Journal of Rare Earths 38 (2020) 339e355

Contents lists available at ScienceDirect

Journal of Rare Earths

journal homepage: http://www.journals.elsevier.com/journal-of-rare-earths

Recovery of rare-earth metals from aqueous solutions by

bio/adsorption using non-conventional materials: a review with
recent studies and promising approaches in column applications*
Talles Barcelos da Costa, Meuris Gurgel Carlos da Silva, Melissa Gurgel Adeodato Vieira*
University of Campinas, School of Chemical Engineering, Albert Einstein Avenue, 500, 13083e852 Campinas, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The recovery of rare-earth metals (REMs) is of great economic and environmental interest, because of
Received 1 March 2019 their high market prices and various industrial applications. Recently, with the increasing demand for
Received in revised form high-purity rare-earth compounds, the separation and purification of these elements have gained
17 June 2019
considerable attention. The bio/adsorption process has been considered an alternative to recover these
Accepted 18 June 2019
elements, by its simplicity, low cost and efficiency for recovery of REMs at low concentrations. This
Available online 23 August 2019
review article presents the recent progress regarding REM bio/adsorption published literature in batch
system by different non-conventional bio/adsorbents, as well as a critical analysis of the technological
Keywords:
Rare-earth metals
challenges to be faced and future prospects. For this purpose, the best application model (isotherm,
Bio/adsorbents kinetics), thermodynamic quantities and selection of eluents for desorption studies are also discussed.
Adsorption kinetics Additionally, in this review, the application of different bio/adsorbent materials were reviewed exten-
Isotherm sively in terms of the removal and recovery of REMs in continuous fixed-bed adsorption and regener-
Batch desorption ation cycles. Finally, future aspects in bio/adsorption research and prospects for commercial applications
Continuous fixed-bed adsorption were discussed.
© 2020 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights reserved.

1. Introduction magnetic, optical and catalytic properties.4e6 China accounts for

almost 90% of the rare-earth metal global production, and has
The REMs are a group of seventeen chemical elements, about 40% of the world reserves, followed by Brazil (20%).7
including scandium (Sc), yttrium (Y) and the series of lanthanides Recently, with the increased demand of high-purity REMs, the
(from lanthanum (La) to lutetium (Lu)). The chemical and physical purification processes of these elements have received considerable
properties of the REMs are very similar, which is a result of the attention.8 Specially, the five critically important REMs (Dy, Eu, Nd,
electronic configuration of these elements and similarity of ionic Tb and Y) have high demand and limited substitutes.9 Such REMs
radius, which decreases as the atomic number increases. It is very are in high demand, as they are used in clean energy technologies
difficult to separate them using common chemical methods.1,2 (e.g., wind turbines and electric vehicles).10 Different conventional
Considered strategic inputs for the high-tech industry, REMs have methods can be applied to separate, purify and preconcentrate
a very broad field of application that contributes to important REMs, such as solvent extraction, chemical precipitation and ion
sectors.3 Their uses include the production of lasers, matches, lens, exchange.11 Among them, adsorption is considered a promising
super magnets, glass and ceramics, microwaves, sensors, dyes, alternative to conventional processes by its simplicity, low cost,
coatings, electronic conductors, catalysts for cracking and oxida- high efficiency and wide availability for recovery of rare-earth ions
tion, because of their various chemical, electrical, metallurgical, at low concentrations from secondary sources as industrial
wastewater.5,7,12
Adsorption is a unit operation in which one or more parts of a
*
Foundation item: Project supported by the Coordination for the Improvement fluid phase is transferred to the surface of a solid phase.13 The parts
of Higher Education Personnel (CAPES), National Council for Scientific and Tech- from the fluid phase are named adsorbates, while the solid phase is
nological Development (CNPq), and grant 2017/18236e1, S~ ao Paulo Research
known as the adsorbent.14 According to Fomina and Gadd,15 the
Foundation (FAPESP).
* Corresponding author. term bioadsorbent refers to adsorbent materials originating from
E-mail address: [email protected] (M.G.A. Vieira). biological materials such as life or dead microorganisms and their

https://doi.org/10.1016/j.jre.2019.06.001
1002-0721/© 2020 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights reserved.
340 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355

components, algae, plants, and industrial, agricultural or natural production of REMs. Loparite [(Ce,Na,Ca)(Ti,Nb)O3] and apatite
wastes. [Ca5(PO4,CO3)3(F,Cl,OH)] are minerals that may contain significant
Furthermore, bio/adsorption has been studied as an alternative concentrations of REMs, but with lower economic value. Clay
in extractive metallurgy processes for recovery and concentration minerals with ions of adsorbed REMs are important sources of
of high-demand and/or high-added value metals, such as gold, heavy REMs, as in Chinese deposits.30 They are: kaolinite
silver, uranium, and, also, REMs. In this sense, the use of bio/ (Al2Si2O5(OH)4), halloysite (Al4Si4OH8O10$8H2O) and the smectite
adsorbent materials is promising, since it also is a cost-effective family [(½Ca,Na)0.7(Mg,Fe,Al)4] or (Si,Al)8O20OH4$nH2O.29,31 How-
industrial process compared with the environmental impact of ever, there are more than 200 minerals that contain REMs as sig-
similar technologies.16,17 nificant elements. Despite the diversity of REM-bearing minerals,
Activated charcoal, silica gel, activated alumina, zeolites and few of them form economically viable deposits.31
synthetic polymeric resins are the main traditional absorbents used China has the largest reserves of REMs (more than 36% of a total
industrially.14,18,19 Despite their high capacity to adsorbe, the use of of 120 million tons), investing in all phases of the processes, from
conventional adsorbents has some limitations, such as their high the extraction to the obtaining of high-purity (>99.99%) com-
production costs, difficulties in regeneration and significant pounds, making the country lead the production and market of
reduction on the adsorption capacity after continuous regeneration REMs. In 1990, the world production of REMs was about 25 thou-
cycles. Therefore, recently, many bio/adsorbents that are abundant sand tons, and China was responsible for half of it. However, the low
and have low costs have been proposed for wastewater treatment cost of the REMs produced by China since the early 1990, with little
in place of traditional adsorbent materials.20 or no environmental control, made it the market leader in the past
Effective adsorbents of rare-earth ions, for practical use, require 20 years.32 Currently, China sells more than 95% of the existent
high selectivity over base metal ions, high adsorption and desorp- REMs, mainly in the form of metals and oxides (United States
tion rates, high adsorptive capacity, durability, low cost and high Geological Survey, 2016), and is also the world's largest producer of
mechanical resistance.5 In recent years, studies have been reported REMs (83% and 67 mineral rights).7
the use of selective bio/adsorbents for rare-earth ions, such as Brazil has the second largest world reserve of REMs (around 18%
grapefruit peel for recovery of Ce and La,21,22 chitosan microparti- of the world total). However, according to the United States
cles and crab shell for recovery of Eu,23 marine sediments for re- Geological Survey report 2016, Brazil has only 1% of the world REMs
covery of Eu,24 biopolymer microparticles containing DEHPA/TOPO production. Recently, the interest in REMs has increased in the
extraction for recovery of Sm and Gd,25 alginate microspheres for Brazilian government because of the realization of the economic
recovery of Nd,26 sericin and alginate crosslinked by proantho- vulnerability that the absence of such resources can bring. This
cyanidins for recovery of La,27 among other alternative non- increased interest is linked to the perception that “clean” and
conventional materials. strategic technologies, such as wind turbines, hybrid vehicles, oil
Review articles reporting the bio/adsorption of REMs using and communication, are limited by the availability of REMs.
different bio/adsorbent materials have been published The latest and more important mobilizations of the business
recently.4,7,28 Here we include many new studies published in the sector to exploit REMs in Brazil come from CBMM (Brazilian Met-
last few years and provide the recent progress regarding the REMs allurgy and Mining Company) and MbAC (Brazilian company
adsorption and bio/adsorption by various non-conventional ma- domiciled in Canada), in Araxa , MG, and Mineraça ~o Serra Verde
terials. Additionally, the adsorption process of REMs in dynamic (part of Mining Ventures Brasil), in Minaçu, GO. According to Lap-
system of fixed bed column still has been scarce. There is a lack of ido-Loureiro,33 several locations can present potential for produc-
studies addressing adsorption/desorption cycles in column for tion of REMs, because they have reserves of great volume and high
regeneration of the bio/adsorbent material and recovery of REMs. content of these metals, such as Pitinga (AM), Catala ~o (GO), Morro
Therefore, this review article also addresses studies in continuous do Ferro (MG), and Rio Sapucaí (MG). It is estimated that the Bra-
fixed-bed adsorption, with important implications for cost reduc- zilian resources of REMs reach 5 million tons, but much of this
tion and commercial applications prospects. These important as- volume correspond to minerals with not established or signifi-
pects of column applications for REMs recovery are reviewed cantly complex processing.
extensively for the first time in this paper. In addition to China and Brazil, significant potential REMs re-
Thus, this review article will cover: (i) mining, production, ap- sources are found in Australia, United States, India, Vietnam and
plications and technologies for recovery of REMs; (ii) bio/adsorp- Malaysia, as well as some Commonwealth of Independent States-
tion process for removal and recovery of REMs; (iii) kinetics, former Soviet Union (CIS) countries. In terms of total global min-
equilibrium, thermodynamic study and desorption in batch ing reserves in REMs, China represents almost half of the total, the
adsorption processes; (iv) adsorption/desorption cycles for regen- CEI countries 17%, the United States 12%, India 3%, Australia 1%, and
eration of bio/adsorbent material and recovery of REMs; (v) others 19%.34
adsorption process in dynamic system of fixed-bed column; (vi)
practical applications and future prospects for bio/adsorption of 3. Technologies for recovery of rare-earth metals
REMs.
The recovery of rare-earth elements is interesting because of
2. Mining and production of rare-earth metals their high market prices, along with their various industrial ap-
plications.4 Recently, with the increasing demand for high-purity
The REMs found in the Earth's crust are not sufficiently rare-earth compounds, the separation and purification of these
concentrated to make them easily exploitable. This is due to the elements have gained considerable attention in the scientific
similarity of their ionic radii, which makes them interchangeable in world.7 Few countries master technologies of separation of REMs,
most minerals and very difficult to separate. REMs are always found which are of great importance for economic policies, since the
in several minerals such as silicates, halides, carbonates and products related to these commodities have a high added value.
phosphates, but never in the form of pure metal.29 The mining and processing for REMs production are usually
Bastna€site [(Ce)2(Ce,La)(CO3)F], monazite [(Ce,La,Nd,Th)PO4] associated with detrimental environment impacts and high costs.
and xenotime (YPO4) are the three REM minerals with greater Preservation of REMs resources calls for the development of effi-
economic importance, corresponding to 95% of the world cient recycling techniques at the piloteplant scale. Due to the
 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355 341

