Wat. Res. Vol. 29, No. 1, pp.

337-347, 1995
Pergamon Elsevier ScienceLtd. Printed in Great Britain
0043-1354(94)E0103-D

MICROPOROUS CARBONS FROM MORINGA OLEIFERA

HUSKS FOR WATER PURIFICATION IN LESS
DEVELOPED COUNTRIES

S. J. T. P O L L A R D , * ~ ) l F. E. T H O M P S O N 1 and G. L. M c C O N N A C H I E 2
IDepartment of Chemistry and 2Department of Civil Engineering and Building Science, University of
Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JJ, Scotland

(First received June 1993; accepted in revised form March 1994)

Almtract--High quality activated carbon can be prepared from the waste husks of Moringa oleifera,
an indigenous tropical plant material. Steam activated husks exhibited a well-developed micropore volume
of 0.57 cm 3 g-~ and a corresponding apparent surface area of 734m 2 g-~, as determined by BET N2
adsorption hysteresis. In an assessment of aqueous phase adsorptive performance, activated Moringa
carbon was found to be comparable to commercial powdered activated water treatment carbons (PACs)
and exhibited a Langmuir monolayer coverage constant (Q 0) of 1.89 mmol g-I for phenol adsorption
from the aqueous phase. Cultivation of Moringa oleifera in developing countries for the coagulant
properties of its seed extract provides a well founded economic incentive for the utilisation of treated waste
husks as activated carbon during in situ water purification.

Key words--activated carbon, Moringa oleifera, microporosity, water purification, low-cost adsorbents,
less developed countries

NOMENCLATURE a necessary condition for overall development, and

Am= molecular cross-sectional area (m 2) remains a central objective of the World Health
b= Langmuir adsorption coefficient Organisation (Reid, 1982). Water and wastewater
CSET= BET constant treatment in developing countries can, however,
Ce = equilibrium concentration of solute (mol dm-3) aspire towards arbitary environmental quality
dW/dR = micropore distribution function (<2 nm)
Kr = Freundlich constant (mol g- l ) guidelines that reflect idealised operating procedures
n= Freundlich constant instead of achievable targets that are realistic and
NA = Avogadro constant (mol- l ) cost-effective. This can result in attempts to
qe = amount solute adsorbed per unit mass implement inappropriate solutions that exceed the
adsorbent (mol g-i)
available resources and practical capability of many
Q 0 = Langmuir monolayer coverage constant
(mol g- 1) communities (Pinfold et al., 1993). In acknowledge-
®n = phase transition during thermal decomposition ment of these difficulties, a substantial research effort
of substrate (°C) has focused on low-cost approaches to water purifi-
p/p°=partial pressure of N 2 in equilibrium with cation and wastewater treatment in L D C s (Shultz
adsorbent surface
SSA = specific surface area (m 2 g- ~) and Okun, 1984). Processes that reduce overall treat-
Rp = effective pore diameter (nm) ment costs through the application of indigenous,
a m e s + mac = external surface area (m 2 g- i ) natural products are particularly attractive because
Sto~= apparent BET surface area by N 2 adsorption they lessen reliance on imported water treatment
(m 2 g- I )
chemicals, have negligible transportation require-
Fads = volume N 2 adsorbed (cm 3 g-i)
Vmes+mac= pore volume attributable to meso and macro- ments and offer genuine, localised and appropriate
pores (cm 3g-i ) solutions to water quality problems (Jahn, 1982).
Vmicro = micropore volume (cm 3g-i ) The preparation of low-cost adsorbents for water
Xm= adsorption monolayer capacity from exper- purification, waste and wastewater treatment has
imental isotherm (mol g-l)
recently been reviewed by Pollard et al. (1992). For
example, a wide range of lignocellulosic agricultural
INTRODUCTION by-products have successfully been converted into
The provision of safe, potable water to communities activated carbons, including coconut coir (Hitchcock
in less developed countries (LDCs) is regarded as et al., 1983), jute stick (Banerjee and Mathew, 1985),
sarkanda grass (Chugtai et al., 1987), palm-tree cobs
*Present address: Aspinwall & Company, 13 Melville Street, (Renouprez and Avom, 1988), rice husk (Nawar and
Edinburgh EH3 7PE, Scotland. Doma, 1989) and tamarind nut shells (Bhargava and

