Separation and Purification Technology 48 (2006) 3644

Boron removal by means of adsorption with magnesium oxide

M. del Mar de la Fuente Garca-Soto a, , Eugenio Munoz Camacho b,1
a Department of Industrial Chemical and Environmental Engineering, Polytechnic University of Madrid, Jose Gutierrez Abascal, 228006 Madrid, Spain
b
Department of Industrial II Engineering, Department of Chemical Analysis, University of A Coruna, Mendizabal s/n 15403 Ferrol, A Coruna, Spain

Received 16 November 2004; received in revised form 25 June 2005; accepted 4 July 2005

Abstract

The presence of boron compounds in waters increases in a continuous and parallel way to industrial development. Therefore, their harmful
effects on living organisms also increases, especially on plants, since this element manifests an important micronutrienttoxic boron duality.
The aim of this study is to investigate the influence of different operation variables within the adsorption process of the boron compounds with
magnesium oxide when liquid waste of urban, agricultural or industrial origin is being treated. The results obtained indicate that the process
is strongly influenced by the quality of added reagent and by the contact time between the reagent and solution. Moreover, the temperature
variable also stands out, as it has a very positive influence, reducing the necessary contact time to obtain specific boron removal yields. On the
one hand, it has been observed that this process appears to be inextricably linked to pH. The removal process improves as the pH increases,
presenting a maximum at pH value between 9.5 and 10.5, which is where borate ion predominates. The reagent used in the study has an
important alkalinising capacity. Due to the fact that the pH of the solutions is situated around this range, it is not necessary to adjust this variable
during the process. Therefore, using this reagent is an attractive option. As for the metallic cations that usually accompany boron in industrial
waste, it seems that the reagents presence also facilitates the removal of these cations and a simultaneous treatment of industrial waste can
thus be carried out. Furthermore, interrelationships between the different variables have been established. When the optimum conditions are
selected, the process reaches over 95% of boron removal.
2005 Elsevier B.V. All rights reserved.

Keywords: Adsorption; Boron; Pollution; Removal; Variable influence

1. Introduction Boron, which is one of the dilute elements in water and

Far from being considered a polluting agent, despite its
multiple applications, boron (in its borate ion form) has
lacked exhaustive control (Adriano [1], Keren and Bingham
[2], Pain et al. [3] and U.S. Borax Inc. [4]).
According to the U.S. Bureau of Mines and U.S. Geologi-
cal Survey [5], world production of mineral borates and boron
chemical derivatives were estimated at (45) 106 tonnes
of B2 O3 every year and reserves were calculated at
270 106 tonnes (in B2 O3 form). The United States (42%),
Turkey (42%) and South America (11%) share about 95% of
borate production worldwide.
Corresponding author. Tel.: +34 91 336 3185; fax: +34 91 336 3009.
E-mail addresses: mmfuente@etsii.upm.es (M. del Mar de la Fuente
Garca-Soto), emucam@cdf.udc.es (E.M. Camacho).
1 Fax: +34 981 337410.
regarded as a minor element, appears in concentrations usu-
ally less than 1 mg B L1 and it seldom exceeds the con-
centration in seawater, estimated to be between 4.4 and
4.6 mg B L1 . Drinking waters does not commonly contain
boron, having typical concentrations of 0.10.2 mg B L1 in
accordance with Adriano [1], Keren and Bingham [2] and
Pain et al. [3]. For most of the world, the concentration range
of boron in drinking water is judged to be between 0.1 and
0.3 mg L1 , according to the guidelines for drinking water
quality of the WHO [6].
The main boron sources, whose presence is detected in
surface waters, are urban wastes rich in detergents and clean-
ing products; industrial wastes, which can come from a wide
range of different activities as well as several chemical prod-
ucts used in agriculture (U.S. Borax Inc. [4]). From the wide
range of boron derived compounds, only oxianions appear in
waters since they are soluble. Moreover, the different uses that