economic and environmental costs of REMs mining, it is desirable Fractional precipitation is a unit operation that involves the
to promote the recycling and reuse of REMs while also minimizing removal of one or more metal ions from an aqueous solution by
the dependency on such resources.35 On the other hand, uncon- adding a chemical agent to form a new less soluble compound. The
ventional REMs containing resources, including produced water elements that still remain in solution can be recovered by precip-
acid mine drainage, fluid catalytic cracking (FCC) catalysts exten- itation with the same chemical agent or by complete precipitation
sively used in the petrochemical industry, and red mud by-product with oxalate, hydroxide, or other compound.48 This method is not
generated after alkali leaching of bauxite for alumina production in effective for low concentrations of metal ions in aqueous solution
the Bayer process, are sources containing significant amounts of (1e100 mg/L), in addition to the large amounts of difficult-to-treat
REMs.9,29,36,37 However, the concentration of REMs in these re- waste.49
sources is several orders of magnitude lower than that of REMs Another method employed for the recovery of REMs is solvent
ores. The recovery of REMs may help reduce the imbalance in REMs extraction, which essentially consists in the treatment of an
supply by enforcing the primary supply chain for some REMs that aqueous phase containing one or more rare-earth ions in solution,
are crucial in particular for industrial applications.38,39 with an organic phase called solvent able to selectively extract the
In addition, despite the environmental problems caused by the species of interest. The advantages of this process are: low power
mining processes for extraction of REMs, there is little information consumption, possibility to keep a continuous system, besides
available in the literature on the toxicity of REMs to the environ- allowing the complete regeneration of the solvent. However,
ment and human health. The presence of these elements in sur- because of the similar physical and chemical characteristics, the
face waters can be associated with multiple sources, such as the difficulty in using solvent extraction to recover several rare-earth
interaction between water-rocks or water-atmospheric particu- ions in a multicomponent solution is the main limitation of this
late matter (including deposition of particulate materials and process.50,51
mixture with rain water), tributary contribution, surface runoff Finally, in the ion exchange unit operation, the ionic species
and anthropogenic discharges. In Brazil, for these metals, there present in a resin (natural or synthetic) are replaced by ions present
are no guidelines for effluent release by the Conselho Nacional de in the solution, which have a higher affinity for the resin.14 Thus,
Meio Ambiente (CONAMA, in english: National Environmental the ions present in the solution are captured by the resin while the
Council). ions present in the resin are transferred to the solution. The resin is
Herrmann et al.,40 evaluating the effects of lanthanum bio- called anionic or cationic resin when anions or cations are the ionic
accumulation in aquatic species, showed that exposure to levels species exchanged, respectively.52 This operation is performed to
above 1.0 mg/L of La, in the forms of La(NO3)3, LaCl3 and La2O3, can recover relatively small amounts of highly pure rare-earth ions and
interfere with the growth, reproduction and cause mortality of is not suitable for treatment of highly concentrated solutions.53
several species in marine and fresh water environments. Olmez Therefore, many conventional methods can be applied to the
et al.,41 in turn, have conducted studies in sediments in a water recovery of REMs; however, in addition to being economically un-
body in California, and found that light REMs sources (La, Ce, Nd attractive, these processes demand a high concentration of rare-
and Sm) came from the oil cracking catalysts and their products, earth ions in solution. Historically, fractional crystallization, was
including ash and wastewater of oilefired power plants and once the only possible way of obtaining pure REMs.54 This is proven
refineries. to be difficult and time-consuming because hundreds of cycles are
According to Goldstein and Jacobsen,42 in water bodies, REMs required and, often, this process is energy-intensive because it is
are present in suspended particulate matter, colloidal particles, and carried out hydrothermally.55 In the case of ion exchange, during
in solution. According to Zhang et al.,43 when comparing results of the Manhattan Project, ion exchange chromatography utilizing
REMs from filtered and nonfiltered water samples, most of the REM organic resins was developed to separate lanthanides and acti-
content in the water is in particulate matter, and only a very small nides.56 The difficulties in large-scale production and organic resin
fraction is dissolved. In addition, pH, temperature and composition regeneration restricted its further full scale. In practice, currently,
of the environment affect the distribution of REMs in water bodies. continuous liquid
liquid extraction (solvent extraction) is the
The composition of the environment refers to the other elements technology for REMs separation on an industrial scale. However,
present, besides the speciation, nature and quantity of the material the liquid waste generation in the solvent extraction process has
e e
in suspension. Inorganic (CO2
2

3 , OH , SO4 and F ) and organic resulted in a search for more eco-friendly separation technol-
binders chelate REMs, and colloidal particles (iron and manganese ogy.55,57 Thus, the operation of bio/adsorption has been considered
oxyhydroxides, clay minerals) adsorb them.44 an alternative to conventional processes because of its simplicity,
The standard techniques used for separation and recovery of low cost, and high efficiency for recovery of rare-earth ions at low
REMs can be classified into two groups: classical methods and concentrations.5,7
modern methods. Classical methods include fractional crystalliza-
tion, fractional precipitation and thermal reactions. Over a long 4. Adsorption process for removal of rare-earth metals
time, these processes had wide industrial applications. However,
their limitations made them obsolete, to the extent that other 4.1. General concepts
modern and more efficient methods were emerging, such as sol-
vent extraction and ion exchange.45e47 Adsorption is a unit operation of mass transfer in which one or
In the process of fractional crystallization, one or more than one more components of a fluid phase (gas, steam or liquid) are
rare-earth metal is precipitated by the changes in the concentra- transferred to the surface of an adsorbent solid and separation is
tions of salts in solution, caused by the evaporation of a saturated performed. The driving force for adsorption is the difference in
solution. If there is any change in the solubility of the compounds, concentration between the fluid phase and the adsorbate. The
the composition of the formed precipitate will be different from the species that accumulates in the interface of the material is usually
composition of the original solution. While the precipitate that called adsorbate, and the solid surface on which the adsorbate ac-
forms is richer in the less soluble component, the more soluble cumulates is called adsorbent.19,20
component will be more enriched in the liquor. Thus, two phases Being a surface phenomenon, adsorption is considered feasible
are formed, each with a different composition from the mother for solids that have large surface and internal areas, since this
liquor.48 process occurs mainly on the pore walls or on active sites within the
342 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355

particle. The separation of a certain adsorbate in a fluid phase can The modification of activated carbons is known to play a key role
occur by differences in molar mass, in the shape or polarity, in enhancing the adsorption efficiency because of the change in the
allowing some molecules to bind more strongly on the surface of surface morphology and the function by particular functional
the adsorbent than others, or also by the size the pores, which, groups.67e69 A novel and low-cost ethylenediaminetriacetic acid-
when very small, cannot admit large molecules.58 functionalized activated carbon (EDTA-AC) was synthesized by
Adsorbate retention can occur by two types of mechanisms, anchoring N-[(3-trimethoxysilyl)propyl]-ethylenediaminetriacetic
according to the nature of the interaction forces between adsorbate acid (TMS-EDTA) to oxidized activated carbon for recovery Nd.70
and adsorbent: physical adsorption and chemical adsorption. In Kano et al.,71 on the other hand, improved the adsorption capac-
physical adsorption (physisorption), the bond of the adsorbate to ity of activated carbon modified with oxidizing agent potassium
the adsorbent surface involves intermolecular interactions of permanganate for recovery La, Yb, Lu, Eu, Y and Sc. The physico-
attraction between the relatively weak species, which can be chemical properties of activated carbon were improved after
attributed to Van der Waals forces. Physisorption occurs at low oxidation, which made activated carbon possess not only a more
temperatures, with possibility of multilayer formation of molecules hydrophilic functional groups (e.g., eCOOH) but also more nega-
in the adsorbed phase. Because it has low intensity interactions, tively charged surface.
physisorption is a reversible process and presents a low value of Silica is a conventional inorganic matrix used for hybridization
enthalpy of adsorption.19,59 with organic matrix. Experimental results showed that CLx/SiO2
On chemical adsorption (chemisorption), in turn, a chemical nanocomposite produced by incorporation of SiO2 in sulfuric acid
interaction between the solid adsorbent and the adsorbate occurs, modified cellulose possesses higher surface area than that of citric
that is, an electron transfer between the species, creating bonds acid modified, whereas the particle size was the same in both
that are stronger than those observed in physisorption. This cases.72 For Eu, La, Nd and Sc recovery, application of gum Arabic
chemical bond generates a monolayer on the surface of the grafted polyacrylamide based silica nanocomposite (GA-g-PAM/
adsorbent. Chemisorption is an irreversible process, since it SiO2) using in-situ radial graft copolymerization method presented
changes the chemical nature of the adsorbate and can occur at high good removal and recovery of Eu, La, Nd and Sc.73 In another study,
temperatures.19,59 nanometer silica powders were successfully synthesized by sol-gel
methods with ammonium hydroxide as catalyst for recovery Yb.74
4.2. Adsorbents Shu et al.75 had reported the synthesis of a novel silica-based
extraction resin (HDEHP/SiO2-P) by impregnating and immobiliz-
The choice of the adsorbent material is essential when one ing of bis(2-ethylhexyl)phosphoric acid extracting into the macro-
wants to study the removal of a given component by the process of porous silica materials. The material exhibited satisfactory
adsorption. Such choice directly affects the economic viability and resistance against nitric acid medium at high temperature for Gd
efficiency of the process. Adsorbents are natural or synthetic sub- adsorption.
stances with microcrystalline or amorphous structure whose sur- In recent years, nanocomposites have gained significant atten-
face can present pores capacity of acting in the separation tion for adsorption process because of their phenomenal proper-
process.60 The pore size of an adsorbent material is crucial for the ties. A large variety of nanocomposites have been prepared based
access of the adsorbate species. According to International Union of on various organic and inorganic matrices. Magnetic nanoparticles
Pure and Applied Chemistry (IUPAC), pore diameters smaller than are another most frequently used inorganic matrix for the synthesis
2 nm characterize microporous materials, diameters between 2 and of hybrids by either functionalization or capsuling in some polymer
50 nm are typical mesoporous materials, and diameters larger than matrixs. The preparation of diethylenetriamine-modified magnetic
100 nm are found in macroporous materials.61 chitosan nanoparticles were employed for Dy, Nd and Er adsorp-
In addition to the steric hindrance caused by the difference/ tion.76 Similarly, bifunctional nanocomposite was synthesized by
similarities in the poro size of the adsorbent and the size of an encapsulating inorganic matrix in xanthan gum anchored by Fe and
adsorbate, other different mechanisms may dominate the adsorp- Zr. The xanthan gum by anchoring metal ions zirconium and
tion process. Based on literatures, five mechanisms governing encapsulating inorganic matrix (Zr@XG-ZA) exhibited good ab-
metal adsorption have been proposed.62e64 They include: (1) sorptivity toward Sc, Nd, Tm and Yb.77 In another research, one-pot
electrostatic interactions between metals and adsorbent surface; co-precipitation method was used for preparation of cellulose
(2) cation exchange between metals and protons or alkaline metals intercalated zinc-aluminium layered double hydroxide nano-
on adsorbent surface; (3) metal complexation with functional composite (CL-Zn/Al LDH) for Y, La and Ce recovery.78
groups on the structure of adsorbent; (4) metal precipitation to Commercially available adsorbents, including oxidized multi-
form insoluble compounds; and (5) reduction of metal species and walled carbon nanotubes for La and Dy,79 graphene oxide for La, Nd,
subsequent adsorption of the reduced metal species. The role of Gd, and Y,80 activated carbon for Ce,81 and activated carbon and
each of adsorption mechanisms and capacity varies considerably silica composites for Sc,82 are some examples of materials that have
with adsorbent properties and target metals.64 shown great potential for the recovery of REMs. Although the
Activated carbon, silica gel, activated alumina, zeolites and commercially available adsorbents offer high surface area, the main
synthetic polymeric resins are the main commercial adsorbents disadvantage of using them is their high cost, compared with
used.19 The requirements for practical applications of adsorbents widely available and low-cost bioadsorbent materials.
include high selectivity for rare-earth ions, adsorbability at low pH,
easy desorption of metal ions, high rates of adsorption and 4.3. Bioadsorbents
desorption, high adsorptive capacity, selectivity, regenerability, low
cost, compatibility, and high mechanical resistance.5 An adsorbent Bioadsorption is an adsorption process that aims to remove or
will hardly be great in all these aspects. However, several adsor- recover organic and inorganic substances in aqueous solutions
bents have been reported in the literature for the recovery of rare- using a biological material that may include live or dead microor-
earth ions. ganisms and their components, seaweed, vegetables, industrial
Activated carbons are widely being explored as adsorbents in waste, agricultural waste, and natural waste as adsorptive medium,
the emerging field of environmental because of their well- named bioadsorbent.15,83e85 The bioadsorption process occurs by
developed porous structure and tunable surface chemistry.65,66 interactions between the metal and certain active sites (carboxyl,
 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355 343

