3. Chem. Tech. Biotechnol.

1991, 50, 265-275

A Low Cost Adsorbent from Spent Bleaching Earth.

I -The Selection of an Activation Procedure
Simon J. T. Pollard, Christopher J. Sollars & Roger Perry
Imperial College Centre for Toxic Waste Management, Imperial College of Science,
Technology and Medicine, London SW7 2BU, UK
(Received 2 April 1990; accepted 15 May 1990)

ABSTRACT

The conversion of a spent filter cake from the edible oil industry to a
heterogeneous clay-carbon adsorbent is reported. Chemical and physical
activation procedures have been applied and the resulting materials screened
by carbon content and aqueous phenol uptake. Full adsorption isotherms are
plotted for sorbents with high phenol capacities and their adsorptive
behaviour is modelled to the Freundlich and Langmuir isotherms.
Key words: spent bleaching earth, soybean oil, activation, adsorption,
phenol, isotherm.

1 INTRODUCTION
Activated carbon adsorption remains the dominant adsorption process for the
removal of organic micropollutants from water. Due to economic restraints,
however, there is a growing interest in the preparation of low cost adsorbents for use
in waste and wastewater treatment. Agricultural by-products such as almond shells,
peach stones, peat and rice hulls have been evaluated, as have fertiliser waste,3
clay minerals4 and scrap t y r e ~Where
.~
the alternative adsorbents are carbonaceous
in nature, the precursors have been activated at elevated temperatures with a variety
of physical and chemical activants which include air, steam,3 carbon dioxide,6
transition metal nitrates, sulphuric acid and zinc chloride.
Spent bleaching earth (SBE) is a solid waste from the edible oil processing
industry. It has two components: residual vegetable oil not removed by filter
pressing and montmorillonite clay. The waste is currently disposed of directly to
landfill either dry or as a wet slurry. The landfill option, however, is not without
265

J . Chem. Tech. Biotechnnl. 0268-2575/90/$03.50 0 1990 SCl. Printed in Great Britain

266

S. J . T. Pollard, C . J . Sollurs, R. Perry

associated problems, the most serious being the pyrogenic nature of the unsaturated
oil, which rapidly oxidises on the clay surface to the point of spontaneous ignition."
Spent filter cake, typically 20 to 40% (w/w) in residual oil" has an available
carbon source adsorbed on a layer silicate support. Chemical activation of the
carbonised oil on the mineral surface produces a heterogeneous claysarbon
adsorbent with associated micro- and meso-porosity and a surface area of c.
240 m2 g - Such an adsorbent may have potential applications in the waste and
wastewater industries as a low cost alternative to activated carbon.
In the first of two papers we present and discuss the selection of an activation
procedure for the forementioned sorbent. The subsequent study discusses the
optimisation of the zinc chloride activation process, making use of adsorption
hysteresis, solution isotherm and pore size distribution techniques.

'.

2 EXPERIMENTAL
2.1 Materials

Soybean oil (virgin) and Fulmont PremiererM acid activated bleaching earth were
supplied by Laporte Industries, Widnes, UK. All laboratory chemicals were
supplied by BDH, Poole, UK, unless otherwise specified. NoritrM and BrimacTMare
registered trademarks of Norit N.V., The Netherlands and British Charcoals and
Macdonalds, UK, respectively. A typical spent filter cake containing 307; (w/w)
residual oil was simulated by adding unbleached soybean oil (300 g) at 80 to 90C to
Fulmont Premiere (700 g) in a domestic food mixer. The mix was homogenised for
5 min, and took the appearance of a brown powdery solid.

2.2 Carbonisation and activation

The carbonisation of soybean oil and simulated SBE was studied, using a Stanton
Redcroft T G 780 Series thermobalance. Samples (10-15 mg) were heated (25C
min-') under flowing nitrogen (87 cm3 min-') to 750C in order to determine the
onset and completion of oil volatilisation and weight loss in each case. Larger
batches of spent clay were sequentially carbonised then activated, using procedures
adapted from the literature (Table 1).
2.2.1 Chemical activution
Samples of SBE were impregnated with selected chemical activants prior to
carbonisation. For the metallic chlorides (A, B, D) and transition metal nitrates (H,
I), 90 g of activant was dissolved in the appropriate amount of distilled water to
produce a 25 ;() (w/w) saturated solution. The hydroxides and CaCO, (E, F, G) were
mixed dry. Activants were then homogenised with 100 g of SBE and oven dried for
16 h at 105C. Carbonisation and activation of mixes A to I were performed in a
Carbolite HTR 11/150 rotary furnace under flowing nitrogen. The 190g charges
were purged (0-5dm3 min-l) for 1 h at 20C and then heated at 5C min-' to
450C. Following a 2 h dwell time, the temperature was raised to 600C for 1 h to
allow activation of the carbonised earths, after which the materials were cooled to
20C. Post-treatment involved a 2 M HCI wash to remove ash and residual activant.

