Materials Letters 57 (2003) 1723 – 1731

www.elsevier.com/locate/matlet

Utilization of agro-residues (rice husk) in small waste water

treatment plans
A.A.M. Daifullah a,*, B.S. Girgis b, H.M.H. Gad a
a
Hot Laboratory and Waste Management Center, Atomic Energy Authority, P.O. 13759, Cairo, Egypt
b
Laboratory of Surface Chemistry, National Research Center, Dokki, Giza, Egypt
Received 2 May 2002; accepted 16 May 2002

Abstract

Surplus, low-value agricultural by-product (rice husk) can be made into sorbent materials which are used in environmental
remediation. This study characterized and evaluated two types of sorbents made from rice husk. The efficiency of both sorbents
in the removal of the complex matrix containing six heavy metals was c 100%. These metals are Fe, Mn, Zn, Cu, Cd and Pb,
which are found in the drain containing the agriculture and sewage wastewater at El-Menofiya Governorate, Egypt. The two
sorbent materials were prepared according to the scheme presented. The two sorbents made from the rice husk have
considerable potential for adsorption of metals of environmental concern.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Rice husk; Agro-residues; Wastewater treatment; Adsorption

1. Introduction water is an important point source of water pollution.

Water pollution is one of the most important envi-
ronmental problems in the world. Fecal pollution of
water, especially drinking water, has frequently caused
waterborne diseases. In general, waterborne diseases
have been well controlled, especially in developed
countries [1].
Today, waterborne toxic chemicals pose a great
threat to the safety of water supplies in developed
and developing countries alike. There are many
sources of toxic chemicals in the environment, such
as badly managed landfills [2], industrial pollution
and pesticide runoff [3]. However, industrial waste-
*
Corresponding author.
Microbial degradation [4], chemical oxidation [5],
photolysis [6] and adsorption [7] are used for the
treatment of wastewater. Activated carbons are the
most common adsorbent, and they are made from
different plants, animal residues and bituminous coal
[8– 10]. Depending on the composition of the indus-
trial wastewater, one type of carbon maybe superior
to another [5].
The production of activated carbons from agricul-
tural by-products serves a double purpose. First, it
converts unwanted, surplus agricultural waste, of
which billions of kilograms are produced annually,
to useful, value-added adsorbents. Many specific
examples are found throughout the country where
disposal of agricultural by-products has become a
major, costly waste disposal problem. Second, acti-

0167-577X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 5 7 7 X ( 0 2 ) 0 1 0 5 8 - 3
1724 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731
vated carbons are increasingly used in water for
removing organic chemical and metals of environ-
mental or economic concern.
Rice husk, a by-product of the rice milling indus-
try, accounts for about 20% of the whole rice [11].
With the estimated annual rice production of 500
million tonnes in developing countries, approxi-
mately 100 million tonnes of rice husk is available
annually for utilization in these countries alone.
However, the amount of rice husk available is far
in excess of any local uses and, thus, has posed
disposal problems.
Rice husk (RH) [12] was chosen to be applied as a
precursor material due to its granular structure, insol-
ubility in water, chemical stability, high mechanical
strength and its local availability at almost no cost.
The advantage in the application of these adsorbents is
that there is no need to regenerate them because of
their low production costs.
The objectives of this study were (1) to determine
selected physical and adsorptive properties of the
two sorbents made from rice husk by two different
routes of preparation, (2) to ascertain the potential of
these sorbents to be used in wastewater treatment
plans, (3) to decide the comparative cost and (4) to
construct the possible sorption mechanisms that can
occur.
Scheme 1.
2. Materials and methods
2.1. Preparation of sorbents
Rice husk was chosen as a precursor material for
preparation of two sorbents, S-1 and S-2 (Scheme 1). In
this concern, 25 g of raw material was soaked in 1.0%
and 0.5% (w/w) KOH for S-1 and S-2, respectively, in
amounts sufficient to cover the raw material com-
pletely, slightly agitated, boiled for 30 min and left
overnight. The impregnated solid was filtered. The
filtrate was washed twice with distilled water (200 ml
each). Then, f 400 ml 10% HCl was added until the
pH reached 5, and the formed precipitate was dried at
110 jC. This was used as a sorbent 1 (S-1). The
remaining residue was transferred to a stainless steel
tube reactor (40
400 mm) fitted at one end with a
perforated disc, and screw caps at both ends with
narrow 10 mm tube openings to release the volatiles
and tarry matter. This reactor was admitted into a
sloping electric tube furnace supplied with a control
for both temperature and rate of heating. The solid mass
was gradually heated (at rate 50 jC/10 min) to allow
free evolution of volatiles up to 623 K. Pure steam was
then introduced to the heated mass, and heating was
continued up to 923 K and thereafter soaked for 1 h.
Evolved gases were vented from the upper outlet to the
 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731 1725