337
338 S.J.T. POLLARDet al.
Sheidarkar, 1993a-c). The suitability of these precur-
sors is determined by their local and bulk availability,
carbon content and the presence of inherent micro-
structure within the substrate itself (Hardman, 1992).
Viability of their ultimate use may be determined as
much by these factors as by the adsorptive capacity,
regenerative characteristics and physical form of the
subsequent carbon product.
In this study we describe the preparation and
characterisation of activated carbon from Moringa
oleifera seed husks. This precursor is suitable due
to its widespread distribution across the tropical
developing world and because of the recognised
potential of Moringa seed extract as a low-cost,
natural coagulant aid for turbidity control in several
LDCs including the Sudan, Central India and
Malawi (Subbaramiah and Rao, 1937; Jahn, 1982;
McConnachie, 1993). Preparation of the endosperm
extract in rural communities typically involves prior
removal of the husk and crushing of the seed with
clarified water to produce a suspension which is then
filtered prior to use (Jahn and Dirar, 1979). Waste
husks could potentially be pyrolysed and gasified
with steam to produce activated carbon for the in situ
purification of stored household water containing
excessive taste and odour contaminants. The follow-
ing examination of preparative requirements and
adsorptive characteristics served to demonstrate the
technological viability of this process.
EXPERIMENTAL METHODOLOGY
Thermal analysis
Finely divided (1 mm dia.) Moringa oleifera husks (Peter
B. Dow & Company, Gisborne, New Zealand) (10 mg) were
placed in the quartz sample crucible of a Stanton Redcroft
thermobalance (STA 780) and heated at 10°C min-t under
dry, flowing nitrogen (30 cm 3min -~) from 25 to 900°C.
Carbonisation temperatures of 360°C and 485°C and dwell
times of 0 and 30 min were selected following examination
of the differential thermal profile (DTA) of Moringa husk
which clearly exhibited thermal behaviour characteristic of
the pyrolytic decomposition of hemicellulose, cellulose and
lignin composite units in plant materials (Shafizadeh, 1984)
(Fig. 1). Decomposition temperature ranges and mid-points
were verified by the thermal analysis of purified cellulose
powder and alkali lignin (Aldrich Chemical Co., U.K.).
Laboratory-scale preparation
Carbonisation and steam activation of Moringa husks
was conducted using an adapted Carbolite CTF 12/65
rotary furnace fitted with an internal silica sleeve (Fig. 2).
Successive charges (30 g) of substrate were placed in a
customised pyrex combustion boat and purged with dry
nitrogen for 10 min. For carbonisation, samples were heated
under N 2 a t a fixed rate of 15°Cmin -~ and held at the
selected temperature +3°C for the predetermined dwell
time. Following carbonisation, the char was removed to a
N2-fiushed desiccator and the yield determined. Following
CHN microanalysis (Perkin Elmer 2400 mieroanalyser) and
phenol screening (below), steam gasification of carbonised
Moringa char was conducted using a steam delivery rate of
4.5 cm 3min-~ from an adjacent steam generator. Prior to
activation the empty silica vessel was flushed with steam for
15 min. Samples of Moringa char (0.5 g) were then placed in
silica boats and partially gasified at 850°C in the furnace
for dwell times of 5 and 15 min, respectively. Under these
conditions, the basic endothermic reaction of steam with
carbon (1) is the equilibrium with the water gas shift
reaction (2) and so partial gasification of Moringa substrate
with carbon dioxide (3) becomes of additional importance
(Wigmans, 1989):
C(s) + H 20(g) --* CO(g) + H 2(g) (1)
CO(g) + H20(g ) ,---, CO2(g ) + H2(g ) (2)
C(s) + CO 2(g) ~ 2CO(g). (3)
Following activation, samples were removed to the
desiccator immediately to cool, were homogenised and
sieved to <250/tm, then washed with 40cm 3 2M HC1
followed by 3 x 40 cm 3 deionised water to remove residual
ash and vacuum filtration (Whatman 45 #m cellulose nitrate
membrane). Finally Moringa carbons were oven-dried
overnight at 85°C and desiccated awaiting CHN micro-
analysis, estimation of C/H quotient and determination of
carbon burn-off, where:
carbon burn-off
%C in raw substrate
%C in char normalised for percentage yield
× 100%. (4)
Solution phase screening and isothermal analysis
The adsorptive efficiencies of carbonised and activated
chars were screened using a single point, aqueous phase
phenol adsorption test. Preliminary tests established that
contact times of 24 h. would ensure steady-state conditions.
pH values of the non-buffered solutions (Milli-Q SP
deionised water) were measured prior to and following
phenol adsorption and were in the range 5.4 7.4, ensuring
predominance of the undissociated form (Ward & Getzen,
1970). Char samples (0.5 g) were added to 50 cm 3 aliquots
of a 10 -2M phenol (BDH, U.K.) solution in 250cm 3
Erlenmeyer flasks and shaken using a temperature-
controlled shaker bath (70 one-inch strokes min- t ) for 24 h
at 37 + 2°C, this value being representative of stored drink-
