water

Article
Evaluation of the Purity of Magnesium Hydroxide Recovered
from Saltwork Bitterns
Giuseppe Battaglia 1 , Maria Alda Domina 1 , Rita Lo Brutto 2 , Julio Lopez Rodriguez 3 ,
Marc Fernandez de Labastida 3 , Jose Luis Cortina 3 , Alberto Pettignano 2 , Andrea Cipollina 1, * ,
Alessandro Tamburini 1 and Giorgio Micale 1

1 Dipartimento di Ingegneria, Università degli Studi di Palermo (UNIPA), Viale delle Scienze,
90128 Palermo, Italy
2 Dipartimento di Fisica e Chimica—Emilio Segrè, Università degli Studi di Palermo (UNIPA),
Viale delle Scienze, 90128 Palermo, Italy
3 UPC-BarcelonaTECH, 08930 Barcelona, Spain
* Correspondence: [email protected]

Abstract: Magnesium has been listed among the 30 critical raw materials by the European Union.
In recent years, many green and sustainable alternative Mg2+ sources have been sought to satisfy
the EU’s demand and to avoid mineral ore consumption. In this context, saltwork bitterns, the
by-products of solar sea salt production, have attracted much attention thanks to their high Mg2+ con-
centrations (up to 80 g/L) and low Ca2+ and bicarbonate contents (<0.5 g/L). Although investigations
on Mg2+ extraction from bitterns in the form of Mg(OH)2 (s) have already been performed, product
purity has never been properly addressed. Mg(OH)2 (s) is a chemical compound of great interest
Citation: Battaglia, G.; Domina, M.A.;
and extensive utility in numerous industrial applications only if the powder’s purity is >95% (w/w).
Lo Brutto, R.; Lopez Rodriguez, J.;
Fernandez de Labastida, M.;
This work presents a comprehensive experimental effort of reactive precipitation tests with NaOH
Cortina, J.L.; Pettignano, A.; solutions at stoichiometric and over-stoichiometric concentrations to: (i) assess the technical feasibility
Cipollina, A.; Tamburini, A.; of Mg2+ recovery from real bitterns collected in saltworks of the Trapani district (Italy) and, (ii) for
Micale, G. Evaluation of the Purity of the first time, conduct an extensive purity investigation of the precipitated magnesium hydroxide
Magnesium Hydroxide Recovered powders as brucite. This experimental investigation demonstrates the possibility of extracting highly
from Saltwork Bitterns. Water 2023, valuable compounds from saltwork bittern waste, embracing the water valorization and resource
15, 29. https://doi.org/10.3390/ recovery approach.
w15010029

Academic Editor: Keywords: Mg(OH)2 (s); brucite; precipitation; mineral recovery; circular economy;
Alejandro Gonzalez-Martinez seawater valorization

Received: 21 November 2022

Revised: 16 December 2022
Accepted: 19 December 2022
1. Introduction
Published: 21 December 2022
Magnesium hydroxide (MH, Mg(OH)2 ) is a chemical compound widely employed in
Publisher’s Note: MDPI stays neutral numerous industrial fields [1]. In the last decade, MH has been established as a promising
with regard to jurisdictional claims in flame-retardant agent thanks to its degradation properties, and smoke- and toxic-free
published maps and institutional affil- characteristics [2]. Furthermore, it has been extensively used as an antibacterial agent,
iations.
a neutralization reagent of acidic liquid waste, as an environmentally friendly material
for reducing the water pollution of heavy metals [3], as a paper preservative and as a
precursor for magnesium oxide preparation [4–6]. Nowadays, commercial MH products
are mainly obtained from minerals (e.g., from serpentinite rock via the Magnifin pro-
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
cess [7]), bischofite brines [7] and seawater using dolomitic lime [8,9]. These processes are
This article is an open access article
high-energy-demanding and generate mineral depletion with a significant impact on the
distributed under the terms and environment. The worldwide market of MH is foreseen to reach 932,000 tonnes by 2022
conditions of the Creative Commons with a compound annual growth rate (CAGR) of 3.4% over 2016–2022, clearly marking a
Attribution (CC BY) license (https:// continuous, growing and attractive market [7]. However, the increasing mineral depletion
creativecommons.org/licenses/by/ and environmental concerns regarding the CO2 (g) footprint of obtaining MH from conven-
4.0/). tional sources have pushed researchers and industrials to seek alternative Mg2+ sources.

Water 2023, 15, 29. https://doi.org/10.3390/w15010029 https://www.mdpi.com/journal/water

Water 2023, 15, 29 2 of 22

Turek and Gnot [10], already in 1995, proposed a two-step process for the purification of
hard coal mine brines produced by coal mines in Poland. The idea was to purify the coal
brines while extracting, at the same time, high-added-value minerals. The brines contained
2.84 g/L of Mg2+ , which was recovered via precipitation in the form of MH. In the last
decade, increasing interest has been placed on seawater desalination [11–13] and the high
magnesium content in lake brines, as in the case of the Uyuni salar (Bolivia), which is one
of the largest sources of lithium and also contains 15–18 g/L of Mg2+ [14,15].
Magnesium is the third most abundant element in seawater after sodium and chloride.
It has a typical concentration of about 1.3 g/L, and its concentration almost doubles in
seawater reverse osmosis desalination brines. Zhang et al. [16], in their recent review,
highlighted the exponential increment of publications dealing with the topic of resource
recovery focused on the exploitation of seawater desalination brines. The reasons behind
that are the high Mg2+ concentration in brines and the ever-growing installed capacity of
desalination plants worldwide for the production of potable water, with the associated
brines being rejected.
Mg2+ is typically recovered from seawater brine as magnesium hydroxide via precip-
itation employing an alkaline reagent [16]. Besides MH, several Mg2+ compounds have
been produced from concentrated brines and wastewaters such as struvite (NH4 )MgPO4
·6(H2 O)(s)) [17,18], magnesium sulphate (MgSO4 7H2 O(s)) [19], and magnesium oxide
(MgO(s)) [20,21]. Furthermore, many alternative processes have been proposed to extract
Mg2+ using electro-membrane applications [22,23] or organic systems containing ionic
liquids [24].
Although, seawater and seawater brine represent a sustainable Mg2+ resource, the
recovery of Mg2+ from such sources is hindered by the presence of many dissolved ions.
The presence of HCO3 − and Ca2+ ions can cause the precipitation of calcium carbonate
(CaCO3 (s)) as calcite or aragonite at solution pH values above nine. In addition, if hydroxyl
ions and sulphate ions are dissolved in the solution, calcium can precipitate as calcium
hydroxide (Ca(OH)2 (s)) or calcium sulphate (CaSO4 ·2H2 O(s)), affecting the purity of the
recovered Mg2+ compounds [21,25].
Gong et al. [26] investigated the feasibility of mineral recovery from seawater brines.
The authors marked the high economic, social and environmental benefits associated with
the brine’s exploitation. Brines from the Perth seawater desalination plant (Perth, Australia)
were treated using lime as a precipitant to recover Mg2+ as MH. Low Mg(OH)2 (s) purity
of ~70% was reported due to the presence of bicarbonates and calcium ions, while it was
possible to reach values up to 91% only after a wet screening of the lime. Recently, Vassallo
et al. [27] have proposed a novel crystallizer, using NaOH, for the selective recovery of
Mg2+ , as MH, and Ca2+ , as calcium hydroxide, from the retentate of a nanofiltration unit
treating spent brine from an industrial water production plant of Evides Industriewater B.V.
(Rotterdam, The Netherlands). The spent brine had a concentration of 3 g/L of Mg2+ and
24 g/L of Ca2+ . The precipitation pH was carefully controlled during the process, leading to
100% Mg2+ and 97% Ca2+ recoveries with cationic purities above 95%. Morgante et al. [28]
characterized the sedimentation and filtration properties of Mg(OH)2 suspensions produced
by adopting the same novel crystallizer. The influence of brine concentrations, solution
flow rates and seeded precipitation (by-products recycled) were addressed. A marked
beneficial influence was observed by adopting seeded precipitation that considerably
reduced sedimentation times (up to four times) and enhanced filtration characteristics. In
the study, only synthetic solutions were employed, and no purity analyses were conducted.
The same research group also proposed an innovative technology to recover Mg2+ as
MH from seawater and industrial waste brines. An innovative ionic exchange membrane
crystallizer (Cr-IEM) was experimentally and numerically studied to recover Mg2+ in a
controlled manner exploiting low-cost alkaline solutions, such as Ca(OH)2 slurries [29,30].
The crystallizer employed an anionic membrane that allows the passage of only hydroxyl
ions, preventing the flux of undesired cations such as, for example, Ca2+ . To reduce the
impact of dissolved ions in brines, Yousefi et al. [31] studied the production of Mg(OH)2
Water 2023, 15, 29 3 of 22

