Separation and characterisation of montmorillonite from a low-grade

natural bentonite: using a non-destructive method

Shima Barakan, Valeh Aghazadeh ✉
Department of Mineral Processing, Faculty of Mining Engineering, Sahand University of Technology, Tabriz, Iran
✉ E-mail: [email protected]

Published in Micro & Nano Letters; Received on 4th July 2018; Revised on 2nd February 2019; Accepted on 25th February 2019

Bentonite clays containing mostly montmorillonite as a nanostructure group of smectite have been used as industrial raw material in many
applications. The presence of the other impurities in bentonite clays reduces the value of bentonite. Therefore, the bentonite purification is
necessary. In this research, the purification and separation of montmorillonite from a low-grade natural bentonite were considered on the
regular and comprehensive plan. For this purpose, a set of methods including dispersion, sodium-activation, sedimentation, sonication and
centrifugation were used. In contrast to many methods, there were often complex, expensive and non-effective; this purification method
was found to be effective for removing almost all quartz, carbonates and clinoptilolite as the major impurities. In this purification method,
the montmorillonite content was increased from 15 to 84% with the separation yield of 80%. The influence of centrifugal force and the
type of ultrasonication indicated the most critical parameters in the purification yield, the physical properties and the crystalline structure
of the final products. The laser particle size distribution analysis, X-ray diffraction, semi-quantitative analysis and Fourier-transform
infrared spectroscopy results showed the decrease of impure phase without any structural changes or damages in clay framework.

1. Introduction: Bentonite is a geological term for soil materials commercially methods have been not observed. In these methods,
with a high content of a swelling mineral, which usually is mont- experimental details regarding purification steps are often different
morillonite. It is produced by in situ devitrifications of volcanic or unspecified.
ash [1]. Although, bentonite chemical composition varies from The gravimetric methods, magnetic separation, sieving [12],
one place to another place [2]. The bentonite clay is often extracted sedimentation (based on Stokes’ law) [11–18], chemical decompos-
from open pit mines with different deposit depths and many impur- ition and dissolution [19, 20] were the conventional methods that
ities. Therefore, bentonite purification is an important process, have been proposed for montmorillonite separation. Previous
which is an expensive and complex procedure for separation of studies have documented the beneficiation of hydrocyclone [21],
montmorillonite. There are various types of bentonite based on its and centrifuged [22] to remove the impurities. Moreover, there
impurities which plays an important role in its processing and appli- are several studies to use ultrasonic device for the particle size dis-
cation [3]. The special properties of bentonite are an ability to form tribution and the separation of the coarsest particle from montmor-
thixotropic gels with water, an ability to absorb large quantities of illonite particles [11, 23, 24]. In this way, the ultrasonic treatment