ing water temperatures in tropical climates (Jahn, 1982).
Phenol removal has been used extensively as an indicator of
progressive char development and, for simple screening
purposes, can be expressed as a removal efficiency (in tool
% removal) where:
removal efficiency
mol phenol adsorbed per g adsorbent
= × 100%. (5)
mol phenol in initial solution
Following uptake, suspensions were vacuum-filtered
(Whatman No. l) and residual phenol concentrations
analysed at 270 nm using a direct u.v. spectrophotometric
method (Shimadzu UV-160A). For raw, carbonised and
activated Moringa materials, and for 2 reference commercial
water treatment carbons (Ceca Acticarbone TE and Euro-
carb YAO), 7-point adsorption isotherms were constructed
using accurately weighed amounts (0.005, 0.01, 0.05, 0.1,
0.2, 0.5 and 1.0 g) of adsorbents added to 100 cm 3 of 10-2 M
phenol solution in 250cm 3 Erlenmeyer flasks as above.
Solution phase adsorptive behaviour was modelled to the
Freundlich and Langmuir isotherms [equations (3) and (4),
respectively] on account of their widespread use to describe
the aqueous phase uptake of organic micropollutants by
activated carbons:
q¢ = KFC ~'" (6)
Q °bCo
q¢ = (7)
l + bC~
 Moringa oleifera carbon in water purification
where qe is the amount of solute adsorbed per unit weight
asdorbate; K F, I/n, and b are characteristic constants; Ce the
residual solution phase concentration; and Q 0, the solid
phase concentration corresponding to complete monolayer
coverage of available adsorption sites. Kv has been used as
a relative measure of adsorption capacity and can thus be
taken as an indicator of surface area, as can QO. 1/n and b
are related to the enthalpy of adsorption and indicate the
intensity of reaction. The former model is purely empirical
and the latter assumes maximum adsorption occurs when
the surface is covered by a uniform monolayer of adsorbate
(Voice and Weber, 1983; Pollard et al., 1992). Estimation of
phenol specific surface area (SSA) was performed employing
the method of Giles and Nakhwa (1962), assuming the
phenol molecule is adsorbed flat-on to the carbon surface
and using a molecular cross-sectiona] area (Am) for the
phenol molecule of 0.522 x 10-is m 2 (Puri, 1980):
SSA = x mN A Am (8)
where x m is the ordinate value at which the initial (negative)
curvature falls to zero, obtained by horizontal extrapolation
of the knee-point on the experimental isotherm to the qe
axis; NA the Avogadro constant; and Am the molecule
cross-sectional area of the phenol molecule.
Continuous gas phase isothermal analysis
Activated Moringa carbon was analysed by continuous
gas phase adsorption hysteresis for surface area charac-
terisation and pore size distribution analysis using a single
channel Omnisorp Model I00 instrument (Centre for
Environmental Control and Waste Management, Imperial
College, London) and a method adapted from Pollard et al.
(1991). A representative carbon sub-sample (0.1027 g) was
outgassed at 250°C for 8 h. under a vacuum of 10 -6 torr.
A full N 2 adsorption/desorption isotherm was obtained
at -196°C using a constant, calibrated N 2 flow rate of
0.27cm3min -I and an adsorption cut off p/p° of ~0.98
(160 torr). Surface characterisation: apparent N2 BET sur-
DTA
-8 TG
-26 DTI
02
0
-.I
03
4)
O1
-62
.801 I I
0 180 3110
TemperRture
Fig. 1. Pyrolytic behaviour of raw Moringa husk by thermal analysis.
339
face area (linear region p/p°= 0.05-0.30); t-plot analysis
(t =thickness of adsorbed monolayer; linear region
t = 0.5-0.9 nm), and pore size distribution was performed
using the associated instrument software, which employs
the BJH method of meso- and macropore size distribution
(Barrett et al., 1951) and the Horwlth-Kawazoe model
(1983) for analysis of the micropore size distribution (pore
widths < 2 nm).
Scanning electron microscopy
Activated Moringa carbon was examined by scanning
electron microscopy (SEM) for a visual inspection of
external porosity and microtexture. Oven-dried samples
were presented on areas of double-sided adhesive tape
(0.5 cm x 0.5cm), mounted on the methanol-cleaned sur-
face of a aluminium microstub. The slides were gold coated
for 5 min (Emscope, UK.) and examined at various mag-
nifications using a Cambridge Stereoscan 90b instrument
and an operating voltage of 10 kV. Representative sections
of surface were recorded and developed on monochrome
paper (Ilford FP4).
RESULTS
Pyrolytic decomposition o f Moringa husks
Figure 1 illustrates the sequential thermal
decomposition processes occurring in Moringa husk
d u r i n g c a r b o n i s a t i o n by means of the experimental
a n d differential t h e r m o g r a m s (TG, D T G a n d DTA).
F o r reference, accounts o f lignocellulose thermo-
chemistry are provided by M a c k a y a n d Roberts
0 9 8 2 ) , Shafizadeh (1984) a n d Shukry et al. (1990).
briefly, ®i (Table l) is indicative of substrate dehy-
d r a t i o n (20-105°C), with transitions Oe, 0 3 , and 0 4
characteristic of pyrolytic decomposition processes
04
0
1 I
540 720 900
(*C)
340 S. J. T. POLLARDet al.