nanoflakes, using poly(ethylene glycol) (PEG 4000) as a surfactant, from the impure brine
of Iranian evaporation ponds that contained ~50 g/L of Mg2+ and ~182 g/L of Ca2+ using
NaOH. To produce a high-purity magnesium hydroxide (purity values ~86%), the authors
carefully controlled the precipitation pH, which was kept between 9 and 9.5. This accurate
pH control reduced the Ca(OH)2 precipitation, with no impurity traces detected through
X-ray diffraction (XRD).
The use of NaOH solutions as alkaline reactants for the recovery of Mg(OH)2 from
brines or seawater allows for the production of highly pure Mg(OH)2 compounds. On the
other hand, NaOH is an expensive reactant. As an alternative, the use of low-cost lime
(Ca(OH)2 ) suspensions is also possible and may lead, in principle, to high Mg(OH)2 purity
if suitable brine or seawater pre-treatments are adopted in order to reduce carbonates,
calcium, and sulphate ions. In the literature, the following strategies have been reported:
(i) the use of highly pure lime suspensions [32]; (ii) decarbonation of brines to avoid calcium
carbonate precipitation by adding sulfuric acid (H2 SO4 ) to lower the solution pH to four,
combined with a carbon dioxide removal step using a desorption tower and a brine aerating
process [32]; (iii) a controlled reaction with Ca(OH)2 to precipitate soluble bicarbonate
as insoluble calcium carbonate without Mg(OH)2 precipitation [32]; and (iv) adoption of
sodium carbonate (Na2 CO3 ) and barium chloride (BaCl2 ) solutions to precipitate calcium
as calcium carbonate (CaCO3 ) and sulphates as barium sulphate (BaSO4 ) [33].
Among the unconventional sources of Mg2+ , bitterns represent a promising one.
Bitterns are highly concentrated solutions and are typically by-products of the natural
evaporation process of seawater from solar salt manufacturers. Lee et al. [34] evaluated
the feasibility of exploiting bitterns for the production of struvite. They employed a food-
grade bittern containing 32 g/L of Mg2+ and 8 g/L of Ca2+ . The bittern showed a similar
performance as a Mg2+ source with respect to seawater for phosphate removal; however,
it performed worse for ammonia removal. Alamdari et al. [35] performed fundamental
research on MH precipitation kinetics from sea bittern. The authors studied the MH
precipitation in seeded reactors using real and artificial solutions of 30 g/L of Mg2+ . A
higher nucleation rate and a slower growth rate were inferred for MH precipitation from
sea bitterns with respect to that from pure artificial solutions. Cipollina et al. [36] studied
the potential Mg2+ recovery from bitterns collected from the final basins of the saltworks
operating in the district of Trapani (Sicily, Italy). Experiments were performed both in
semi-batch and continuous crystallizers treating a ~23 g/L bittern. A high Mg(OH)2 purity
and a total Mg2+ recovery (e.g., >99%) were reported. However, no details were provided
regarding solid mass purity, which is a fundamental market requirement to be fulfilled.
The present work aims at filling this gap, thoroughly investigating Mg2+ recovery
and, for the first time, precipitated Mg(OH)2 (s) mass purity from real saltwork bitterns to
pursue a strategy for valorizing waste bitterns as sustainable Mg2+ sources. Such bitterns
are characterized by high Mg2+ content (>20 g/L) and very low Ca2+ and bicarbonate
concentrations (<0.3 g/L) thanks to the fractionated precipitation process that occurs along
the initial evaporative ponds [37]. Such low Ca2+ concentration makes them the perfect
candidates for the recovery of high purity Mg2+ compounds. This research is carried out
within the framework of the EU-funded “Circular Processing of Seawater Brines from
Saltworks for Recovery of Valuable Raw Materials” (SEArcularMINE) project. The overall
project objective aims to valorize the spent bitterns of ancient and still-used saltworks
located in the Mediterranean Sea. The target is to extract minerals and produce on-site
chemical reagents and energy embracing the circular economy approach. It has been
reported that almost 10 million tonnes per year of sea salt is produced in the Mediterranean
Sea alone, generating about 10 million m3 /year of exhausted bitterns. Considering an
average Mg2+ content of 50 g/L, ~1.2 million tonnes of Mg(OH)2 (s) can be produced
covering 30% of the Mg(OH)2 global demand [38]. Concerning the economics of the
proposed approach, with a focus on Mg(OH)2 production, only external electric energy
would be required. Therefore, no reagent transport costs or NaOH pellets are foreseen.
In the integrated SEArcularMINE scheme, NaOH solutions will be produced in loco by
 Mg(OH)2 global demand [38]. Concerning the economics of the proposed approach, with
a focus on Mg(OH)2 production, only external electric energy would be required. There-
Water 2023, 15, 29 fore, no reagent transport costs or NaOH pellets are foreseen. In the integrated SEArcu- 4 of 22

larMINE scheme, NaOH solutions will be produced in loco by adopting an EDBM (elec-
trodialysis with a bipolar membrane) unit. Culcasi et al. [39] discussed the economics of
adopting
NaOH an EDBM
production (electrodialysis
through with a bipolar
EDBM, showing membrane)
manufacturing costsunit. Culcasi
in the same et al. [39]
range as
discussed theavailable
commercially economics of NaOH
NaOH production
products. An EDBM through
unitEDBM, showing manufacturing
is an energivorous unit, but it
costsalso
will in the same acids
provide rangestreams
as commercially available NaOH
for the regeneration products.
of selective An EDBM
adsorbent unit is
columns em-an
energivorous
ployed for the unit, but itofwill
recovery also
trace providefrom
elements acids streamsNote
bitterns. for the
thatregeneration
EDBM unitsof canselective
be in-
adsorbent
tegrated columns
into employed
green power fore.g.,
grids, the recovery of trace
wind or solar, elements
thus fromreducing
drastically bitterns. Mg(OH)
Note that 2
EDBM units can be integrated into green power grids, e.g., wind
production costs. Life-cycle assessments and economic feasibility analyses will be con-or solar, thus drastically
reducing
ducted Mg(OH)
in the 2 production
SEArcularMINE costs.toLife-cycle
project assessments
better address and economic
the associated impacts andfeasibility
costs
analyses
of will be conducted in the SEArcularMINE project to better address the associated
the process.
impacts
The and costs
present of the
work process.
reports an extensive and detailed experimental campaign aimed at
The present work reports
assessing MH recovery and purity an extensive
from twoand detailed
bitterns experimental
collected from the campaign
Margi and aimed
Galia at
assessing MH recovery and purity from two bitterns collected from the
evaporation ponds of the Trapani saltworks (Sicily, Italy). Artificial bitterns were also pre- Margi and Galia
evaporation
pared, ponds
mimicking theofmacro-element
the Trapani saltworks
composition(Sicily, Italy).
of the real Artificial bitterns
ones, in order were any
to study also
prepared, mimicking the macro-element composition of the real
possible influence of the real nature of the employed bitterns on the MH precipitation ones, in order to study
any possible
process. Margi influence
bitterns ofhadtheareal
Mg2+ nature of the employed
concentration up to ~60 bitterns on theGalia
g/L, while MH bitterns
precipitation
had
process. Margi bitterns had a Mg 2+ concentration up to ~60 g/L, while Galia bitterns
concentrations ~24 g/L. Ca was 2+ 2+ lower than 200 mg/L in both bitterns. MH was precipi-
had concentrations
tated ~24 g/L. Ca and
by employing stoichiometric wasover-stoichiometric
lower than 200 mg/L NaOHin both bitterns.
solutions. A 2 MHmm was cir-
precipitated by employing stoichiometric and over-stoichiometric NaOH
cular, cross-sectional T-mixer reactor was adopted to ensure fast mixing of the reactants, solutions. A 2 mm
circular, cross-sectional
mimicking the conditions T-mixer reactor
in large was adopted
industrial to ensure
stirred-tank fast mixing
crystallizers. Forofthe
thefirst
reactants,
time,
mimicking the conditions in large industrial stirred-tank crystallizers. For the first time,
MH purity, produced from real Trapani bitterns, was thoroughly investigated analyzing
MH purity, produced from real Trapani bitterns, was thoroughly investigated analyzing
(i) digested samples of MH through ion chromatography and inductively coupled plasma
(i) digested samples of MH through ion chromatography and inductively coupled plasma
spectrometry techniques and (ii) MH powdered samples using SEM-EDS, thermogravi-
spectrometry techniques and (ii) MH powdered samples using SEM-EDS, thermogravimet-
metric (TGA) and XRD analysis. The reported results are very promising in view of de-
ric (TGA) and XRD analysis. The reported results are very promising in view of designing
signing a process for bittern valorization, exploiting saline water in all its forms, and mit-
a process for bittern valorization, exploiting saline water in all its forms, and mitigating
igating mineral ore consumption and its related environmental issues.
mineral ore consumption and its related environmental issues.
2.2.Materials
Materialsand andMethods
Methods
2.1.
2.1.Experimental
ExperimentalSet-Up
Set-Up
The
Theprecipitation
precipitationof ofMHMHfrom
fromreal
realand
andartificial
artificialbitterns
bitternswas
wasstudied
studiedby byemploying
employingaa
simple
simpleexperimental
experimentalsetup,setup,asasshown
shownFigure
Figure1.1.The
Theset-up
set-upconsisted
consistedofof(i)
(i)aa22mm
mmdiameter,
diameter,
circular,
circular, cross-sectional
cross-sectionalT-mixer,
T-mixer, drilled
drilled into
into aa polymethyl
polymethyl methacrylate,
methacrylate,PMMA,PMMA,block,
block,
(right
(rightupper
upper part
part of
of Figure
Figure 1)
1) and (ii) two gear pumps (FG200/FG300
(FG200/FG300 series,
series,TEOREMA
TEOREMA
Pump Technology® ®
PumpTechnology , Italy) controlled
, Italy) controlled byby
a dedicated
a dedicated LabVIEW
LabVIEW code. The T-mixer
code. had two
The T-mixer had
two horizontal
horizontal feed pipes
feed pipes 20 mm 20 long
mm long that merged
that merged in mm
in a 40 a 40 long
mm long vertical
vertical channel,
channel, i.e.,
i.e., the
the mixing
mixing channel.
channel. The T-mixer
The T-mixer was chosen
was chosen as an effective
as an effective laboratory-scale
laboratory-scale reactor
reactor to achieve to
aachieve a high mixing
high reactant reactantdegree
mixingindegree
a shortinmixing
a shorttime
mixing timethus
[40,41], [40,41], thus guaranteeing
guaranteeing a homog-a
homogenized
enized supersaturation
supersaturation level throughout
level throughout the entiretheprecipitation
entire precipitation
process.process.

Figure 1. Schematic representation of the employed experimental set-up: (1) a 2 mm diameter

circular, cross-sectional T-mixer; (2.a–2.c) beakers containing reactants, namely NaOH and bitterns,
and produced Mg(OH)2 suspensions; (3.a,3.b) gear pumps controlled by a dedicated LabVIEW code.
In the (upper right), a picture of the employed T-mixer.
Water 2023, 15, 29 5 of 22

The main reaction occurring in the crystallizer is the precipitation of magnesium

hydroxide that is described in the following equation:

Mg2+ + 2 NaOH → Mg(OH )2 (s) + 2 Na+ (1)

Real bitterns contain not only Mg2+ ions but also many other elements (e.g., Ca2+ ,
K+ , B(OH)4− , Br− , SO4 2− ) or dissolved natural organic matter (DOM). Therefore, co-
precipitation, inclusion or substitution of ions in the MH crystal structure or sorption onto
the crystal faces of further compounds could also take place.