1383-5866/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2005.07.023
 M. del Mar de la Fuente Garca-Soto, E.M. Camacho / Separation and Purication Technology 48 (2006) 3644
can cause liquid spillages directly involve orthoboric acid or
borax, or transformation reactions of the by-products towards
these more soluble, oxidised and stable states.
Orthoboric acid is a very weak acid with a pK of 9.2 and,
therefore, not very susceptible to transfer protons in an aque-
ous solution. In its dissociation B(OH)3 does not ionise by
losing a proton from the molecule and forming the anion
H2 BO3 , but B(OH)4 and H3 O+ are formed by the addition
of one OH , acting as a Lewis acid, in the most general sense.
The borate ion B(OH)4 in aqueous solution exhibits a tetra-
hedral structure as opposed to the planar trigonal structure of
orthoboric acid. For dilute solutions (0.10.001N) the consec-
utive dissociation constants have been calculated. However,
the second and third dissociations are not important enough
to explain the reactions taking place in environments with a
pH less than 13. From this it can be inferred that, in order
to explain the vast majority of practical cases occurring in
waters, soils or solids, the species B(OH)3 and B(OH)4 are
enough.
It is also important to indicate that, depending on the con-
centration of orthoboric acid, different species of ions formed
by the condensation of several borate molecules called polyb-
orates (monoborates, diborates, triborates, tetraborates and
pentaborates) can exist in the solution. As indicated by Na
and Lee [7], there are no species that do not satisfy the con-
dition a/b > 1 in the expression Bb (OH)3b+a a , where a and
b indicate the ionic valence and the number of atoms, respec-
tively. With a boron concentration under 0.025 mol L1 , the
only species, which appear in solution, are the monomolecu-
lar ones, that is, the orthoboric acid and its borate anion. The
triborate ions appear for concentrations >0.025 mol L1 , that
is, the hydroxiborane and its conjugate acid. The remaining
polyborate ions exist for boron concentrations greater than
0.1 mol L1 .
In nature, this element appears in the following forms:
(1) in mineral compounds (borosilicates and borates), (2)
adsorbed by clays, (3) adsorbed by organic matter and (4)
in aqueous solution. The total content of boron in solids is
normally in the range of 2 and 100 mg B L1 , with an average
value of 30 mg B L1 as reported by Adriano [1]. The total
quantity of boron depends on many factors, but the main vari-
able is the type of soil.
The process of boron adsorption (free form) in soils dif-
fers substantially from the other essential anions for plants.
In contrast with what happens with phosphates, sulphates
or nitrates, boron adsorption in soils increases when pH
rises. The adsorption maximum ranges between pH 7.0 and
11.0, depending on soil composition according to Adriano
[1] and Keren and Bingham [2]. Many researchers (Adri-
ano [1], Goldberg and Glaubig [8], Keren and Bingham [2],
Keren and Sparks [9], Mattigod et al. [10] and Singh and
Mattigod [11]) have highlighted the important role iron and
aluminium oxides play in boron adsorption by soil particles.
These authors found greater adsorption as the pH increased,
with an adsorption maximum between pH 6.0 and 7.0 for
Al2 O3 and between pH 8.0 and 9.0 for Fe2 O3 , and decreas-
37
ing adsorption at higher pH. Organic matter, in the form of
humic acids, has been suggested by Gu and Lowe [12] and
by Meyer and Bloom [13] as an important factor in boron
adsorption processes in soils due to the presence of large
amounts of OH groups.
In recent years, studies of the beneficial/toxic effects of
boron in irrigation waters, living organisms and diffusion
in soils have proliferated. Nowadays solutions that involve
reducing the high boron concentration in some industrial
liquid wastes in the sewage system (Integral System of San-
itation (I.S.S.)) are being studied by de la Fuente [14], de
la Fuente and Munoz [15,16] and Martnez et al. [17]. The
variety of ways boron is used in industry has encouraged
the development of a number of boron removal methods,
including the techniques based on precipitation, adsorption,
ion exchange, extraction with organic solvents and reverse
osmosis.
This study focuses on boron removal by means of a precip-
itation/adsorption process. The influence of reagent quality
and quantity, the physical variables such as contact time or
temperature and the chemical variables such as pH and the
presence of other ions have been studied.
2. Selecting the removal method
There are a great variety of possible removal methods of
borate ions in industrial waste.
Boron precipitation/adsorption in the form of sparingly
soluble compounds has been selected because, on the one
hand, there is little need to process and condition the aqueous
solutions and, on the other hand, this method is very simple
according to Kim and Gee [18], Matsumoto et al. [19], Okay
et al. [20], Pain et al. [3] and Rodionov et al. [21].
As for the adsorption methods by compounds of nat-
ural origin (Goldberg and Glaubig [8], Keren and Sparks
[9], Meyer and Bloom [13] and Singh and Mattigod [11]),
at first, the processes are analogous to selected precipita-
tion/adsorption. However, these materials have drawbacks
since they need complex pre-treatments in order to achieve
appropriate particle sizes (20.2 m), property homogeneity