Table 1. Thermal analysis of lignoeellulosic materials

Substrate Aldrich~ Aldrich~ alkali
Phase transition ("C) Moringa husk cellulose powder lignin
(9~ (dehydration) 20-105 (55) 30-130 (70) 30-135 (70)
02 (hemicetlulose) 120-280 (180) 155-275 (210)
03 (cellulose) 255-360 (345) 315-370(345) 280-395(350)
04 (lignin) 420-485 (460) 400-520 (465)
O5 ("rearrangement") 615-685 (650) 630-740 (685)

Table 2. Elemental microanalysis and apparent carbon activities

Overall yield C H N C/H Carbon Phenol removal
Moringa substrate (%W/w) (%~/w) (%W/w) (%W/w) quotient burn-off(%) (mmolg-i) (mol %)
Raw husk 100 46.89 7.06 3.00 6.6 0 0.38 + 0.01 (19)
Carbonised 360.0 33.7 66.31 3.90 3.29 17.0 52 0.44 + 0.01 (22)
Carbonised 360/30 34.1 68.75 3.81 1.49 18.0 50 0.42 __.0.01 (21)
Carbonised 485/0 28.7 74.76 3.20 1.27 23.4 54 0.64 + 0.01 (32)
Carbonised 485/30 27.6 75.20 2.93 1.36 25.7 56 0.61 + 0.01 (30)
Activated 850/5 9.6 82.35 1.45 14.58 56.8 83 1.42 ___0.03 (71)
Activated 850/15 1.1 00.97 0.23 0.01 4.2 98 ND

in hemicellulose (120-280°C), fl-l,4-glycosidic bond
cleavage in cellulose units (255-360°C) and thermal
depolymerisation in lignin (420-485°C), respectively.
Progressive heating results in char formation via
internal thermal rearrangement (05) of the sugar
anhydride sub-unit residues, eventually providing
pseudographitic layers with microporous interstices
(Mackay and Roberts, 1982) that can be further
developed during their activation with steam.
Moringa husk appears to have structural similarities
with lignin, with a minimal contribution of hemi-
cellulose sub-units as evidenced by negligible weight
loss during Oz. This is advantageous for carbon
production because significant hemicellulose contri-
butions would otherwise result in substantial volatil-
isation during carbonisation and, subsequent heavy
carbon loss. Selection of carbonisation and activation
temperatures is always a compromise between carbon
and structural development, both of which progress
with increasing temperature, hence the selection of
360°C and 485°C as initial carbonisation tempera-
tures, which correspond to the completion of 03 and
®4 processes, respectively.
Aromaticity of carbon product
C H N microanalyses, char yields and carbon burn-
off values are presented in Table 2 with the phenol
adsorption efficiencies of the carbonised and acti-
vated products. C/H quotients reflect the degree
of aromaticity or extent of thermal rearrangement
experienced by the carbonised sub-units (Lewis,
1982) and increase with structural development of
first the carbonised, and subsequently, the activated
carbon product. Examination of Table 2 allows
identification of the 485°C/30min Moringa char
as the primary candidate of steam gasification trials
on the basis of retained carbon and apparent
structural development. Continued loss of yield
following a 30min dwell at 485°C, however,
appears to eliminate extended carbonisation times,
the husks clearly sensitive to elevated processing
temperatures. Steam activation, performed at a

glass wool plug

I
internal
"furnace
silica
vessel

l
heat
(steam activant)
combustion boat
and Morlnga
charge

Fig. 2. Schematic of experimental apparatus.

 Moringa oleifera carbon in water purification 341
4.0-
-I- Raw Moring8

3.5. 0 CarbonisedMoringa

[] ActivatedMoringa

:-~ 3.0" • EurocadoYAO

E
g
o- 2.5'

3
~ 2.0.
0
C
0
~ 1.5"

0
E 1.0.
,<

0.5'

0.0 ~.~.
0 1 2 3
!

4
!

6 7 8 9 10
Equilibrium phenol concentration, Ce (mmol/I)

Fig. 3. Phenol adsorption: experimental isotherms for study adsorbents.

minimum feasible temperature of 850°C, resulted in
successful development of microstructure as evidence
by a substantially enhanced phenol uptake during
screening (l.42mmolg -1, equivalent to 71mol %
removal efficiency from the 10 mM solution) and a
further increase in the C/H quotient of the activated
product. Maximum phenol removal efficiency was
observed for the 5 min gasified char and this product
subsequently subjected to detailed isothermal
analysis for water treatment applications.
Phenol adsorption isotherms and microporosity of
Moringa carbon
Experimental phenol isotherms for raw, carbon-
ised and activated Moringa are compared in Fig. 3
with those for selected comparable reference car-
bons. With the exception of the raw husk, which
demonstrated erratic isothermal behaviour, the
adsorbents demonstrated sigmoidal behaviour typical
of Type II isotherms (Shaw, 1980) and characteristic
of monolayer followed by multilayer adsorption.
Linearised Langmuir and Freundlich plots with
correlation coefficients are provided in Figs 4-5 for
relevant carbons. Deviations from idealised model
behaviour are attributed to multilayer adsorption
evidenced by the S-shaped experimental isotherm.
The related isothermal parameters are listed in
Table 3. Activated Moringa carbon exhibited an
intermediate specific surface area and monolayer
coverage coefficient (Q0) between the commercial
lignocellulosic-based PACs, Eurocarb ~ YAO and
Ceca ~ Acticarbone TE. Phenol specific surface areas
(SSA) for Moringa carbon determined using (i) the
Giles and Nakhwa method 0962); and (ii) by con-
version of Q 0 were 465 m 2 g- 1 and 594 ___79 m 2 g- ~,
respectively. Progressive development of porosity in
the activated product from the carbonised Moringa
char is confirmed by increases in the relevant iso-
thermal parameters (x,,, SSA, Q0, K~) and the
skeletal morphologies observed in representative
SEM micrographs of activated Moringa surfaces
(Figs 6 and 7).