2.2. Solution Preparation and Compositions

The precipitation of MH from two different bitterns collected from the Margi and
Galia saltworks, located in district of Trapani (Italy), was studied.
Two artificial bitterns were also prepared mimicking the macro-components contained
in the real ones in order to better understand the influence of the real nature of the employed
bitterns on the MH precipitation process. Specifically, similar concentrations of Na+ , K+ ,
Mg2+ , Ca2+ cations and Cl− , SO4 2− ions were targeted. Artificial bitterns were prepared by
dissolving KCl (Honeywell|Fluka™), NaCl (Volterra saltworks), MgCl2 ·6H2 O (Geo-Green
Snow Melter), Na2 SO4 (Honeywell|Fluka™) and CaCl2 (Honeywell|Fluka™) pellets.
Ion compositions in real and artificial bitterns were assessed using ion chromatography
(IC), flame-atomic absorption spectroscopy (F-AAS), inductively coupled plasma optical
emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-
MS) techniques as discussed in Section 2.4. The bitterns’ compositions are listed in Table 1.

Table 1. Ion composition of real and artificial bitterns adopted in the here-reported experimental
campaign.

Real Galia Artificial Galia Real Margi Artificial Margi

Macro
g/L g/L g/L g/L
Components
Na 83.7 ± 0.5 82.2 ± 0.7 44.6 ± 1.6 38.0 ± 0.4
K 7.4 ± 0.3 7.7 ± 0.1 11.9 ± 2.6 14.8 ± 0.1
Mg 23.0 ± 4.4 24.0 ± 1.5 60.5 ± 0.5 65.4 ± 0.6
Cl 193 ± 6 179.5 ± 0.6 200 ± 14 176 ± 1
SO4 35 ± 1 36.0 ± 0.6 83.0 ± 5.5 85.7 ± 0.2
Br 1.3 ± 0.2 - 2.5 ± 0.2 -
Micro
mg/L mg/L mg/L mg/L
Components
Ca 232 ± 40 270 ± 20 139 ± 32 112 ± 2
B 110 ± 22 18.7 ± 0.2 187 ± 8 46.6 ± 0.5

All MH precipitation tests were carried out using NaOH solutions prepared by dis-
solving NaOH pellets (Honeywell|Fluka™, with a purity of >98%) in deionized water.
NaOH solution concentrations were checked via titration using a standard HCl solution.

2.3. Experimental Tests and Methodological Procedures

MH precipitation experiments were conducted to identify the best operating conditions
for the complete recovery (i.e., >99.9%) of Mg2+ from bitterns producing high-purity MH
powders. Two main operating parameters were investigated: (i) the flow-rate ratio between
the NaOH and Mg2+ -containing solutions; and (ii) the hydroxyl/magnesium ion (OH− /Mg2+ )
ratio, with values corresponding to stoichiometric and 20% over-stoichiometric OH− .
The flow-rate ratio (i) was preliminarily studied performing stoichiometric precipita-
tion tests employing artificial solutions of MgCl2 at Mg2+ concentration levels of 12.2 g/L
(0.50 M) and 24 g/L (1.00 M). The NaOH/Mg2+ -solution flow-rate ratio was varied from
0.5 to 2.0 for the 0.50 M case and from 1.0 to 3.0 for the 1.00 M case. Note that artificial
Water 2023, 15, 29 6 of 22

MgCl2 solutions were used only for the NaOH/Mg2+ -solution flow-rate assessment. Sub-
sequently, the flow-rate ratio was investigated employing only Margi bitterns at selected
NaOH/bittern flow-rate values of 2.0 and 3.0.
The hydroxyl/magnesium ion (OH− /Mg2+ ) ratio (ii) was studied performing stoi-
chiometric and 20% over-stoichiometric OH− precipitation tests treating Margi and Galia
bitterns with a NaOH/bittern flow-rate ratio value of 2.0. NaOH stoichiometric amounts
were calculated based on an OH− /Mg2+ molar ratio taking Equation (1) into account; e.g.,
if a 1.0 M Mg2+ solution is targeted, a 2.0 M NaOH solution would be prepared. In the
NaOH solution preparation, Ca2+ precipitation was neglected, since its concentration is
100 times lower than that of Mg2+ .
All precipitation tests were carried out at room temperature. Table 2 lists all the
operating details of the experimental tests.

Table 2. Operating conditions of experimental tests. The first 6 rows refer to precipitation tests
performed using artificial MgCl2 solutions. From row 7 to row 16, information regarding tests with
real bitterns is listed. The first letter in the Tests column refers either to the Margi (M) or Galia (G)
bitterns; (ii) the second letter specifies the nature of the bittern, i.e., real (R) or artificial (A); (iii) the
third letter and numbers indicate stoichiometric (S) or 20% OH− excess (E) precipitation conditions
and NaOH/bittern flow-rate ratios of 2.0 or 3.0.

Bittern Flow NaOH/Bittern

Bittern Mg2+ NaOH
Tests OH− /Mg2+ Rate Flow Rate
Solution (M) (M)
(mL/min) Ratio
1M_S1 1160 ± 30 1.0 2.00 ± 0.04
1M_S2 Artificial MgCl2 Stoichiometric 780 ± 20 2.0 1.00 ± 0.02 1.00 ± 0.02
1M_S3 547 ± 10 3.0 0.67 ± 0.01
0.5M_S0.5 1560 ± 40 0.5 2.00 ± 0.04
0.5M_S1 Artificial MgCl2 Stoichiometric 1160 ± 30 1.0 0.50 ± 0.01 1.00 ± 0.02
0.5M_S2 780 ± 20 2.0 0.50 ± 0.01
M_R_S2 780 ± 20 2.0 2.50 ± 0.05
Real Margi Stoichiometric 2.48 ± 0.05
M_R_S3 547 ± 10 3.0 1.70 ± 0.03
M_R_E2 20% excess OH− 780 ± 20 2.0 3.00 ± 0.06
M_A_S2 780 ± 20 2.0 2.70 ± 0.05
Stoichiometric
M_A_S3 547 ± 10 3.0 1.80 ± 0.03
Artificial Margi 20% excess 2.69 ± 0.05
M_A_E2 780 ± 20 2.0 3.00 ± 0.06
OH−
G_R_S2 Stoichiometric 780 ± 20 2.0 1.00 ± 0.02
Real Galia 20% excess 0.96 ± 0.18
G_R_E2 780 ± 20 2.0 1.20 ± 0.03
OH−
G_A_S2 Stoichiometric 780 ± 20 2.0 1.00 ± 0.02
Artificial Galia 20% excess 0.97 ± 0.06
G_A_E2 780 ± 20 2.0 1.20 ± 0.03
OH−

Mg2+ -solutions and NaOH flow rates were calculated in order to achieve a total fluid
flow rate of ~2340 mL/min in the vertical channel of the T-mixer (i.e., the mixing channel),
resulting to a mean linear velocity of ~12.0 m/s. Under such flow conditions, short mixing
times can be achieved leading to a good reactant homogenization [42].
After precipitation, MH suspensions were collected in glass beakers and the pH was
measured within 30 s using a pH-meter WTW™ pH/Cond 3320. The suspension settled
for 48 h and was then filtered using a Buchner funnel and 1.8 µm glass fiber filters (GE
Healthcare Life Science Whatman™). The MH cake was washed using a deionized water
volume at least equal to that of the filtered suspension. The cake was then dried at 105 ◦ C
in an oven for 24 h. Finally, solids were crushed using a mortar and pestle. Figure 2 shows
a schematic representation of the adopted experimental procedure along with details of the
employed techniques used for the Mg2+ recovery and purity assessment; see Section 2.4 for
further details.
Water 2022, 14, x FOR PEER REVIEW 7 of 23

Water 2023, 15, 29 7 of 22

the employed techniques used for the Mg2+ recovery and purity assessment; see Section
2.4 for further details.

Figure2.2.Adopted
Figure Adoptedexperimental
experimentalprocedure:
procedure: (1)
(1)Mg(OH)
Mg(OH)22(s)(s) was
was produced
produced usingusing aa 22mmmmdiameter
diameter
circular,cross-sectional
circular, cross-sectionalT-mixer;
T-mixer;(2)(2) suspensions
suspensions were
were settled
settled andand filtered;
filtered; (3) (3) Mg(OH)
Mg(OH) (s)2(s) cake pu-
cake purity
2
rity analyzed
was was analyzed viaSEM/EDS,
via TG, TG, SEM/EDS, ICP-OES/MS
ICP-OES/MS and IC and IC techniques,
techniques, while while
(4) the(4) the Mg(OH)
Mg(OH) (s) 2(s) re-
recovery
2
covery was assessed by analyzing the total Mg 2+ in the filtrate via the F-AAS technique.
was assessed by analyzing the total Mg2+ in the filtrate via the F-AAS technique.

