as HNO3 and NaOH (Qajar et al., 2015;
Zheng et al., 2016) should be avoided. In this sense, aerobic oxida-
tion at relatively low temperature should be investigated as a potential
approach to enhance adsorption behaviour (Jin et al., 2020; Travlou
and Bandosz, 2017). In addition, the selection of appropriate modifi
7
cation approach depends on factors like the initial concentration, waste-
water component, capital investment and operational cost.
Despite above mentioned challenges, all those well-investigated ma-
terials and modification methods form a solid basis for the development
of novel technologies which are inexpensive, environmentally friendly
and highly efficient.
F
4. Mechanisms
OO
Mechanism studies reveal common principles underlying adsorption
process, which would provide guidelines for systematic design of novel
efficient adsorbent materials. In this section we firstly try to identify
adsorption sites on representative substrates based on published litera-
ture. For gas phase NH3 adsorption, it is worth mentioning that the pres-
ence of water plays an important role in adsorption sites and mechanism
pathways. For NH4+ adsorption in the aqueous phase, isotherm and ki-
netic model fitting provide insights into chemical/physical adsorption
PR
pathways. At last, the effect of temperature on adsorption was explained
by thermodynamic analysis.
4.1. Adsorption sites
NH4+ adsorption sites: The NH4+ adsorption sites and underly-
ing mechanisms depend on the nature of the adsorbent materials and
the interactive processes. Generally, since NH3/NH4+ are small mole-
cules/ions, their physical interactions with surface of adsorbent materi-
als are expected to be very weak. As to chemical adsorption, electrostatic
interaction induces the transfer of target ion from liquid phase to solid
surface, while ion exchange involves a reversible replacement of ions of
the same charge on solid surface. So far intensive efforts have focussed
on novel modification methods to enhance chemical adsorption, which
is preferable due to strong adsorption affinity.
It is generally agreed that biochar and activated carbon's capaci-
ties to sorb NH4+ depend on their physical (surface area) and chemical
(functional groups) properties. However, Yu et al. (2016) found that
the specific surface area, pore volume and micromorphology in biochar
materials had no direct correlation with the NH4+ adsorption capacity.
Furthermore, Yang et al., 2018 found that the dominant mechanism
was chemical bonding and electrostatic interaction between NH4+ and
surface functional groups. In this case, surface functional groups rather
than surface area of carbonaceous materials seem to play the domi-
nant role for NH4+ adsorption. Furthermore, a fast adsorption kinetic
of NH4+ is preferred to obtain a high selectivity over other pollutants.
It was suggested that surface functional groups and porous structure ex-
hibit faster adsorption kinetics for small NH4+ than larger and nonpolar
molecules (Tu et al., 2019).
In contrast, clay materials exhibit versatile mechanism pathways.
Similar to functionalized carbonaceous surface, electrostatic interac-
tion could cause NH4+ adsorption to bentonite, which has negatively
charged surface due to the isomorphous substitution of Si4+ and Al3+.
The occurrence of Ca2+, Na+ and Mg2+ that balance electrons con-
tributes to high ion-exchangeability of bentonite. However, Alshameri
et al. (2018) found that halloysite represent more negative surface
charge than other natural clay materials but lower NH4+ adsorption,
indicating that the electrostatic interaction was not the only adsorp-
tion pathway. Instead, cation exchange was believed to be the dominant
mechanism for natural clay such as zeolite (Wang and Peng, 2010).
This is further supported by observation of NH4+ deformation by FTIR
analysis at 1430 cm−1 (Alshameri et al., 2018). This mechanism also
allows NH4+-saturated clay material to be regenerated by Na or K ion
exchange besides heat treatment for NH3 devolatilization (Wang and
Peng, 2010). Recently, Zhang et al. (2019) also demonstrated a dif-
ferent removal pathway by monitoring Ca2+ and Al(OH)4- concentra-
tions in aqueous solution: Al(OH)4- from tricalcium aluminate can react
8 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
with NH4+ to produce Al(OH)3(H2O) and NH3 and contributes to the re-
moval of NH4+.
NH3 adsorption sites: Regarding to NH3 gas, different adsorption
mechanisms have been reported. Thanks to the lone pair of electrons in
NH3, Lewis and Brønsted acid sites can facilitate adsorption. Ye et al.
(2016) investigated the atomic positions and interactions between ad-
sorbed NH3 in zeolite by in situ synchrotron powder X-ray diffraction.
It was found that NH3 can interact strongly with the Brønsted acid site
to form NH4+ species (O … +HN), while another two NH3 molecules
can only form typical hydrogen bonding (N–H…N) along the sinusoidal
channel. Silva et al. (2019) studied adsorption mechanism of FeIII met-
allacycle complex. Thermogravimetric-mass spectrometry (TG-MS) and
NH3 isotherm experiments showed that 8 NH3 molecules were phys-
iosorbed by the complex cavity and 4 NH3 molecules were chemisorbed
per dinuclear metallacycle unit. Nijem et al. (2015) showed that NH3
adsorbed to the Cu2+ in HKUST-1 through Lewis base interactions,
while for Cu1+ the interaction is electrostatic in nature. Generally, in-
creasing the amount of acidic functional groups can enhance NH3 cap-
ture capacity (Lee et al., 2017; Moribe et al., 2019). Specifically,
Van Humbeck et al., 2014 prepared a functionalized organic poly-
mer which exhibited NH3 loadings of >289 mg g−1 under 1 bar. The
low-pressure uptake is also as high as ~14 mg g−1 at 0.01 kPa which
is important for practical application. However, Jasuja et al. (2015)
found that bulky surface groups such as COOH and HSO3 can block
D
small pores in framework, resulting in reduction of NH3 adsorption ca-
pacity.
4.2. Effect of water
TE
NH3 gas adsorption experiments are performed in both dry and hu-
mid air to investigate how water modulates the removal efficiency as