Table 3. Phenol adsorption isotherm parameters

Giles and N a k h w a Langmuir Freundlich
Parameter xm SSA Q0 b K~- n
Adsorbent (mmol g- i ) (m 2 g - ) ) (mmol g i ) (dm 3 m m o l i) (din 3 g i )
Carbonised 485/30 0.60 188.6 NA NA 0.02 + 0.18 0.52
Activated 850/5 1.48 465.2 1.89 + 0.25 1.98 1.12 + 0.15 3.80
Eurocab RYAO 2.78 873.9 3.05 +_ 0.27 2.93 1.80 + 0.08 3.31
Ceca K Acticarbon¢ TE 1.34 421.2 1.53 __.0.94 0.4 1.05 __. 0.12 0.38
342 S. J. T. POLLARDet al,
0.6"

0.5-
J.
0,4- []
&,=
o.3-"
0.2" gl,
0
0.1 i
0.0
o
E -0.1
E
-0.2 ,,
2
o -0.3
-0.4 0 Carbonised Moringa (R^2 = 0,916)

-0.5 [] Activated Moringa (R^2 = 0.837)

-0.6
• Eurocarb YAO (R^2 = 0,973)
-0.7
• CECAActicarboneIE (R"2 = 0.869)
-0.8
-0.9
-1.0 -
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

log [Ce (mmol/t)]

Fig. 4. Phenol adsorption: Freundlich isotherms for study adsorbents.

301
2.8

2.6
0

[]
Carbonised Moringa

Activated Moringa
(R^2 = 0,958)

(R^2 = 0.851)

2 . 4 "! • Eurocarb YAO (R^2 = 0,975)

2.2" • CECAActicarboneTE (R"2 = 0,836)

2.0 "1

0
E
1.6-

1.2"

1.0-

0.4"

0.2-

0.0 0.5 1.0 1.5 2.0 2.5 3,0 3.5 4.0 4.5 5.0 5.5 6.0

liCe (I/mmol)

Fig. 5. Phenol adsorption: Langmuir isotherms for study adsorbents.

 Moringa oleifera carbon in water purification 343

Fig. 6. Representative SEM micrograph of activated Moringa carbon surface (808 × ).

The a d s o r p t i o n - d e s o r p t i o n i s o t h e r m of N : o n Table 4. Summary of continuous volumetric adsorption data

Moringa c a r b o n at - 1 9 6 ° C is s h o w n in Fig. 8 a n d Absorbent Activated Peat-based PAC
c o m p a r e d with t h a t of a peat-based commercial
Parameter Moringa (Norit'~SA4)
c a r b o n o b t a i n e d in earlier studies (Pollard et al., Mass (g) 0.1027 0.2770
Find~ (cm3g i ) 4352.2 49667.0
1991). Surface area a n d porosity d a t a o b t a i n e d by CBET 168.8 161.9
c o n t i n u o u s gas phase hysteresis for the two adsor- Stot (m2g_ j ) 734.3 704.5
bents is s h o w n in Table 4. A p p a r e n t surface areas
Sm~s+,,at (m2 g ~) 77.9 283.9
Vmicro(cm3 g I) 0.569 0.141
for Moringa a n d the peat-based commercial p r o d u c t Vm~.mac(cm~ g- ~) 0.071 0.285
d e t e r m i n e d using the linearised B E T e q u a t i o n a n d Microporosity (% v/v) 88.9 33.1
a molecular area of 0.162 x 10 ~8m2 for N 2 at
- 196°C (Gregg a n d Sing, 1982) were 734 m 2 g i a n d pore filling processes (Sing, 1989) a n d true surface
704 m 2 g-~ respectively, d e m o n s t r a t i n g the superior areas may be significantly greater t h a n these a p p a r e n t
quality of the Moringa product. F o r m i c r o p o r o u s values. F o r Moringa carbon, the c o n t r i b u t i o n from
solids, the B E T model takes no a c c o u n t o f micro- the external surface area (S~e~+ ma~) was determined to