or the removal of possible superficial coatings of the active
adsorption sites. These treatments are, in general, complex
and time-consuming in terms of the laboratory and espe-
cially in the context of industry. Therefore, they have not
been selected.
Another attractive method, ion exchange (Ishihara et al.
[22], Na and Lee[7], Pain et al. [3], Okay et al. [20], Rodionov
et al. [21], and Sahin [23]), has been discarded because it is
only effective with low boron concentrations, it involves pre-
treating the waste to eliminate solids and fats, and it has costs
related to specific resin and its regeneration.
As regards to the extraction methods with solvents accord-
ing to Kahraman [24], Pilipenko et al. [25], Rodionov et
al. [21] and Su and Suarez [26] they are considered highly
efficient and selective. However, they have several disad-
38 M. del Mar de la Fuente Garca-Soto, E.M. Camacho / Separation and Purication Technology 48 (2006) 3644
vantages: the complexity of the equipment, the high costs
involved and the partial solubility of the organic extractants
and dilutants used in water. Thus, their use is limited due to
their environmental risk.
The need to maintain membrane stability for the methods
of reverse osmosis, ultrafiltration or nanofiltration (Alvarez
et al. [27], Marinas [28], Nirmal et al. [29], Rodionov et
al. [21] and Smith et al. [30]) in the face of pH and tem-
perature variations, the presence of oxidating agents and, in
general, the need to pre-treat waste to lengthen the useful
life of the membrane, makes these elimination methods more
expensive. Moreover, electrochemical methods described by
Rodionov et al. [21] have been discarded since they present,
in general, low yields and high costs relating to the electrol-
yser construction. Methods with membranes are, in general,
non-selective techniques. Finally, thermal methods reported
by Rodionov et al. [21] and Pocovi et al. [31] are very energy
consuming and, therefore, discouraging from the economic
point of view.
3. Experiments and discussion
3.1. Reagents and equipment
Magnesium oxide reagents used in this study were pro-
cured from Panreac Chemical (Spain) and Quimipur (Spain).
Properties of these magnesium oxide adsorbents were listed
in Table 1. Boron stock solution (500 mg L1 ) was prepared
by dissolving an appropiate quantity of boric acid (H3 BO3
supplied by Merck Darmstadt, Germany) in double distilled
water, and the working solutions were prepared by dilut-
ing this solution with double distilled water. For the study
presence of other ions, highly soluble salts of cation and
dodecilbenzenesulfonic acid, sodium salt (tensioactive) were
used supplied by Merck Germany or by Aldrich Chemical
Company Inc. The other chemicals used, such as Azome-
thine H, HCl, NaOH, Na2 EDTA, HAc, NH4 Ac, etc. were of
analytical reagent grade supplied by Merck Germany and all
the solutions in the study were prepared using double distilled
water.
Other, only polymeric: P.E., P.T.F.E., quartz glass and
platinum laboratory material can be used to minimise the
contamination or the increase of boron content. For this study
P.E. material was used except pH measure electrodes, quartz
glass spectrophotometric cell and quart glass vessels for high
temperature.
Table 1
Magnesium oxide quality
Reagent A Reagent B
MgTOTAL : 57.23% MgTOTAL : 44.71%
Weight loss at 100 C: 0.48% Weight loss at 100 C: 2.66%
Weight loss at 570 C: 2.26% Weight loss at 570 C: 18.55%
Mg5 (CO3 )4 (OH)2 : 4.60% Mg5 (CO3 )4 (OH)2 : 37.82%
MgO: 92.56% MgO: 54.88%
The following analytical equipment has been employed:
Shimadzu UV-260 Spectrophotometer/Perkin Elmer 1100
Atomic Absorption Spectrophotometer/pHmeter Micro
pH 2001 Crison/Heto Thermostated Water Bath (Den-
mark)/Heidolph Stirrer/KS 501 D Janke & Kunkel Stirrer.
3.2. General operating procedure
The experiments have been carried out using two syn-
thetic samples, one of them with a high concentration,
500 mg B L1 and the other, with a low concentration,
50 mg B L1 . These values have been selected, according to
Na and Lee [7] in an effort to avoid the appearance of polyb-
orates. B polymers are negligible at this concentration, the
molar fraction of trimolecular species is <0.003 and it is con-
sidered that the only existing species in solution are boric acid
and borate ion. Throughout this study, the concentrations of
these species will be designated as a sample of high or low
concentration, unless otherwise indicated.
The amount of boron retained is given as:
(c0 cf )
%= 100
cf
where c0 and cf are the initial and residual boron concentra-
tion in the solution. The analysis method that has been used
was Molecular Absorption Spectrometry in the UVvisible
range using Azomethine H as a colorimetric reagent accord-
ing to the procedure of Lopez et al. [32]. This compound
is not considered a standardised reagent for boron analy-
sis in waters [33]. However, it has been selected owing to
its simplicity and competitiveness over other Spectrophoto-
metric reagents, according to de la Fuente and Munoz [16].
Concurrent with the boron determination, the analysis of
residual magnesium cation (in the pH variable) has been car-
ried out in each solution by means of tritation with Na2 EDTA
or Atomic Absorption Spectrophotometry depending on the
concentration range; this analysis shows to what degree the
adsorbent reagent has been dissolved. The residual con-
centration of the corresponding cation has also been anal-