shown in Table 3. Khabzina and Farrusseng, 2018 investigated NH3
uptake by functionalized UiO-66 and 5 different other MOF type ma-
terials using dynamic breakthrough experiments in both dry and hu-
EC
mid condition. It was found that in the presence of water, the NH3 up-
take by most MOFs increased with increasing water adsorption capac-
ity except Cu-based MOF. In these cases, the H-bonding between the
water and NH3 enhances the metal-NH3 interaction through coopera-
tive interactions and water can promote acidic group dissociation and
NH3 protonation. In addition, water can also alter pathway of chemical
RR
reaction between NH3 and adsorbent materials. For example, the reac-
tion between anhydride functional groups and NH3 were investigated
(Zheng et al., 2016). Whether the final products are in amide or imide
form depends on the presence of water and is critical for NH3 regen-
eration. In these cases, the presence of moisture in air was expected to
be beneficial for the NH3 adsorption process. Nevertheless, it is worth
CO
mentioning that water can deteriorate performance of zeolites (Grant
Glover et al., 2011). Seredych et al. (2016) also reported that on
phenolic-formaldehyde resin/bentonite the adsorption capacity of NH3
reached in dry conditions (38.0 mg g−1) is greater than that in moist
conditions (12.4 mg g−1), and ascribe that to blocking of surface pores
by reaction products such as reversal of the exfoliation process. There-
fore, the presence of water can either enhance or deteriorate NH3 gas
adsorption depending on the mechanism pathway.
UN
4.3. Effect of water pH
Water pH is an important parameter that influences sorption
processes at water/adsorbent interfaces (Fu et al., 2020). In aqueous
solutions, NH3 is a Brønsted base forming a conjugated pair with the
NH4+ ion, according to the reversible reaction:
NH3+H+↔NH4+ (1)
The pKa of the reaction is 9.3 at room temperature, which indicates
that the concentration of the ionized (NH4+) and molecular (NH3) forms
are equal at this pH value. At pH > 9.3, NH4+ tended to be hydrolysed
to NH3·H2O, making it uncharged and resulting in the decreased adsorp-
tion capacity. Given that NH3 in solution can easily volatilate into the
atmosphere, increasing the pH of the aqueous solution will further ac-
celerate the release of NH3 from the solution. Therefore, low NH4+ ad-
F
sorption capacity is expected for solution with pH > 9.3. On the other
hand, exceedingly acidic pH will cause enrichment of proton in the so-
OO
lution, and the ionization of acidic functional groups on adsorbents are
restrained, leading to the decrease of ion-exchange positions for the ad-
sorption of NH4+. For example, -COO- groups are converted into –COOH
groups at pH < 3, which decreases ion-exchange positions and electro-
static force between NH4+ and adsorbent surface, reducing the effective-
ness of adsorption process. Karri et al. (2018) summarized investiga-
tions on the multiple ranges of pH (2–13) in a review, which concluded
that the efficiency of NH4+ removal is reduced for c.a. pH < 3 and pH
PR
>7, whereas removal of NH4+ increases gradually with increase of pH
for a range of 3–8. Specifically, Eturki et al. (2012) investigated the ef-
fect of solution pH on the NH4+ removal by clay materials and it was
shown that the best performance was achieved at an optimum pH be-
tween 6 and 8 (Eturki et al., 2012). Wang et al. (2016) found that
with pH increasing from 2 to 4, the adsorption capacity of amphoteric
straw cellulose (ASC) for NH4+ increased and then kept almost constant
in the pH range from 4 to 9. Therefore, both acidic and alkaline condi-
tions were not favourable for ion-exchange adsorption of NH4+ on ad-
sorbents, while the maximum equilibrium adsorption amount was usu-
ally obtained at the pH of 6–9 (Dong et al., 2019a; Huang et al.,
2018; Tu et al., 2019).
4.4. Effect of pore structure
The effects of the pore structure of the adsorbent materials can be
discussed from prospective of pore size distribution, pore stability and
pore blockage by functional groups. Pore size distribution and void vol-
ume are crucial parameters governing the sorption of NH3/NH4+. In
general, adsorbents for NH3/NH4+ prefer a well-developed pore struc-
ture, with the pore sizes comparable to the size of the NH3/NH4+ (3 Å)
(Bashkova and Bandosz, 2014). This is imperative as the small sizes
of NH3/NH4+ lead to exceedingly weak retention forces for conven-
tional adsorbents such as zeolites and activated carbon (Vikrant et al.,
2017). Pore modulation has been employed for optimization of NH3 ad-
sorption by MOFs. In this case the ability to finely tune the pore size
and shape of MOFs to microporous dimensions is advantageous in re-
moving NH3/NH4+ (Vikrant et al., 2017). However, stability remains
important, as pore collapse during use can affect the adsorption perfor-
mance (Rieth et al., 2019a). Some applications may require exten-
sive NH3 cycling stability. For instance, NH3 is a common impurity in
feed gas streams and can poison catalysts and membranes, necessitat-
ing the use of sorbents to capture NH3 prior to the desired chemical
process. On a thermodynamic basis, NH3 is an excellent working fluid
for heat transfer in adsorption heat pumps, which require many thou-
sands of adsorption cycles and materials with extreme stability to this
corrosive gas (de Lange et al., 2015). The above-mentioned factors
are important for physical interactions, whereas in some cases chemical
interactions play dominant role. Recently, we found that after dewater-
ing at 200 °C NH4+ adsorption by lignite increased from 2.25 mg g−1
to 3.73 mg g−1, while the BET surface area reduces from 2.92 m2 g−1
to 2.41 m2 g−1 (Han et al., 2020). Furthermore, the linear correlation
between adsorbed NH4+ and the total concentration of acidic groups
on the lignite surface was high (R2 = 0.93). This is consistent with ob-
servations for NH3 adsorption on activated carbon prepared from pe-
troleum coke by KOH chemical activation (Mochizuki et al., 2016).
 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611 9

