Curhon. Vol. 30. No. 4. pp.

639-645,

1992

OWJS-6223192 $5.00 + Gil

Copyright 0 1992 Pergamon Press Ltd.

Printed I Great Bntain.

A CLAY-CARBON ADSORBENT DERIVED FROM SPENT

BLEACHING EARTH: SURFACE CHARACTERISATION
AND ADSORPTION OF CHLOROPHENOLS
FROM AQUEOUS SOLUTION
SIMONJ.T.POLLARD,*CHRISTOPHERJ.SOLLARS~~~ROGERPERRY
Imperial College Centre for Toxic Waste Management, Imperial College of Science, Technology and
Medicine, London, SW7 2BU. U.K.
(Received

I7 September

I99

I : uccepted

in revised,/i,rm

26 November

I99

I)

Abstract-An
active carbonaceous char supported on a aluminosilicate matrix has previously been prepared by the chemical activation of spent bleaching earth, a sol d waste from the edible oil industry. The
underlying mineral structure was characterised in this study by XRG and SEM and shown to consist of
ill-defined montmorillonite lamellae, with significant loss in crystallinity from the parent material being
observed. The adsorption of phenol, 3-chlorophenol and 2,3-dichlorophenol was assessed and found to
conform to a Langmuir isotherm model, and a comparison with commercial powdered water-treatment
carbons suggested that the surface char of the treated spent clay was sufficiently active to warrant a pilotstudy investigation of this low-cost adsorbent for applications relating to wastewater treatment,
Key Words-Clay-carbon
characteristics.

adsorbent, spent bleaching earth, montmorillonite.

1. INTRODUCTION

The term activated carbon is formally used to describe a broad range of carbonaceous materials that
exhibit a high degree of porosity and extended interparticulate surface area[l]. Active carbons can be
prepared from a huge range of carbon-containing
feedstocks by the catalytic activation of an initially
pyrolysed char, and are commercially exploited for a
diverse number of adsorptive cleansing operations.
Despite the extensive use of this adsorbent throughout the process industries, carbon adsorption remains an expensive treatment process and, consequently, over recent years this has prompted a
growing research interest into the production of lowcost alternatives to active carbon from a range of carbonaceous industrial and agricultural byproducts[261. Our own studies in this area have focussed on
spent bleaching earth (SBE), a solid waste from the
edible oil-processing industry typically comprising
25%-40% w/w of residual vegetable oil adsorbed
onto phyllosilicate mineral clay[7]. Carbonisation of
the chemically impregnated feedstock, followed by
activation of the resultant carbonaceous char under a
variety of thermal conditions, yielded a clay-carbon
product with a developed microporosity and an associated affinity for phenol from the aqueous
phase[8,9]. The microstructure of ZnCI,-activated
spent bleaching earth has been proposed as a microporous carbon char supported on an amorphous
montmorillonite
matrix and is analogous to similar
reported materials derived from intercalated clay-organic precursors[ IO- 121.
*Currently Postdoctoral Research Fellow, Environmcntal Health Program, Faculty of Medicine, University of Alberta, Edmonton, Alberta, Canada, T6G 2G3.

chlorophenols. structural

As part of a continuing research programme into

the adsorptive properties of this and similar adsorbents for applications relating to environmental control[ 131, we now extend our structural characterisation of activated spent bleaching earth and report our
investigations for the uptake of chlorophenols from
the aqueous phase. These particular adsorbates are
frequently encountered contaminants
in the waste
streams of the pesticide, pulp and paper, and woodpreserving industries[ 14- 161.

2. EXPERIMENTAL

2.1 Adsorbents
Calcium montmorillonite
(Fullers earth) is a
dioctahedral aluminosilicate
with an idealised formula of (Sis)(A13.15Mg0.85)020(OH)4Ca0.85.
n&O] 171.
The true structure of the raw earth deviates significantly from the ideal as a result of a number of isomorphous substitutions, and acidulation with sulphuric acid prior to use for edible-oil bleaching
further disrupts the mineral lattice to leave an ill-defined lamellar microstructure[ 181. The simulated
spent clay employed in this study consisted of 30%
w/w residual crude soybean oil adsorbed onto the
surface of Fulmont Premiere@ acidulated bleaching
earth representing an available carbon source of
-24% /w. The optimised activation procedure for
SBE previously described[9] involved impregnation
of the spent clay with 25% saturated ZnC1, solution
followed by carbonisation under N2 at 450C for 2
hours, with activation at 600C for I hour. The resultant material, found to be 20.1% w/w in surface carbon, displayed a micropore volume of 0.050 cm3g~.,
a mesopore volume of 0. I40 crng- and an apparent
N2 BET area of 239 mg-[9].
639

640

S.