ysed in the study of the variable presence of other ions
by means of Atomic Absorption Spectrophotometry. The
anionic tensioactive content has also been analysed (stated
as sodium dodecylsulfonate) by titration with bencetonium
chloride (hyamine) or Molecular Absorption Spectrophotom-
etry with methylene blue depending on the concentration
range. Lastly, the boron stock solution has been standardised
through acidbase titration in mannitol.
The general operating procedure that has been used is a
discontinuous contact-filtration method. The first step con-
sists of taking a sample of 100 mL, which is put in a 250 mL
P.E. vessel. It may be necessary to heat the sample up in a
thermostated water bath if the required temperature is higher
than room temperature. This sample is mixed on a stirrer
under the selected conditions, with a speed of 200 rpm and
with a specific quantity of previously pulverised adsorbent.
The sample is allowed to equilibrate (contactrepose) for
 M. del Mar de la Fuente Garca-Soto, E.M. Camacho / Separation and Purication Technology 48 (2006) 3644
Fig. 1. Effect of Mg/B mol ratio on adsorption of boron by magnesium oxide.
[() low concentration sample; () high concentration sample] (variables:
stirring, 2 h; repose, 48 h; room Ta ; pH 9.5010.50).
a predetermined time. Then the clarified solution is filtered
using Whatman 31 filter paper. The residue is washed sev-
eral times and the filtered substances and the backwash waters
are gathered in a precipitating vessel. The pH of this purified
solution is set to 5.20 (a suitable pH for a subsequent analysis
according to de la Fuente and Munoz [16]) by adding diluted
hydrochloric acid and ammonia solutions and using a com-
bined glass membrane electrode as a pH sensor. This solution
is diluted to 200 mL in a P.E. volumetric flask and the analysis
of the residual boron is carried out according to the referenced
method. Moreover, the resulting solids are dried, weighed and
stored.
3.3. Selection of variables: results and discussion
3.3.1. Magnesium/boron mol ratio
The removal yield has been studied according to the quan-
tity of the magnesium oxide added. It is essential to determine
the optimum Mg/B mol ratio in order to avoid an excessive
consumption of magnesium oxide, which makes the process
more expensive without achieving a significant increase in
the removal yield. The influence of this variable has been
studied in both synthetic samples following the procedure
previously described, at room temperature and with stirring
and repose times high enough to eliminate their influence (2
and 48 h, respectively).
The Mg/B mol ratios studied and their corresponding
amounts of boron removal, stated as a percentage, are shown
in Fig. 1. The similarity between both curves allows them to
be analysed at the same time so the optimum Mg/B mol ratio
can be found. It can be observed that the process is strongly
influenced in the beginning by the quantity of reagent that
is added. A significant positive slope is revealed. In the high
concentration sample studied it is also observed that the Mg/B
mol ratio, beyond which the increase in removal yield is not
significant, is about 20. The low concentration sample does
not get to become stabilized completely. This value has been
selected to carry out the tests requiring a constant Mg/B mol
ratio value.
39
Fig. 2. Influence of reagent quality on adsorption of boron by magnesium
oxide: (a) correction factor applied fT and (b) correction factor applied fO
[() reagent A, (
) reagent B, () corrected reagent A, () corrected
reagent B] (variables: stirring, 2 h; repose, 48 h; room Ta ; pH 9.5010.50).
3.3.2. Reagent quality
If the boron removal process is strongly influenced by the
quantity of reagent, selecting a reagent that has a different
quality from the one used in the experiments can result in
removal yield increases or decreases. In the laboratory, it is
easy to have reagents with such a high purity, but at industrial
level, reagents of commercial qualities are preferred because
they are cheaper. Another important point here has to do with
the easy carbonation and hydration of magnesium oxide when
it is stored under unsuitable conditions. For the laboratory,
this aspect is easily controlled, but this is not the case for
industry.
Accordingly, two reagents have been tested; their experi-
mental characterisation is shown in Table 1. Reagent A is used
in the remaining studies, whereas reagent B is an alternative
reagent of worse quality. An X-ray spectrum has been car-
ried out on reagent B (of worse quality) in order to know its
components. This spectrum reveals the presence of hydro-
magnesite [Mg5 (CO3 )4 (OH)2 4H2 O] in a periclase matrix
(MgO). No other component has been determined. The ther-
mal decomposition temperature for this form of magnesium
carbonate is between 300 and 570 C, losing at first the struc-
tural water and then CO2 . The weight loss value during
calcination at 570 C, shown in Table 1, can be identified
with this compound, estimating the magnesium content for
this carbonate.
In Fig. 2, the study of the influence of Mg/B mol ratio is
shown, over a high concentration sample, for both reagents,
without taking their composition into account. Moreover,
given the characterisation analysis, the experimental results
40 M. del Mar de la Fuente Garca-Soto, E.M. Camacho / Separation and Purication Technology 48 (2006) 3644