water, and a high cation exchange capacity (CEC) [4, 5]. The prop- and the centrifugation methods showed the high yielding for separ-
erties of bentonite are derived from the crystal structure of the ation of montmorillonite [23]. The best montmorillonite separation
smectite group, which is an octahedral alumina sheet (O) between in the size fractions lower than 2 μm was obtained by centrifugation
two tetrahedral silica (SiO2) sheets (T) with two tetrahedral layers at 8000 rpm for 40 min [10]. In the literature, low-speed centrifuga-
consisting of [SiO4] tetrahedrons that enclose a central [M(O5, tion and gravity sedimentation introduced a simple method to
OH)]− octahedral layer (Tetrahedral- Octahedral- Tetrahedral reduce impurity phase in clay minerals. Therefore, the incorporation
(TOT)), (M: aluminium (Al), magnesium (Mg) mainly). of centrifugation, ultrasonication and sedimentation showed the
Isomorphic-cation substitution in the octahedral layer lead to a effective method to remove impurities [11]. In another approach,
weak negative surface charge that is compensated by adsorption of to purify bentonite clay, the elutriation technique has been used
other cations, most often calcium (Ca), Mg and sodium (Na) [6]. to select montmorillonite based on Stokes’ law [25]. For removing
The montmorillonite ideal formula may consequently be written an organic component from bentonite clay, hydrogen peroxide
[7]: Si 8–x Alx Al4–y Mgy (Fe) O20 (OH)4 (x + y cations) n(H2O) treatment, Na hypochlorite and disodium peroxodisulphate reaction
(x < y and 0.4<x + y < 1.2). The bentonite structure schematically has been used [26]. To remove carbonate impurities, the diluted
illustrates in Fig. 1. hydrochloric/acetic acid solution at pH < 3.5 was traditionally
Bentonite is usually found in its Ca form with lower CEC, which used which could cause the structural damage for clay minerals.
is an essential property for many applications. To improve CEC, Therefore, the Na acetate solution at pH = 5 was the suitable
Na-activation is a promising method to enrich bentonite with method to carbonate decomposition [27]. To remove the other
Na cations without any structural damages [8]. Furthermore, the impurities in clay minerals such as soluble salt, oxide/hydroxide
Na-activation could help to separate the montmorillonite layers of silicon and Al, Na chloride (NaCl) and Na carbonate or
from impurities such as α-quartz and cristobalite usually found in Na hydroxide aqueous were used [28]. The ferro/ferric iron and
fine sizes [9]. Al were removed by ammonium oxalate, oxalate acid solution
The range of montmorillonite particle size is usually between and other acidic treatment [29].
0.1 and 2 μm with an average particle diameter of 0.5 μm. According to the purification methods reported in the literature,
The smectite content of bentonites can be improved by removing the wide ranges of techniques for montmorillonite nanosheets
impurities such as sand, gravel, quartz, feldspars, calcite, iron separation was used. Most frequently research on natural clay
oxides and humic acids [10, 11]. Several methods have been used mineral modification is carried out with the use of a homoionic
for separation and purification of clay minerals in many applica- Na form of montmorillonite, as it is easily exchangeable and pro-
tions, but the available specific and general recognition vides uniform properties for intercalation [30]. Pacuła et al. [23]