2.4. Analytical
2.4. Analytical Equipment
EquipmentandandProcedures
Procedures
Several analytical
Several analytical techniques
techniques were
wereemployed
employedto
toassess
assessbittern
bitternconcentrations, Mg2+2+
concentrations,Mg
recoveryand
recovery andthethepurity
purityofofproduced
producedMHMHsolids.
solids.
1.1. Bittern concentration.
concentration.Na Na++,, K
K++,, Mg
Mg2+, ,Cl Cl,−SO 42− and Br−Br
2− and ions were
− ions assessed through ion
2+ −
Bittern , SO 4 were assessed through
chromatography
ion chromatography (IC,(IC,
Metrohm
Metrohm 882882Compact
Compact IC IC
plus
plusandandDionex
Dionex ICS-1000/1100,
ICS-1000/1100, lo-
cated atatUNIPA
located UNIPAand andUPC UPClaboratories);
laboratories); Ca Ca2+2+waswasmeasured
measuredvia via flame-atomic absorp-
flame-atomic absorp-
tion spectroscopy
tion spectroscopy(F-AAS, (F-AAS,AAnalyst
AAnalyst200 200PerkinElmer
PerkinElmer (United States)
(Waltham, MA, USA) spectrometer,
spectrom-
located at UNIPA) and inductively coupled plasma
eter, located at UNIPA) and inductively coupled plasma mass spectrometry (ICP-MS,mass spectrometry (ICP-MS,
7800 ICP-MS from Agilent Technologies (United States),
ICP-MS from Agilent Technologies (Santa Clara, CA, USA), located at UPC) located at UPC) techniques;
and B(III) was
techniques; anddetermined
B(III) wasusing inductively
determined usingcoupled plasma
inductively opticalplasma
coupled emission spec-
optical
trometry spectrometry
emission (ICP-OES, Optima (ICP-OES,2100Optima
DV PerkinElmer (United States)
2100 DV PerkinElmer (Green spectrometer,
Bay, WI, USA) lo-
cated at UNIPA)
spectrometer, and the
located ICP-MS.and
at UNIPA) Bittern samples Bittern
the ICP-MS. were diluted
samples in deionized
were diluted water
in
before measurement.
deionized water before measurement.
2.
2. Mg2+2+ recovery
recovery(ion (ionconcentrations
concentrationsin infiltrates,
filtrates,see seeFigure
Figure2). Mg2+2+and
2).Mg and 2+ 2+
CaCa concentra-
concen-
trations
tions in thein the filtrates
filtrates werewere measured
measured usingusingthe F-AASthe F-AAS technique.
technique. Samples Samples were
were diluted
diluted in deionized
in deionized water before
water before measurement.
measurement. Samples Samples were diluted
were diluted and acidified
and acidified with
with
HNOHNO 3 (Sigma–Aldrich,
3 (Sigma–Aldrich, ≥65%) ≥65%,
to reachSainta pHLouis, MO, USA)
of around to reach
5 before a pH of around 5
measurement.
3. before
Mg(OH) measurement.
2 cationic purity (e.g., total content of cations in the precipitated MH). Ap-
3. Mg(OH)
proximately 2 cationic
100 mg purity
of MH (e.g.,
powdertotal was
content of cations
dissolved in 1 Min the
HClprecipitated
(Honeywell|FlukaMH). Ap- TM).

proximately 100Namgconcentrations
of MH powderwere wasmeasured
dissolved via in 1ICMatHCl (Honeywell|Fluka TM ).
Mg , Ca and
2+ 2+ + UNIPA laboratories. B(III)
Mg 2+ , Ca2+ and Na+ concentrations were measured via IC at UNIPA laboratories.
traces were also measured though ICP-OES. The same samples were also analyzed
B(III)
at UPC traces were also
laboratories bymeasured
dissolvingthough50 mg ICP-OES.
of MH in 100 ThemL same samples
of aqua were
regia andalso ana-
employ-
lyzed at UPCand
ing ICP-MS laboratories
an inductively by dissolving
coupled plasma50 mg of MH in
optical 100 mLspectrometer
emission of aqua regia(5100and
employing ICP-MS and an inductively
ICP-OES from Agilent Technologies, United States). coupled plasma optical emission spectrometer
4. (5100
Mg(OH) ICP-OES
2 massfrom purity.Agilent
TheTechnologies, United States).
crystalline structure and impurities present in the
4. Mg(OH) mass purity. The crystalline
Mg(OH)22 powders were semi-quantitatively analyzed structure and impurities
throughpresent in thediffraction
an X-ray Mg(OH)2
powders were semi-quantitatively
(XRD, Empyrean, Malvern PANalytical, analyzed
Unitedthrough
Kingdom, an diffractometer,
X-ray diffraction (XRD,
at UNIPA
Empyrean, Malvern PANalytical, United Kingdom, diffractometer, at UNIPA lab-
oratories) technique using CuKa radiation (1.542◦ A, 40 KV, 40 mA) in the 2θ range
of 10–70◦ at a step size of 0.05 and a step time of 144 s. The solids’ purity was also
Water 2023, 15, 29 8 of 22

investigated via thermogravimetric analysis (TGA, STA 449 F1 Jupiter analyzer, NET-
ZSCH, at UNIPA laboratories). TGA analyses were conducted at a heating rate of
10 ◦ C/min from 30 ◦ C to 1000 ◦ C, under a constant nitrogen flow of 20 mL/min. The
solids’ mass purity and morphological shapes were further assessed via scanning
electron microscopy (SEM FEI, United States, Quanta 200 FEG and JEOL, Japan, JSM-
7001F equipment at UNIPA and UPC laboratories, respectively) and via elemental
microanalysis adopting energy dispersive X-ray spectroscopy (EDS).

2.5. MH Precipitation Performance Parameters

The Mg2+ recovery and the produced MH-solids purity were assessed for each experi-
mental test in order to identify the best operating conditions at which high Mg2+ recovery
and high MH purity products can be achieved from bitterns.
The Mg2+ recovery was calculated as the difference between the initial and final mass
of magnesium in the solution divided by the initial mass. The final solution volume was
calculated as the sum of the volumes of the feed bitterns and the NaOH solution:
C Mg2+, bittern ∗ Vbittern − C Mg2+, f iltrate ∗ Vf inal
Mg recovery % = ·100 (2)
C Mg2+, bittern ∗ Vbittern

The presence of Ca2+ ions can affect MH purity. Therefore, Ca2+ recovery was also
calculated as it was for Mg2+ :

CCa2+, bittern ∗ Vbittern − CCa2+, f iltrate ∗ Vf inal

Ca recovery % = ·100 (3)
CCa2+, bittern ∗ Vbittern

Mg(OH)2 purity was calculated as:

1. The ratio between the Mg2+ ion concentration (mg/g) in the dissolved solids with
respect to all the other cations (cationic purity) detected through IC measurements:

C Mg2+
Cationic purity = ·100 (4)
∑iN=1 Ci
where N is the total number of cations and Ci (mg/g) is the concentration of the i-th cation.
◦
2. The ratio between the Mg(OH)2 mass (m∆T =320−480 C
Mg(OH )2
) associated with water-mass
loss in a temperature range between 320 C and 480 ◦ C (see Section TG analysis
◦

for further details), measured using TG analysis, over the dry sample mass (mass
purity). Note that the dry mass was calculated by subtracting the humidity content
=30−200◦ C
(m∆T
H2O ) determined in a temperature range between 30 ◦ C and 200 ◦ C to the
total initial sample mass. Therefore, mass purity from TG analysis was calculated as:

◦C
m∆T =320−480
Mg(OH )2
Mass purity % = Total − m∆T =30−200 ◦C ∗ 100 (5)
msample H2O

3. Results
The main objective of the present study was the assessment of the influence of two
main operating parameters on Mg2+ recovery from bitterns and on precipitated MH purity,
as detailed in the following Sections 3.1 and 3.2, respectively. In particular, the precipitation
of MH from two real and artificial bitterns, namely Margi and Galia, was carried out by
(i) varying the NaOH/bittern flow-rate ratio and (ii) performing stoichiometric and 20%
OH− over-stoichiometric tests; see Table 2.
Water 2023, 15, 29 9 of 22

Water 2022, 14, x FOR PEER REVIEW 9 of 23

3.1. Magnesium Recovery
3.1.1. Influence of the NaOH/Mg2+ -Solution Flow-Rate Ratio
The
Theinfluence
influenceofofthe NaOH/Mg2+
theNaOH/Mg 2+-solution flow-rate ratio
ratio was
was investigated
investigatedstudying
studying
only
onlystoichiometric
stoichiometricMg(OH)Mg(OH)22precipitation
precipitationtests.
tests.Stoichiometric
Stoichiometrictests
testswere
werefirst
firstcarried
carriedout
out
using 2+ 2+
usingMg Mg2+ 0.50
0.50 M Mand
and1.00
1.00MMartificial
artificialMgCl
MgCl 2 solutions. NaOH/Mg
2 solutions. NaOH/Mg2+-solution
-solution flow-rate
flow-rate
ratios
ratiosranging
rangingfrom from0.5
0.5toto2.0
2.0and
andfrom
from1.0 1.0to
to3.0
3.0were
wereadopted
adoptedforforthe
the0.50
0.50M Mand
and1.00
1.00MM
artificial solutions, respectively.
artificial solutions, respectively.
Mg 2+
Mg2+ concentration
concentration in in the
the filtrates,
filtrates, recovery
recovery andand pH
pH values
values (measured
(measured after
after the
the pre-
pre-
cipitation) are shown in Figure 3. Note that, Mg 2+ concentrations values are reported as
cipitation) are shown in Figure 3. Note that, Mg2+ concentrations values are reported as
the
themeasured
measuredconcentrations
concentrations in in the
thefiltrates
filtratesmultiplied
multiplied by
bythe
thedilution
dilutionfactor
factoroccurring
occurring
during the addition of NaOH solutions, e.g., a dilution factor of 2.0 or 3.0
during the addition of NaOH solutions, e.g., a dilution factor of 2.0 or 3.0 is used when is used when the
NaOH/Mg 2+ -solution flow-rate ratio is equal to 1.0 or 2.0.
the NaOH/Mg -solution flow-rate ratio is equal to 1.0 or 2.0.
2+

Figure 3. (a,b), Final Mg2+2+ concentrations in the filtrates; (c,d), Mg recovery; (e,f), pH values, for
Figure 3. (a,b), Final Mg concentrations in the filtrates; 2+
(c,d), Mg recovery; (e,f), pH values, for
stoichiometric
stoichiometricprecipitation
precipitation tests
testsperformed
performedusing
usingMgMg2+ 0.50
0.50 M
M (a,c,e)
(a,c,e) and
and 1.00
1.00 M
M(b,d,f)
(b,d,f)artificial
artificial
MgCl 2+
MgCl22solutions
solutionsatatNaOH/Mg -solution flow-rate
NaOH/Mg2+-solution flow-rate ratios
ratios ranging
ranging from
from 0.5
0.5 to
to 2.0
2.0 and
and from
from 1.0
1.0 to
to 3.0,
3.0,
respectively.
respectively.