should be multiplied by a correction factor when representing

the data of removal percentage versus real mol ratio. Accord-
ing to two factors, Mg/B values have been corrected.
The fT factor has been estimated taking the total magne-
sium content into account, the one from either the oxide or
the carbonate. fT was calculated by the following equation:
MgTOTAL (Table 1)
Mg real
fT = = 100
Pa Mg
Mg theoretic
PM MgO

These values for fT were 0.95 and 0.74 for reactives A and
B, respectively.
In contrast, the fO factor which has been estimated with
only the magnesium from the magnesium oxide is considered
active. fO was calculated by the following the equation:
Fig. 3. Effect of contact time on adsorption of boron by magnesium oxide.
[() low concentration sample, () high concentration sample] (variables:
Mg/B mol ratio, 20; stirring, 30 min; room Ta ; pH 9.5010.50).

Mg real
MgO(Table 1)
100 PPMaMgO
Mg As can be observed in Fig. 3, the curves show an initial
fO = = Pa Mg
portion with a high slope and a second portion in which the
Mg theoretic development tends to become asymptotic. This is a typical
PM MgO
development pattern in adsorption processes where, as the
These values for fO were 0.93 and 0.55 for reactives A and process goes on, the solute diffusion towards the sorbent is
B, respectively. It can be noted that fO for reactive B is almost slower due to a decrease in its concentration. In this first
half. Fig. 4 it is also observed that the optimum repose time is
It can be observed, also, that the modified curves accord- between 6 and 10 h depending on Mg/B mol ratios. These
ing to the fO correction factor correspond with the ones for times (<10 h) are not accompanied by high related costs but
reagent A as they develop without correction. The presence they do involve an effluent immobilisation, and, in specific
of magnesium carbonate in the reagent does not encourage cases, this is a determining factor.
the adsorption process as it should be considered an inert Starting from the results obtained, for the contact time, the
component and, therefore, the reagent quality is a variable to value of 30 min for stirring time and at least 6 h for repose
be taken into account. time at room temperature is accepted for superior tests.