Table 2
Adsorption capacity and other parameters of adsorbent materials for NH4 + removal.

Capacity (mg Concentration range Optimized removal Contact Temperature

a
Adsorbent materials g −1) (mg L −1) efficiency (%) time (h) Size (μm) pH (°C) Ref.

Natural bentonite 19.01 10–1000 81.2 80 7.0 30 Angar et

Langmuir al. (2017)

F
Modified bentonite 5.85 0–350 71.7 1.0 7.5 25 Cheng et
Langmuir al. (2019)
Bentonite/Chitosan 15.90 10–40 100 3.0 6.0 25 Yadi et al.

OO
Langmuir (2016)
Bentonite/Chitin 16.16 10–40 100 3.0 6.0 25 Yadi et al.
Langmuir (2016)
Natural Na-bentonite 33.33 20–480 24.0 25 Zhou et al.
Langmuir (2015)
Natural Ca-bentonite 0.5 10.5 48 3.75 75 7.6 18 Sahin
(2018)
Natural Ca-bentonite 26.63 3–11 1.5 7.0 20 Sun et al.
Langmuir (2015)

PR
Purified bentonite 43.22 3–11 1.5 7.0 20 Sun et al.
Langmuir (2015)
Modified bentonite 46.90 3–11 1.5 7.0 20 Sun et al.
Langmuir (2015)
Chinese zeolite 13.18 5–500 10.0 6.8 26 Wang, X.L.
Langmuir et al.
(2016)
Synthesized zeolite 22.90 100 0.67 6.0 25 Liu et al.
(2018)
Zeolite/hydrogel 60.61 20–400 3.0 4040 ± 130 5.7 20 Putra and

D
Langmuir Lee (2020)
Modified zeolite 21.31 0–70 95.0 25 25 Zhang et
Langmuir al. (2016)
Iron oxide/zeolite 3.47 5–100 43.3 1.0 6.4 30 Xu et al.
TE
Langmuir (2020)
Natural vermiculite 22.61 10–1000 2.0 7.0 25 Alshameri
Langmuir et al.
(2018)
Natural montmorillonite 50.06 10–1000 2.0 7.0 25 Alshameri
Langmuir et al.
(2018)
Natural Palygorskite 40.40 10–1000 2.0 7.0 25 Alshameri
EC

Langmuir et al.
(2018)
Natural Sepiolite 21.51 10–1000 2.0 7.0 25 Alshameri
Langmuir et al.
(2018)
Natural Kaolinite 17.27 10–1000 2.0 7.0 25 Alshameri
Langmuir et al.
RR

(2018)
Natural Halloysite 15.58 10–1000 2.0 7.0 25 Alshameri
Langmuir et al.
(2018)
Modified birnessite 22.61 2–50 5.0 5.8 10 Cheng et
Langmuir al. (2017)
Natural halloysite 1.66 600 5.6 30 Jing et al.
(2017)
CO

Geopolymer 21.07 1000 80 24.0 63–125 6.0 22 Luukkonen

et al.
(2016)
Clinoptilolite-heulandite zeolite 14.42 1000 80 24.0 6.0 22 Luukkonen
et al.
(2016)
Tricalcium aluminate 155.40 92.5 4.0 25 Zhang et
al. (2019)
Polymer hydrogel 32.20 180 80 0.5 7.0 23 Cruz et al.
UN

(2018)
Biochar 0.84 300 24.0 7.0 Fidel et al.
(2018)
Biochar 13.66 100 4.0 5.0 30 Yu et al.
(2016)
10 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611

Capacity (mg Concentration range Optimized removal Contact Temperature

a
Adsorbent materials g −1) (mg L −1) efficiency (%) time (h) Size (μm) pH (°C) Ref.

Biochar 5.38 100 16.0 7.0 20 Yang et

al., 2018
Biochar 5.86 250 120.0 25 Zheng et
al. (2018)

F
Biochar 114.84 3200 24.0 88–917 7.0 36 Fan et al.
(2019)
Biochar 2.86 12 43 1.5 7.5 23 Khalil et

OO
al. (2018)
Biochar 43.29 60–480 24.0 <500 7.0 20 Li et al.
Langmuir (2018)
Modified biochar 5.44 0–100 16.0 Wang et
Langmuir al. (2015)
Modified biochar 22 Li et al.
(2017)
Modified biochar 23.67 200 6.0 149–177 6.0 30 Ismadji et
al. (2016)

PR
Modified biochar 47.50 75 24.0 25 Xu et al.
(2018)
Straw cellulose 64.80 50 2.0 7.0 25 Wang et
al., 2016
Fe3O4 NPs 140 93.12 0.67 10.0 25 Zare et al.
(2016)
Lignite 3.43 50–450 2.0 25 Tu et al.
(2019)
Lignite 0.45 2–60 72.0 500–2000 6.0 25 ± 2 Nazari et
Langmuir al. (2018)

D
Base-washed lignite 0.67 2–60 72.0 500–2000 6.0 25 ± 2 Nazari et
Langmuir al. (2018)
Aged coconut shell-based activated 5.47 5–500 24.0 2000 25 Sumaraj et
carbon Langmuir al. (2020)
TE
Ni foam-supported activated carbon 5–7 20–500 1.3 7.0 Shih et al.
(2020)
Commercial activated carbon 0.5 660 24.0 600–2000 25 Carey et
al. (2015)
NaOH treated corncob activated 17.03 10–105 2.0 500–2000 7.0 20 Vu et al.
carbon Langmuir (2018)
Avocado seed-activated carbon 5.4 Langmuir 50–450 6.0 5000 5.0 25 Zhu et al.
(2016)
EC

Canola meal-based KOH activated 148 260 4.0 100–2500 9.0 20 Rambabu
carbon et al.
(2015)
Canola meal-based ammonia-treated 56.7 260 1.5 100–2500 9.0 20 Rambabu
activated carbon et al.
(2015)
Canola meal-based steam activated 55.4 260 2.0 100–2500 9.0 20 Rambabu
RR

carbon et al.
(2015)
Canola meal-based CO2 activated 17.9 260 0.5 100–2500 9.0 20 Rambabu
carbon et al.
(2015)

a The maximum adsorption capacities calculated from Langmuir model were shown as “number + Langmuir” and the adsorption capacities obtained by fixed NH + concentrations
4
were only displayed with “number”.
CO

From these results, it is suggested that the chemical interaction be-
tween NH3/NH4+ and surface acidic functional groups rather than the
pore structure would be dominant in adsorption processes. Nonethe-
less, those acidic functional groups sometimes have adverse effect. In
spite of the acidic chemical nature of functional groups such as –SO3H
and –COOH that are favourable for the adsorption of alkaline NH3,
UN
4.5. Adsorption isotherms
The most widely used adsorption isotherms are Langmuir (eq. (2))
and Freundlich (eq. (3)) models. The former assumes that adsorption
takes place at specific homogeneous sites on adsorbent material surface,
also known as monolayer adsorption (Alshameri et al., 2018). The lat-

UiO-66-SO3H and UiO-66-(COOH)2 showed lower NH3 sorption capaci- ter one recognizes surface heterogeneity and assumes that the adsorp-
ties than UiO-66-OH and UiO-66-NH2 (Jasuja et al., 2015). This is as- tion sites have various adsorption energy (Alshameri et al., 2018).
cribed to a significant decrease in the surface area and pore volume of Their linear equations are:
the MOF by the addition of excessively bulky groups such as –SO3H and
–COOH. These examples illustrate the importance of rigorous design of (2)
pore structure for improvement of adsorption property.
(3)
 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611 11

Table 3
Summary of NH3 gas adsorption conditions, capacities and methods for adsorbent materials.