In 2+ 2+
Inthe
thecase
caseofofartificial
artificialMg
Mg2+0.50
0.50M MMgCl
MgCl2 2solutions,
solutions,final
finalMg
Mg2+ concentrations
concentrationsin
inthe
the
filtrates
filtratesranged between ~600 mg/L and ~900 mg/L (Figure 3a). Consequently,
ranged between ~600 mg/L and ~900 mg/L (Figure 3a). Consequently, similar Mg2+ similar
Mg 2+ recovery values of ~93–95% were calculated for all the investigated NaOH/Mg2+ -
recovery values of ~93–95% were calculated for all the investigated NaOH/Mg2+-solution
2+ concentration differences can be
solution flow-rate ratios (Figure 3c). The small Mg
flow-rate ratios (Figure 3c). The small Mg concentration differences can be caused by
2+
caused by either
either the use ofthe use of stoichiometric
stoichiometric MgCl2 and MgCl
NaOH2 and NaOH solutions
solutions thatexactly
that are not are not100%
exactly
or
100% or small fluid flow-rate unbalances that can lead to slightly different equimolar
small fluid flow-rate unbalances that can lead to slightly different equimolar precipitation
conditions, as suggested by the small differences of the final suspension pH values; see
Figure 3e.
Water 2023, 15, 29 10 of 22

Water 2022, 14, x FOR PEER REVIEW 10 of 23

precipitation conditions, as suggested by the small differences of the final suspension pH
values; see Figure 3e.
2+ -solution flow-rate ratio on Mg2+ recovery
AAnegligible
negligible influence
influence of NaOH/Mg
of the the NaOH/Mg 2+-solution flow-rate ratio on Mg2+ recovery is
is also observed for the precipitation cases performed with Mgartificial Mg 2+ 1.00 M MgCl
also observed for the precipitation cases performed with artificial 2+ 1.00 M MgCl 2 so- 2
solutions. In this 2+
lutions. In this case,case,
finalfinal
Mg2+Mg concentration
concentration values values in the filtrates
in the filtrates range between
range between ~1900 ~1900
and~2100
and ~2100mg/L,
mg/L, as reported
as reported in Figure
in Figure 3b, leading
3b, leading to similar
to similar Mg2+ recovery
Mg2+ recovery values ofvalues
about of about
~92% for all the investigated NaOH/Mg 2+
~92% for all the investigated NaOH/Mg -solution flow-rate ratios (Figure 3d). the
2+-solution flow-rate ratios (Figure 3d). For For the sake
sake of completeness,
of completeness, final
final suspensionpH
suspension pHvalues
valuesafter
after precipitation
precipitationare arereported
reportedin in
Figure
Figure 3f.
3f.
3.1.2. Influence of the NaOH/Bittern Flow Rate Ratio
3.1.2. Influence of the NaOH/Bittern Flow Rate Ratio
Based on results of Section 3.1.1, only two NaOH/bittern flow-rate ratio values of
Based
2.0 and 3.0onwere
results of Section 3.1.1,
investigated only two NaOH/bittern
by preforming flow-rate
stoichiometric ratio values
Mg(OH) of 2.0
2 precipitation tests
and 3.0 were investigated by preforming stoichiometric Mg(OH)2 precipitation tests using
using real and artificial Margi bitterns. In this case, both Mg2+ and Ca2+ ions in the filtrates
real and artificial Margi bitterns. In this case, both Mg2+ and Ca2+ ions in the filtrates were
were studied.
studied. 2+ and Ca2+ concentrations in the filtrates, recovery, and pH values (measured
FinalMg
Final Mg2+ and Ca2+ concentrations in the filtrates, recovery, and pH values (meas-
after the precipitation) areare
ured after the precipitation) reported
reportedininFigure
Figure4.4.Note
Note that, alsoininthis
that, also thiscase,
case, concentrations
concen-
are reported taking into account the dilution factor occurring during the
trations are reported taking into account the dilution factor occurring during the precipi- precipitation
process
tation (see Section
process 3.1.1).
(see Section 3.1.1).

Figure
Figure4.4.(a,b):
(a,b):MgMg 2+ and
2+ and Ca2+Ca 2+ concentrations
concentrations in the in
filtrates for Testsfor
the filtrates M_R_S2 and M_R_S3
Tests M_R_S2 and(real
M_R_S3 (real
Margi bitterns) and Tests M_A_S2 and M_A_S3 (artificial Margi bitterns) under stoichiometric
Margi bitterns) and Tests M_A_S2 and M_A_S3 (artificial Margi bitterns) under stoichiometric
Mg(OH)2 precipitation conditions for NaOH/bittern flow-rate ratios equal to 2.0 and 3.0; (c,d): Mg2+
Mg(OH)2 precipitation
and Ca2+ recovery;
conditions for NaOH/bittern flow-rate ratios equal to 2.0 and 3.0; (c,d): Mg2+
(e): final measured pH values.
and Ca2+ recovery; (e): final measured pH values.
Comparable final Mg2+ concentrations of ~4900 mg/L were observed in the filtrates of
Comparable final of
Mgthe2+ concentrations of ~4900 mg/L were observed in the filtrates of
real bitterns regardless employed NaOH/bittern flow-rate ratio; see Figure 4a.
real bitterns
Lower regardless
final Mg of the employed
2+ concentrations NaOH/bittern
of ~2250 and 3500 mg/L were flow-rate
obtainedratio; see
in the Figurein4a. Lower
filtrates
final 2+ concentrations of ~2250 and 3500 mg/L were obtained
MgM_A_S2 in the filtrates
the case and M_A_S3, respectively. The different final Mg2+ concentrations in thein the case
artificial
M_A_S2bittern case can be
and M_A_S3, associated with
respectively. The adifferent
final suspension
final MgpH2+ concentrations
value that is higher in artificial
in the
the M_A_S2
bittern sample
case can than in the
be associated M_A_S3
with sample, as shown
a final suspension pH value in that
Figure 4e. Calcium
is higher in the M_A_S2
sample than in the M_A_S3 sample, as shown in Figure 4e. Calcium concentrations of
~70 and ~88 mg/L were measured for real and artificial bitterns, respectively. Calcium
Water 2023, 15, 29 11 of 22

concentrations were influenced neither by the different NaOH/bittern flow-rate ratio nor
by the final pH values; see Figure 4b.
Mg2+ recovery of ~92% was calculated from real bitterns, while recovery increased
using artificial ones reaching values up to ~96% (Figure 4c). Ca2+ recovery was ~44% in
the case of real bitterns, while it decreased down to ~20% in artificial ones (Figure 4d).
These small recovery differences may be attributed to the different nature of the employed
bitterns that contain many other chemical compounds which may interfere with Mg(OH)2
precipitation. A detailed characterization of the minor and major elements in the bitterns
of the Trapani saltworks was presented by Vicari et al. [43].
Overall, the results obtained using both artificial MgCl2 solutions and bitterns do
not show a significant Mg2+ recovery variation as a function of the NaOH/Mg2+ -solution
flow-rate ratio. In addition, in all cases, the recovery never reached a 100% value. Based on
the latter observation, only tests at a flow-rate ratio of 2.0 are discussed hereinafter.
The NaOH/Mg2+ -solution flow-rate results also highlight the possibility of using di-
luted NaOH solutions to treat highly concentrated Mg2+ solutions by adopting NaOH/Mg2+ -
solution flow-rate ratios higher than 1.0 without affecting Mg2+ recovery. As an example, a
5.0 M NaOH solution would be required to treat Margi bitterns adopting a NaOH/bittern
flow-rate ratio of 1.0; such a concentrated NaOH solution would be difficult to handle,
while in adopting a NaOH/bittern flow-rate ratio of 2.0 or 3.0, a NaOH solution of 2.5 M
and 1.7 M, respectively, would be needed.

3.1.3. Influence of the OH− /Mg2+ Ratio

The influence of the OH− /Mg2+ ratio on Mg2+ recovery was assessed performing
Mg(OH)2 precipitation tests for Margi and Galia bitterns under hydroxyl ions in sto-
ichiometric and over-stoichiometric conditions. All tests were carried out setting the
NaOH/bittern flow-rate ratio to the value of 2.0.

Margi Bittern
Figure 5 reports Mg2+ and Ca2+ concentrations in the filtrates, recovery and final
pH values obtained by treating real and artificial Margi bitterns with OH− stoichiometric
(M_R_S2 and M_A_S2) and 20% over-stoichiometric amounts (M_R_E2 and M_A_E2).
Again, as discussed in Section 3.1.1, concentration values in the filtrates were corrected in
order to take dilution effects during the precipitation process into account.
In Figure 5, a strong effect of the over-stoichiometric NaOH amount is observed.
Specifically, Mg2+ and Ca2+ concentrations decreased from their stoichiometric values
of ~4950–2250 mg/L and ~74–88 mg/L, respectively, to values lower than 30 mg/L;
see Figure 5a,b.
This result is somehow expected, since the OH− excess ensures a total consumption of
both Mg2+ and Ca2+ ions, as is also indicated by the final suspensions pH values (Figure 5e).
The pH values, in fact, are higher than 12, showing a residual amount of hydroxyl ions in
the suspensions.
Consequently, Mg2+ and Ca2+ recoveries reached values up to >99.99% (Figure 5c,d).
In the case of over-stoichiometric NaOH solutions, Ca2+ concentration values were lower
than their limit of quantification (LOQ). Recovery values higher than 92% are indicated in
Figure 5d, although a >99.9% recovery can be assumed.

Galia Bittern
Mg2+ and Ca2+ concentrations in the filtrates, recovery and final pH values for
Mg(OH)2 precipitation tests treating real and artificial Galia bitterns under stoichiometric
(G_R_S2 and G_A_S2) and 20% OH− over-stoichiometric amounts (G_R_E2 and G_A_E2)
are reported in Figure 6. Also in this case, concentrations take dilution effects during
precipitation into account.
WaterWater
2023,2022, 14, x FOR PEER REVIEW
15, 29 12 of 23 12 of 22

Figure
Figure5.5.(a,b): MgMg
(a,b): 2+ and
2+ and Ca2+ Ca 2+ concentrations
concentrations in the filtrates
in thefor Mg(OH)
filtrates 2 precipitation
for Mg(OH)2 tests using
precipitation tests using
real and artificial Margi bitterns under stoichiometric (M_R_S2 and M_A_S2) and 20% OH− over- − over-
real and artificial Margi bitterns under stoichiometric (M_R_S2 and M_A_S2) and 20% OH
stoichiometric (M_R_E2 and M_A_E2) conditions; (c,d): Mg2+ and Ca2+ recovery; (e): final measured
stoichiometric (M_R_E2 2+ 2+
pH values. Note that in someand M_A_E2)
cases, conditions;
Ca2+ concentration (c,d):
values wereMglowerand Catheirrecovery;
than (e): final measured
limit of quan-
Water 2022, 14, x FOR PEER REVIEWtification. All tests were carried out adopting a NaOH/bittern 13 of 23
pH values. Note that in some cases, Ca2+ concentration flow-ratevalues were
ratio value lower
of 2.0. than their limit of
quantification. All tests were carried out adopting a NaOH/bittern flow-rate ratio value of 2.0.
In Figure 5, a strong effect of the over-stoichiometric NaOH amount is observed. Spe-
cifically, Mg2+ and Ca2+ concentrations decreased from their stoichiometric values of
~4950–2250 mg/L and ~74–88 mg/L, respectively, to values lower than 30 mg/L; see Figure
5a,b.
This result is somehow expected, since the OH− excess ensures a total consumption
of both Mg2+ and Ca2+ ions, as is also indicated by the final suspensions pH values (Figure
5e). The pH values, in fact, are higher than 12, showing a residual amount of hydroxyl
ions in the suspensions.
Consequently, Mg2+ and Ca2+ recoveries reached values up to >99.99% (Figure 5c,d).
In the case of over-stoichiometric NaOH solutions, Ca2+ concentration values were lower
than their limit of quantification (LOQ). Recovery values higher than 92% are indicated in
Figure 5d, although a >99.9% recovery can be assumed.