688 Micro & Nano Letters, 2019, Vol. 14, Iss. 6, pp. 688–693
& The Institution of Engineering and Technology 2019 doi: 10.1049/mnl.2018.5364
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used to prepare homoionic products by 1 M NaCl solution (1:100
S/L) for 2 h. The sedimentation and ultrasonic process were used
in the next steps. The obtained suspensions were subjected to
acetic acid and Na acetate to remove carbonates impurities. In
this step, the titration with 0.5 M Na acetate buffer in the constant
stirring on the magnetic stirrer (at 90°C, 500 rpm) was happened
and continued until the CO2 bubbles were not observed. This tech-
nique aims to decompose carbonates including CaCO3, MgCO3 and
Na2CO3 to soluble compounds including carbon dioxide, water and
metallic salts. Finally, the prepared suspensions were centrifuged in
two stages. In the first stage, to prepare P1 and P2, the suspensions
Fig. 1 Layer structure of bentonite clay
were centrifuged at a lower force in the range of 479 g, and to
prepare P3, the suspension was centrifuged at 1914 g until the prob-
studied the textural effects in powdered montmorillonite induced by able impurities were removed. In the second stage, to collect clay
freeze drying and ultrasound pretreatment in this way, the signifi- minerals, the supernatant liquids containing clay-sized particles
cant differences in the intensity ratios of 001 and 020 reflections were centrifuged at 14,475 g. In this step to remove residual chlor-
were found. Both the freeze drying and the sonication led to the dis- ide from the previous step, washing was done carefully more times
ruption of clay agglomerates into smaller particles, more prone to with the AgNO3 test. Subsequently, obtained purified clays (P1, P2
mutual self-orientation particles. Sonication has constituted a and P3) were ground and sieved. The schematic diagram of the ben-
more efficient means of clay disintegration and induces larger tex- tonite purification process is shown in Fig. 2.
tural ordering. For the purification of raw bentonites, Thuc et al.
[11] used three different methods including centrifugation and son- 2.3. Characterisation techniques: The dried NB and purified ben-
ication, sonication coupled with sedimentation or single centrifuga- tonite clay powders (P1, P2 and P3) were characterised for CEC
tion. Chemically purified by three steps was also applied (i.e. the by using Bower (ammonium acetate) method [32, 33]. Therefore,
carbonates were dissolved with acetic acid; organic molecules the flame photometer device (360, Sherwood) was used to
were oxidised by hydrogen peroxide; and iron (hydr)oxides were measure exchangeable cations. The grain density (Ds) was calcu-
removed by several complexation and redox reactions). In this puri- lated by (1) for all samples. The procedure, which was used to de-
fication method, the dried material shows stronger self-ordering termine Ds, is described by several authors [34, 35]
than the freeze-dried sample. The dispersion-sedimentation ms
method was used by Hayakawa et al. [31] to increase the smectite Ds = (1)
VT − ((mT − ms+f )/DL )
content from 40 to 75%. In this way, a large number of chemicals
and reagents with harmful influence on clay application have been
used. In some physical treatments, the high-quality bentonite could where ms is the mass of the solid (g); VT is the volume of the flask
not attain, general or uniform experiments for clay purification were (ml); mT is the total mass (g); ms+f is the mass of solid and flask (g);
not obtained and some structural damages were accrued. Therefore, and DL is the liquid density (g/cm3).
the main objective of this research is to use the convenient and re- Test method ASTM-D5890 is used to determine the swelling
liable procedures for the purification of natural bentonite (NB) clay, index (SI) for all samples [36]. A 2 g sample of dried and finely
without any destructive effects on clay structures and avoiding any ground bentonite clay is dispersed into a 100 ml graduated cylinder
harsh chemical treatments that may cause a human health risk for in 0.1 g increments at minimum 10 min. The sample is then kept for
some application in food and pharmaceuticals. The incorporation a period of 16–24 h to record the volume changes. The particle size
of Na-activation, sedimentation, ultrasonication and centrifugation distribution has been analysed with laser particle size analysis
methods were considered on the regular and comprehensive plan. (LPSA, Analysette 22 NanoTec). The preparation method for
Moreover, in this present research, the effect of ultrasonic power LPSA consists of the suspension preparation (5 wt%) for each
(before granular sedimentation) and the centrifuge force have
been attended to the montmorillonite nanosheets separation. All ex-
perimental details and observations were analysed and showed that
the recommended method improved the montmorillonite purifica-
tion and preserved the clay framework.