Dry NH3 capacity (mg Wet NH3 capacity (mg NH3 gas concentration/
Adsorbent materials g −1) g −1) pressure Method Ref.

Carbon beads 111.4 200 ppm NH3 breakthrough Wang et al. (2017)
Bentonite/resin 38.0 1000 ppm NH3 breakthrough Seredych et al. (2016)

F
Modified zeolite 6.4 4.1 4500 ppm NH3 breakthrough Kang et al. (2015)
Nano porous carbon 306.0 1.0 bar Cyclic NH3 adsorption Qajar et al. (2015)
Activated carbon 50.0 22 500 ppm NH3 breakthrough Zheng et al. (2016)

OO
Activated carbon 73.0 1000 ppm NH3 breakthrough Travlou and Bandosz
(2017)
Boron doped graphene oxide 293.4 2.0 bar Isothermal NH3 Yang et al. (2017)
adsorption
Boron nitride nanosheets 91 1.0 bar Dynamic NH3 Yang et al., 2018
adsorption
Modified ionic liquid 27.5 39.6 0.01 kPa NH3 breakthrough Ruckart et al. (2016)
MOF 62.6 73.1 1500 ppm NH3 breakthrough Mounfield et al. (2016)
Multi-walled carbon nanotubes 22.69–90.05 0.368–0.744 MPa Isothermal NH3 Yan et al. (2015)

PR
adsorption
Nano TiO2-activated carbon 3.22–7.73 0.051 kPa NH3 breakthrough Rezaei et al. (2017)
composites

where is the maximum adsorption capacity (mg g−1), the concen- sorbed at any time (min) and equilibrium time, respectively; (min−1)
tration of NH4+ at equilibrium (mg L−1), the adsorption capacity (mg and (g mg−1 min−1) and (mg g−1 min−0.5) are the rate constants of
g−1) of NH4+ at equilibrium and the Langmuir adsorption constant; the three kinetics equations, respectively. is proportional to the ad-

D
is Freundlich adsorption constant (L g−1), the characteristic con-
stant related to adsorption capacity and adsorption strength. It is gener-
ally known that 1/n = 0.1–1 is favourable for adsorption while n = 1
indicates a linear adsorption relationship, and the reaction is difficult to
TE
occur when 1/n is greater than 2 (Tu et al., 2019).
In many studies, the Langmuir equation represents experimental data
better than Freundlich (Table 4). Work by Ismadji et al. (2016)
showed that R2 of Langmuir model is closer to 1 than that of Fre-
undlich model for bentonite, biochar and bentonite hydrochar compos-
ite. However, Freundlich model also provides insights into the adsorp-
EC
sorption rate and is inversely proportional to the adsorption rate.
(mg g−1) is the characteristic parameter representing the diffusion film
thickness. For eq. (6), indicates that the adsorption is dominated
by the intra-particle diffusion and otherwise controlled by both film dif-
fusion and intra-particle diffusion. Furthermore, higher value of rep-
resents significant film diffusion.
Generally, pseudo-second order kinetics represented a better correla-
tion with the adsorption process of NH4+ (Table 5). According to Al-
shameri et al. (2018), well fitted pseudo-second-order indicates three
steps involved: (i) the NH4+ diffusion from liquid phase to liquid-solid

tion process. Cheng et al. (2019) found that the value of 1/n in Fre-
undlich equation was ~0.2, indicating that the adsorption of NH4+ on
modified bentonite was favourable. As temperature is increased, the
value of 1/n becomes lower, which suggests that the adsorption process
is an exothermic process. Furthermore, Xu et al. (2020) observed the
value of 1/n < 1 for NH4+ adsorption onto modified zeolite and as-
RR
interface; (ii) the NH4+ movement from liquid-solid interface to solid
surfaces; and (iii) the NH4+ diffusion into the particle pores. Xu et
al. (2020) found simultaneous removal of NH4+ and PO43+ by mod-
ified zeolite is more consistent with the pseudo-second order kinetic
and ascribed it to either electrostatic adsorption or ligand exchange
between NH4+-PO43+ and modified zeolite, but individual NH4+ re-

cribed it to chemical adsorption. Other mathematic models were also
explored. Recently, Putra and Lee, 2020 used the Dubinin-Radushke-
vitch isotherm model to describe NH4+ adsorption process on zeo-
lite-entrapped hydrogel and found that the obtained mean free energy
was higher than 8 kJ mol−1, indicating the adsorption process is mainly
through chemical ion exchange mechanism.
CO
moval was due to electrostatic physical adoption. Wang et al. (2016)
found NH4+ adsorption onto amphoteric straw cellulose (ASC) fitted
better with pseudo-second-order model, which implies the existence of
both chemisorption and physisorption. The chemisorption might be the
rate-determining step, where valent or coordinate bonds were intro-
duced by sharing or exchange of electrons between adsorbate ions and
adsorbent material.