amino, sulfate groups, among others), present in the coatings of the related to the mass transfer from within the fluid to the outer
biomaterial.86e88 surface of the adsorbent; and resistance to intraparticle diffusion,
Bioadsorption has been studied as an alternative in extractive related to the mass transfer from the outer surface of the adsorbent
metallurgy processes for recovery and concentration of high- to its porous structure.111 In addition, knowledge about kinetics is
demand and/or high-added value metals, such as gold, silver, ura- required to select the optimum conditions for the design of full-
nium, and, also, REMs.89 In this sense, the use of bioadsorbents is scale processes.112
promising, since it is also a cost-effective industrial process In recent years, different kinetic models, mainly represented by
compared with the environmental impact of similar the pseudo first-order113 (Eq. (1)) and pseudo-second-order114 (Eq.
technologies.16,17,90 (2)) models, have been applied to study the adsorption of REMs.
Applications of bioadsorbents for the uptake of REMs have been
studied by many research groups. In recent years, majority of the

authors studied the potential of bioadsorbents including Pseudo- qt ¼ qe $ 1
e
k1 $t (1)
monas sp. for recovery La91 (Kazy et al., 2006), brown marine alga
Turbinaria Conoides for recovery of La, Ce, Eu and Yb,92 prawn
carapace for recovery of La and Ce,93,94 neem sawdust and fish scale k2 $q2e $t
qt ¼ (2)
for recovery of La,95 grapefruit peel for recovery of La and Ce,21 1 þ k2 $qe $t
poly(carboxymethyl)-cellulose (PCMC) for recovery of La,96 and
microalgae Acutodesmus acuminatus for recovery of Eu,97 without where qe is the concentration of adsorbate retained in equilibrium
any prior treatment. on the solid phase or the capacity of adsorption at equilibrium (mg/
Furthermore, since bioadsorption is a surface-based process, g), qt the concentration of adsorbate retained in the solid phase at
bioadsorbents can possess selectivity and affinity for REMs time t (min) or the capacity of adsorption at time t (mg/g), k1 the
enhanced by modifications on their surface. Chemically modified constant of the adsorption rate of pseudo-first-order (min
1), and
bioadsorbents were also investigated and reported to achieve k2 the constant of adsorption rate of pseudo-second-order (g/
improved REMs bioadsorption. For example, Sargassum polycystum (mg$min)).
Ca-loaded biomass was modified with CaNO3 for recovery of La, Eu Along with these two most used models, some other kinetic
and Yb,98,99 while Agrobacterium sp. HN1 was chemically modified models reported are the intraparticle diffusion model115 (IPD),
by HCl and NaOH for recovery of La and Ce,100 biohydrogel was Boyd's model116 (BM) and mass transfer model in external film115
modified by sporopollenin and xylan for recovery of Ce,101 cellulose (MTM). The IPD model, considers the transport of adsorbate from
(cell) was chemically modified by grafting thiourea (Thio-Cell) and the bio/adsorbent external surface into the pores as the rate con-
glutaraldehyde cross-linked chitosan was functionalized by poly(- trolling step. The BM helps to determine the bio/adsorption slowest
aminocarboxymethylation) (PCM-Chit) for recovery of Er,102 and step (external diffusion). The EMTR model assumes that the bio/
cellulose functionalized with thiourea for recovery of Eu and Nd.103 adsorption limiting step is the external diffusion. In other words,
Although different bioadsorbents represent an attractive alter- the solute mass transfer from the fluid phase to the external film
native to remove and recover REMs, carbon materials, such as formed on the surface of the bio/adsorbent material controls the
bamboo charcoal for recovery of La,104 activated carbon from rice process.
husks for recovery of La and Er,105 activated biochars from cactus Table 1 shows the fitting of the pseudo-first-order (PS1) and
fibres for recovery of Sm,106 and ammonium citrate-modified bio- pseudo-second-order (PS2) models to the experimental kinetic
char for recovery of La,107 appear to be good substitutes of activated data of adsorption of rare-earth ions in different bio/adsorbent
carbon. They disclose a high adsorption capacity and a high volume materials. One can observe that, in almost all the cases, the pseudo-
of microporosity, which is desirable in a great adsorbent. However, second-order model adjusts the experimental data, indicating the
they usually present a high cost involved and their regeneration by mechanism of chemical adsorption of REMs on most bio/adsor-
chemical and thermal procedures usually results in adsorbent bents reported in the literature.
deactivation.20,108 In this way, several features must be present in Iftekhar et al.78 applied the PS1 and PS2 models to adjust the
the bioadsorbent in order to make the bioadsorption process as a experimental kinetic data for the adsorption of Y, La and Ce in CL-
cost-effective technology, such as high versatility, effortless Zn/Al LDH nanocomposite. The results showed that the experi-
regeneration, high bioadsorption capacity, rapid kinetics, metal mental data were adjusted well to the PS2 equation, supporting the
selectivity, low cost and availability in large quantities in nature. hypothesis of chemisorption.
These properties coupled with characteristics related to techniques Iftekhar et al.72 found that the adsorption of Eu and La in sulfuric
and cost are key factors to replace conventional adsorbents in in- acid modified cellulose based silica nanocomposites (CLN/SiO2)
dustry.5,109,110 Finally, although these studies show that the use of followed a PS2 kinetics with the highest R2 value, while the value of
these bioadsorbent materials is promising for the REMs bio- R2 obtained by the PS1 equation was greater for Sc, compared with
adsorption, further studies are needed to compare the different the PS2 kinetics, and thus that the adsorption of Eu, La and Sc in
biomaterials based on the criteria for defining which material is CLN/SiO2 nanocomposite supports the hypothesis of chemisorption
most promising. for the first two and physisorption for the latter. In addition, IPD
and BM models were used to investigate the contribution of the
4.4. Adsorption kinetics various steps involved in the process of adsorption, i.e., intraparticle
diffusion and diffusion in external film. The fit of the experimental
The kinetics of adsorption is expressed as the adsorbate removal data indicated that the adsorption process of Eu, La and Sc in CLN/
rate in the fluid phase over time. The study of kinetics is extremely SiO2 nanocomposite was governed by diffusion in external film.
important to understand the mechanisms of the adsorption process Zhao et al.117 adjusted the experimental data of adsorption ki-
and its limiting steps. Depending on the temperature and pressure netics to the PS2 and IPD models. The fit results showed that the
conditions and the nature of the adsorbent and adsorbate, there are PS2 model is applicable for the kinetics of adsorption of La, Eu and
different resistances to mass transfer that can limit the overall rate Er in polyethylenimine-cross-linked cellulose nanocrystals (PEI-
of adsorption. The adsorbent material offers two resistances to CNC), suggesting that both adsorption and diffusion affected ab-
mass transfer: resistance to external diffusion (intraparticle), sorption because of the bond with surface ligands of PEIeCNC.
344 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355

Table 1
Parameters of pseudo-first-order and pseudo-second-order models adjusted to kinetic adsorption data obtained under experimental conditions of initial concentration of
REMs, pH, agitation speed, contact time and dosage of different bio/adsorbent materials.

REMs Bio/adsorbents Experimental conditions Pseudo-first-order Pseudo-second-order References