Galia Bittern
Mg2+ and Ca2+ concentrations in the filtrates, recovery and final pH values for
Mg(OH)2 precipitation tests treating real and artificial Galia bitterns under stoichiometric
(G_R_S2 and G_A_S2) and 20% OH− over-stoichiometric amounts (G_R_E2 and G_A_E2)
are reported in Figure 6. Also in this case, concentrations take dilution effects during pre-
cipitation into account.

(a,b):
Figure6.6.(a,b):
Figure MgMg 2+ and
2+ and Ca2+ concentrations
Ca2+ concentrations in thefor
in the filtrates filtrates
Mg(OH)for Mg(OH)2 tests
2 precipitation precipitation
using tests using
real and artificial Galia bitterns
real and artificial Galia bitterns underunder
stoichiometric (G_R_S2 and
stoichiometric G_A_S2)
(G_R_S2 andand 20% OH−and
G_A_S2) over-20% OH− over-
stoichiometric (G_R_E2 and G_A_E2) conditions; (c,d): Mg2+ and Ca2+2+recovery; (e): final pH values.
stoichiometric (G_R_E2 and G_A_E2) conditions; (c,d): Mg and Ca2+ recovery; (e): final pH values.
In over-stoichiometric NaOH precipitation cases, Ca2+ concentrations were lower than their limit of
In over-stoichiometric
quantification. NaOH
All tests were precipitation
carried out adopting acases, Ca2+ concentrations
NaOH/bittern wereof
flow-rate ratio value lower
2.0. than their limit of
quantification. All tests were carried out adopting a NaOH/bittern flow-rate ratio value of 2.0.
In Figure 6, similar final Mg2+ and Ca2+ concentration values of ~1020–1150 mg/L and
~125–130 mg/L in the cases G_R_S2 and G_A_S2, respectively, were obtained when per-
forming stoichiometric precipitation tests using real and artificial bitterns (Figure 6a,b).
Consequently, Mg2+ and Ca2+ recoveries are ~96–95% and ~44–52%, respectively; see Fig-
ure 6c,d. Such recovery values are close to those observed in the case of MH precipitation
from Margi bitterns under stoichiometric conditions (Figure 4), where, in all cases, recov-
ery did not reach a 100% value.
Water 2023, 15, 29 13 of 22

In Figure 6, similar final Mg2+ and Ca2+ concentration values of ~1020–1150 mg/L
and ~125–130 mg/L in the cases G_R_S2 and G_A_S2, respectively, were obtained when
performing stoichiometric precipitation tests using real and artificial bitterns (Figure 6a,b).
Consequently, Mg2+ and Ca2+ recoveries are ~96–95% and ~44–52%, respectively; see
Figure 6c,d. Such recovery values are close to those observed in the case of MH precipitation
from Margi bitterns under stoichiometric conditions (Figure 4), where, in all cases, recovery
did not reach a 100% value.
In addition, as also shown in the Margi bittern study, the strong effect of the NaOH
excess can be seen in Figure 6. Mg2+ and Ca2+ concentrations diminished from their
stoichiometric values to concentrations lower than 10 mg/L (Figure 6a,b). Therefore, Mg2+
and Ca2+ recoveries were >99.9% for both artificial and real bitterns. This is due to the
OH− excess that ensures a total consumption of Mg2+ and Ca2+ ions (final suspension
pH values >12, Figure 6e).
Overall, results of the Margi (Figure 5) and Galia (Figure 6) precipitation tests con-
firmed that >99.9% Mg2+ recovery can be achieved from artificial and real bitterns em-
ploying over-stoichiometric NaOH solutions in accordance with data reported in the
literature [13,21,25,36].

3.2. Mg(OH)2 Purity Assessment

Cipollina et al. [36] have already demonstrated the possibility of achieving a >99.9%
Mg recovery from saltwork bitterns. The authors also discussed the influence of several
operating parameters on the cationic purity of produced MH particles, e.g., the influence
of NaOH concentration and the volumetric flow rate in semi-batch systems. However, no
information regarding solids mass purity was reported.
MH products must have a mass purity higher than 95% to be commercially attrac-
tive [26]. To better evaluate the possibility of producing high-mass-purity MH products
from saltwork bitterns, thus turning waste into a valuable product, several analytical tech-
niques were employed. In the following sections, first cationic purity is discussed; then
attention is placed on solid mass purity.

3.2.1. Cationic Purity of MH

Cationic purity, understood as the presence of other cations than Mg2+ , was investi-
gated by assessing cation concentrations in dissolved MH solids (see Section 2.4 for further
details). The measured concentrations in the dissolved solids along with calculated cationic
purity values, Equation (4), for Margi and Galia bitterns are reported in Table 3.

Table 3. Cation concentrations in dissolved Mg(OH)2 solids assessed via IC analysis.

Cationic Purity
Tests Ca (mg/g) Mg (mg/g) Na (mg/g)
(%)
M_R_S2 <2.0 * 376.0 ± 0.6 1.82 ± 0.46 >99.0
M_R_E2 <2.0 * 375.0 ± 1.4 3.51 ± 0.03 >99.0
M_A_S2 <2.0 * 387.0 ± 0.8 <0.5 * >99.0
M_A_E2 <2.0 * 385.0 ± 0.9 <0.5 * >99.0
G_R_S2 <2.0 * 371.0 ± 3.4 2.49 ± 1.14 >99.0
G_R_E2 <2.0 * 376.0 ± 0.1 <0.5 * >99.0
G_A_S2 <2.0 * 378.0 ± 0.3 3.20 ± 0.19 >99.0
G_A_E2 <2.0 * 382.0 ± 0.9 <0.5 * >99.0
Note: * Concentrations lower than the limit of quantification.

From Table 3, Ca2+ concentration is always below its limit of quantification (LOQ), even
for samples obtained under NaOH over-stoichiometric solutions. This result is due to a very
low initial Ca2+ concentration in the bitterns that is 100 times lower than that for Mg2+ .
Water 2023, 15, 29 14 of 22

In same samples, traces of Na+ are found. These traces can be mainly attributed to
the need of a further cake-washing step, since some residuals of very soluble compounds,
e.g., NaCl and Na2 SO4 , may be still present in the cake. For the sake of completeness, the
M_R_S2 and M_R_E2 MH powders were further washed using ultrapure water. After
washing, Na+ concentrations were found to be lower than their limit of quantification,
while Mg2+ concentrations increased up to 390.0 mg/g, thus confirming the assumed need
for a better washing of the MH cakes during filtration to remove displacement of the brine
from the surface of MH crystals.
Magnesium is the most abundant ion, and its cationic purity, calculated using
Equation (4), is higher than ~99% in all cases regardless of the employed bittern or the
operating conditions.

3.2.2. MH Mass Purity

Cationic purity was found to be very high (>99%); however, even very low concen-
trations of light elements, e.g., boron, can greatly affect mass purity, since light elements
can precipitate production of high-weight compounds. B(III) is a light element forming
a hydroxyl-acid type of species (e.g., H3 BO3 and H2 BO3 − ) whose presence on the MH
crystal structure could be more strongly associated with superficial sorption or occlusion
phenomena than potential inclusion in the crystal structure substituting Mg2+ ions, as may
happen with Ca2+ . In order to assess the MH samples, mass purity thermogravimetric
(TG), X-ray and SEM-EDS analyses were conducted.

TG Analysis
Thermogravimetric (TG) analysis is a commonly employed technique for the study of
a powder’s mass purity. Thermogravimetry (TG) and derivative thermogravimetry (DTG)
curves for MH powders produced from real Margi and real Galia bitterns are shown in
Figure 7. The TG curves report the sample mass variations as functions of an imposed
temperature change. The DTG curves plot the rate of change of mass with respect to
temperature against temperature. In the latter case, downward and upward curves indicate
endothermic and exothermic phenomena, respectively.
Three main weight losses can be identified in the TG curves:
1. The first weight loss, observed between 30 ◦ C and 320 ◦ C, is attributed to the mass
sample loss due to residual humidity, free water and adsorbed water in the sample. In
this temperature range also, water of crystallization can be lost by hydrate compounds,
e.g., hydrate sulphates or borates. The mass loss in the temperature range between
30 ◦ C and 200 ◦ C, however, can be attributed to the samples’ humidity [19,44]; there-
fore the mass losses in the 30 ◦ C and 200 ◦ C temperature range were subtracted from
the total initial sample mass to determine the dry one.
2. The second major weight loss occurred in the temperature range between 320 ◦ C and
480 ◦ C. It is related to thermal decomposition of Mg(OH)2 (s) and transformation onto
MgO(s) particles:

Mg(OH )2 (s) → MgO(s) + H2 O(v) ∆H298K = 1300 kJ kg−1 (6)

In this thermal range, weight losses from 27.2% to 28.6% were measured. These values
are lower than the theoretical one of 30.8% wt calculated on a dry mass base [45]. In fact, the
former values increase up to 27.8% and 29.8%, respectively, if a dry mass sample is considered.
3. A further mass loss, between 480 ◦ C and 1000 ◦ C, was also noticed after Mg(OH)2
decomposition. Ardizzone et al. [46] and Wang et al. [47] attributed this mass loss to
the slow and continuous desorption of residual OH− groups bonded to the MgO(s)
lattice. Ardizzone et al. [46] and Wang et al. [47] based their consideration on Fourier
transform infrared spectroscopy studies that showed a strong MgO(s) affinity towards
the surface chemisorbed-OH groups. It should be noted that, if the mass loss would
be correlated to further Mg(OH)2 (s) decomposition, the final mass purities of the
Water 2022, 14, x FOR PEER REVIEW 15 of 23

Water 2023, 15, 29 15 of 22

(DTG) curves for MH powders produced from real Margi and real Galia bitterns are
shown in Figure 7. The TG curves report the sample mass variations as functions of an
imposed temperature change. The DTG curves plot the rate of change of mass with respect
samples would increase. Therefore, the here-reported mass purity values are likely to
to temperature against temperature. In the latter case, downward and upward curves in-
be an underestimation of the actual Mg(OH)2 (s) powder’s purity.
dicate endothermic and exothermic phenomena, respectively.