2. Materials and methods

2.1. Materials: The NB clay was obtained from Dr. Mojallali Co.,
Ltd., Iran. NaCl, NH₄CH₃CO₂ and silver nitrate (AgNO3) were pur-
chased from Merck Co., Ltd., Germany, to purify and characterise
bentonite.

2.2. Purification method: In the purification process, the purified

NB were produced in three different methods; these final products
were introduced as P1, P2 and P3. In this way, the ultrasonic effect
(in different powers and times) before granular sedimentation,
Na-activation and centrifugation (under different forces) on NB
were investigated. To remove the organic matters, the NB sample
was heated first at 300°C. Then, the NB suspension (S/L = 1:20)
was prepared, stirred magnetically for 7 h at 5000 rpm and kept
all night without stirring. To prepare P1, the propping ultrasonic
was used with the power of 90 W for 2 min. To prepare the other
products (P2 and P3), the bath ultrasonic was used with the
power of 400 W for 30 min. Then, the Na-activation was also Fig. 2 Schematic diagram of the bentonite clay purification process

Micro & Nano Letters, 2019, Vol. 14, Iss. 6, pp. 688–693 689
doi: 10.1049/mnl.2018.5364 & The Institution of Engineering and Technology 2019
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sample with ultrasonic treatment (100 W, 5 min) for breaking up amounts of clinoptilolite (natural zeolite) from NB sample.
loosely held clay agglomerates. To identify crystalline mineral The presence of clinoptilolite, as the major impurity, had made
phase, X-ray diffraction (XRD) patterns were recorded by a higher CEC and SI rather than purified samples due to the strong
Philips APD PW 3020 X’Pert diffractometer using a graphite affinity of clinoptilolite for cation exchange in its open-framework
monochromator and CuKα radiation. X-ray fluorescence (XRF) crystal lattice rather than montmorillonite [38]. Moreover, the small
analysis (ARL 9400 XP + spectrometer) was used to determine change of Ds for all purified products resulted from the similar spe-
the chemical compositions of the initial sample and products. The cific gravities of all impure phases such as clinoptilolite, quartz and
morphological structures of products were determined by scanning calcite with montmorillonite [9].
electron microscopy (SEM, Hitachi S3000N) device and the X-ray
energy-dispersive spectroscopy (EDS) was used to measure the
3.2. Laser particle size distribution analysis: The LPSA data is
abundance of specific elements. The Fourier-transform infrared
shown in Fig. 3. The particle diameter of NB is in the range of
spectroscopy (FTIR) of bentonite samples was recorded to identify
the functional groups on a Perkin Elmer 783 dispersive spectrom-
eter in the range of 400–4000 cm−1. To disperse clay particles for Table 2 Laser particle size distribution data
impurity separation, ultrasonic cleaner and propping ultrasonic
(Beijing co. Ltd.) were used. Moreover, centrifuge device Sample D10, D50, D90, Median, Mean Mode,
(Classic universal Hettich 320) was used mainly to separate mont- µm µm µm µm value, µm µm
morillonite particles.
NB 2.47 11.18 24.20 10.14 3.77 14.52
P1 0.04 3.66 9.98 3.33 2.35 3.34
3. Results and discussion P2 0.02 3.28 8.94 3.31 2.25 3.20
3.1. Physical properties of bentonite samples: CEC, Ds and SI are P3 0.01 0.44 2.51 0.92 1.01 1.14
the most important parameters to determine bentonite physical
properties. The CEC presents the molar charge of exchangeable
ions of the bentonite clay, and it is a term to describe the exchange
of one cation to another cation in solution [37]. The SI and Ds have Table 3 XRD pattern information for NB, P1, P2 and P3
reported the volume of swelled material in an aqueous medium and
dry grain density, respectively. The Ds is the main parameter to de- Sample Pos., °2Th. Height, cts Full width at half d-spacing, Å
termine the performance of the sedimentation method for the separ- maximum, °2Th.
ation of montmorillonite particles smaller than 2 μm (based on
Stokes’ law). These physical parameters could be affected to evalu- NB 6.7300 60.93 0.0900 13.13452
ate the purification method for separation of montmorillonite layers P1 6.82 60 1.41 12.97058
in wet sedimentation. Furthermore, these physical parameters could P2 7.17 84 1.3 12.33226
be used to determine the quality of each purified product. P3 8.24 47 2.4 10.72858
Table 1 shows the CEC, Ds and SI amounts of NB, P1, P2
and P3. The results showed that the purification method could
clearly change the CEC, Ds and SI of all samples. SI and CEC
were decreased after processing due to the separation of the large

Table 1 Physical properties of NB, P1, P2 and P3

Sample CEC, meq/100 g clay Ds, g/cm3 SI ml/2 g

NB 101 2.51 16
P1 88 2.48 14
P2 75 2.47 14
P3 73 2.42 14

Fig. 4 XRD patterns of NB, P1, P2 and P3, M: montmorillonite, C: clinop-

tilolite, Q: quartz and Ca: calcite

Table 4 Quantitative amount of each phase in NB, P1, P2 and P3

Sample Montmorillonite Clinoptilolite Quartz Calcite

(M%) (C%) (Q%) (Ca%)

NB 15 51 72.3 84
P1 64 37 18.8 13
P2 13 9 6.9 3
P3 8 3 2 —
Fig. 3 Laser particle size distribution graphs of NB, P1, P2 and P3

690 Micro & Nano Letters, 2019, Vol. 14, Iss. 6, pp. 688–693
& The Institution of Engineering and Technology 2019 doi: 10.1049/mnl.2018.5364
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Fig. 5 Graphical output from the IRI quantitative analysis from X’Pert HighScore Plus software showing the measured XRD pattern, M: montmorillonite,
C: clinoptilolite, Q: quartz and Ca: calcite