J. POLLARD e(al

Reference powdered water-treatment

carbons
were obtained from Sutcliffe Speakman Ltd (grade
338P), Norit (UK) Ltd (grade SA4) and British CECA
(grade 3SA). This series represents a range in apparent surface areas (BET N2) from -500 to - 1200
m2g-. Fulmont
Premiere@ acidulated bleaching
earth was provided by Laporte Industries, UK. CHN
elemental microanalysis for the commercial materials was performed using a Perkin Elmer 240 microanalyser. The detection limits of this instrument were
0.3% /w for elemental N and H and 0.1% /w for C.
All other reagents were supplied by BDH in
AnalaR@ grade unless otherwise stated.

2.2 X-ray dlfraction

Powder diffractograms were collected for the primary acidulated material (Fulmont Premiere@) and
the optimised SBE in order to observe changes in
crystallinity as a result of ZnCl,-activation,
and the
extent of layer collapse for the mineral support as a
result of additional thermal treatment. Dry sieved
samples (< 150 pm) were scanned using a Phillips
PW 1700 instrument (Cu-K (Yradiation) between 28
I-65 with a generating voltage of 50 kV (25 mA).

2.3 Scanning electron microscopy

Clay-derived adsorbents were examined by scanning electron microscopy for a visual inspection of
external porosity and microtexture. Dried adsorbent
samples (-20 mg; lOSC, 16h) were presented on
areas of double-sided adhesive tape (0.5 cm X 0.5
cm), three of which were each mounted to the methanol-cleaned surface of a glass microslide. The slides
were gold coated for 10 mins (Emscope, UK) and examined at 2000X using a Hitachi 2500 SEM and an
operating voltage of 15 kV. Representative sections
of surface were recorded and developed on monochrome paper (Ilford FP4).

2.4 Equilibrium adsorption studies

Single component, solution-phase adsorption isotherms were constructed at 20 f 2 C for all materials
using phenol, 3-chlorophenol
and 2,3-dichlorophenol adsorbates. The batch adsorption experiments were run at pH 4.1-5.9 using non-buffered solutions in order to eliminate competitive adsorptive
effects from buffer components. This pH range was
sufficiently below the pK, values of the adsorbates
used to ensure the predominance
of the undissociated and preferred form during adsorption[ 191.
Equilibrium contact times of 3 hours had previously
been established for this set of carbons. Dry sorbents
(105C, 16h) were sieved to < 150 pm (100 mesh)
prior to use. Aliquots ( 100 cm3) of 30-0.5 mM adsorbate (20-0.5 mM, 2,3-dichlorophenol
on account of
its reduced aqueous solubility) were added to 1.0 g
sorbent samples in 120 cm3 glass screw-cap bottles,
which were then rotated at 40 rpm for 3 hours. Equilibrium adsorbate concentrations were then monitored at 500 nm by visible spectrophotometry (Perkin Elmer Lambda 3 UV/VIS spectrophotometer)
using a standard calorimetric 4-aminoantipyrine

2.5i

----_
Zinc chloride activated SBE

0.04
0

IO

20

30

40

50

60

70

Diffraction Angle 2 8 (Degrees)

Fig. 1. XRD diffractograms for Fulmont Premieremand activated clay-carbon adsorbent.

method[20]. Langmuir isotherm parameters
calculated for each adsorbent-adsorbate pair.

were

3. RESULTS AND DISCUSSION

3.1 Surface characterisation

Figure 1 illustrates the X-ray powder diffractograms of Fulmont Premiere@ and ZnCl,-activated
spent bleaching earth. Clearly, ZnCl,-activation
(450C/2hr followed by 600 C/ 1hr) resulted in a total
loss of observable crystallinity. This loss may be interpreted in terms of the corrosive action of ZnCl,
and HCl gas produced during chemical activation of
the impregnated substrate. Partial loss in crystalline
structure from that of the raw montmorillonite
mineral is an accepted result of H2S04 acidulation during
the industrial production of bleaching earths[ 181 and
further acid attack coupled with progressive dehydration of interlamellar water serves, in this instance, to
accentuate the change in morphology of the underlying clay structure. Absence of the d(O0 1) basal spacing peak in the range 20 o-20 for the ZnC&-activated sample prevented quantification of the extent
of layer collapse upon thermal treatment.
Several materials composed of a carbon deposit
between montmorillonite
lamellae have been recorded in the literature[ lo- 12,2 l-231. Sonobe et
al.[ lo] reported the preparation ofa polyacrylonitrile
char in the two-dimensional
interlamellar space of
Ca-montmorillonite.
The char was later graphitised
at extreme temperatures (>25OOC) and the aluminosilicate template structure removed by HF treatment to reveal a graphite thin film. Similarly, oya et
al. described the carbon&ion
of the intercalated
product
of montmorillonite
and a-naphthylamine[22, 231. Of interest to our own study in both
cases is the gradual loss in mineral crystallinity experienced as a result of thermal treatment. Sonobe et
al. also recorded a shift in the d(001) spacing to
slightly larger diffraction-angle values, which was attributed to a narrowing of the interlamellar spacing
upon char deposition[ lo]. Layer collapse of the Caanalogue was noted to be initiated at temperatures as
low as 2OOC,but the presence of the char considerably reduced the extent of collapse. This is an important consideration for activated SBE. for which the