3.3.3. Contact time 3.3.4. Temperature

The contact time was defined by two processes: (1) stirring In general, an increase in temperature has an influence
only and (2) repose after stirring. on adsorptiondesorption processes. Therefore, it is impor-
The importance of stirring lies in the fact that it maintains tant to know its influence on the adsorption process of boron
the magnesium hydroxide in suspension, offering the maxi-
mum surface to boron precipitation/adsorption but when the
boron concentration in the solution is so low that stirring does
not encourage the diffusion of borate ions towards the surface
with the same effectiveness found during the first few min-
utes of the process. Stirring for a long time elevates associate
cost.
Repose time is understood as the time in which the solution
and solid keep interacting while the samples are in repose.
The importance of this variable lies in the fact that it can be
known if the process makes progress with time. It is a useful
variable to apply the results obtained in a laboratory to a pilot
plant and at an industrial level.
To study this variable with both synthetic samples, the
following variables have been used: at room temperature,
and with a stirring time of 30 min, changing repose times.
For the high concentration sample, the test was carried out at
20 C for three different Mg/B mol ratios (10, 20 and 30) in
order to study the interaction of this variable with the repose Fig. 4. Effect of contact time and Mg/B mol ratio on adsorption of boron
time. As for the low concentration sample the study has been by magnesium oxide (variables: high concentration sample; stirring, 30 min;
done for an Mg/B mol ratio of 20 at 25 C. room Ta ; pH 9.5010.50).
 M. del Mar de la Fuente Garca-Soto, E.M. Camacho / Separation and Purication Technology 48 (2006) 3644
Fig. 5. Effect of contact time and temperature on adsorption of boron by
magnesium oxide. (a) Low concentration sample and (b) high concentration
sample (variables: Mg/B mol ratio, 20; stirring, 30 min; pH 9.5010.50).
with magnesium oxide. Besides, the reactivity of magnesium
oxide (solubility and hydration) also depends on temperature.
Four temperatures have been studied: 20, 30, 50 and 70 C.
The samples were heated in a thermostated water bath, a
Mg/B mol ratio of 20 was used and the reagent was added
once the samples reached their corresponding temperatures.
Under these conditions the samples could be stirred with a
paddle agitator for 30 min. Then the samples were allowed
to sit while a constant temperature was maintained.
These tests have been carried out changing the repose
time to obtain additional information about the interaction
between temperature and contact time. The data for a tem-
perature of 20 C, a Mg/B mol ratio of 20 and changing repose
time appear in previous tests. As observed in Fig. 3, in the
beginning that curve shows a period with a high slope. It is
vital to control the influence on temperature in this interval,
rather than during the asymptotic period to which the process
is prone, regardless of the variables applied. For this reason
the influence of this variable for relatively short repose times
has been studied.
Fig. 5 shows the yields obtained for each temperature
and for high and low concentration samples, respectively.
As it has been previously shown, it can be noted that a great
increase in the curve slope at an early stage occurs for the
highest temperature values in these figures. This involves a
41
significant decrease in the repose time needed to obtain a
specific yield. The rise in effluent temperature through direct
heating involves high costs. An alternative route could be
transferring heat from a hot residual source.
3.3.5. pH
To carry out this study, 14 P.E. vessels have been prepared;
in which 14 identical samples containing an initial boron
concentration of 500 mg L1 have been introduced. The oper-
ating procedure used has been a discontinuous method of
contactfiltration. The samples are stirred under the selected
conditions: Mg/B ratio, 20; stirring speed, 200 rpm; stirring
time, 30 min; repose time, 24 h; room temperature. Then, they
are, allowed to sit for the predetermined time. Before being
filtered, the pH of each solution is adjusted to the correspond-
ing value by adding HCl or NaOH and using a combined
glass membrane electrode for control purposes. Then all the
samples are stirred once more during 30 min so as to guar-
antee homogeneity, the clarified solutions are filtered and the
residue is washed several times. The filtered solution and the
backwash waters are gathered in a P.E. vessel, where their
pH is set at a value of 5.20.
Two systems are implied in the process in study. The
first one is the orthoboric acid/borate ion equilibrium
(500 mg B L1 0.047 mol B L1 ). It has been considered
that the only boron species present in solution which can be
helpful are the monomeric species orthoboric acid and borate
ion. At pH values between 5.5 and 7.5, which are the most
common in waters, there is an extreme shift to the left with
the equilibrium of dissociation. Therefore, the predominant
species in waters will be the acid species H3 BO3 or B(OH)3 .
However, it has been observed that the majority of boron reac-
tions with OH groups of polyalcohols, clays, humic acids
and so on, occur with the borate ion. These reactions will
be favoured at a pH greater than 9.2, where these species
predominate.
The second important system is related to the reagent
(Mg/B mol ratio: 20 0.93 mol L1 ). Magnesium oxide
in contact with an aqueous solution hydrates, creating the
hydroxide, which presents a solubility product of 1011 and
precipitates at a pH near 8.5, decreasing the free concentra-
tion of magnesium ion in solution. Also, it is soluble in excess
of alkali but it dissolves in all acids. The data indicates that
the reagent used in this process ultimately cannot be regen-
erated using acids since the dissolution of adsorbed boron
and of the reagent will occur, thus, losing all its interesting
properties from the point of view of adsorption. That is, the
adsorption process is irreversible.
A last consideration is the borate ion reactivity to create