qe (mg/g) k1 (min
1) R2 qe (mg/g) k2 (g/(mg$min)) R2

La3þ Kenaf cellulose C0: 13890.6 mg/L, Dosage: 335.0 0.0251 0.945 280.0 0.00357 0.977 Rahman et al.124
Ce3þ 15.0 g/L, pH: 6, 2 h, 200 r/min 344.0 0.0251 0.928 265.0 0.00377 0.975
Nd3þ 305.0 0.0228 0.928 232.0 0.00430 0.976
Pr3þ 307.0 0.0228 0.946 268.0 0.00372 0.962
Sm3þ 245.0 0.0228 0.965 215.0 0.00465 0.969
Eu3þ 327.0 0.0225 0.985 218.0 0.00458 0.966
Gd3þ 313.0 0.0229 0.926 241.0 0.00414 0.979
La3þ KMnO4-AC C0: 0.1 mg/L, Dosage: 0.25 g/L, 0.0697 7.33  10
3 0.959 0.0999 0.26 0.999 Kano et al.71
Eu3þ pH: 3 0.0821 8.82  10
3 0.968 0.104 0.402 1.00
Yb3þ 0.0850 7.13  10
3 0.959 0.102 0.3 1.00
Lu3þ 0.0660 6.35  10
3 0.907 0.0991 0.332 0.99
Y3þ 0.0793 7.7  10
3 0.959 0.103 0.272 0.999
Sc3þ 0.0667 9.22  10
3 0.951 0.100 0.317 1.00
La3þ PEI-CNC C0: 100.0 mg/L, Dosage: 1.0 g/L, e e e 70.84 0.00265 0.9999 Zhao et al.117
Eu3þ pH: 5.4, 6 h e e e 83.12 0.00191 0.9998
Er3þ e e e 94.33 0.00198 0.9998
La3þ Co0.2Mn0.8Fe2O4 C0: 100.0 mg/L, Dosage: 0.3 g/L, 125.0 0.071 0.700 334.0 0.002 0.999 Ghobadi et al.126
Ce3þ pH: 7, 30 min, 250 r/min 25.0 0.092 0.969 334.0 0.008 0.999
La3þ CL-Zn/Al LDH C0: 50 mg/L, Dosage:1.2 g/L, pH: 79.92 0.56 0.80 52.74 9.5  10
3 0.98 Iftekhar et al.78
Ce3þ 7, 10 min, 150 r/min 115.85 0.57 0.94 55.83 4.3  10
3 0.95
Y3þ 68.87 0.46 0.81 53.45 6.07  10
3 0.99
La3þ CLN/SiO2 C0: 25 mg/L, Dosage: 3.0 g/L, 10.55 0.16 0.853 10.55 7.8  10
3 0.948 Iftekhar et al.72
Eu3þ pH: 6, 50 min, 200 r/min 10.57 0.08 0.933 10.57 0.02 0.988
Sc3þ 9.41 0.079 0.964 9.41 7.4  10
4 0.797
La3þ PCMC C0: 100 mg/L, Dosage: 0.2 g/L, 134.7 2.63  102 0.995 150.5 0.23  103 0.987 Tolba et al.96
pH: 5, 3 h, 200 r/min
La3þ GA-g-PAM/SiO2 C0: 25 mg/L, Dosage: 3.5 g/L, 5.64 3.27  10
3 0.947 5.64 8.4  10
3 0.944 Iftekhar et al.73
Nd3þ pH: 6, 60 min, 200 r/min 7.30 3.57  10
3 0.968 7.30 2.47  10
3 0.958
Eu3þ 5.77 4.23  10
3 0.942 5.77 1.32  10
3 0.815
Sc3þ 5.17 5.64  10
3 0.821 5.17 2.83  10
4 0.555
Nd3þ Zr@XG-ZA C0: 25 mg/L, Dosage: 3 g/L, pH: 7.37 0.08 0.97 7.37 1.23  10
2 0.94 Iftekhar et al.77
Tm3þ 4, 80 min 8.89 0.14 0.99 8.89 2.18  10
2 0.96
Yb3þ 7.41 0.11 0.98 7.41 1.59  10
2 0.95
Sc3þ 9.18 0.13 0.98 9.18 1.94  10
2 0.96
Nd3þ EDTA-AC C0: 144.24 mg/L, Dosage: 2.0 g/ e e e 55.12 0.042 0.999 Babu et al.70
L, pH: 5, 15 min, 250 r/min
Nd3þ Cellulose functionalized C0: 50 mg/L, Dosage: 4.0 g/L, T: 11.68 0.0552 0.6238 13.86 3.55  10
3 0.9729 Negrea et al.103
Eu3þ with thiourea 25  C, 30 min 10.26 0.0317 0.4342 11.57 4.11  10
3 0.9849
Gd3þ P-SBA-15 C0: 200 mg/L, Dosage: 0.5 g/L, 194.99 9.601 0.9658 202.8525 0.111 0.9987 Gao et al.134
pH: 4, 2 min, 200 r/min
Gd3þ MIL-101-PMIDA C0: 100 mg/L, Dosage: 1.0 g/L, 86.6 0.046 0.953 89.3 0.002 0.994 Lee et al.170
pH: 5.5, 2 h
Er3þ PCM-Chit C0: 100 mg/L, Dosage: 0.2 g/L, 114.86 2.34  102 0.989 130.53 2.25  104 0.990 AbdEleMagied et al.102
pH: 5, 4 h, 200 r/min
Yb3þ Nanometer Silica Powders C0: 8.6688 mg/L, Dosage: 33.9176 0.1999 0.7835 35.7926 0.0106 0.9827 Liu et al.74
0.245 g/L, pH:7.3

Table 1 shows the comparison of the adsorption performance of suitable project and analysis for the adsorbent/adsorbate sys-
REMs between the different non-conventional bio/adsorbent ma- tem in a process of separation by adsorption.112 When a solid
terials studies based on the maximum capacities of adsorption and adsorbent comes into contact with a given volume of a liquid
equilibrium times. In the case of magnetic nanoparticles of phase containing the adsorbate, adsorption occurs until equi-
Co0.2Mn0.8Fe2O4, they showed greater capacity of adsorption for La librium is achieved.118 At equilibrium, the adsorbed amount by
and Ce, in low kinetic equilibrium time. On the other hand, kenaf the adsorbent mass depends only on the final pressure and
cellulose-based poly (hydroxamic acid) ligand showed high temperature, thus, the evaluation of adsorption can be devel-
adsorption capacity for La, Ce, Pr, Gd, Nd, Eu and Sm, in higher ki- oped in constant temperature (adsorption isotherms). The
netic equilibrium time. adsorption isotherms provide ways to evaluate other features
It is important to note that the hybrid material based on LDH concerning the adsorption process, such as the volume of pore
with biopolymer in the intermediate layer (CL-Zn/Al LDH nano- distribution of the adsorbent and the magnitude of adsorption
composite) achieved equilibrium in only 10 min and showed enthalpy.
greater adsorption capacity compared with materials with higher Over the years, several models of isotherms have been
kinetic equilibrium time, such as the spheres of PEI-CNC. employed to describe the adsorption equilibrium. The modeling of
adsorption isotherms is essential to properly evaluate and design
4.5. Adsorption equilibrium adsorption systems. The Langmuir119 (Eq. (3)), Freundlich120 (Eq.
(4)), and Dubinin-Radushkevich121 (Eq. (5)) models are the most
The information on the adsorption equilibrium is usually a known and used to predict behavior in the adsorption process of an
crucial step for obtaining relevant knowledge about the adsorbate in a liquid phase.
 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355 345

 
qmax $KL $Ce Polanyi potential calculated by ε ¼ R$T$ln 1 þC1e (J/mmol), R the
qe ¼ (3)
ð1 þ KL $Ce Þ
ideal gas constant (8.314 J/(mol$K)) and T the temperature (K).
Table 2 shows the maximum values of adsorption capacity
1=n
qe ¼ KF $C e (4) (qmax) for the Langmuir and Freundlich isotherm models for the
adsorption equilibrium of various rare-earth ions from different
qe ¼ Xm $e
KD $ε
2
(5) bio/adsorbent materials. Compared with other models, Langmuir
and Freundlich models are widely used by researchers to describe
where qe is the concentration of adsorbate retained at equilibrium adsorption equilibrium.
on the solid phase or the adsorption capacity at equilibrium (mg/g), From Table 2, with the exception of some bio/adsorbent mate-
qmax the maximum concentration of adsorbate retained on the rials, the other ones followed the Langmuir model for adsorption of
solid phase or the maximum adsorption capacity (mg/g), KL the REMs. The adsorption of Sc and Y in hybridized silica-chitosan
Langmuir equilibrium constant for each adsorbate, corresponding (APTES silica-chitosan-PAN)122; Sc in CLN/SiO2 nanocomposite72;
to the ratio between the rates of absorption and desorption (L/g), Ce Sc, Tm, Yb and Nd in Zr@XG-ZA77 and Sc in GA-g-PAM/SiO2 nano-
the concentration of adsorbate in the fluid phase at equilibrium composite73 followed the Freundlich model assuming a heteroge-
(mg/L), KF the Freundlich constant related to the adsorption ca- neous surface with a non-uniform distribution of sorption heat.
pacity [(mg/g)$(L/mg)1/n], n the empirical constant related to the Meanwhile, Zhao et al.117 applied three isotherms, Langmuir,
intensity of adsorption (dimensionless), Xm the maximum Freundlich and Sips,123 to elucidate the data of equilibrium in PEI-
adsorption capacity for the formation of a monolayer (mg/g), KD the CNC, and found that the experimental data were more adjusted
constant associated with the adsorption energy (mol2/J2), ε the to the Sips model compared with the others. In addition to

Table 2
Langmuir and Freundlich isotherms parameters for REMs bio/adsorption onto different bio/adsorbent materials.

REMs Bio/adsorbents Experimental conditions Isotherm models qm (mg/g) References

La3þ kenaf cellulose C: 5e1400 mg/L, Dosage: 7.5 g/L, pH: 6, T: 32  C L 259.0 Rahman et al.124
Ce3þ L 244.0
Nd3þ L 208.0
Pr3þ L 235.0
Gd3þ L 219.0
La3þ KMnO4eAC C: 0.1e180 mg/L, Dosage: 0.25 g/L, pH: 3, T: 25  C L 0.071 Kano et al.71
Eu3þ L 0.0972
Yb3þ L 0.0846
Lu3þ L 0.0759
Y3þ L 0.0895
Sc3þ L 0.1215
La3þ GO Nanosheets C: 5e50 mg/L, Dosage: 1.0 g/L, pH: 6, T: 25  C L 85.67 Ashour et al.80
Nd3þ L 188.6
Gd3þ L 225.5
Y3þ L 135.7
La3þ Co0.2Mn0.8Fe2O4 C: 50e500 mg/L, Dosage: 0.3 g/L, pH: 6, T: 25  C L 750.0 Ghobadi et al.126
Ce3þ L 748.0
La3þ APTES silica-chitosan-PAN C: 1e250 mg/L, Dosage: 1.0 g/L, pH: 4, T: 23  C L 120.7 Ramasamy et al.122
Y3þ F 158.8
Sc3þ F 175.22
La3þ CL-Zn/Al LDH C: 50e150 mg/L, Dosage: 1.2 g/L, pH: 7, T: 25  C L 92.51 Iftekhar et al.78
Ce3þ L 96.25
Y3þ L 102.25
La3þ CLN/SiO2 C: 1e100 mg/L, Dosage: 3.0 g/L, pH: 6, T: 25  C L 29.48 Iftekhar et al.72
Eu3þ L 24.27
Sc3þ F 23.76
La3 PCMC C: 25e200 mg/L, Dosage: 0.2 g/L, pH: 5, T: 50  C L 170.2 Tolba et al.96
La3þ GA-g-PAM/SiO2 C: 20e140 mg/L, Dosage: 3.5 g/L, pH: 6 L 7.9 Iftekhar et al.73
Nd3þ L 12.24
Eu3þ L 10.11
Sc3þ F 11.05
La3þ MIL-101-PMIDA C: 20e150 mg/L, Dosage: 1.0 g/L, pH: 5.5, T: 25  C L 37.4 Lee et al.170
Ce3þ L 49.0
Nd3þ L 70.9
Sm3þ L 72.7
Gd3þ L 90.0
Nd3þ Zr@XG-ZA C: 20e100 mg/L, Dosage: 3 g/L, pH: 4 F 14.01 Iftekhar et al.77
Tm3þ F 18.15
Yb3þ F 25.73
Sc3þ F 132.30
Nd3þ EDTA-AC C: 10e300 mg/L, Dosage: 2.0 g/L, pH: 5, T: 20  C L 71.42 Babu et al.70
Nd3þ Cellulose functionalized with thiourea C: 10e300 mg/L, Dosage: 4.0 g/L, T: 25  C L 73.0 Negrea et al.103
Eu3þ L 32.0
Gd3þ P-SBA-15 C: 10e300 mg/L, Dosage: 0.5 g/L, pH: 4, T: 40  C L 209.1425 Gao et al.134
Gd3þ CNTs/GO C: 2e10 mg/L, pH: 5.9, T: 30  C L 534.76 Guo et al.125
Gd3þ HDEHP/SiO2eP C: 629e2044.25 mg/L, Dosage: 0.1 g/L, pH: 1, T: 50  C L 50.949 Shu et al.75
Er3þ PCM-Chit C: 25e200 mg/L, Dosage: 0.2 g/L, pH: 5, T: 50  C L 140.31 AbdEleMagied et al.102
346 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355