Low cost udsorbent from spent bleaching earth. I

261

TABLE 1

Activation Procedures
Procedure

Temp.
("C)

Time
(h1

7
7

600
600
600
600
600
600
600
600
600

1
1
1
1
1
1
1
1
1

J
K
L

14
3
3

850
450
700

2
1
1

13
15
3

350
350
3501450

5
5
4

C (control)
A
B
D
E
F
G
H
I

N
P

Activant

Reference

12
12
12
13
13

none

Finally, the clays were vacuum filtered (Whatman No. l), washed with hot and cold
distilled water, then acetone (Rathburn, UK), and dried for 16 h at 105C.
Impregnation with H,S04 and polyphosphoric acid (82-85 % P,O,) was
performed by mixing 10 g of acid with 30 g of SBE into a paste, which was then
carbonised in a static air muffle furnace in covered crucibles at 350C for 5 h (M, N).
Hydrogen peroxide treatment (100 vol.) was carried out similarly by using a 1:2
paste at 350C for 4 h (covered) followed by a 0.5 h treatment (uncovered) at 450C.
Post-treatment was as above.
2.2.2 Physical activation
Treatment of SBE with CO, and air (J, K) was performed by using the rotary
furnace. For CO,, a 100 g charge of SBE was purged for 1 h in CO, at 20C prior to
heating (5C min-') to 850C where the material dwelled for 2 h before cooling
under nitrogen to 20C. Air treatment employed a carbonisation step at 450C
under nitrogen, followed by a further 1 h at 450C under flowing air
( 0 5 dm3 min-'). Steam trials (L) were conducted with a tube furnace (Carbolite
CTFl2/65) in which carbonised earth was further heated at 700C for 60 min under
flowing steam (delivery rate of 8 cm3 min-').
2.3 Batch adsorption studies

Adsorption of aqueous phenol was used to screen all materials. Dry sorbents were
sieved to below 150pm (100 mesh) prior to adsorption. Aliquots of 100cm3 of
1 0 m ~aqueous phenol were added to 1.Og sorbent samples in 250cm3
polyethylene screw cap bottles. Preliminary tests established that contact times of
3 h end-over-end rotation (40 rpm) were sufficient to establish equilibrium at

268

S. J . T. Pollard, C. J . Sollars, R . Perry

2 0 5 2C. Residual phenol was monitored after filtration (Whatman No. l), using a
direct UV spectrophotometric method.I6 Full isotherms were constructed for those
materials with high adsorption capacities of > 20 mol%.
2.4 Microanalysis
The CHN microanalyses were performed by Butterworth Laboratories, UK, using
a Perkin Elmer 240 microanalyser.

3 RESULTS AND DISCUSSION

The thermogravimetric (TG)decomposition curves for soybean oil and synthesised

SBE are shown in Fig. l(a) and (b), respectively. For oil alone, the extrapolated
onset of volatilisation occurs at c. 420C with carbonisation complete by 480"C, the
maximum rate of weight loss being at 450C. This was the chosen temperature for
carbonisation, a lower heating rate of 5"Cmin-' being used to prevent flash
volatilisation of the oil. Activation temperatures were selected from the literature.
Where a temperature range was specified, minimum values were used in order to
delay layer collapse of the clay support, which occurs as a result of structural water
loss at elevated temperatures. Figure l(b) shows that carbonisation of oil on the
montmorillonite substrate is slightly retarded, the differential weight loss peak
(DTG) appearing at 458C. This is presumably a template effect due to the
adsorption of interlamellar oil.
Carbon burn-off values are difficult to estimate from the T G curve due to
accompanying dehydration and dehydroxylation processes, which also contribute
to weight loss.' ' The thermal decomposition of SBE involves the following stages:
(i) loss of 'free water' between 80" and 120C;
(ii) further dehydration processes (360"-400"C)-loss of physically bonded
surface water and hydrated water molecules from the clay;"
(iii) carbonisation of residual soybean oil between 420" and 500C;
(iv) dehydroxylation of montmorillonite (700"-750"C), the onset of which can be
seen in Fig. I(b).
The carbon contents of the treated materials and their associated phenol uptakes
are shown in Table 2. Phenol removal can be expressed as adsorption capacity
( m o l x ) where
Adsorption capacity =

moles phenol adsorbed per g adsorbent

x 100%
moles phenol in initial solution

(1)