4.6. Adsorption kinetics
Three kinetic models have been proposed, pseudo-first order by
Lagergren (eq. (4)) (Lagergren, 1898), pseudo-second order by Ho and
Mckay (eq. (5)) (Ho and McKay, 1999), and intra-particle diffusion
by Weber and Morris (eq. (6)) (Weber and Morris, 1963). The linear
form of these three model equations can be expressed as:
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The intraparticle diffusion model was also employed when both
boundary layer diffusion and intera-particle diffusion are rate-limiting
steps. Wang et al. (2016) found intraparticle diffusion plots onto
amphoteric straw cellulose (ASC) adsorbent material exhibit multilin-
earity. Putra and Lee, 2020 compared zeolite particles (ZPs), zeo-
lite beads (ZBs) and polyvinyl alcohol alginate-ZPs (PAZ) and found
that the overall adsorption process is divided into one linear segment

for ZBs and two linear segments for ZPs and PAZ (Fig. 6). Therefore,
(4) NH4+ adsorption onto ZBs is mainly controlled by intra-particle dif-
fusion, while the rate-determining steps using ZPs and PZA are both
(5) boundary layer diffusion (the first linear stage) and the intraparticle
diffusion (the second linear stage). Tu et al. (2019) compared diffu-
(6) sion kinetics of NH4+ and naphthalene sulfonic acid sodium formalde-
hyde condensate (NSF) which is a considerably larger molecule. Both
where (mg g−1) and (mg g−1) represent the amount of NH4+ ad
obtained values of by eq. (6) are not 0, indicating the adsorption
process were controlled by both liquid film diffusion and internal diffu
12 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611

Table 4
Isotherm parameters of Freundlich and Langmuir models for NH4 + adsorption.

Adsorbent materials Temperature (°C) Freundlich Langmuir Ref.

1/n kf (mg g −1) R2 qs (mg g −1) k1 (L mg −1) R2

Modified bentonite 30 0.24 1.79 0.882 5.85 0.077 0.999 Cheng et al. (2019)

F
Natural bentonite 30 0.67 0.61 0.980 50.00 0.006 0.990 Angar et al. (2017)
Bentonite/Chitosan 25 2.33 1.96 0.990 15.90 0.050 0.971 Yadi et al. (2016)
Bentonite/Chitin 25 2.38 2.05 0.990 16.16 0.050 0.973 Yadi et al. (2016)

OO
Natural Ca-bentonite 20 0.76 2.84 0.897 26.63 0.111 0.936 Sun et al. (2015)
Purified bentonite 20 0.82 3.37 0.979 43.22 0.081 0.993 Sun et al. (2015)
Modified bentonite 20 0.77 6.86 0.973 46.90 0.111 0.996 Sun et al. (2015)
Natural zeolite 26 0.42 1.21 0.878 13.18 0.021 0.981 (Wang, X.L. et al., 2016)
Synthesized zeolite 25 0.44 3.00 0.832 25.13 0.006 0.997 Liu et al. (2018)
Modified zeolite 30 0.42 1.05 0.708 5.44 0.100 0.955 Xu et al. (2020)
Modified zeolite 25 0.40 4.24 0.996 21.31 0.130 0.936 Zhang et al. (2016)
Modified birnessite 10 0.51 3.17 0.904 22.61 0.147 0.982 Cheng et al. (2017)
Natural vermiculite 0.41 8.81 0.965 50.06 0.301 0.967 Alshameri et al. (2018)

PR
Natural montmorillonite 0.51 6.81 0.957 40.40 0.227 0.976 Alshameri et al. (2018)
Natural Palygorskite 0.70 5.21 0.945 21.51 0.223 0.968 Alshameri et al. (2018)
Natural Sepiolite 0.55 5.05 0.878 17.27 0.156 0.954 Alshameri et al. (2018)
Natural Kaolinite 0.50 4.00 0.964 15.58 0.143 0.926 Alshameri et al. (2018)
Natural Halloysite 0.97 2.14 0.906 9.97 0.092 0.939 Alshameri et al. (2018)
Natural Halloysite 15 0.42 0.06 0.981 0.51 0.043 0.944 Jing et al. (2017)
Geopolymer 22 0.27 4.45 0.833 22.82 0.051 0.950 Luukkonen et al. (2016)
Biochar 20 0.51 0.40 0.970 5.38 0.026 0.940 (Yang, H.I. et al., 2018)
Modified biochar 0.41 1.05 0.987 5.44 0.140 0.988 Wang et al. (2015)
Modified biochar 0.17 20.13 0.885 22.10 0.018 0.989 Li et al. (2017)

D
Modified biochar 30 0.34 2.13 0.941 12.37 0.050 0.983 Ismadji et al. (2016)
Modified biochar 25 3.13 11.17 0.870 51.48 0.093 0.963 Xu et al. (2018)
Straw cellulose 25 0.63 6.63 0.831 94.90 0.048 0.909 (Wang, X.G. et al., 2016)
Lignite 25 0.47 0.15 0.964 3.43 0.007 0.992 Tu et al. (2019)
TE
Lignite 25 ± 2 0.73 0.02 0.992 0.45 0.034 0.975 Nazari et al. (2018)
Base-washed lignite 25 ± 2 0.43 0.17 0.957 0.67 0.392 0.997 Nazari et al. (2018)
Avocado seed-activated carbon 25 0.45 0.26 0.967 5.4 0.006 0.995 Zhu et al. (2016)
NaOH treated corncob activated carbon 20 2.05 1.61 0.965 17.03 0.039 0.995 Vu et al. (2018)
Aged coconut shell-based activated carbon 25 0.75 0.04 0.980 5.47 0.003 0.98 Sumaraj et al. (2020)
EC

Table 5
Pseudo-first-order and pseudo-second-order kinetic model constants for the removal of NH4 +.

Adsorbent Temperature
materials (°C) Pseudo-first order Pseudo-second order Ref.

qe qe
RR

(exp.) (cal.)
k1 qe (exp.) (mg qe (cal.) (mg k2 (g mg −1 (mg (mg
(min −1) R2 g −1) g −1) min −1) R2 g −1) g −1)

Lignite 25 0.533 0.708 1.31 0.33 5.949 0.999 1.31 1.27 Tu et al. (2019)
Modified bentonite 5 0.016 0.797 5.00 4.90 0.194 0.999 4.98 4.90 Cheng et al.
(2019)
Bentonite/Chitosan 25 1.29 1.29 Yadi et al. (2016)
CO

Bentonite/Chitin 25 1.04 1.01 Yadi et al. (2016)

Modified zeolite 25 0.028 0.957 2.80 0.012 0.993 Zhang et al.
(2016)
Modified zeolite 20 0.378 0.927 37.99 0.002 0.977 3.93 Xu et al. (2020)
Tricalcium 25 0.358 0.778 37.30 0.067 0.999 136.90 Zhang et al.
aluminate (2019)
Natural zeolite 0.016 0.898 2.46 2.759 0.944 2.80 (Wang, X.L. et al.,
2016)
Straw cellulose 25 0.247 0.944 18.4 0.015 0.994 21.70 (Wang, X.G. et al.,
UN

2016)

sion. Furthermore, the calculated value of NH4+ was greater than

that of NSF. This is ascribed to (i) the rich pore structure of lignite
facilitates easy transport of the small NH4+ ion to pores; (ii) ion ex-
change of NH4+ with H+ ionized from surface acidic functional groups
 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611 13

Table 6
Thermodynamic parameters for NH4 + adsorption.