Freundlich, the Langmuir isotherm was followed by most of the not available at lower temperature.127 Likewise, the enthalpy values
adsorbent materials for adsorption of La. obtained for CL-Zn/Al LDH nanocomposite, GA-g-PAM/SiO2 and
On the other hand, the adsorption performance of La, Eu and Nd Zr@XG-ZA suggest the chemisorption process for REMs.73,77,78
in GA-g-PAM/SiO2 nanocomposite was elucidated using four equi- In general, the phenomenon of adsorption is a spontaneous and
librium models (Langmuir, Freundlich, Tempkin72 and Elovich), but exothermic process with entropy decrease.128 However, there are
the higher R2 values indicated that the process was well explained cases of process in which the enthalpy and entropy of bio/adsorp-
by the Langmuir model with the maximum adsorption capacity of tion are positive, suggesting the endothermicity and the growing
7.9, 10.11 and 12.24 mg/g, respectively.73 randomness in the solid/fluid system interface during the adsorp-
Notably, the adsorption capacity of La, Eu and Sc in CLN/SiO2 tion process, respectively.129 A possible explanation for the endo-
nanocomposite72; La, Yb, Lu, Eu, Y and Sc in activated carbon thermicity in terms of enthalpy of adsorption is that when ions or
modified with KMnO471; Nd, Yb and Tm in Zr@XG-ZA77; and La, Nd, molecules are close to be adsorbed, they have to lose part of their
Eu and Sc in GA-g-PAM/SiO2 nanocomposite73 was smaller than for hydration sheath. This dehydration process consumes energy that
other bio/adsorbent materials, such as La, Ce, Pr, Gd and Nd in kenaf exceeds the exothermicity of surface-related ions.130
cellulose124 and Gd in hydrosols of carbon nanotubes/graphene The magnitude of DH0 can also give an idea of the type of
oxide (CNTs/GO).125 On the other hand, the maximum adsorption adsorption. The heat developed during physical adsorption is of the
capacities were found to be 750.0 and 748.0 mg/g for La and Ce, same order of magnitude as the heat of condensation, i.e.,
respectively, in magnetic nanoparticles of Co0.2Mn0.8Fe2O1264 . 2.1e20 kJ/mol, whereas the heat of chemisorption usually varies
between 80 and 200 kJ/mol.131 In general, the change in free energy
is between 0 and 20 kJ/mol for physisorption and 80 and 400 kJ/mol
4.6. Thermodynamic quantities for chemisorption.132 Electrostatic attractions may be between 30
and 70 kJ/mol.7
The study of thermodynamic parameters, such as enthalpy
change ðDH 0 Þ, entropy change ðDS0 Þ, and Gibbs free energy change
ðDG0 Þ are used to understand the characteristics of the adsorption 5. Desorption of rare-earth metals in batch
process. When the adsorption process is exothermic, there is a
decrease of the adsorbed amount of solute with increasing tem- Desorption for recovery of the adsorbed metal is one of the most
perature (ðDH 0 < 0Þ), otherwise, the process is endothermic important aspects of any successful development of the bio/
ðDH0 > 0Þ. Regarding the spontaneity of the system, it is possible to adsorption process.91 It is possible to decrease the cost of the pro-
determine if the adsorption process occurs spontaneously (DG0 < cess and also the dependency of the process in a continuous supply
0) or not spontaneously ðDG0 > 0Þ. Finally, the adsorbent can pre- of the bio/adsorbent by desorption. A successful desorption process
sent high ðDS0 > 0Þ or low ðDS0 < 0Þ affinity for the adsorbate. requires the proper selection of eluents, which depends on the
These thermodynamic quantities can also indicate whether the nature of the bio/adsorbent and on the mechanism that governs the
adsorption process occurs by chemisorption or physisorption. adsorptive process. The selection of an efficient and effective eluent
From the results of the study of the adsorption equilibrium at for desorption and regeneration is of utmost importance. Various
different temperatures, the parameters of Gibbs free energy (Eq. solvents with different concentrations have been used for desorp-
(6)) and enthalpy and entropy (Eq. (7)) can be calculated. tion and regeneration, such as HNO3, HCl, NaCl, thiourea, and CaCl2.
Eluents must be not harmful to the bio/adsorbent material, less
DG0 ¼
R$T$lnKC (6) expensive, environmentally sound, and effective.133
Only some studies reported in the literature have focused on
DG0 ¼ DH 0
T$DS0 (7) carrying out batch experiments to identify the suitable eluents for
the recovery of REMs. Table 4 presents a summary of recent studies
where KC is the constant of chemical equilibrium, R the ideal gas on the desorption of REMs and regeneration of different bio/ad-
constant (8.314 J/(mol$K)), and T the temperature (K). sorbents, in addition to the recovery efficiency of substances used
Table 3 shows the thermodynamic parameters reported in the as eluents and the number of regeneration cycles.
literature for the bio/adsorption process of rare-earth ions in Zhao et al.117 tested different concentrations of HNO3 for the
several bio/adsorbent materials. desorption of La in PEIeCNC. Regeneration efficiency for La
From Table 3, it can be concluded that REMs bio/adsorption on remained above 95% after three regeneration cycles using 0.1 and
most of the bio/adsorbents reported was endothermic. The 1.0 mol/L HNO3, confirming the stability of PEI-CNC in dilute nitric
adsorption of Gd on HDEHP/SiO2-P was observed to be exothermic acid medium, attributed to the cross-linked network structure.
as verified by the negative value of DH0 (
6.77 kJ/mol).75 In addi- Ashour et al.80 evaluated different concentrations of HNO3 for
tion, adsorption process seems to be spontaneous and favorable the desorption of La, Nd, Gd and Y in graphene oxide nanosheets
due to negative DG0 along with positive DS0. In a study carried out (GO nanosheets). 0.1 mol/L HNO3 presented the highest desorption
by Iftekhar et al.72 on CLN/SiO2 nanocomposite for adsorption of La, efficiency (>95.0%) for the REMs after one regeneration cycle.
Eu and Sc, the negative values of DG0 increased (
1.89 Gao et al.134 evaluated the reusability capacity of Inorganic
to
14.51,
1.91 to
17.48, and
0.75 to
19,12 kJ/mol, respec- phosphorous acidemodified mesoporous SBA-15 (P-SBA-15) in six
tively) with temperature from 293 to 323 K indicating that consecutive adsorption/desorption cycles for the recovery of Gd.
adsorption was favorable at a higher temperature.72 The same was The HCl solution (0.2 mol/L) was used as elution solvent. After the
observed by Iftekhar et al.73,77 in a temperature range of sixth regeneration cycle, the desorption efficiency can still reach
298e328 K. 92.3%. The reduction in capacity is mainly due to loss of a small
In addition, from Table 3, the majority of studies reported the amount of binding sites during the regeneration process.
adsorption process of REMs was endothermic in nature. For Iftekhar et al.78 verified the reusability capacity of CL-Zn/Al LDH
example, Iftekhar et al.72 investigated the effect of temperature nanocomposite. After five regeneration cycles using 0.1 mol/L HCl, a
from 293 to 323 K. The increase in removal of Eu, La and Sc on CLN/ high desorption percentage of the REMs Y, La and Ce was observed.
SiO2 nanocomposite may be due to the pore size enlargement This shows that CL-Zn/Al LDH nanocomposite was a high-
which provides new adsorbent sites for the interaction which were performance recyclable adsorbent for the treatment of Y, La and Ce.
 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355 347

Table 3
Thermodynamics parameters for bio/adsorption of REMs by non-conventional bio/adsorbent materials.

REMs Bio/adsorbents T (K) DG0 (kJ/mol) DH0 (kJ/mol) DS0 (J/mol$K) References

La3þ Co0.2Mn0.8Fe2O4 298
7.39 5.14 42.0 Ghobadi et al.136

313
8.02
333
8.86
Ce3þ Co0.2Mn0.8Fe2O4 298
7.27 3.41 35.0 Ghobadi et al.136
313
7.81
333
8.53
La3þ CL-Zn/Al LDH 293
15.54 50.73 276.81 Iftekhar et al.89
303
16.14
313
17.69
323
19.69
Ce3þ CL-Zn/Al LDH 293
9.61 58.49 266.78 Iftekhar et al.89
303
11.6
313
12.40
323
13.76
Y3þ CL-Zn/Al LDH 293
5.10 61.77 222.07 Iftekhar et al.89
303
6.03
313
6.35
323
12.72
La3þ CLN/SiO2 293
1.89 188.95 644.96 Iftekhar et al.83
303
5.88
313
8.86
323
14.51
Sc3þ CLN/SiO2 293
0.75 24.12 82.42 Iftekhar et al.83
303
4.69
313
14.23
323
19.12
La3þ GA-g-PAM/SiO2 298
0.15 32.57 110.14 Iftekhar et al.84
308
1,35
318
2.82
328
3.31
Nd3þ GA-g-PAM/SiO2 298
0.13 41.33 138.51 Iftekhar et al.84
308
0.86
318
3.15
328
3.99
Eu3þ GA-g-PAM/SiO2 298
3.98 12.55 54.92 Iftekhar et al.84
308
4.29
318
4.53
328
5.77
Sc3þ GA-g-PAM/SiO2 298
1.10 46.37 157.47 Iftekhar et al.84
308
1.41
318
3.36
328
5.79
Nd3þ Zr@XG-ZA 298 1.61 51.53 166.85 Iftekhar et al.88
308 0.42
318
1.41
328
3.37
Tm3þ Zr@XG-ZA 298
1.34 53.62 184.25 Iftekhar et al.88
308
2.91
318
5.23
328
6.17
Yb3þ Zr@XG-ZA 298
0.83 160.78 535.28 Iftekhar et al.88
308
2.71
318
5.19
328
18.32
Sc3þ Zr@XG-ZA 298
1.98 105.4 357.93 Iftekhar et al.88
308
4.32
318
7.11
328
13.14
Gd3þ HDEHP/SiO2eP 298
11.86
6.77 17.0 Shu et al.86
303
11.95
313
12.12
323
12.29

Iftekhar et al.72 verified that the regeneration of CLN/SiO2 solution of HNO3 on the desorption efficiency of Gd was studied.125
nanocomposite was very efficient for recovering Eu, La and Sc up to The desorption of Gd reached a 95.4% recovery percentage in pH 0.1.
three adsorption/desorption cycles, using 0.5 mol/L HCl as eluent. After five regeneration cycles, the CNTs/GO hybrid hydrosols still
However, in the third cycle, the recovery of Eu, La and Sc decreased showed a high desorption rate, over 80%.
to 59.9%, 57.6% and 49.9%, respectively. Thus, additional cycles were Iftekhar et al.77 investigated the reusability capacity of
not investigated. Zr@XG-ZA nanocomposite using 0.1 mol/L HNO3 for recovery of
In the case of hydrosols of carbon nanotubes/graphene oxide Nd, Yb, Tm, and Sc, in five regeneration cycles. Regeneration ef-
(CNTs/GO), the effect of different values of pH of an aqueous ficiency was higher during the first cycle and decreased to 50%
348 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355

Table 4
Recovery of REMs and reuse of different bio/adsorbent materials in batch.