The two factors in conjunction were used to screen materials A-P, with phenol
uptake taken to indicate the development of an activated char. Phenols are common
pollutants in industrial wastewaters" and have been studied extensively with
regard to carbon adsorption from
The physical activation trials proved ineffectual with the resulting clays
exhibiting no affinity for aqueous phase phenol. The chars produced appear
carbonaceous without activation. This may be a result of layer collapse at the

Low cost udsorhent from spent bleuchiny earth. I

269
100

-LO0
k

200

100

300

500

ux)

Temperoture

600

700

100

(Cl

(a1
I

->

-1

Oil Volotilisotion
458%

Primory Dehydrotion

-loo

'

'

'
rn

200

300

a0
Temperoture

503

600

700

IC)

(b)

Fig. 1. Thermogravimetric decomposition curves for (a) soybean oil, and (b)synthesised spent filter cake.
(Heating rate 25C min-*; 87 cm3 min-' flowing N ; 25"-750"C.)

temperatures required for CO, and steam treatment. Air treatment at 450C also
resulted in a nonactive char. The oxidising atmospheres employed in these trials
cause considerable burn-off of surface carbon. The use of elevated temperatures or
extended dwell times, which may yield active materials, would almost certainly
reduce the surface carbon to a minimum with little associated silicate support.
Chemical activation produced adsorbent chars. In particular, the ZnC1, and
H,SO, treated earths (A, M) adsorbed > 20 mol X of phenol. A control material
(C), prepared without activant under identical reaction conditions to adsorbent A,

270

S . J . T. Pollard, C. J . Sollars, R . Perry

TABLE 2
Screening of Adsorbents
Material

Carbon content
( % >w l w )

C (control
A

B
D
E
F
G
H
I
J
K
L
M
N
P
Fulmont
Filter Cake
Norit SA4
Brimac CC

Phenol adsorbed
(ms g-l)

10.3
10.5
6.1
1.4
6.5
10.2
8.4
6.0
4.9
9.0
7.1
6.6
18.3
11.0
9.8
0.2
24.2
86.4
9.8

Adsorption capacity
(mol %)

23.2
11.6
2.6
10.1
10.5
7.0
8.0
6.3

27.8
12.3
2.8
10.7
11.2
7.5
8.6
6.7

19.0
11.4
2.4
-

20.2
12.15
2.6
-

85.6
18.3

91.0
19.5

was nonadsorbing, as was the base montmorillonite (Fulmont Premiere) and the
uncarbonised filter cake.
Full isotherms for sorbents A and M are given in Fig. 2. The commercial
materials with which comparisons have been made are Norit SA4, a water
treatment carbon and Brimac CC, a sugar refining bone char, which is conceptually
similar to the clayxarbon with an inorganic supporting structure (hydroxyapatite)
and c. 10% (w/w) surface carbon. Both ZnC1, and H,SO, are known dehydrating
catalysts and it is proposed that they enhance dehydration of the soybean oil and
facilitate partial aromatisation of the condensed triglyceride to yield a
pseudographitic microporous char within the body of the montmorillonite
template. Work is currently underway to investigate this hypothesis by Fourier
transform infrared spectroscopy. Similar models have been proposed for
montmorillonite with interlamellar polyacrylonitrile char2, and carbonised
lubricating oil.*
The adsorptive behaviour in solutions of adsorbents, A, M, Norit SA4 and
Brimac CC has been modelled to the Freundlich and Langmuir isotherms (Figs 3
and 4 respectively). These two models (eqns (2) and (3), respectively) are widely
used, the former being purely empirical and the latter assuming that maximum
adsorption occurs when the surface is covered by a uniform monolayer of
adsorbate.,
qe = K&"