chimney of a fume cupboard, and condensed liquids of the sorbent. One gram of iodine (molecular area:
passed down through an air-cooled condenser to a 0.15– 0.42 nm2) adsorbent is considered to represent
water-cooled receiver. Then, the condensed liquor 1-m2 internal surface. Methylene blue (molecular area:
was injected directly to GC for PAH analysis [13]. 0.54– 1.97 nm2) value reveals the adsorptive proper-
This was used as sorbent 2 (S-2). The yields were ties of a carbon towards larger organic molecules. The
28.4% and 33.4% for the two sorbents, S-1 and S-2, scanning electron microscope (SEM) was additionally
respectively. The PAH compounds were analyzed by used to examine the surface of the two sorbents.
gas chromatograph (model HP-6890) with flame ion- Samples for SEM examination were mounted on
ization detector (GC-FID) according to US-EPA (610) SEM stubs using a synthetic adhesive. No pretreat-
method [13]. ment was used for the removal of debris in order to
avoid the creation of artifacts. The FTIR samples were
2.2. Waste water samples examined as KBr discs by using MATTSON 5000
FTIR Spectrometer.
In Egypt, The River Nile bifurcate into two Sorption experiments were carried out by taking
branches, named Damietta and Rosetta, at the Delta equal volumes (250 ml) of wastewater samples
of El-Kanater El-Khyria. Rosetta branch flows (SOBLE drain). Each sample was mixed with various
through El-Menofiya, Governorate. The SOBLE drain quantities of S-1 or S-2 ranging from 0.010 to 0.150 g
at El-Menofiya, Governorate, was selected because it and agitated for 4 h. The concentration of heavy
pours its agriculture and sewage wastes directly into metals was measured in the filtrate using atomic
the Rosetta branch. Water samples were collected by absorption (model Z-8100 Hitachi Atomic/Flame
using Van Dorn plastic bottles (capacity 1.5 l) and Spectrophotometer).
were kept in well-stopped polyethylene bottles at  5
jC. The different water parameters were determined
according to the standard methods. The analysis of 3. Results and discussion
samples were determined after collection immediately.
The determination of heavy metals were done, after The rice husk used was a locally available material
digestion using HNO3, by atomic absorption (model and had the following approximate dimensions [18]:
Z-8100 Hitachi Atomic/Flame Spectrophotometer). 8– 10 mm long, 2.0– 2.5 mm wide and 0.1– 0.15 mm
thick. The RH sample was analysed according to
2.3. Techniques and methods of analysis standard ASTM:D-3172-73 method and was found
to contain 64.3% volatile matter, 15.9% fixed carbon
For pH determination, 1 g of the dry, powdered and 19.8% ash (Table 1).
carbon sample was mixed with 100 ml of bidistilled Moreover, the main constituents of the metallic
water and allowed to equilibrate for 3 days in a residues (ash content) are: silica 94.5%, calcium oxide
stopped glass bottle. At end of this period, the pH 0.25%, magnesium oxide 0.23%, sodium oxide 0.78%,
of the carbon slurry was determined, allowing 5 min potassium oxide 1.10%, ferric oxide trace ( < 0.5),
for the pH probe to equilibrate. phosphorous pentoxide 0.53% and sulfur oxide 0.6%.
The bulk density was determined by a standard
procedure by weighing a known volume of gently Table 1
tapped sorbent granules. The apparent density was The microanalysis of rice husk and the two sorbents
calculated from the volume of the graduated cylinder Component Contents (%)
closely packed with the powdered sample and from the Rice husk Sorbent 1 Sorbent 2
sample weight. (Rh) (S-1) (S-2)
Iodine and methylene blue adsorption was deter- Carbon 37.0 8.5 44.3
mined according to NORIT [14]. These kinds of Oxygen 36.0 1.0 10.4
measurements are generally applied as fast industrial Hydrogen 5.1 2.1 2.6
test methods for controlling the quality of the adsorb- Nitrogen 0.4 0.4 –
Ash 20.5 88.0 42.6
ents. Iodine number informs about the internal surface
1726 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731