metallic complexes in solution with alkali and alkaline-earth
cations. With the borate, magnesium forms an ionic pair by
means of the following equilibrium:
Mg2 + + B(OH)4 [MgB(OH)4 ]+ pK 1.65
The reaction between these two species is going to be
influenced by two main reactions: the acidbase reaction
42 M. del Mar de la Fuente Garca-Soto, E.M. Camacho / Separation and Purication Technology 48 (2006) 3644
Fig. 6. Effect of pH on adsorption of boron by magnesium oxide. [()
amounts of boron removal, ( ) Mg2+ residual in solution] (variables: high
concentration sample; Mg/B mol ratio, 20; stirring, 30 min; repose, 48 h;
room Ta ).
of the orthoboric acid/borate ion, only being possible at
a basic pH where the borate ion predominates, and the
precipitation (or solubilisation) reaction of the magnesium
hydroxide. It can be said that the higher the pH values
(for instance, pH 10), the less quantity of Mg2+ remains
in solution to form the ionic pair. Therefore, the quantity
of borate ion which takes part in the complex is insignifi-
cant (2 105 mol L1 0.22 mg B L1 ), in contrast with
the concentration that is free (4.6 102 mol L1
500 mg B L1 ). This indicates that the influence of the ionic
pair formation is negligible for this study.
Fig. 6 is a representation of the B amounts retained found
for each pH value, as well as the magnesium percentages in
the solution. In this figure three areas can be clearly distin-
guished: for a pH < 8.0 the removal yields are very low and
practically constant; for a pH between 8.0 and 10.0 a maxi-
mum in the curves development appears and for a pH > 10.0
the yields decrease, but remain far from zero.
According to this data and taking the previous consider-
ations into account, it can be suggested that a complexation
reaction of B(OH)3 and B(OH)4 species occurs with the
OH groups on the reagent surface. At a pH below 8.0 the
predominating species is orthoboric acid and, owing to its
low electrical activity, the adsorbed quantity is insignificant.
This species presents a low affinity. As expected, when the pH
increases, to an identical pH to the pK value, the adsorption
process is more effective. It reaches a maximum, the borate
ion concentration rises quickly and the adsorbed boron con-
centration increases to a maximum of pH 10.0. Later, the
pH increases raising the concentration of hydroxyl ions in
relation to the concentration of borate ions and, owing to the
competitiveness of these two species for adsorption sites, the
adsorbed boron decreases. However, a reaction among the
borate ion and the active hydroxyl groups of the adsorbent
reagent still exists. This explains the presence of a down-
ward curve with a reduced slope. It is also observed in Fig. 6
that the concentration of magnesium ion in solution is very
high for a pH below 8.5. This encourages low boron removal
in the form of orthoboric acid, since the active surface for
adsorption decreases. Moreover, the quantity of magnesium
cation in solution readily decreases for a pH above 8.5 and,
therefore, the solid keeps the optimum qualities for borate
ion adsorption within these ranges.
3.3.6. Presence of other ions
Wastes rich in boron compounds can contain substances
coming from industrial or urban processes. These substances
are mainly metallic ions: Ni2+ , Fe3+ , Zn2+ , Cr3+ and Cr(VI)
from metal plating processes, and the typical tensioactives
of urban wastewaters. It would be interesting if a positive
influence of these compounds on the process existed, since it
would help to reduce the boron concentration.
Moreover, clays have an important ability to boron fixation
in soils. The main components of clays associated with this
process are iron, aluminium and calcium. For this reason the
influence of Ca2+ and Al3+ ions has been also studied.
For these studies the highly soluble salts from their cor-
responding ions have been used. The tests have been carried
out on four samples containing the following boron and ion
concentrations under study:
Sample0 : (500 mg L1 of B).
Sample500 : (500 mg L1 of B + 500 mg L1 of ion).
Sample1000 : (500 mg L1 of B + 1000 mg L1 of ion).
Sample5000 : (500 mg L1 of B + 5000 mg L1 of ion).
Here, the procedure has been the usual one, with the fol-
lowing maxima in the process variables: sample volume,
100 ml; Mg/B mol ratio, 20; stirring time, 30 min at 200 rpm;
repose time, 24 h; room temperature; pH 9.5010.50.
For the pH range used, the majority of ions that will
be studied predominate in their hydroxide form, except for
Cr(VI) and the tensoactives. Therefore, this process can let us
purify the boron and the metallic cations of an industrial liq-
uid effluent simultaneously, along with the other advantages
arising from this aspect.
The B removal percentage obtained and the residual con-
centrations of the ion in solution are shown for each tested
sample in Table 2. In the case of nickel, iron and aluminium a
slight increase in boron elimination is observed as the quan-
tity of cations in the samples rises. This process is due to the
precipitation of nickel hydroxide at an approximate pH of
7.0, iron hydroxide at pH values over 2.0 and hydrated alu-
minium oxide (commonly known as hydroxide) at pH values
near 3.5 which adsorbs a part of the boron. However, the
quantity of magnesium oxide is so high that the influence of
cations is negligible. As is observed in Table 2, in the case
of zinc, its yields decrease as the content of Zn increases,
but the magnitude is limited. As with the previous cations,
the precipitation of amorphous zinc hydroxide occurs in the
test conditions and begins at a pH of 11.5 to yield a zin-
cate ion. The decrease may suggest that Zn does not bind the
borate ion in its precipitation. Nevertheless, it may be inter-
fering in the adsorption sites of the magnesium hydroxide.
The tests which correspond to ion Cr(VI) cannot be analysed
due to the great coloration of the samples. At pH values of the
tests, Cr(VI) predominantly appears as chromate ion with a
typical yellow coloration which interferes in the Spectropho-
 M. del Mar de la Fuente Garca-Soto, E.M. Camacho / Separation and Purication Technology 48 (2006) 3644 43