0.1–40 μm. The particle size distribution profile obtained from three the weak van der Waals bonds that attract and loosely bind clay
purified samples (P1, P2 and P3) is shifted to the smaller particle minerals together. The frequency range of 20–100 kHz represents
diameter. The results showed that the propping ultrasonic (90 W, that most commonly used for power ultrasonic is mainly used for
2 min) represented relatively the same effect with bath ultrasonic non-intrusive purposes. The investigation of centrifugation force
(400 W, 30 min). However, the centrifuges were more efficient on NB purification showed the higher g-force (1914 g) in the first
than ultrasonic, especially at high g-forces to separate the fraction stage significantly increased the relative intensity of montmorillon-
lower than 2 μm in particles diameter. As shown in Fig. 3, P3 repre- ite peak to clinoptilolite and quartz peaks for P3 products.
sented the finest particles with the homogeneous distribution due to Therefore, the proposed method significantly decreased the undesir-
suitable removal of impurities. able compound peak intensities. The results are also in agreement
Table 2 showed the laser particle size parameters and size distri- with LPSA data. The purified samples illustrated the peak broaden-
bution data. The D10, D50 and D90 of all samples represented the ing due to the presence of finer particle size rather than NB. In this
range of the particle sizes by 10, 50 and 90% of mass fraction. The Letter, the quantitative analyses of NB, P1, P2 and P3 products
median, mean and mode of particles diameter of NB, P1, P2 and P3 were determined by reference intensity ratio (RIR) method. The
were shown in Table 2. These data confirmed that the particle size RIR method is also known as the ‘matrix flushing’ method after
in the range of 0.01–2 μm had more amplified the chance of mont- Chung (1974), since matrix absorption effects are ‘flushed’ out of
morillonite attendance in P3. Therefore, P3 included a wide range the equation for quantitative analysis [40]. Analysis by the more
of montmorillonite mineral with maximum purity compared with traditional RIR method is based on measuring the intensity of one
the other products. or more peaks for each mineral present with the added standard
powder diffract file (PDF2). This method analyses the diffraction
3.3. Result of XRD analysis: XRD is a fast and simple method of clay minerals which have been incorporated into software
which most widely used for identification of fine-grained minerals. codes by X’Pert HighScore Plus. Table 4 and Fig. 5 showed the
This method is based on the diffraction of very short-wave electro- quantitative amount of each phase in bentonite samples. The
magnetic radiation in the ranges of 0.01 and 100 Å [39]. The XRD obtained results from RIR method showed that the montmorillonite
patterns of all samples are given in Table 3 and Fig. 4 shows the content of the bentonite was changed from 15 to 84% (with mont-
information of XRD patterns. The hkl indexes of (001), morillonite yield over 80%) after NB purification with higher yield
(020–100), (130–200) and (060) reflections of the main montmor- with respect to those reported by Hayakawa et al. [31].
illonite component in NB were observed at 2 Th = 6.73°, 20.95°,
35.17° and 60.15°. Clinoptilolite, quartz and calcite were also
observed a 2 Th = 9.67°, 28.98° and 30.99°, respectively, as the
impure phases for NB sample. The purification processes in P1,
P2 and P3 shifted the position of the 001 basal reflections to
lower angles after Na-activation (i.e. Na-smectites form single
layer water hydrates).
The utilisation of propping ultrasonic (90 W, 2 min) in the P1 and
bath ultrasonic (400 W, 30 min) in P2 and P3 products showed the
preservation of clay structure. Furthermore, the ultrasonic treatment
was efficient for the selection and purification of montmorillonite
without any clay structural damage, whereas Pacuła et al. [23]
found the differences in the intensity ratio of the main montmoril-
lonite peaks in the freeze-dried sample. In the ultrasonication, the
vibration causes the generation of small bubbles in water that
rapidly implodes causing a shock wave to transmit through the
liquid. Therefore, the clay separator employs cavitation to disrupt Fig. 6 FTIR patterns of NB, P1, P2 and P3

Micro & Nano Letters, 2019, Vol. 14, Iss. 6, pp. 688–693 691
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Table 5 XRF results of bentonite samples

Samples Element, wt%

SiO2 Al2O3 Na2O CaO K2O MgO Fe Loss on Ignition (LOI)

NB 61.30 12.90 1.83 4.03 1.13 1.61 2.10 13.60

P1 58.19 17.23 3.11 1.79 1.11 1.43 1.01 13.10
P2 53.57 19.90 3.49 1.34 1.10 1.29 0.98 12.98
P3 48.40 23.30 3.83 1.07 1.09 1.07 0.60 12.30