Fig. 7. Representative Moringa carbon surface showing skeletal structure of activated surface (1610 × ).
344 S.J.T. POLLARDet al.
be 78 m 2 g - 2, this representing the meso- and macro-
pore surface alone (pore widths 2-200 nm). Mesopore
and micropore distributions were determined using
the Barrett et al. (1951) and the Horvhth-Kawazoe
models (1983), respectively. A basis for the appli-
cation of these models to the characterisation of
microporous carbon adsorbents and the significance
of their limitations is provided by Pollard (1990).
Moringa carbon exhibited near Type I isothermal
behaviour according to the BDDT classification
(Brunauer et al., 1940), and Type H4 de Boer
hysteresis (Sing et al., 1985) with an onset of isotherm
closure at p / p ° ~ 0 . 4 , indicative of the presence
of microporosity within the structure. Angular
deviation of the experimental isotherm plateau from
the strict horizon (compared to classical microporous
solids) reflects partial mesoporosity, desirable for
solute transport to adsorption sites. Activated
Moringa demonstrated a substantial micropore vol-
ume of 0.57 cm 3 g-1 compared to 0.18 cm 3 g - l pre-
viously determined for a peat-based water treatment
carbon of similar surface area (Pollard et al., 1991).
The pore volume of Moringa carbon above 2 nm
was determined to be 0.07cm3g -~ yielding a
micropore volume contribution of ~ 8 9 % v / v to the
total pore volume. The Horvfith-Kawazoe plot
(Fig. 9) illustrates the extent of micropore develop-
ment, with the micropore distribution function
( d W / d R = 6 . 7 , R p = O . 5 4 n m ) exceeding that pre-
viously determined for peat-based carbon (d W / d R =
4.9, Rp0.63 nm; Pollard et al., 1991) by a factor of
400
• Norit SA4
= Activated Moringa
300
0ffl
"~ 200
Z
E
0
100
0T
0.0 0.2 0.4
Fig. 8. Experimental isotherms for N 2 adsorption at - 196°C on commercial water treatment carbon and
activated Moringa husk.
1.4 in peak height. These results clearly indicate the
viability of Moringa husks as a suitable precursor
for the preparation of microporous activated carbon
with adsorptive properties similar, if not superior,
to some commercial carbons from industrialised
countries.
DISCUSSION
The potential applications for low-cost active
carbons in developing countries include the adsorp-
tion of excessive concentrations of Fe, Mn from
groundwater supplies, taste and odour compounds
from "foul-smelling" stored water, adsorption of
bacterial and viral pathogens in stored water and the
tertiary treatment of domestic and industrial waste-
waters with excessive nutrient or contaminant load
(Jahn, 1982; Bhargava and Sheidarkar, 1993a). The
current emphasis on natural treatment processes for
direct water purification in developing countries seeks
to address a number of broad-based developmental
problems associated with poor water quality: (a) an
overall need for the provision of safe, potable water
to rural communities in the developing world (Reid,
1982); (b) an established requirement for appropriate
water and wastewater treatment processes that can be
implemented at a local level (Schulz and Okun, 1984);
and (c) a specific need for low-cost adsorbents for
the removal of micropollutants and taste and odour
compounds from contaminated and "foul-smelling"
water supplies. Among these problems lie some
pip °
0 6 0 8 ,i0
 Moringa oleifera carbon in water purification 345

i • Norit SA4

A Activated Moringa

oE
•&

::!
AA
5
g
=o •&
4
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3
,
,,
,ft
All
0

¢•
el.
o
2
A •

0 I I I I I ! i - - ~ -- ! ~ | "-- I

0.0 0,2 0.4 0.6 0.8 1.0 1.2 1.4 1,6 1.8 2.0
Effective pore diameter (nm)
Fig. 9. Horvfith-Kawazoe plots of micropore distribution in commercial water treatment carbon and
activated Moringa husk.