REMs Bio/adsorbents Eluent for desorption Regeneration cycles Recovery percentage References

La3þ KMnO4-AC HNO3 (10%) 5 71%e9% Kano et al.71

La3þ GO Nanosheets 0.1 mol/L HNO3 1 99% Ashour et al.80
Nd3þ 1 99%
Gd3þ 1 96%
Y3þ 1 95%
La3þ PEI-CNC 0.1 mol/L HNO3 3 98.88%e95.68% Zhao et al.117
La3þ Co0.2Mn0.8Fe2O4 0.2 mol/L HNO3 3 90.0%e90.0% Ghobadi et al.126
Ce3þ 3 90.0%e90.0%
La3þ CL-Zn/Al LDH 0.1 mol/L HCl 5 100.0%e91.0% Iftekhar et al.78
Ce3þ 5 98.0%e92.0%
Y3þ 5 90.0%e80.0%
La3þ CLN/SiO2 0.5 mol/L HCl 3 96.0%e57.6% Iftekhar et al.72
Eu3þ 3 97.0%e59.9%
Sc3þ 3 90.0%e49.9%
La3þ PCMC 0.5 mol/L HNO3 5 94.4%e91.8% Tolba et al.96
La3þ GA-g-PAM/SiO2 0.1 mol/L HCl 3 80%e50% Iftekhar et al.73
Nd3þ 3 81%e56%
Eu3þ 3 91%e50%
Sc3þ 3 90%e41%
Ce3þ Kenaf cellulose 2 mol/L HCl 10 98%e92.5% Rahman et al.124
Nd3þ Zr@XG-ZA 0.1 mol/L HNO3 5 86%e43% Iftekhar et al.77
Tm3þ 5 90%e53%
Yb3þ 5 92%e56%
Sc3þ 5 97%e70%
Nd3þ EDTA-AC 1 mol/L HCl 5 >90% Babu et al.70
Gd3þ P-SBA-15 0.2 mol/L HCl 6 92.3% Gao et al.134
Gd3þ CNTs/GO HNO3 (pH ¼ 1) 5 95.40%e80.04% Guo et al.125
Gd3þ MIL-101-PMIDA 0.1 mol/L HCl 5 88%e80% Lee et al.170
Gd3þ HDEHP/SiO2eP 2 mol/L HNO3 1 95% Shu et al.75
Er3þ PCM-Chit 0.5 mol/L Thiourea, acidified with H2SO4 5 93.95%e91.99% Abd El-Magied et al.102

after the fifth cycle. The possible reason for the reduction in REM (MIL-101-PMIDA) and Zr@XG-ZA. Thus, one can conclude that
removal after each cycle can be because of the hydraulic shear LDH-based materials and grafted hybrids show better adsorption
force in the adsorption process, which damages the surface of and regeneration capacity than silica-based and commercially
Zr@XG-ZA nanocomposite, reducing the availability of adsorption available materials, such as activated carbon.
sites.
The effect of HNO3 concentration as eluent on the desorption 6. Bio/adsorption of rare-earth metals in dynamic system
percentage of Gd from HDEHP/SiO2eP, used as adsorbent material,
was investigated by Shu et al.75 The desorption percentage The choice of the operating system for adsorption depends
increased significantly with the increasing concentration of HNO3, mainly on the volume of fluid to be treated, its continuity and
between 0.1 and 2 mol/L, and reached about 95% recovery in the composition, as well as the regeneration conditions of the adsor-
concentration of 2 mol/L HNO3. bent. Batch system tests are used for preliminary studies of an
Babu et al.70 evaluated the Nd recovery using acidic solutions adsorbent material, since they provide information on the effec-
containing various concentrations of HCl, ranging from 0.01 to tiveness of the adsorption for removal of specific impurities and the
1 mol/L, for the regeneration of EDTA-AC particles. The increase maximum amount that can be adsorbed by a particular unit.
in the HCl concentration resulted in an increase in desorption However, these experiments are limited to the treatment of small
efficiency of up to 99% of desorption, in only one regeneration volumes of effluent, and do not provide data for exact dimension of
cycle, with a 1 mol/L HCl solution. Since reutilization plays a vital the continuous treatment systems.135,136 In industrial applications,
role in the process of large-scale production, the regeneration of continuous adsorption processes in fixed bed columns are generally
the adsorbent was tested in five regeneration cycles. Regenera- used for the treatment of wastewater, on a large scale, because of
tion efficiency was maintained up to 90% after the fifth regen- their simplicity and high removal efficiency.137 In the fixed-bed
eration cycle, showing the potential of EDTA-AC for industrial adsorption process, adsorbent solids are packaged and immobi-
applications. lized in a column through which a fluid is drained. Along the col-
A comparison based on the maximum capacities of adsorption, umn, the solute is adsorbed until the adsorbent reaches a certain
equilibrium times and regeneration cycles between the different state of saturation.19
materials studied for bio/adsorption of REMs was carried out. To evaluate the adsorption profiles of a solute in a given column,
Among the bio/adsorbent materials studied, kenaf cellulose breakthrough curves are constructed. Breakthrough curves relate
showed potential to be used for up to 10 cycles, but its equilibrium the ratio between the solute concentration at the output of the
time is high compared with other hybrid materials. Similarly, P- column and the concentration at the input (C/C0) and the flow time
SBA-15 seems to be even better than many commercially available of the solution through the column (t) (or effluent volume). The
materials studied for bio/adsorption of REMs, because of its high shape of the breakthrough curves is affected by parameters such as
adsorption capacity, low kinetic equilibrium time, and good reuti- fluid flow, concentration of adsorbate in feed, properties of the
lization. In addition, regeneration was not efficient for activated adsorbent and bed height.138,139
carbon modified with KMnO4 (KMnO4-AC), CLN/SiO2 and GA-g- The application of mathematical models is essential to extend a
PAM/SiO2 nanocomposites, carbamoylmethylphosphine oxide- fixed-bed column from a laboratory scale to an industrial scale.140
functionalized with (N-(phosphonomethyl)iminodiacetic acid) Several mathematical models can be used to describe the profile
 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355 349

of concentration vs. time of the column, including the models of of the Yoon and Nelson model (min
1), t the time required for
Bohart and Adams141 (Eq. (8)), Thomas142 (Eq. (9)), Yoon and 50% breakthrough of adsorbate (min), AC the constant of the Clark
Nelson143 (Eq. (10)), Clark144 (Eq. (11)), Yan et al.145 (Eq. (12)) and model, r the constant of the Clark model (min
1), n the exponent
Bed depth service time146 (BDST) (Eq. (13)). of the Freundlich isotherm, qy the maximum adsorption capacity
  of the Yan et al. model (mg/g), AY the constant of the Yan et al.
H model, N0 the bed adsorption capacity (mg/g), v the linear ve-
KB $C0 $ t
vt
C e locity (cm/min), Ka the rate constant (L/(mg$min)), and Z the bed
¼     (8) height (cm).
C0 H KB $qB $Ht
KB $C0 $ t
vt v
$ 1
ε
ε The characteristics of the breakthrough curves are described by
e þe
1 several parameters, such as breakthrough time (tb , min), volume of
treated effluent until tb (Vb , L), adsorption capacity until the
C 1 breakthrough point (qb , mg/g), exhaust/saturation time of the
¼   (9)
C0 KTh $qTh $m column (ts ), volume of treated effluent until ts (Vef , L), adsorption
Q

KTh $C0 $t
1þe capacity until saturation (qs , mg/g), and height of the mass transfer
zone (zm , cm). The breakthrough point is usually established ac-
cording to the effluent, therefore varying from one paper to
C 1
¼ (10) another. The saturation point, in turn, can range from C/C0 ¼ 0.9 to
C0 1 þ e½KYN ðt
tÞ
C/C0 ¼ 1.

C 1
¼1
 1 (11) 6.1. Bio/adsorption in fixed-bed column
C0 1 þ AC $eðr$tÞ n
1
The literature on the dynamic bio/adsorption process in fixed-
C 1 bed column for REMs is rarely available. During the literature
¼1
!AY (12) survey for bio/adsorption of REMs, only eleven studies were
C0
C0 $Q found for bio/adsorption in continuous system. However, for
1þ qy $m$t
practical applications, the behavior of the adsorbate/adsorbent
system is the best explained by the dynamic adsorption in fixed-
 
 bed columns.28
C0
ln ¼ ln eKa $N0 $Z=v
1
Ka $ c0 $t (13) Table 5 presents the experimental data of breakthrough curve
C
1
for continuous adsorption of REMs in different bio/adsorbent ma-
Where KB is the kinetic constant of adsorption of the Bohart e terials, as well as the parameters obtained in the fitting of the
Adams model (L/(mg$min)), v the bed surface speed (cm/s), qB the Thomas model, which was the best adapted to the experimental
adsorption capacity of the Bohart-Adams model (mg/g), ε the data.
porosity of the bed, KTh the kinetic constant of adsorption of the To explain the dynamic performance of the bio/adsorption
Thomas model (L/(mg$min)), qTh the maximum adsorption ca- process of La, Chen,104 Wu et al.,22 Oliveira et al.,147 and Das
pacity of the Thomas model (mg/g), KYN the adsorption constant et al.95 used the models of Thomas, Bohart-Adams, Yoon-Nelson

Table 5
Parameters of continuous fixed-bed adsorption of REMs onto different bio/adsorbent materials, under operating conditions (Length
inner diameter ratio (L/Di), pH, tem-
perature (T), bed height (z) and flow rate (F)) and the parameters from Thomas model.