Fig. 7 SEM–EDS image of bentonite samples before and after purification

3.4. Results of FTIR: FTIR spectra of all NB and purified products the purification method could well help to reduce the amount of
are presented in Fig. 6. The basic peaks of starting clay remain even CaCO3 for P1, P2 and P3 similarly reported by Arroyo et al. [28].
after purification through Na-activation, sedimentation, ultrasonica-
tion and centrifugation. The peak observed in NB at 3429 cm−1 3.6. Results of SEM: The SEM–EDS images of bentonite samples
represents the fundamental stretching vibrations of different –OH before and after purification at different magnification are shown in
groups presented in Mg–OH–Al, Al–OH–Al and Fe–OH–Al units Fig. 7. SEM image of NB before purification shows irregular shapes
in the octahedral layer [41]. The peak around 3447 cm−1 is the and aggregation of particles mostly belonged to impure phases with
stretching vibration of the interlayer water molecule and the peak a larger diameter.
at 1637 cm−1 is its bending vibration. Moreover, the peak observed The micrographs of P1–P3 products represent improved particle
at 1035 cm−1 belongs to the Si–O–Si stretching vibration region size distribution and decrease the aggregation after purification pro-
[29]. The peaks at 468 and 524 cm−1 are assigned to the symmetric cesses. It is clear that ultrasonication and centrifugation were much
stretching vibration bands of Si–O/Al–O and O–Fe–O functional affected to remove impure phases and separate montmorillonite par-
groups, respectively [42]. The stretching at 1455 cm−1 corresponds ticles. P3 showed the fine platy structure compared with the other
to CO3 stretching for calcite. After purification of NB clay, the products.
CO3 stretches were observed to have disappeared for all EDS analyses of NB, P1, P2 and P3 were used to determine their
products [43]. semi-quantitative elemental composition of bentonite sample before
and after purification (Fig. 7). In this analysis, the weight per cents
of O, Si and Al are important to evaluate the purification method.
3.5. Results of chemical analysis from XRF: The XRF results of The increase of Al and decrease of Si, O, K, Ca, Fe, Mg, Cl
NB, P1, P2 and P3 are shown in Table 5. These results represented and S indicated the success of the purification method to separate
the difference between the chemical compositions of all samples, montmorillonite and remove impure phases. Similar results were
before and after purification. The percentage of SiO2 amount is reported by XRD–RIR method analysis and XRF data.
related to quartz impurities and silicate structure of silicate minerals
such as bentonite and clinoptilolite. Al2O3 is mainly related to 4. Conclusion: In this research to purify NB sample, the effect of
montmorillonite and clinoptilolite (belong to phyllosilicate and tec- ultrasonic before granular sedimentation, Na-activation and centri-
tosilicate minerals, respectively). fugation at different forces were studied. In the purification
The results showed that the amount of Al2O3 in purified products process to produce P1–P3, the bath ultrasonic (400 W, 30 min)
compared with NB clearly increased and the amount of SiO2 were more effective than propping ultrasonic (90 W, 2 min). In
decreased. Leading to these results, the proposed purification P3 product, high centrifugation force (1914g) in the first stage com-
process caused to change in the concentrations of K2O, MgO, pared with low centrifugation force (479g) for P1 and P2 products
CaO, Na2O and Fe2O3 (belonged to the isomorphic substitution showed a considerable increase in montmorillonite contents. As
of clay mineral and their interlayer cations). In this way, the mentioned in XRD and FTIR results, the basic peaks of starting
Na-activation increased Na2O and the decrease of K2O percentage clay remained even after the purification process. The results of
which was resulted from clinoptilolite removal. Since one of the LPSA showed that the particle size distribution profiles obtained
major impurities was calcite, the utilising of Na acetate buffer in from P1 to P3 were shifted to the lower particle size with

692 Micro & Nano Letters, 2019, Vol. 14, Iss. 6, pp. 688–693
& The Institution of Engineering and Technology 2019 doi: 10.1049/mnl.2018.5364
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Micro & Nano Letters, 2019, Vol. 14, Iss. 6, pp. 688–693 693
doi: 10.1049/mnl.2018.5364 & The Institution of Engineering and Technology 2019