ΔH° ΔS° (J
(kJ mol −1
Sample mol −1) K −1) ΔG° (kJ mol −1) Ref.

Lignite −6.16 −6.39 −14.33 −14.04 −13.76 Tu et

F
(298 K) (308 K) (318 K) al.
(2019)
Modified −80.56 −0.79 −13.91 −8.87 −7.37 Cheng

OO
bentonite (278 K) (298 K) (308 K) et al.
(2019)
Synthesized −11.61 −30.00 −2.60 −2.37 −1.99 Liu et
zeolite (298 K) (308 K) (318 K) al.
(2018)
Modified −3.40 9.60 −0.60 −0.48 −0.41 Xu et
zeolite (293 K) (303 K) (313 K) al.
(2020)
Modified −8.12 35.19 −17.95 −18.50 −19.05 Cheng

PR
birnessite (283 K) (293 K) (303 K) et al.
(2017)
Tricalcium 21.96 5.89 4.36 3.92 3.17 Zhang
aluminate (298 K) (308 K) (318 K) et al.
(2019)
Biochar −8.07 41.6 −3.48 −3.79 −4.11 Fan et
(277 K) (285 K) (293 K) al.
(2019)
Straw −38.53 154.8 −7.59 −9.14 −10.68 (Wang,
cellulose (298 K) (308 K) (318 K) X.G. et

D
al.,
2016)
TE
ture is favourable. In other words, the dissociation of ions (i.e., Na+
in natural zeolites) from the adsorbent materials requires more energy
than that released by combining with NH4+ (Fu et al., 2020). Cheng
et al. (2019) found that the obtained values of were consistent
with the Freundlich isotherm analysis where the value of 1/n decreases
EC

Fig. 6. NH4+ adsorption data fitted by Weber and Morris’ intra-particle diffusion model with increasing temperature (Cheng et al., 2019). This is in contrast
(ZP: zeolite particles, PAZ: polyvinyl alcohol (PVA)-alginate-ZPs, ZB: zeolite bead) (Putra
with the removal of Zn2+ and Cr3+ by Al-pillared bentonite, which are
and Lee, 2020).
endothermic reactions and not favourable at low temperature (Ghnimi
and Frini-Srasra, 2018). The positive ΔS implies that the adsorption
(e.g. –OH and –COOH) is faster than adsorption of NSF at hydrophobic
process creates randomness. Wang et al. (2016) observed ΔS > 0 indi-
sites driven by intermolecular forces on the lignite surface.
cating that the affinity of the adsorbent materials toward NH4+ and also
RR

suggest the randomness at the solid/liquid interface increased as a re-

4.7. Thermodynamic analysis
sult of adsorption. Tu et al. (2019) compared adsorptive behaviour of
naphthalene sulfonic acid sodium formaldehyde condensate (NSF) and
Thermodynamic analysis can provide valuable information to the in-
NH4+ on lignite and it was found that the adsorption of NH4+ was
ternal energy changes during the adsorption process, which indicates
ΔH < 0 and ΔS < 0, whereas the adsorption of NSF was ΔH > 0 and
the effect of temperature on NH4+ adsorption. The parameters are de-
ΔS > 0, but was observed for both adsorbates. The adsorption
termined from (the thermodynamic distribution coefficient) and the
CO

onto NaOH-treated activated carbon was a spontaneous process (Vu et

standard Gibbs free energy
(kJ mol−1), and standard entropy change
culated using Eqs.
UN
(kJ mol−1), standard enthalpy change
al., 2018a). Furthermore, the positive ΔS suggests that the organiza-
(J mol−1 K−1) are cal-
tion of NH4+ ions at the solid/solution interface during the adsorption
process becomes more random. Additionally, the negative ΔH° reflects
(7) the exothermic nature of the adsorption process demonstrated by the
decrease in the adsorption capacity. However, the thermodynamic para-
(8) meters show that the adsorption process on clinoptilolite was non-spon-