Low cost adsorbent from spent bleaching earth. I

27 1

," 150
v

B8

4
<
0
5
k*

100

50

3
0

250

500
750
lo00
1250
Ce Equilibrium Concentration ( mg / L )

1500

1750

1500

1750

(a)

250

500

750

1000

1250

Ce Equilibrium Concentration (mg / L )

(b)

Fig. 2. Adsorption of aqueous phase phenol by (a) activated SBEs A (W) and M (O),
and (b) commercial
and Brimac CC (0).
adsorbents Norit SA4 (A)

where qe is the amount of solute adsorbed per unit weight of adsorbate, K,, l/n and
b are characteristic constants, C, is the residual solution phase concentration, and
Q" is the solid phase concentration corresponding to complete coverage of available
adsorption sites. The isotherm constants are given in Table 3, together with the
curve lit correlation coefficients.The value of K , has been used as a relative measure

S. J . T. Pollard, C. J . Sollars, R. Perrji

272

10
100
Ce Equilibrium Concentration ( mg / L )

lo00

10000

(a)

.1

100

10

1000

10000

Ce Equilibrium Concentration (mg / L )

(b)

Fig. 3. Freundlich adsorption isotherms for (a) activated SBEs A ( W ) and M (O),
and (b) commercial
and Brimac CC (0).
adsorbents Norit SA4 (A)

of adsorption capacity24 and can thus be taken as an indicator of surface area, as

can Q"; l/n and b are related to the enthalpy of adsorption and indicate the intensity
of reaction. Both models are applicable, the Langmuirian isotherm being favoured
by the clay-carbon sorbents, showing agreement with a mixed adsorbent of similar
structure.* The performance of Norit SA4 is typical of a highly developed micropore
structure (pore widths not exceeding 2 nm), hence high initial uptake and limiting
Q" at low phenol concentrations. Several isothermal analyses are available for the
rigorous treatment of microporous carbon.I5 For Brimac bone char l/n> 1, hence

Low cost adsorbent from spent bleaching earth. 1

0.005

213

0.010

0.015

0.020

1/Ce

(a)
1.2
1.o

0.8

.
%

0.6
0.4

0.2
0.0
0.01

0.02

0.03

0.04

0.05

0.06

1/Ce
(b)

Fig. 4. Langmuir isotherms for activated SBEs A (W) and M ( O ) and

, commercial adsorbents Norit SA4
(A)and Brimac CC (0).

the characteristic Freundlich curve for this condition.23 It is proposed from this
initial study that the clay-carbon adsorbents have a hybrid porosity between that of
Norit SA4 (surface area 650 m2 g - ') and Brimac bone charcoal (100 mz g-').
Adsorbents activated with ZnC1, are now being prepared in our laboratory with
20% (w/w) surface carbon, and the optimisation of this procedure is the subject of
the following paper.

S. J . T.Pollard, C . J . Snllars, R . Perry

274

TABLE 3
Phenol Adsorption Isotherm Constants
Adsorbent

Freundlich constants
KF

lln

Langmuir constants
r

Q0

(dm3 g - ' )
A

M
Norit SA4
Brimac CC

0.220
0.756
20.427
0402

0.658
0.482
0.324
1.419

0.945
0-952
0.906
0.983

33.30
29.74
79.23
- 14.03

b
(dm3 rng

r
-

1)

1.56 x
2.55 x 103.29 x 10-7.65 x

0.978
0.989
0.920

0.985

4 CONCLUSIONS
We have produced a novel clay-carbon adsorbent from SBE and demonstrated its
potential application within the wastewater industry as a low cost adsorbent. While
this work is still at an initial stage, there are a number of conclusions which can be
drawn.

(1) Residual soybean oil adsorbed on the surface of montmorillonite in SBE is an

available carbon source suitable for activation.
(2) Zinc chloride and sulphuric acid can be used as chemical activants to effect
the transformation of carbonised oil to an active char.
( 3 ) The resulting mixed clay-carbon materials adsorb > 20 mol % aqueous
phenol from solution, their adsorption isotherms conforming to a
Langmuirian -type model.
The following paper describes the optimisation of the zinc chloride activation
process.

ACKNOWLEDGEMENTS
One of us (S.J.P.)wishes to thank the Science and Engineering Research Council for
a studentship and Laporte Inorganics for technical and materials support.

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