specific objectives related to low-cost carbon pro-
duction: (d) a need for locally-available, low-cost
precursors to activated carbon that allow success-
ful application of adsorption technology without
enforcing reliance on commercial carbon from indus-
trialised countries (Khare et al., 1988; Pollard et al.,
1992); and (e) a need for simple, preparative pro-
cedures for low-cost activated carbon that incur
negligible environmental impacts. The latter usually
places a requirement for physical activation (partial
gasification) on the preparative process because acti-
vation of carbon precursors with ZnCI2, H3PO4,
H2SO4 and other chemical activants can lead to
process difficulties (corrosion of plant) and pollution
problems with rinsewater if full activant recovery is
not feasible. Furthermore, leaching of residual acti-
vant from the activated product may prove problem-
atical, esiaecially if water purification applications are
being considered. Examples of successful gasification
plants currently operating in developing countries
have been described by Hardman (1992). On this
basis of the above criteria, Moringa carbon is
clearly a potential candidate for the direct purifi-
cation of drinking water by adsorption and may have
additional uses as (i) an effective replacement for
sand in fine or dual filter units operating at low
filtration rates; and (ii) in tertiary wastewater treat-
ment, providing it can be produced in sufficient
quantity.
Precedents already exist for the use of ashes, chars
and soils for the treatment of stored water in LDCs
(Jahn, 1982). For example, the water purification
characteristics of certain adsorptive "plant ashes"
added to storage jars containing drinking water are
well known by indigenous peoples throughout the
developing world. In certain parts of India, "foul-
smelling" water is mixed with wood ash from the
sal-tree (Shorea robusta) and then cloth-filtered
before use. In Kerala, India, burnt coconut shells,
carbon adsorbents with an extended microporosity
(Bansal et al., 1988), are frequently added to well
water supplies. Carbonaceous materials are generally
collected from the ashes of the fire for these appli-
cations, but these materials generally have poor
adsorptive capacities and hence require high dosages
(Jahn, 1982). The adsorptive capacities of the chars
obtained could be substantially enhanced if controlled
pyrolysis and activation were applied rather than
uncontrolled combustion and use in the form of
"plant ash". Furthermore, selective use of specific
precursors for activated carbon has substantial
advantages over the indiscriminate use of fire ash of
mixed, and often low adsorptive quality. Use of
Moringa carbon, therefore, is fully consistent with
accepted water purification practices for rural com-
munities in many developing countries and is
especially attractive because of the highly-developed
microporosity attainable with this substrate. An
additional advantage of the recovery and reuse of
waste Moringa husk is that increased utilisation
of the plant may encourage further development of
Iocalised Moringa ole!f'era plantations with long-term
346 S.J.T. POLLARDet al.
benefits for rural communities in terms of natural
water purification.
Within the range of activated carbons prepared
from similar lignocellulosic precursors, Moringa car-
bon compares very favourably in terms of apparent
surface area (734m2g -~) and phenol adsorptive
capacity ( 1 . 8 9 m m o l g - l ) . For example, Renouprez
and A v o m (1988) prepared carbons with N 2 BET
surface areas of 23-1078 m 2 g-~ from palm tree cobs
using a variety of physical and chemical activation
procedures. Likewise, Tanin and Giirgey (1987) pre-
pared rice hull ash carbons with a range of surface
areas from 482 to 788 m 2 g - l . Tamarind nut shell
carbons, prepared and assessed for their water
treatment properties on the basis of their phenol
adsorption capacity were highly active with surface
areas of 218m2g i (H2SO4 activant) to 2810m2g
(direct pyrolysis) and reported phenol uptakes of
3-32 # m o l g-~ (Srinivasan et al., 1988). Activated
Moringa in this study exhibited a micropore volume
(0.57 cm 3 g - l ) comparable to the highly adsorptive
materials prepared by Linares-Solano et al. (1984)
from olive stones and almond shells. These
materials displayed a developed meso- and micro-
porosity, with the olive stones showing a greater
degree of macroporosity (pore widths 50-200 nm).
Whilst both materials yielded highly active carbons,
800-1300 m 2 g-1 in surface area and 0.3-0.8 cm 3 g J
in total pore volume, olive stones were the preferred
choice for the adsorption of textile dyes from
industrial waste waters. Potential substrates of com-
parable importance to Moringa oleifera, currently
being grown for the coagulant properties of their
seed extracts, include Moringa peregrina, Nirmali
(Strychnos potatorum ), Tamarind nuts ( Tamerindus
indica), and G u a r (Cyamopsis psoraloides) (Shulz and
Okun, 1984). Moringa peregrina seeds have an aver-
age endosperm mass of 0.32 g compared to 0.23 g for
Moringa oleifera (Jahn, 1982) and are of particular
future interest.
CONCLUSION
High grade microporous activated carbon can be
prepared from waste seed husks from the Moringa
oleifera tree. Beneficiaries of a development in the
utilisation of the waste husks would be communities
using natural Moringa polyelectrolytes for turbidity
control (e.g. Sudan, Egypt, Niger, Southern and
Central India). Future work will focus on developing
an optimised and implementable preparative pro-
cedure for Moringa carbon, evaluating the adsorptive
properties of carbons produced from similar plant
material wastes and demonstrating in-situ the pilot-
scale use of Moringa carbon in passive uptake storage
jars and downflow treatment columns.
Acknowledgements--This work was partially funded by the
Royal Society. The authors gratefully acknowledge the
technical assistance of Geoff Fowler (Centre for Environ-
mental Control & Waste Management, Imperial College of