641

A clay-carbon adsorbent

(a)

Fig. 2. SEM photographs for (a) Fulmont Premiere@ and(b) activated clay-carbon adsorbent. Length bars
(dashed) represent I5 pm.

adsorptive properties depend on accessibility to the

interlamellar active char.
Representative
SEM micrographs of Fulmont
Premiere@ and activated SBE are shown in Fig. 2

(a,b). The clay-carbon adsorbent was observed to be

similar in external surface appearance and microtexture to the acidulated clay, retaining the ill-defined
structure often referred to as being akin to a disorgan-

350

300

250

200

150

100

50

0
0

500

Equilibrium

1000

Phenol

1500

Concentration

2500

2000

Ce (mg/dm3

Fig. 3. Phenol adsorption isotherms for activated spent bleaching earth and commercial adsorbents

S.J. POLLARD etal.

642

Equilibrium

3-Chlorophenol

Concentration

Ce (mg/dm3 )

Fig. 4. 3-Chlorophenol adsorption isotherms for activated spent bleaching earth and commercial adsorbents.

ised bundle of bank notes[24]. Acidulation generally disrupts the structure ofbleaching earths, causing
them to deviate from both the exfoliated appearance
usually associated with phyllosilicate materials and
the hypothesised model of evenly stacked silicate lamellae[ 18,24,25]. The bottom edge of the particle
shown in Fig. 2b, however, reveals that a basic sheetlike structure was retained from the mineral support
in the clay-carbon composite materials. The surface
characterisation of activated SBE thus confirms the
proposed model[9] of an active carbonaceous char
supported on the interlamellar surface of an ill-defined, amorphous montmorillonite
matrix.
3.2 Adsorption of phenol, 3-chlorophenol and
2,3-dichlorophenol
Figures 3 to 5 illustrate the experimental isotherms obtained for SBE and the commercial carbons in the case of phenol, 3-chlorophenol and 2,3dichlorophenol, respectively. A Langmuir model was
subsequently applied on account of its widespread
use to describe the aqueous-phase uptake of organic
micropollutants by activated carbons[26-281. While
acknowledging the absence of a universal model for
clays and carbons alike, this isotherm has also been

employed extensively for both the adsorpion of pigments from edible oils by layer silicates[29,30], and
for describing the adsorptive behaviour of clay-carbon materials analogous to activated SBE[ 11,121. In
addition, a Langmuir fit has previously been found to
be slightly favoured over the Freundlich isotherm in
our own studies for this material[8]. The model can
be described by the eqn:

QbCe
1 + bC,

where qe is the amount of solute adsorbed per unit

mass of adsorbent and C, the equilibrium adsorbate
concentration.
The parameters Q and b were obtained from linear plots of l/ qPvs.l/C,. @represents
the solid-phase concentration corresponding to complete coverage of available adsorption sites and b can
tentatively be related to the intensity of the adsorption reaction. Table 1 gives the Langmuir isotherm
parameters for the selected series of adsorbent-adsorbate pairs and the parameter qc. This parameter represents the ordinate value at which the initial (negative) curvature falls to zero, and is obtained by
horizontal extrapolation from the knee-point of the

A clay-carbon adsorbent

Equilibrium
Fig. 5. 2,3-Dichlorophenol

2,3-Dichlor~phenol

643

Concentration

Ce fmg/dm3

adsorption isotherms for activated spent bleaching earth and commercial

adsorbents.

experimental isotherm to the q,,axis as described by

Giles and Nakhwa[3 I]. This provided an additional
quantitative method of assessing the adsorptive capacity of materials which do not exhibit a strictly limiting adsorption plateau.
SBE exhibited near-Langmuirian
behaviour and
showed an increasing affinity (@, qG) for individual
adsorbates with increase in molecular weight and hydrophobicity along the series: phenol < 3-chlorophenol < 2.3-dichlorophenal.
Both the adsorptive

bchaviour and range in c$ vaiues compare favourably with those noted by Korczak and Kurbiel[ 121 for
a mineral-carbon adsorbent derived from spent clay
used in the raffination of lubricating oil. These workers evaluated their material for the removal oforganic
carbon from pesticide wastewaters and reported values of 4.85 mg g- and 0.00056 dm mg for the
Langmuir parameters p and h. respectively. The
poor adsorptive performance observed was explained
by these investigators in terms of bound acidic oxy-