Water 2022, 14, x FOR PEER REVIEW 16 of 23

lattice. Ardizzone et al. [46] and Wang et al. [47] based their consideration on Fourier
transform infrared spectroscopy studies that showed a strong MgO(s) affinity to-
wards the surface chemisorbed-OH groups. It should be noted that, if the mass loss
would
Figure
Figure 7. be correlated(TG)
7. Thermogravimetric
Thermogravimetric to further
(TG) Mg(OH)
and 2(s) decomposition,
derivative
and derivative thermogravimetric
thermogravimetric thecurves
curves final (DTG)
(DTG) mass purities
of Mg(OH)
of Mg(OH) 2 sol-
of 2
the
solids samples
precipitated would
from increase.
real Margi andTherefore,
real Galia the here-reported
bitterns under mass
stoichiometric purity
(M_R_S2 values
and
ids precipitated from real Margi and real Galia bitterns under stoichiometric (M_R_S2 and G_R_S2) are
G_R_S2)
andand likely to be an underestimation
over-stoichiometric
over-stoichiometric (M_R_E2
(M_R_E2 andand of theNaOH
G_R_E2)
G_R_E2) actual
NaOH Mg(OH)
solution
solution 2(s) powder’s purity.
conditions.
conditions.
MH mass purities calculated using Equation (5) are reported in Figure 8 both for ar-
ThreeMHmain
mass purities calculated using Equation (5) curves:
are reported in Figure 8 both for
tificial and real weight losses
Margi and canbitterns.
Galia be identified in the TG
artificial and real Margi and Galia bitterns.
1. The first weight loss, observed between 30 °C and 320 °C, is attributed to the mass
sample loss due to residual humidity, free water and adsorbed water in the sample.
In this temperature range also, water of crystallization can be lost by hydrate com-
pounds, e.g., hydrate sulphates or borates. The mass loss in the temperature range
between 30 °C and 200 °C, however, can be attributed to the samples’ humidity
[19,44]; therefore the mass losses in the 30 °C and 200 °C temperature range were
subtracted from the total initial sample mass to determine the dry one.
2. The second major weight loss occurred in the temperature range between 320 °C and
480 °C. It is related to thermal decomposition of Mg(OH)2(s) and transformation onto
MgO(s) particles:
𝑀𝑔(𝑂𝐻)2 (𝑠) → 𝑀𝑔𝑂(𝑠) + 𝐻2 𝑂(𝑣) ΔH298K = 1300 kJ kg −1 , (6)
Figure 8. Mg(OH)2 mass purities calculated using Equation (5) from TG curves for real and artificial
In this
Figure thermal
8. Mg(OH) range,
2 mass weight
purities losses using
calculated from Equation
27.2% to(5)
28.6%
fromwere measured.
TG curves for realThese val-
and artificial
Margiand
Margi andGalia
Galiabitterns
bitternsunder
understoichiometric
stoichiometricand
andover-stoichiometric
over-stoichiometricNaOH
NaOHsolution
solutionconditions.
conditions.
ues are lower than the theoretical one of 30.8% wt calculated on a dry mass base [45].
In fact,
Fromthe former
Figure values
8, very increase
high MH mass up purity
to 27.8% and (>90%)
values 29.8%, respectively, if a Interestingly,
can be observed. dry mass
From is
sample Figure 8, very high MH mass purity values (>90%) can be observed. Interest-
considered.
solids produced using over-stoichiometric NaOH solutions show higher purity values with
3.ingly, solids produced
A further
respect mass loss,
to samples
using over-stoichiometric
between
precipitated 480stoichiometric
in °C and 1000 NaOH solutions
°C, was
conditions,
show higher
alsoreaching
noticed purity val-
after Mg(OH)
values 2
up to ~97%
uesdecomposition.
with respect to Ardizzone
samples precipitated
et al. in stoichiometric
[46] and Wang conditions,
et al. [47] reaching values
attributed this mass loss to up
for the G_R_E2 sample, a value complying with market requirements.
to ~97%
the To for the
slow andG_R_E2 sample,
continuous a value complying
desorption of residual with
OH − market
groups requirements.
bonded to the MgO(s)(see
further understand this trend, boron concentration in the solids was assessed
To further understand this trend, boron concentration in the solids was assessed (see
Section 2.4), as reported in Table 4.
Section 2.4), as reported in Table 4.

Table 4. Boron concentration in dissolved solids obtained employing ICP-OES and IPC-MS tech-
niques.

Tests B (mg/g)
M_R_S2 1.71 ± 0.18
 Water 2023, 15, 29 16 of 22

As reported in Table 4, boron traces are higher in solids precipitated under stoichio-
metric NaOH conditions with respect to those obtained at over-stoichiometric conditions.
Boron concentration decreases from ~1.71 mg/g to ~0.90 mg/g in M_R_S2 and M_R_E2
samples, or from ~1.40 mg/g in the G_R_S2 samples to a concentration lower than its limit
of quantification in the G_R_E2 samples. The different boron concentration is attributed
to the different value of pH at the end of the precipitation process. At pH values higher
than 12, it has been described that the adsorption of borate ions onto the surface of magne-
sium hydroxide is hindered; thus, lower boron is entrained in MH solids [32]. The latter
consideration explains the mass purity trend shown in Figure 8.

Table 4. Boron concentration in dissolved solids obtained employing ICP-OES and IPC-MS techniques.

Tests B (mg/g)
M_R_S2 1.71 ± 0.18
M_R_E2 0.91 ± 0.33
M_A_S2 0.81 ± 0.21
M_A_E2 0.38 ± 0.08
G_R_S2 1.40 ± 0.05
G_R_E2 <0.3 *
G_A_S2 0.45 ± 0.03
Water 2022, 14, x FOR PEER REVIEW 17 of 23
G_A_E2 <0.3 *
Note: * Concentrations lower than the limit of quantification.

For the sake of completeness, the Mg(OH)2 solid mass purity values of samples pro-
For the sake of completeness, the Mg(OH)2 solid mass purity values of samples
duced from real Margi bitterns under stoichiometric and over-stoichiometric conditions
produced from real Margi bitterns under stoichiometric and over-stoichiometric conditions
adopting NaOH/bittern flow rate ratios of 2.0 and 3.0 are reported in Figure 9.
adopting NaOH/bittern flow rate ratios of 2.0 and 3.0 are reported in Figure 9.

Mg(OH)
Figure9.9.Mg(OH)
Figure 2 mass
2 mass
purity
purity calculated
calculated using
using Equation
Equation (5)(5)from
fromTGTGcurves
curvesfor
forMg(OH)
Mg(OH) 2 solids
2 solids
precipitated from Margi bitterns under stoichiometric and 20% OH − over-stoichiometric conditions
precipitated from Margi bitterns under stoichiometric and 20% OH over-stoichiometric conditions
−

adopting
adopting NaOH/bittern
NaOH/bittern flow-rate
flow-rate ratios
ratios of of
2.02.0
andand 3.0.
3.0.

Comparablemass
Comparable masspurity
purityvalues
valueswere
wereobtained
obtainedby byadopting
adoptingdifferent
differentNaOH/bittern
NaOH/bittern
flow-rate ratios. Mass purity values were 2% higher in samples produced at NaOH/bittern
flow-rate ratios. Mass purity values were 2% higher in samples produced at a a NaOH/bit-
flow-rate
tern flow-rateratio of 3.
ratio of Such
3. Suchlow differences
low cancan
differences be be
attributed
attributed to to
measurement
measurement errors oror
errors the
the slightly higher or lower presence of soluble impurities in the samples rather than toan
slightly higher or lower presence of soluble impurities in the samples rather than to
aneffective
effectiveinfluence
influenceofofthe
theNaOH/bittern
NaOH/bitternflow-rate
flow-rateratio.
ratio.InInaddition,
addition,the
thesame
samemass
masspurity
pu-
trend as the function of precipitation conditions, shown in Figure 8, was observed,
rity trend as the function of precipitation conditions, shown −in Figure 8, was observed, namely
mass purity always increases from 90–92% to 93–95% in OH over-stoichiometric tests.
namely mass purity always increases from 90–92% to 93–95% in OH− over-stoichiometric
Overall, traces of boron base compounds (H2 BO3 − ) and magnesium carbonates
tests.
(MgCO3 ), due to the aqueous precipitation system, are− the expected species hindering
Overall, traces of boron base compounds (H2BO3 ) and magnesium carbonates
the Mg(OH) mass purity (values lower than 100%) [48] that, however, achieve very high
(MgCO3), due2to the aqueous2+ precipitation system, are the expected species hindering the
values thanks to the low Ca concentrations in the bitterns. The formation of Mg-borates
Mg(OH)2 mass purity (values lower than 100%) [48] that, however, achieve very high val-
ues thanks to the low Ca2+ concentrations in the bitterns. The formation of Mg-borates has
been described in the literature; however, the values of the total concentration of B in the
bitterns are too far away to justify the precipitation of those mineral phases.
Water 2023, 15, 29 17 of 22

has been described in the literature; however, the values of the total concentration of B in
the bitterns are too far away to justify the precipitation of those mineral phases.