REMs Bio/adsorbents Operating conditions tb qu ts qs zM KTh qTh R2 References

(min) (mg/g) (min) (mg/g) (cm) (mL/(mg.min)) (mg/g)

La3þ Bamboo C0: 41.0 mg/L, L/Di: 23.5/0.45, pH: 7.2, 2632a e e 121.0 e 2.07  10
2 128.0 0.9798 Chen104
charcoal T: 25  C, z: 7.4 cm, F: 0.076 mL/min
La3þ Fe3O4@Ca-Alg C0: 138.9 mg/L, L/Di: 20/2, pH: 5.0, 750a e e e e e e e Wu et al.22
T: 25  C, z: 3.5 cm, F: 1.0 mL/min
La3þ Sargassum sp. C0: 50.0 mg/L, L/Di: 25/2.5, pH: 5.0, 14750a e 19075b e 3.66 2.02  10
2 77.79 0.910 Oliveira et al.147
T: 25  C, F: 1.0 mL/min
La3þ Fish scale C0: 250.0 mg/L, L/Di: 15/3, pH: 6.0, 200a e 250 e e 1.6  10
5 716.64 0.965 Das et al.95
powder T: 25  C, z: 12.0 cm, F: 1.0 mL/min
Nd3þ D113resin C0: 100.0 mg/L, pH: 6.9, T: 25  C, 982a e e 216.7 e 1.36  10
3 231.1 e Xiong et al.152
F: 0.28 mL/min
Nd3þ Sargassum sp. C0: 50.0 mg/L, L/Di: 25/2.5, pH: 5.0, 17675a e 23475b e 3.99 2.01  10
2 76.45 0.956 Oliveira et al.147
T: 20e25  C, F: 1.0 mL/min
Sm3þ D152 resin C0: 200.0 mg/L, L/Di: 11/0.6, pH: 6.7, 1522a e e 495.0 e 7.36  10
3 507.0 e Xiong et al.148
T: 25  C, F: 0.23 mL/min
Er3þ D113 resin C0: 200.0 mg/L, L/Di: 23.5/0.45, pH: 6.04, 769a e e 269.0 e 4.31  10
2 257.0 0.9803 Xiong et al.149
T: 25  C, z: 7.4 cm, F: 0.208 mL/min
Ce3þ D151 resin C0: 200.0 mg/L, L/Di: 30/0.3, pH: 6.5, 556a e e 321.0 e 2.39  10
2 315.0 0.976 Yao150
T: 25  C, F: 0.27 mL/min
Eu3þ D113 resin C0: 100.0 mg/L, L/Di: 23.5/0.45, pH: 6.5, 1743a e e 255.4 e 0.0168 255.4 0.9908 Xiong and Zheng151
T: 25  C, F: 0.109 mL/min
Yb3þ Gel-type weak C0: 100.0 mg/L, L/Di: 23.5/0.45, pH: 5.5, 357a e e 305.0 e 9.7  10
2 311.0 0.9869 Zheng and Xiong153
acid resin T: 25  C, z: 7.4 cm, F: 0.28 mL/min
Pr3þ D72 resin C0: 100.0 mg/L, L/Di: 23.5/0.45, pH: 3.0, 1974a e e 201.0 e 1.42  10
2 203.0 0.9725 Xiong et al.154
T: 25  C, F: 0.152 mL/min
a
C/C0 ¼ 0.05.
b
C/C0 ¼ 0.9.
350 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355

and BDST. In addition to these four models, the influence of The evaluation of the adsorption process of REMs in multi-
the process parameters, bed height and flow rates was also component systems, in turn, is a way to approach a real effluent
investigated. containing those metals, in continuous processes. A limited number
The recovery of La in fish scale powder was studied by Das of publications have explored bio/adsorption of REMs in multi-
et al.95 The results showed that when the bed height and the flow component systems in continuous fixed-bed adsorption.
rate were 12 cm and 1 mL/min, respectively, the maximum removal Diniz et al.155 evaluated the bioadsorption of a ternary system of
efficiency achieved 88.5%. In addition, the increased flow rate was La, Eu, and protons Hþ in fixed-bed column with protonated
inversely related to the removal of La in fish scale powder. The S. polycystum biomass. One can observe that the biomass has higher
experimental data of bioadsorption of La in fish scale powder were affinity for Eu than for La, indicating that La occupied the binding
well-adjusted by the BSDT model. To evaluate the data of the sites more quickly. The overshoot of La observed in the column
breakthrough curve, the Thomas model was employed and pre- output showed that this element occupied binding sites more
sented a good fitting. Also, with an increase of the dilution rate quickly and with lower affinity than Eu, which was gradually
(0e50%), the kinetic constant of the Thomas model (KTh) increased replacing La, until saturating the column. Another study in fixed-
from 1.6  10
5 to 1.9  10
5 mL/(mg$min). Chen104 also reported bed column using immobilized cells of Pseudomonas aeruginosa
that the experimental data of the breakthrough curve presented and the ternary mixture of lanthanides (La, Eu and Yb)156 resulted
good fitting by the Thomas model using bamboo charcoal, and the in the following sequence of bioadsorption: Eu>Yb>La, evidenced
maximum value of qTh was very close to the experimental data. in the following breakthrough times: 83, 79 and 66 min, respec-
Nevertheless, in the case of the iron oxide loaded calcium alginate tively. Similarly, the overshoot in the output concentration of La
beads (Fe3O4@Ca-Alg) at higher flow rates, the breakthrough was also observed. Oliveira et al.147 investigated the bioadsorption
occurred more quickly. At lower flow rates, the breakthrough curve of a binary mixture of La and Nd in Sargassum sp. The Sargassum sp
became less pronounced, which suggests that the diffusion of La biomass adsorbed Nd more strongly than La, evidencing a slight
through the Fe3O4@Ca-Alg spheres was more pronounced at low selectivity of the biomass for Nd over La, since the bioadsorption of
flow rates.22 Nd partially dislocated the La already adsorbed.
The bioadsorption performance of La and Nd in mono- Therefore, there is a lack of comprehensive studies on bio/
component solutions, using Sargassum sp. as bioadsorbent, was adsorption of REMs in continuous system in fixed-bed column.
studied by Oliveira et al.147 The experimental data of the break- Studies involving the bio/adsorption of toxic metals157e160 have
through curves showed good agreement with the Thomas, Bohart- comprehensively evaluated the fit of different mathematical
Adams and Yoon-Nelson models. The tb values indicated that the models to explain the experimental data of breakthrough curve,
Nd ions were more strongly linked to the biomass than the La ions. and to determine the performance indicators of the column. This is
The breakthrough of La occurred about 3 min before that of Nd. The important for projects scaling-up the bio/adsorption process.
height of the mass transfer zone for both metals was narrow
(3.3e4.0 cm) compared with the total height of the column (25 cm). 6.2. Desorption in fixed-bed column
The sharp increase in the concentration of output between tb and ts
has shown that the fixed-bed column system was appropriate to The recovery of the adsorbed REMs in continuous fixed-bed
recover the REMs using Sargassum sp. biomass, and that the adsorption and later reuse of bio/adsorbent are key issues for
mechanisms of resistance to intraparticle diffusion and diffusion in successful industrial applications of any material. The desorption
external film were probably not the limiting step of the process in process must be able to release the rare-earth ions retained in the
the experimental conditions used. bio/adsorbent material and ensure that it is effectively regenerated.
The Thomas model was also successfully applied to adjust the The reutilization of the biomaterial in consecutive adsorption/
experimental data of breakthrough curve to study the adsorption desorption cycles presents as advantages the reduced cost of the
process of Sm,148 Er,149 Ce,150 Eu,151, Nd,152 Yb153 and Pr,154 in overall process and the dependence on the continuous supply of
continuous fixed-bed adsorption. the bio/adsorbent.161
The D113 resin was evaluated for recovery of Er,149 Nd152 and The recovery of REMs from different bio/adsorbents has the
Eu.151 The Thomas model was welleadjusted to the data of the following advantages: (a) regeneration and reuse of the bio/
experimental study in column, with high value of R2 for adsorption adsorbent material, (b) recovery of REMs, and (c) reduction of
of Er, Nd and Eu. In addition, the value of qTh for REMs was very sludge and of the process cost.4
close to the experimental data. Xiong et al.148 investigated the The success of a desorption process requires the proper selection
performance of the D152 resin for recovery of Sm. The coefficients of eluents in batch, which depends on the bio/adsorbent and the
of the Thomas equation for adsorption of Sm were KTh of bio/adsorption mechanism, for application in continuous adsorption
7.36  10
3 mL/(mg$min) and qTh ¼ 507.0 mg/g. Yao,150 evaluating operation. According to Das47 the eluent must present low cost, be
the recovery of Ce in D151 resin, also reported that the experi- effective in removing the adsorbed elements, not damage the bio-
mental data of breakthrough curve showed good fit by the Thomas adsorbent, and not impact the environment. Considering that the
model. The recovery of Yb in gel-type weak acid resin was evalu- bond between the surface of the bio/adsorbents with rare-earth ions
ated by Zheng and Xiong.153 The Thomas model was successfully involves passive ion exchange, a slightly to strongly acidic condition
applied to the experimental data to predict the breakthrough is enough for desorption to occur.162 However, the desorption is very
curves. In addition, the maximum value of qTh was very close to the specific for each system and an acid is typically used for desorption if
experimental qu. Finally, the recovery of Pr in D72 resin was the bio/adsorbent possess hydroxyl groups which need to be re-
investigated by Xiong et al.154 The experimental data were well generated from the previously adsorbed rare-earth ions. The use of
adjusted by the Thomas model, and the theoretical value of qTh was acids in desorption is also an advantage, since acidic solutions are
very close to the experimental. common effluents in almost all industries.
Thus, one can infer that the experimental data were well Most studies for recovery of REMs in dynamic system reported
adjusted to the Thomas model, which indicates that this model was in the literature use HCl as eluent. This acid presented promising
successfully used to predict the breakthrough curves of REMs and results in the desorption of 93.9% and 100% of La and Nd, respec-
can be used to determine the characteristic parameters of fixed-bed tively, in the algae Sargassum sp.147 This high performance is due to
column, useful to design the bio/adsorption process. the presence of excess of Hþ ions in acid medium, which efficiently
 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355 351