Table 1. Adsorption isotherm parameters

Adsorbate
Phenol

Adsorbent
SBE

Norit SA4
ss 338 P
CECA 3SA
3-chlorophenol

2,3-dichlorophenol

SBE
Norit SA4
ss 338 P
CECA 3SA
SBE
Norit SA4
SS 338 P
CECA 3SA

ck(mgg
20

150
106
207
54
255
181
295
64
>250
>255
>320

h (dmi mg )

1
33.3
46.3
141.3
211.7
53.1
25.3
164.7
341.1
91.6
124.4
347.6
142.0

2 E-03
114 E-03
I E-03
16 E-03
40 E-03
41 E-03
6s E-03
13 E-03
I8 E-03
89 E-03
3 E-03
370 E-03

0.98
0.85
0.99

0.73
0.97
0.99
0.99
0.77
0.97
0.86
0.93
0.98

S. J. POLLARD et al.

644

Table 2. Elemental microanalysis and apparent carbon activities

Adsorbent

c (%/w)

H (%/w)

N (%/w)

(mg g- C)

qGc 3- chlorophenol
(mg g- C)

SBE
Norit SA4
ss 338 P
CECA 3SA

20. I
85.4
82.4
81.1

0.92
0.60
0.69
0.49

CO.30
CO.30
2.53
9.18

100
176
129
255

269
299
220
364

qGC

gen groups inhibiting the chemisorption of phenolic

adsorbates at the adsorbent surface. Extensive characterisation of this analogous material[ 121 demonstrated that the adsorption kinetics were controlled
by an intraparticulate diffusion process, with adsorptive capacity dependent on adsorbate molecular
mass, electrostatic charge, and the hydrogen bonding
with surrounding water molecules. In an additional
study, Kalapusha et al.[ I 1] reported Langmuir isotherm behaviour for an adsorbent produced by steam
activating
a spent palygorskite-montmorillonite
mineral used initially to remove unsaturated hydrocarbons from aromatic petroleum products.
Commercial carbons displayed corresponding adsorptive behaviour (qG) in accordance witn their reported apparent BET surface areas; SS 338P (500
mg-) < Norit SA4 (650 rng-) < CECA 3SA (1200
m2gg), the disubstituted chlorophenol being most
strongly adsorbed. Such behaviour is in agreement
with similar studies performed with commercially
available carbons and increasingly chlorinated phenolic adsorbates[28]. Construction of full isotherms
for 2,3-dichlorophenol
was restricted due to the reduced aqueous solubility of this compound.
The diminished adsorptive performance observed
for SBE in comparison with the commercial carbons
is primarily attributed to the reduced active-carbon
content (20.1 %/w) of activated SBE (Table 2). The
capacity of the mineral support alone for these adsorbates was found to be negligible. A comparison of uptake on a gram carbon basis, however (Table 2), suggested a high activity for the surface char of SBE
within the range of the selected water-treatment
carbons. Application of this adsorbent for wastewater
treatment, therefore, would require correspondingly
higher doses for equivalent micropollutant removal.
Cost-benefit analyses and pilot-scale studies to determine mass transfer coefficients, breakthrough curves,
and competitive adsorption effects will therefore be
required further to this study before activated SBE
can be finally affirmed as applicable for the removal
of chlorophenols from industrial waste waters.
4. CONCLUSION

The structure of activated spent bleaching earth

can be confirmed as comprising an adsorptive carbon
char supported on the interlamellar surface of an
amorphous montmorillonite
matrix. The activity of
the carbonaceous deposit for the phenolic adsorbates

phenol

examined was considered sufficient to propose a

pilot-study investigation for removal of chlorophen01s from industrial waste waters of varying organic
strength. Low-cost alternatives to commercial carbon, such as activated spent bleaching earth, are of
particular relevance to developing countries where
economic restraints severely limit the widespread application of industrial adsorbents[32]. With these
countries sharing an increasing percentage of world
vegetable oil production and processing[33], spent
bleaching earth may represent a locally available
bulk feedstock for conversion into a clay-carbon
adsorbent.
Acknowledgements-SJP
gratefully acknowledges the Science and Engineering Research Council for the provision of
a Research Studentship and Dr. D. B. Mobbs of Laporte Inorganics for the invaluable technical discussions relating to
this work.
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