Mineralogical Characterization of MH Samples Using XRD

The XRD patterns of MH solids produced from real Margi bitterns under NaOH
stoichiometric precipitation conditions (M_R_S2) and adopting 20% OH− excess (M_R_E2)
are shown Figure 10a,b, respectively.

Figure 10. XRD patterns of Mg(OH)2 solids produced from real Margi bitterns under NaOH stoichio-
metric precipitation conditions (M_R_S2), (a), and adopting an 20% OH− excess (M_R_E2), (b).

All XRD patterns exhibit typical diffraction peaks that are assigned to planes of the
brucite crystalline form of Mg(OH)2 (JCPDS 7-239) [44,49]. No extra diffraction peaks
from impurities were identified in the XRD spectra (e.g., all of them are below 1%), thus
indicating high MH purity and a high degree of crystallinity. No extra diffraction peaks
were identified in the XRD spectra of all other MH precipitation tests (see Table 2); thus, for
the sake of brevity, results are here omitted.
In Figure 10, it can also be noted that the XRD peaks’ diffraction intensity and sharp-
ness increase from samples produced under stoichiometric conditions (M_R_S2, Figure 10a)
to those precipitated using a 20% OH− excess (M_R_E2, Figure 10b), thus indicating a
higher crystallinity degree for solids produced using NaOH excess [50].

Morphological and Chemical Characterization of the MH Solids Using SEM-EDS

SEM-EDS analysis can provide information regarding particle shapes and local semi-
quantitative chemical composition analysis using EDS. Figure 11 shows SEM-EDS results,
relevant to Mg(OH)2 samples, precipitated from real Margi bitterns using stoichiometric
(M_R_S2) and over-stoichiometric NaOH solutions (M_R_E2).
Mg and O elements are the predominant ones associated with brucite. Traces lower
than 0.5% wt of Na, Al, Si, S and Cl are also found. The presence of Na, Cl, and S traces can
be due to either (i) a limited washing stage of the samples to displace the reacting bittern or
(ii) entrained crystals during the filtration and solid drying processes. Si presence at trace
levels can be attributed to the use of glass fiber filters, while carbon is mainly correlated
to the use of carbon tape adopted to ensure solid attachment on SEM stubs. Other SEM
 Water 2023, 15, 29 18 of 22

images, at higher magnifications of 3000 ×, 24,000× and 80,000/100,000×, for the same
Water 2022, 14, x FOR PEER REVIEW Margi solid samples M_R_S2 and M_R_E2 are shown in Figure 12, along with local19 ofEDS
23
micro-analysis.

Figure 11.11.
Figure SEM-EDS
SEM-EDSanalysis of Mg(OH)
analysis 2 samples
of Mg(OH) produced
2 samples fromfrom
produced real Margi bitternbittern
real Margi using using
stoichio-
stoi-
metric (M_R_S2) and over-stoichiometric NaOH solutions (M_R_E2). Images were collected at
chiometric (M_R_S2) and over-stoichiometric NaOH solutions (M_R_E2). Images were collected at UPC
laboratories.
PUPC laboratories.

Mg
In and O elements
Figure 12, globular arebrucite
the predominant
shapes can be ones associated
observed with brucite.
in M_R_S2 Tracessamples.
and M_R_E2 lower
than
The0.5% wt ofshape
globular Na, Al, Si, typical
is the S and Cloneare also found.
reported whenThe presence
brucite of Na, Cl,using
is precipitated and Satraces
NaOH
can be due
solution to either
[51]. (i) a limited
Interestingly, washing
SEM images stage
of the of the
sample samples
M_R_E2 to showed
also displacethe
theco-presence
reacting
of sand-rose/lamellar-like
bittern or (ii) entrained crystals structures.
during theLamellar-like
filtration andbrucite
solid shapes have been Si
drying processes. reported
pres-
in precipitation
ence at trace levelscases
can be adopting
attributed ammonia
to the use[51], but rarely
of glass for samples
fiber filters, precipitated
while carbon from
is mainly
NaOH solutions.
correlated to the useThe of sand-rose
carbon tape structures
adoptedcan to probably be attributed
ensure solid attachment toon
theSEM
co-presence
stubs.
of many
Other SEMother ionsatin
images, the real
higher bittern influencing
magnifications of 3000the nucleation
×, 24,000× and and growth processes
80,000/100,000×, for theof
precipitated brucite particles.
same Margi solid samples M_R_S2 and M_R_E2 are shown in Figure 12, along with local
EDS micro-analysis showed no impurities, as only Mg and O elements were detected.
EDS micro-analysis.
The carbon (C) and gold (Au) element traces can be attributed to the use of carbon tape for
sample attachment on the SEM stub and the initial spattering of a thin gold layer to better
visualize the brucite structures at high magnifications, since brucite is a non-conductive
material. For the sake of brevity, no other SEM images were reported as similar results as
those of the M_R_S2 samples were obtained. Note that the sand-rose/lamellar shapes of
sample M_R_E2 were not observed in the Galia bitterns even for samples produced at the
Water 2023, 15, 29 19 of 22

Water 2022, 14, x FOR PEER REVIEW 20 of 23

NaOH over-stoichiometric amount, probably due to the different chemical composition of
the bitterns.

Figure 12.SEM-EDS
Figure12. SEM-EDSmicro-analysis
micro-analysisof ofMg(OH)
Mg(OH)22samples
samples produced
produced from
from real
realMargi
Margibitterns
bitternsusing
using
stoichiometric (M_R_S2)
stoichiometric (M_R_S2) and
and over-stoichiometric
over-stoichiometric NaOH
NaOH solutions
solutions (M_R_E2)
(M_R_E2) at
atmagnifications
magnificationsof of
3000×,
3000 ×, 24,000×
24,000×and and80,000/100,000×.
80,000/100,000×Images were
. Images obtained
were obtainedatat
UNIPA
UNIPAlaboratories.
laboratories.The
Thepeak
peakofofAu
Auis
isassociated
associatedtotothe
thesample
sampletreatment
treatmenttotoimprove
improvethe
thequality
qualityofofthe
theimages.
images.

4. Conclusions
In Figure 12, globular brucite shapes can be observed in M_R_S2 and M_R_E2 sam-
ples.The
Therecovery
globularof Mg2+isfrom
shape exhausted
the typical bitterns, the
one reported whenby-products of the sea-salt
brucite is precipitated pro-a
using
duction process, [51].
NaOH solution was investigated
Interestingly,with
SEMspecial
images attention on the purity
of the sample M_R_E2 of the
alsoprecipitated
showed the
Mg(OH) 2 , to of
co-presence assess its potential application
sand-rose/lamellar-like in the market.
structures. Lamellar-like brucite shapes have been
The reactive crystallization method
reported in precipitation cases adopting ammonia made use [51],
of NaOH solutions
but rarely to precipitate
for samples Mg2+
precipitated
in the NaOH
from form ofsolutions.
Mg(OH)2 The fromsand-rose
two bitterns collected
structures canfrom Margi be
probably andattributed
Galia final toevaporation
the co-pres-
ponds
ence ofofmany
the Trapani
other ionssaltworks (Italy).
in the real bittern influencing the nucleation and growth processes
A 2 mm diameter
of precipitated brucitecircular, cross-sectional, T-shaped mixer was employed to ensure fast
particles.
mixing of the reactants. The influence of reactantas flow-rate − /Mg2+ ratio
EDS micro-analysis showed no impurities, only Mgratios
and O and the OHwere
elements detected.
was
Theinvestigated.
carbon (C) and Experiments
gold (Au)were alsotraces
element carriedcan
outbe using artificial
attributed to bitterns
the use mimicking
of carbon tapethe
composition of the macro-compounds of real bitterns to better study the
for sample attachment on the SEM stub and the initial spattering of a thin gold layer to precipitation process.
The
better reactantthe
visualize flow rate structures
brucite ratios did atnothigh
affect the Mg2+ recovery,
magnifications, as similar
since brucite is a final ion
non-con-
concentrations
ductive material. in the
Forfiltrates
the sakewere measured.
of brevity, On the
no other SEMother hand,were
images as expected,
reportedthe use of
as similar
20% over-stoichiometric NaOH solutions allowed the total recovery of Mg 2+ ions.
results as those of the M_R_S2 samples were obtained. Note that the sand-rose/lamellar
shapes of sample M_R_E2 were not observed in the Galia bitterns even for samples
Water 2023, 15, 29 20 of 22

As far as the Mg(OH)2 powder’s purity is concerned, cationic purity of >~99% was
obtained regardless the employed bitterns or the operating conditions, while mass purity
between 90% and 96% was measured. XRD analysis confirmed the presence of brucite with a
high value of MH purity, since no other peaks associated with impurity traces were reported.
Overall, thanks to the low calcium concentration in the bitterns, it is feasible to
use an excess of OH− ions for the precipitation of brucite from bitterns. The final high
pH environment reduces boron adsorption on the precipitated brucite particles, thus
ensuring a very pure product (mass purity >96%). The here-reported findings mark the
actual possibility of producing high-purity brucite powders from waste saltwork bitterns
complying with industrial requirements, thus making the bitterns sustainable alternative
Mg2+ sources.

Author Contributions: G.B.: conceptualization, methodology, formal analysis, data curation, vali-
dation, investigation, writing—original draft, visualization; M.A.D.: methodology, formal analysis,
data curation, validation, investigation, writing—review and editing, visualization; R.L.B.: data
curation, investigation; J.L.R.: data curation, investigation, formal analysis; M.F.d.L.: data curation,
investigation, formal analysis; J.L.C.: data curation, investigation, formal analysis, conceptualization,
resources, supervision; A.P.: conceptualization, resources, supervision; A.C.: conceptualization,
methodology, writing—review and editing, supervision, project administration, funding acquisition;
A.T.: methodology, formal analysis, resources, supervision; G.M.: conceptualization, resources, super-
vision, writing—review and editing, project administration, funding acquisition. All authors have
read and agreed to the published version of the manuscript.
Funding: This project has received funding from the European Union’s Horizon 2020 research and
innovation program under Grant Agreement No. 869467 (SEArcularMINE). This output reflects
only the author’s view. The European Health and Digital Executive Agency (HaDEA) and the
European Commission cannot be held responsible for any use that may be made of the information
contained therein.
Data Availability Statement: Data is available on Zenodo.
Conflicts of Interest: The authors declare no conflict of interest.

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