remove the rare-earth ions from the carboxylic sites. In addition, dynamic performance. Besides, the studies reported in the litera-
few chemical reagents are effective and not harmful for different ture are limited to laboratory scale to examine the adsorption
bio/materials, including CaCl222 and NaCl.154 Table 6 presents a mechanism and capacity. There is a lack of studies on practical
summary of the studies reported in the literature about the re- applications, particularly industrial ones, of adsorption processes
covery of REMs in continuous fixed-bed adsorption and regenera- for recovery of REMs. This depends on the transfer of adsorption
tion of bio/adsorbents after adsorption/desorption cycles, as well as experiments in fixed-bed column in batch scale to pilot plants,
the desorption efficiency of substances used as eluents and the aiming at an industrial-scale project.163
number of regeneration cycles. Scale-up studies can be carried out by different approaches,
Wu et al.22 investigated the desorption efficiency of La in including computer simulation, tests on small-scale columns, and
Fe3O4@Ca-Alg spheres in continuous fixed-bed. The authors response surface methodology. Anastopoulos et al.7 and Iftekhar
concluded that breakthrough curves for lanthanum recovery did et al.28 advocate the idea that the best way to predict the long-term
not show significant changes during the cycles, indicating that the performance of the adsorption process is by industrial-scale tests
Fe3O4@CaeAlg spheres have a good durability, as well as good under specific conditions of continuous flow.
desorption efficiency in three cycles of regeneration. Important indicators of performance of an adsorption column,
Das et al.95 carried out adsorption and desorption cycles for the such as behavior of the breakthrough curves and mass transfer
regeneration of fish scales used as bioadsorbent material and areas, are optimized in pilot-scale column studies, which connect
simultaneous recovery of La. The maximum recovery obtained for applications of adsorption in laboratory scale and industrial scale.
La was 84.6%. The bioadsorbent recovered up to 81.3% of La at the The increase of the fixed-bed column scale must consider charac-
end of the sixth cycle. After the sixth cycle, a drastic decrease was teristics of the adsorbent materials, such as shape, diameter, and
observed in the recovery of La, which can be attributed to damage density, to avoid operational problems in practical applications of
on the bioadsorbent surface, by the continuous contact with the the adsorption process, including hydrodynamic limitations and
desorbent agent. fouling in the column. The position of the feed solution in the
The efficient elution of the earth-rare ions adsorbed in China column is another operational aspect to be considered in the scale-
weak acid cation resin (D113-III resin) was essential to ensure the up project. Although the descending flows are generally adopted,
reuse of D113-III resin in repeated regeneration cycles. The resin ascending flows offer a more uniform solute distribution and
showed 100% desorption efficiency for recovery of Sm,148 minimize the pressure gradients and the fouling potential of the
Er,149 Ce,150 Eu,151 Nd,152 Yb153 and Pr,154 in repeated cycles of adsorbent in the column. In addition, when the solution is fed on
adsorption/desorption in continuous fixed-bed adsorption, indi- upward flow, particles of the adsorbent material with reduced di-
cating that D113-III resin can be regenerated and reused. ameters can be used, requiring smaller volumes of adsorbent and
As reutilization plays a vital role in the processes of large- leading to higher adsorption rates.164,165
scale production, the regeneration of the bio/adsorbent and re- To the best of our knowledge, no study in the literature has
covery of REMs are crucial to production process from an eco- investigated the removal and recovery of REMs in continuous fixed-
nomic point of view, to reduce costs in industrial bed adsorption pilot-scale or large scale, using non-conventional
applications.70,95 Moreover, a limited number of publications bio/adsorbents. According to Chen et al.,166 the greatest difficulty
have explored the removal and recovery of REMs, as well as the to change the scale of the adsorption process occurs because it is an
reuse of non-conventional bio/adsorbents spent after the unsteady-state process.
removal of these metals. This study has presented recent data on In addition to further study on fixed-bed adsorption, regenera-
the bio/adsorption of REMs in continuous fixed-bed, aiming at tion of adsorbents, and cost evaluation, studies that reflect real
the regeneration and reuse of non-conventional bio/adsorbents systems are also needed, since most studies found employs mono-
after adsorption/desorption cycles. component solutions of REMs, at higher concentrations than what
is usually detected in the environment. So far, the only study re-
7. Practical applications and future prospects of the bio/ ported in the literature involving the recovery of REMs in real
adsorption process effluent is the study conducted by Das et al.,95 involving the re-
covery of lanthanum in ceramic industrial effluent using fish scales
This literature survey has shown that, to date, most of research powder as bioadsorbent material. Furthermore, for the bio/adsor-
available on bio/adsorption of REMs using low-cost alternative bent material to be promising in practical applications, its regen-
bio/adsorbents are restricted to investigations of batch systems eration performance must be considered, since it is a significant
(kinetics and adsorption equilibrium). Little attention has been factor to reduce the cost of wastewater treatment.
given to regeneration and continuous fixed-bed adsorption studies, Therefore, the application of non-conventional bio/adsorbents
which are essential for the simulation and prediction of the for removal and recovery of REMs in continuous systems of

Table 6
Recovery of REMs and reuse of different bio/adsorbent in continuous fixed-bed adsorption.

REMs Bio/adsorbents Eluent Cycles Recovery percentage References

La3þ Fe3O4@Ca-Alg 0.05 mol/L CaCl2 3 e Wu et al.22

La3þ Sargassum sp. 0.10 mol/L HCl e 93.3% Oliveira et al.147
La3þ Fish scale powder 0.1 mol/L HCl 6 84.6%e81.3% Das et al.95
Nd3þ D113 resin 1 mol/L HCl 1 100.0% Xiong et al.152
Nd3þ Sargassum sp. 0.10 mol/L HCl e 100.0% Oliveira et al.147
Sm3þ D152 resin 0.5 mol/L HCl e 100.0% Xiong et al.148
Er3þ D113 resin 4.0 mol/L HCl e 100.0% Xiong et al.149
Ce3þ D151 resin 0.5 mol/L HCl e 100.0% Yao150
Eu3þ D113 resin 3.0 mol/L HCl e 100.0% Xiong and Zheng151
Yb3þ Gel-type weak acid resin 3.0 mol/L HCl e 100.0% Zheng and Xiong153
Pr3þ D72 resin 1.0 mol/L HCle e 100.0% Xiong et al.154
0.5 mol/L NaCl
352 T.B. Costa et al. / Journal of Rare Earths 38 (2020) 339e355

bio/adsorption for the treatment of industrial effluents, or even on effluents; and the effectiveness of non-conventional bio/adsorbent
a pilot scale, is not yet common. Currently, the literature on bio/ materials in pilot plant applications to be subsequently evaluated
adsorption of REMs is limited to batch systems, aiming to under- on a large scale.169
stand the adsorption mechanism, the equilibrium time, and the
effect of parameters such as pH, temperature, contact time and 8. Conclusions
initial concentration. However, the increasing number of studies on
this subject in recent years indicates that batch studies must be Before the current scenario, the production of REMs tends to
accompanied by column studies, because it is a promising alter- significantly increase over the next few years. As much as REMs
native for the recovery of REMs, in addition to being more contribute with small fractions, their strategic importance is large
economical and effective in large-scale processes. enough. The “small” consumed volumes of REMs are limiting in the
Studies involving the removal of toxic metals in a fixed-bed confection of technological products (computers, lamps, and mo-
column using different non-conventional bio/adsor- bile phones), the development of clean technologies (hybrid cars,
bents157,158,160,167,168 have investigated in greater depth the influ- wind and solar energies), petroleum cracking, communication,
ence of adsorption process parameters, such as bed height, flow defense applications, among others. Thus, the availability of REMs
rate and an initial adsorbate concentration. Cantuaria et al.160 is a matter of extreme importance for technological purposes.
investigated the removal and recovery of Ag using a fixed-bed In Brazil, one of the main recent challenges is the development
column and a calcined bentonite clay called Verde-lodo as an of the separation and purification processes of REMs on a large
adsorbent. Results have shown that when comparing the parame- scale, requiring, therefore, the incentive for the improvement of
ters obtained for the different flow rates, the 5 mL/min flow came purification techniques. For this purpose, several conventional
up with better results for the length of mass transfer zone and the methods can be applied, such as solvent extraction, chemical pre-
percentage of removal. The regeneration cycles were carried out cipitation, ion exchange and bio/adsorption. Among them, bio/
with the selected flow rate and nitric acid as the eluent. The adsorption is considered a promising alternative to conventional
adsorbent recovered up to 68.50% of Ag at the end of the third cycle. processes because of its simplicity, low cost, high efficiency and cost
In addition, all breakthrough curves were well adjusted by the effectiveness compared with the environmental impact of similar
Bohart-Adams model. The removal of Zn, Ni and Cu in alginate technologies, for recovery of rare-earth ions at low concentrations.
extraction residue from Brazilian Sargassum filipendula was studied This article gathered recent studies (after 2016) related to the
by Cardoso et al.,158 Moino et al.167 and Freitas et al.,168 respectively. use of non-conventional bio/adsorbents for recovery of REMs in
The results found by Cardoso et al.158 showed that the best oper- batch. We have found that Langmuir isotherm and the pseudo-
ating conditions were 0.5 mL/min and 1.0 mmol/L of zinc, providing second-order model fit well the experimental data in most cases.
lower mass transfer zone and higher uptake. Elution percentages of Furthermore, thermodynamic studies have shown that the
52% and 73% were obtained for the first and second desorption adsorption process of REMs is predominantly endothermic and
cycles, respectively, using CaCl2 as eluent. The Yan et al.145 model spontaneous, which confirms the existence of chemisorption. Is-
was more representative of the experimental data. Moino et al.167 sues related to the selection of solvents and regeneration of the bio/
in nickel bioadsorption experiments in fixed-bed column also adsorbent material are also important for the viability of the
showed that the maximum removal percentage (45%) was obtained process.
employing 0.5 mL/min and 1.0 mmol/L (best operation conditions). In conclusion, although a growing number of studies were
The regeneration evaluation showed that the column would not published on low-cost non-conventional bio/adsorbents for
efficiently perform other adsorption cycles, after the second removal of REMs, there is still a great need for real application on an
desorption step (elution percentage of 73%). Freitas et al.,168 in turn, industrial scale. In addition to further studies on fixed-bed
found a higher percentage removal of copper at the feed flow rate of adsorption, regeneration of bio/adsorbents, and cost evaluation,
0.5 mL/min and the inlet concentration of 1.0 mmol/L. Column data publications that reflect real systems are also needed, since most of
were best described by the Yan et al.145 model. Copper desorption the current studies employ synthetic and mono-component solu-
presented the highest value of elution efficiency with HNO3. The tions, at concentrations higher than those normally found in the
performance of Verde-lodo clay for binary silver and copper environment. Therefore, several points still need to be explored for
adsorption in fixed bed dynamic system was studied by Freitas industrial application. Future studies must explore multicompo-
et al.157 Based on efficiency and mass transfer parameters, 3.0 mL/ nent bio/adsorption, treatment of real effluents, continuous
min was determined as the optimum flow rate. High initial con- adsorption, regeneration of bio/adsorbent, and recovery of REMs in
centrations provided the best efficiency and removal results. successive absorption and desorption cycles.
Considering selectivity parameter, Verde-lodo clay showed to be
more selective for copper. Adsorption and desorption cycles were
Acknowledgments
carried out and revealed that the maximum number of cycles was
two and that HNO3 was an efficient eluent of copper and silver from  eReitoria de Pesquisa
The authors thank Espaço da Escrita e Pro
the adsorbent.
e UNICAMP e for the language services provided.
The transfer from adsorption processes using non-conventional
bio/adsorbents on a laboratory scale to industrial applications
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