taneous and adsorption rate decreased with an increase in the temper-

where (K) was the absolute temperature, and R was molar gas con- ature, thus showing the exothermic nature of the adsorption (Tosun,
stant. The value of , and were calculated from the slope 2012). Therefore, both adsorbate and adsorbent materials determined
and intercept of the plot of versus 1/T. the thermodynamic behaviour of adsorption process.
Table 6 listed thermodynamic parameters for NH4+ adsorption
process. The negative values of in most studies indicate that the ad- 4.8. Field trials
sorption process was spontaneous. The reaction is generally considered
to proceed via physical sorption (ΔG value between 0 and -20 kJ mol−1) Laboratory experiments alone are unable to give a comprehensive
and chemical sorption (ΔG value between −80 and −400 kJ mol−1) picture of the dynamic removal of NH4+. Therefore, field trials should
(Bhatt et al., 2012). observed by many studies indicate that be carried out in order to validate the practical application. Wang et
adsorption of NH4+ is exothermic and low tempera al. (2016) explored the dynamic adsorption efficiency of NH4+ in
14 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
wastewater from a paddy rice field using natural Chinese zeolite during
rainfall runoff, which indicates that the adsorption rate was the highest
when the base angle of adsorption barrier is 45°. Moreover, a high initial
removal rate was obtained at low flow rates while high adsorption was
achieved at high flow rates. Ismadji et al. (2016) demonstrated that
5 kg bentonite-hydrochar composite could almost completely remove
the NH4+ from the Koi fish tank system (500 L of water and 30 Japanese
Koi) within 60 min. This meets of healthy aquaculture requirement of
NH4+ content <0.1 ppm. Zhang et al. (2019) applied tricalcium alu-
minate (a mineral phase of discarded concrete) to remove NH4+ from
digested piggery wastewater and demonstrated a maximum water treat-
ment capacity of 200 L water kg−1 that meets the discharge standard of
<80 mg L−1 for livestock and poultry breeding (Fig. 7). Furthermore,
the recovery rate of NH3 was 90.5%. Zhang et al. (2016) used modi-
fied zeolite to treat secondary effluent from WWTP in Nanjing. The coat-
ing of an anion exchange resin onto the Na-form zeolite increased the
NH4+ removal efficiency from 78% to 95% and increased the treatment
volume of the Na-form zeolite from 51 to 76 bed volume. Those field tri-
als would provide precious experience for NH4+ removal in real world
applications, but more field trials are needed for comprehensive study.
4.9. Regeneration
Regeneration and reusability of adsorbents are pivotal to the ability
D
to recycle NH3/NH4+ during successive rounds of adsorption and des-
orption processing, because one-time use of adsorbent materials is not
economically feasible. The key is to develop cost-effective adsorbents
that are viable for regeneration that would yield a concentrated NH4+
TE
stream and completely desorb the NH4+ without affecting the material's
structural integrity and adsorption performance over a guaranteed ser-
vice life. Well-demonstrated options include chemical washing, biologi-
cal regeneration, electrochemical regeneration, mild heating and use of
an electric field (; Han et al., 2019; Rahmani et al., 2009; Shelp and
Seed, 2007).
EC
Chemical washing involves displacement of the target ions into the
acid/base/salt solution and has been the most commonly used method
for regenerating adsorbents, where low regenerant volume and high re-
generation rate were preferred (Malovanyy et al., 2013). A single
component or mixture of NaCl, NaClO, KOH, and NaOH in solution were
selected as the regenerant (Cruz et al., 2019; You et al., 2017; Zhang
RR
et al., 2016, 2017bib_Zhang_et_al_2016bib_Zhang_et_al_2017).
Hermassi et al. (2017) showed that NH4+ desorption efficiency in-
creased with in
CO
UN
Fig. 7. Treatment capacity of tricalcium aluminate for NH4+ contaminated digested pig-
gery wastewater (Zhang et al., 2019).
crease of NaCl ratio from 0 to 10 wt%, whereas there was no significant
change above 10 wt%. However, NaCl regeneration requires periodical
replacement due to the accumulation of NH4+ in the regenerant solu-
tion, which resulted in secondary pollution that needs further treatment
(Zhang et al., 2017). Alkaline regeneration by NaOH solution success-
fully avoided NH4+ accumulation by air stripping but was restrained by
F
its high cost in regenerant and gaseous pollution control (Sancho et al.,
2017; Zhang et al., 2017). Similarly, regeneration with HCl did not
prove to be more beneficiary than regeneration with NaCl as the low pH
OO
of spent regenerants had implications in consequent treatments (Huang
et al., 2018). Therefore, the high chemical requirements for regener-
ation was also considered a major drawback. Generally, NH4+ loading
capacity decreased after each sorption-desorption cycle, probably due to
an incomplete desorption of NH4+ which results in less available sites
on the adsorbent surface after each cycle (You et al., 2017). Recently,
Fu et al. (2020) showed that the NH4+ removal rate of natural zeolite
is 81.7%, and that of the recycled zeolite fluctuates within 79.4–84.8%
PR
over six cycles of regeneration. Nonetheless, the presence of alkaline or
oxidative components could lead to more favoured sorption conditions
(You et al., 2017). Zhang et al. (2017) found that zeolites regen-
erated by mixed NaClO–NaCl solution showed higher NH4+ adsorption
rate and lower capacity than unused zeolite.
Compared to chemical washing, the biological regeneration method
was developed to remove adsorbed NH4+ from zeolite through nitri-
fication and/or denitrification process. It avoids the cost of chemical
reagents or complicated configuration and thus shows advantages in an
environmental-friendly and economical manner. Hence, biological re-
generation was the relatively expected choice, even though the regen-
eration rate is generally not as good and fast as other methods. Han et
al. (2019) treated anaerobically digested dispersed swine wastewater
with a pilot-scale zoning tidal flow constructed wetland (TFCW) with a
bottom wastewater saturation layer, and found that nitrification-denitri-
fication which accounted for 80.32% of total N removal was the main N
removal pathway.
Other cost-effective regeneration methods that do not rely heavily on
chemical dosing were also developed for regeneration of NH4+ adsor-
bents. Thermal regeneration of adsorption materials is an interesting op-
tion among them. An increase in temperature or vacuum treatment may
account for the desorption of absorbed NH3 to prepare the MOFs for the
next round of NH3 uptake (Vikrant et al., 2017). Depending on the
binding strength of NH4+ ions onto the functional groups in the adsor-
bent surface, the removal of NH4+ ions can be initiated by heat through
the thermal transformation of NH4+ into NH3. In particular, the fact that
heat can be used for regeneration purposes offers opportunities to ben-
eficially reuse low value heat released during electricity generation us-
ing combined heat power (CHP) systems at Wastewater Treatment Plant
(WWTPs) that implement anaerobic digestion. This requires the struc-
tural integrity of the adsorbent materials to remain intact after multiple
thermal regeneration cycles, which is a major concern that needs to be
taken into consideration during material development.
5. Outlook
Finding suitable adsorbent materials constantly remains a challenge.
Lignite (brown coal) which has rich pore structure and high density of
surface functionalities has emerged as a promising adsorbent material
for cations. Although there is no academic reference, the market price
of lignite is about 16.5 times lower than that of natural zeolite (Nazari
et al., 2018). Particularly in Australia, the Latrobe Valley in Victoria
has around 25% of the world's known lignite reserves, which is mined