Table 2 ion, which has been fixed at 500 mg L1 of B in this study.

Effect of presence of other ions on adsorption of boron by magnesium oxide
(Mg/B mol ratio, 20; stirring, 30 min; repose, 24 h; room Ta , pH 9.5010.50)
The economyresults balance will decide if the application
of the proposed methodology for the effluent purification is
Sample B removal Ion solution Sample B removal Ion solution
(%) (mg L1 ) (%) (mg L1 )
feasible or not.
Besides, the behaviour of boron adsorption with pH
Ni0 95.44 Cr(III)0 97.49
Ni500 96.69 <0.01 Cr(III)500 97.98 <0.01
(chemical variable) is quite similar to the one observed in
Ni1000 97.20 <0.01 Cr(III)1000 97.81 <0.01 natural materials such as clays or humic acids. The addition
Ni5000 98.53 <0.01 Cr(III)5000 98.46 <0.01 of the reagent, with high alkalising ability, gives a pH value
Fe0 95.44 Al0 95.44 between 9.5 and 10.5, which is in accordance with the max-
Fe500 98.45 <0.01 Al500 97.06 <0.1 imum value appearing in Fig. 6. Therefore, the control of
Fe1000 98.30 <0.01 Al1000 97.71 <0.1 this parameter will not be necessary since, with the study,
Fe5000 98.58 <0.01 Al5000 97.53 <0.1 it is known for certain that work is being carried out in the
Zn0 97.49 Ca0 95.44 optimum conditions with respect to this variable. The use of
Zn500 98.60 <0.01 Ca500 95.92 231.66 this reagent introduces this advantage in establishing a pro-
Zn1000 97.07 <0.01 Ca1000 95.72 519.33 cess of purification at an industrial level. Furthermore, this
Zn5000 96.53 <0.01 Ca5000 95.01 3080.34
reagent presents similar effectiveness to natural adsorbent
Tens0 97.49 Tens1000 92.79 120.30 materials such as clays or humic acids. It holds an advantage
Tens500 98.94 62.47 Tens5000 92.11 558.02
over them, since the latter need previous treatments to ready
them in terms of particle sizes, to achieve homogeneity in
their properties and to eliminate possible superficial cover-
tometric measurements. The presence of chromium with an ings of the active sites for adsorption. These treatments are, in
III oxidation state has been studied. The results in Table 2 general, complex and time-consuming at an industrial level.
indicate that this cation has a similar performance to that of As for the analysis of the experimental data regarding the
the other metallic ions studied: slight yield increases due to presence of other ions in the adsorption process in study, the
coprecipitation of the corresponding hydrated hydroxide at following conclusions can be drawn. Firstly, the presence of
a pH about 5.0. The addition of calcium ion by means of a cations can be beneficial as it increases the removal yields.
neutral soluble salt results in the same conclusions observed Secondly, an interesting parallel purification of the metallic
in the tests corresponding with ions Ni2+ , Fe3+ , Cr3+ and cations occurs due to precipitation in oxide form. Lastly, the
Al3+ . presence of tensioactives must be controlled since they have
As it is observed in Table 2, the content of all cations in a negative influence on the process.
treated solutions is under the limit of detection, which cor-
responds to each element. Therefore, the removal procedure
under study for the case of boron is also useful for the removal
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