Science and Technology), Alistair Dunlop and Jim Nee
(Chemistry Department, University of Edinburgh).
REFERENCES
Banerjee S. K. and Mathew M. D. (1985) Carbonisation of
jute stick, an agricultural waste. Agricultural Waste 15,
225-229.
Bansal R. P., Donnet J-P. and Stoeckli F. (1988) Active
Carbon. Marcel Dekker, New York.
Barrett E. P., Joyner L. G. and Halenda P. P. (1951)
The determination of pore volume and area distributions
in porous substances I. Computations from nitrogen
isotherms. J. Am. Chem. Soc. 73, 373-380.
Bhargava D. S. and Sheldarkar S. B. (1993a) Use of TNSAC
in phosphate adsorption studies and relationships. Liter-
ature, experimental methodology, justification and effects
of process variables. Wat. Res. 27, 303-312.
Bhargava D. S. and Sheldarkar S. B. (1993b) Use of
TNSAC in phosphate adsorption studies and relation-
ships. Effect of operating variables and related relation-
ships. War. Res. 27, 313-324.
Bhargava D. S. and Sheldarkar S. B. (1993c) Use of TNSAC
in phosphate adsorption studies and relationships.
Isotherm relationships and utility in the field. Wat. Res.
27, 325-335.
Brunauer S., Deming L. S., Deming W. S. and Teller E.
(1940) Theory of the van der Waals adsorption of gases.
J. Am. Chem. Soc. 62, 1723-1732.
Chughtai F. A., Fakhar-un-Nisa, Illahi A., Ejaz-ul-Haque
and Parveen N. (1987) Activated carbon from a tropical
carbonaceous material. J. Pure Appl. Sci. 6, 57-60.
Giles C. H. and Nakhwa S. N. (1962) Studies in adsorption
XVI. The measurement of specific surface areas of finely
divided solids by solution adsorption. J. appl. Chem. 12,
266--273.
Gregg S. J. and Sing K. S. W. (1982) Adsorption, Surface
Area and Porosity, 2nd edn. Academic Press, New York.
Hardman J. (1992) More than just a dry drupe. Chem. Brit.
28, 711-715.
Hitchcock S. J., McEnaney B. and Watling S. J.
(1983) Fibrous active carbons from coir. J. chem. Tech.
Biotechnol. 33A, 157-163.
Horvfith G. and Kawazoe K. (1983) Method for the calcu-
lation of effective pore size distribution in molecular sieve
carbons. J. chem. Engng. Japan 16, 470 476.
Jahn S. A. A. (1982) Traditional Water Purification in
Tropical Developing Countries: Existing Methods and
Potential Application, pp. 137-189. German Agency for
Technical Cooperation (GTZ).
Jahn S. A. A. and Dirar H. (1979) Studies on natural
water coagulants in the Sudan, with special reference to
Moringa oleifera seeds. Water SA 5, 90-97.
Khare S. K., Srivastava R. M., Panday K. K. and Singh
V. S. (1988) Removal of basic dye (crystal violet) from
water using wollastonite as adsorbent. Envir. Technol.
Lett. 9, 1163-1172.
Lewis I. C. (1982) Chemistry of carbonization. Carbon 20,
519-529.
Linares-Solano A., Rodriguez-Reinoso G., Molina-Sabio
M. and L6pez-Gonzfilez J. de D. (1984) The two-stage
air-CO2 activation in the preparation of active carbons. II
Characterisation by adsorption from solution. Ads. Sci.
Technol. 1, 223-234.
McKay D. M. and Roberts P. V. (1982) The dependence
of char and carbon yield on lignocellulosic precursor
composition. Carbon 20, 87-94.
McConnachie G. L. (1993) Water treatment for developing
countries using baffled-channel hydraulic flocculation.
Proc. Inst. Civil Engrs 101, 55-61.
Nawar S. S. and Doma H. S. (1989) Removal of dyes
from effluents using low-cost agricultural by-products.
Sci. Total Envir. 79, 271-279.
 Moringa oleifera carbon in water purification
Pinfold J. V., Horan N. J., Wirojanagud W. and Mara D.
(1993) The bacteriological quality of rainjar water in rural
northeast Thailand. Wat. Res. 27, 297-302.
Pollard S. J. T. (1990) Low-cost adsorbents from industrial
wastes. Ph.D. thesis, Imperial College of Science, Tech-
nology and Medicine, University of London.
Pollard S. J. T., Sollars C. J. and Perry R. (1991) A low-cost
adsorbent from spent bleaching earth. II. Optimisation
of the zinc chloride activation procedure. J. chem Tech.
Biotechnol. 50, 277-292.
Pollard S. J. T., Fowler G. F., Sollars C. J. and Perry R.
(1992) Low-cost adsorbents for waste and wastewater
treatment: a review. Sci. Total Envir. 116, 31-52.
Puri B. R. (1980) Carbon adsorption of pure compounds
and mixtures from solution phase. In Activated Carbon
Adsorption of Organics from the Aqueous Phase (Edited by
I. H. Suffet and M. J. McGuire), pp. 353-378. Ann Arbor.
Sci., Mich.
Reid G. W. (1982) Appropriate Methods o f Treating Water
and Wastewater in Developing Countries, pp. 1-16. Ann
Arbor Sci., Mich.
Renouprez A. and Avom J. (1988) Characterisation of
active carbons from palm tree fibres using nitrogen
adsorption and small angle x-ray scattering. In Charac-
terisation of Porous Solids (Edited by Unger K. K.,
Rouguerol J. and Sing K. S. W.), pp. 49-54. Elsevier,
Amsterdam.
Schulz C. R. and Okun D. A. (1984) Surface Water
WR 29/I--W
347
Treatment for Communities in Developing Countries.
pp. 1-8. Wiley, New York.
Shafizadeh F. (1984) Thermal degradation of cellulose.
In Cellulose Chemistry and Its Applications (Edited by
Nevell T. P. and Zeroman S. H.). Ellis Horwood,
Chichester.
Sing K. S. W. (1989) The use of physisorption data for
characterisation of microporous carbons. Carbon 27,
5-11.
Sing K. S. W., Everitt D. H., Haul R. A. W., Mouscou L.,
Pierotti R. A., Roquerol J. and Siemiemiewska T. (1985)
Reporting physisorption data for gas/solid systems. Pure
appl. Chem. 57, 603-619.
Srinivasan K., Rao P. B. S. and Ramadevi A. (1988b)
Studies on characteristics of carbon obtained from
tamarind nuts. Ind. J. envir. Health 30, 303-305.
Subbaramiah K. and Sanjiv Rao B. (1937) Mechanism of
clarification of muddy waters with Strychnos potatorum
seed. Proc. Ind. Acad. Sci. 7, 59-70.
Tanin S. and Giirgey I. (1988). Bleaching of cottonseed and
sunflower oils by active carbons from rice hulls. Chimica
Acta Turica 16, 209-219.
Voice T. C. and Weber W. J. Jr (1983) Sorption of
hydrophobic compounds by sediments, soils and sus-
pended solids I. Theory and background. Wat. Res. 17,
1433-1441.
Wigmans T. (1989) Industrial aspects of production and use
of activated carbons, Carbon 27, 13-22.