in huge quantities mainly for burning to generate electricity (Barton et
al., 1993). Recently, Tu et al. (2019) reported that NH4+ adsorption
capacity of lignite is 3.43 mg g−1 using Langmuir analysis and the ad
 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
sorption process is driven by ion-exchange interactions with H+ of –OH
and –COOH on the lignite surface. In 2017, Nazari et al. (2018) ex-
plored the influence of pH, NH4+ concentration and lignite dosage for
removal of NH4+ from synthetic wastewater. It was found that lignite
treated with base solution has greater NH4+ removal efficiency in com-
parison with raw material. In a field trial, Chen et al. (2015) found
that application of 4.5 kg m−2 lignite significantly reduced NH3 gas loss
from cattle pen by about 66% (Fig. 8). Nevertheless, lignite's optimal
adsorption for NH3 and detailed mechanisms of lignite-NH3 interaction
remains elusive. In addition, regeneration of lignite using simple and
cost-effective methods for adsorbent material recycling should also be
investigated in future research and whether lignite has toxicity to the
subsequent biological treatment must be clarified.
Both chemical and physical modifications are important for lignite to
be used as an adsorbent material. It was reported that treatment using
chemical reagents can alter the surface chemistry of lignite (Cihlář et
al., 2014; Tu et al., 2019), potentially enhancing their NH4+ and NH3
capture capacity (Fig. 9). However, modifying a large quantity of lig-
nite via addition of chemical reagents during the manufacturing process
is not always ideal because this can produce secondary pollution such as
formaldehyde and surfactants (Cihlář et al., 2014; Tu et al., 2019).
On the other hand, physical modifications of lignite such as dewatering,
pelletisation, granulation are even crucial. For example, by decreasing
water content (~60% dry weight of lignite), the transportation cost can
D
be dramatically decreased; Turning lignite powder into porous pellets,
granules or concrete bricks can not only prevent humic acid dissolving
into water which darkens the colour and increases the dissolved organic
carbon (DOC) content of water, but also improves animal well-being
TE
when used in animal feedlot by reducing the dust content. Thus, more
efforts should focus on developing effective “green” modification meth-
ods to enhance the functions but minimize the drawbacks of lignite.
In the past, most tests for NH4+ removal of lignite were conducted
in short-term batch experiments using synthetic solutions (Nazari et
al., 2018; Tu et al., 2019), focusing on adsorption capacity and re-
EC
moval efficacy. However, dynamic breakthrough analysis is lacking, and
more efforts should be dedicated to the interaction of each parame
RR
CO
UN
Fig. 8. Hourly NH3 emissions and air temperature from 13.11.4 to 13.12.13 where cattle moved in pens at 9–11 a.m. on 4th November and moved out at 1–3 pm (Chen et al., 2015).
15
ter with one another in terms of removal efficiency, due to the com-
plexity of the wastewater treatment process. Moreover, once laboratory
experiments are accomplished, work should be directed to the design
and implementation of pilot-scale studies to validate their industrial fea-
sibility. Importantly, real wastewater rather than synthetic wastewater
should be tested, where other components in solution such as heavy
F
metal ions and organics will reduce ammonium exchange capacity due
to competitive adsorption (Wang and Peng, 2010).
The reutilization and disposal of adsorbed NH4+ together with ad-
OO
sorbent materials is another challenge. While in some regions food pro-
duction leads to vast losses of N to the environment, in other regions
not enough N is available for sustainable agricultural crop production.
Hence there is a need to develop alternative NH4+ management ap-
proaches that center around recovery of NH4+ rather than deal with
its destruction into elemental dinitrogen. The NH3/NH4+-saturated ad-
sorbent materials have been widely proposed to be used as fertilizer
which have advantages over traditional treatments. Such approaches not
PR
only to reduce the capital and energy costs required in the adsorption
processes by supplementing industrial Haber-Bosch process, but also re-
duce the environmental footprint by reducing N2O production which
is a potent greenhouse gas comprising the equivalent of 14–26% of
the overall carbon footprint of wastewater treatment plants (WWTPs)
(Cruz et al., 2019; Service, 2018). For example, after the last sorp-
tion desorption working cycle, loaded zeolites can be used as fertilizer
after a separation process by filtration (Hermassi et al., 2017). Zeo-
lite, biochar and other adsorbent materials were reported to be capa-
ble for improving soil physicochemical properties, microbial capacity
and soil fertility (Ding et al., 2016). When adsorbent materials exhibit
strong binding to NH3/NH4+, the loaded adsorbent materials could be
used as a carrier slow-release fertilizer (Kotoulas et al., 2019). Note
that the concentrated effluent is also a promising precursor for fertilizer
production after the concentration stage, i.e., using liquid-liquid mem-
brane contactors (Sancho et al., 2017). However, only a few stud-
ies have investigated recycling of NH4+ for nutrients release (Malekian
et al., 2011). Wang et al. (2016) prepared a novel multifunctional
slow-release compound fertilizer using recovered NH4+ and H2PO4−
from aqueous solutions. There is a bright future for marketing recycled
N. In Australia, 1.678 Mt urea was applied in 2017 which is an equiva
16 B. Han et al. / Journal of Cleaner Production xxx (xxxx) 124611
Fig. 9. Modification of lignite to enhance NH4+ adsorption.
lent amount of N (0.772 Mt) as that contained in 15.44 Mt manure dry
solid (5% N), but feedlot herds are only estimated to produce 3.29 Mt
per annum. Nevertheless, in this case the recycled N from feedlots alone
has the potential to supply about 21% of the N fertilizer market share
in Australia. Therefore, the potential of NH4+ adsorption to generate
value-added product is very evident, despite challenges that remain to
be addressed.
6. Conclusion
D
Effective removal of NH4+ and mitigation of NH3 emissions from
various hotspots are critical for not only protection of water resources
but also reduction of atmospheric PM2.5 pollution. Adsorption by
TE
low-cost abundant materials is regarded as an effective approach, and
promising modification methods have been investigated to increase ad-
sorption capacity of NH3/NH4+. Although both conventional and nanos-
tructured materials face challenges regarding economic cost, energy
consumption, secondary pollution and adsorption efficiency, these can
be tackled by adopting a variety of advanced options. We envision that
EC
the pursuit of strategies for surface modification of natural abundant re-
sources will lead to a bright future of adsorbent materials suited to low
NH3/NH4+ concentration conditions.
Uncited reference
RR
,,.
Declaration of competing interest
The authors declare that they have no known competing financial in-
terests or personal relationships that could have appeared to influence
the work reported in this paper.
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Acknowledgements
This work was financially supported by the Australia-China Joint
Research Centre – Healthy Soils for Sustainable Food Production and
Environmental Quality (ACSRF48165) and Cooperative Research Cen-
tres Projects (CRC-P) ‘Optimising Nitrogen Recovery from Livestock
UN
Waste for Multiple Production and Environmental Benefits”, Natural
Science Foundation of China (22002032), Hebei Key R&D Program
(20327303D, 19223811D), Natural Science Foundation of Hebei
Province (B2019201064) and Advanced Talents Incubation Program of
the Hebei University (1081/801260201284).
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