Table 2
Some data of the prepared sorbents
No. Density pH Percent Phenol/24 h PNP/24 h Ash (%) Methylene Iodine number
Apparent Packed yield (percent removal) (percent removal) blue (mg/g) (mg/g)

S-1 0.534 0.641 3.51 28.4 – – 88.00 34.6 68.00

S-2 0.109 0.328 11.00 33.4 81.8 97.93 42.65 67.8 122.00

3.1. Characterization of the prepared sorbents
Table 2 illustrates the physicochemical character-
istics of the two sorbents, S-1 and S-2. The higher
ash content (88.0%) in S-1 is reflected in its higher
density compared to sorbent 2. As was found in
Table 2, the pH measurements indicate that S-1 is
acidic in nature (3.51) and S-2 is basic (11.0),
whereas the pH of the rice husk is neutral (7).
Phenol and p-nitrophenol are weak acids (pKa = 9.9
and 8.2, respectively) [7] and will be under the
repulsive forces of sorbent 1. Moreover, water mol-

Fig. 1. Scanning electron micrographs of the two sorbents: sorbent 1 (A, B) and sorbent 2 (C, D).
 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731
ecules favorably adsorbed, thus, cluster at the
entrance and inside the pores [15], and seriously
hinder the approaching organic molecules to the
surface and, thus, the uptake is zero as shown in
Table 2. The percent yield of S-1 is less than that of
S-2 depending on the amount of silica dissolved in
1% KOH and precipitated by HCl.
Sorbent S-1 exhibited a lower surface area (by the
N2/77 K method) and internal pore volume, viz. 128
m2/g and 0.135 ml/g compared to 280 m2/g and
0.206 ml/g for S-2. Because of the possible practical
applications of the two sorbents, the gas adsorption
results were complemented by adsorption from sol-
ution in order to test the potential use of these
sorbents. For this reason, methylene blue and phenol
were used as solutes in the aqueous solution. The
results obtained in Table 2 indicate a large retention
of methylene blue for S-2 than S-1. This reveals that
the adsorptive capacity of S-2 towards organic mol-
ecules is nearly twice than that of S-1. This is
logical, as sorbent 1 is essentially silica whereas S-
2 is an activated carbon with higher affinity towards
organics. Iodine number informs that the internal
Fig. 2. FTIR spectra of (I) rice husk, (II) sorbent 1 and (III) sorbent 2.
1727
surface area of S-2 is greater than that of S-1. This
is confirmed by the SEM. The SEM photographs
(Fig. 1) also show progressive changes in the surface
of the particles. There are clear differences between
the lower (Fig. 1A) and the higher magnifications
(Fig. 1B). Thus, the initial morphology of the sorb-
ent 1 extracted with alkaline treatment (1% KOH)
followed by HCl looks like a collection of flowers or
a tree leaves at low magnification (Fig. 1A). In the
higher magnification (Fig. 1B), some needles or rods
can be seen. This can be acceptable because S-1 is
mainly amorphous silica on the surface. For carbons
treated with lower concentrations of KOH (0.5%)
followed by heat treatment at 923 K, S-2 (Fig. 1C
and D), the morphology retains the cellular structure
of the parent material, but it is more attacked,
especially the intercellular walls, the composition
of which is mainly cellulose [16]. It is well known
[17] that the alkaline metal salts have catalytic
effects on the gasification of carbonaceous materials.
This catalytic action increases the surface area of
active carbon. In particular, potassium hydroxide
shows large effects.
1728 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731

Table 3 band near 460 cm  1 due to metalUhalogen bond.

Physicochemical parameters of SOBLE drain water during Sorbent 1 spectrum shows bands at 1651, 1519 and
1998 – 1999
967 cm  1 due to hydrogen bonded CMO stretch
Station ! S
band, NMO stretch band and its NUO stretch band,
Parameter respectively [19]. The peaks at 2852 and 2921
Physical parameters cm  1 in sorbent 2 are assigned to the CUH
Air temperature (jC) 24.5 symmetric and asymmetric stretches of residual
Water temperature (jC) 18.0
methylene groups on the surface. The two peaks at
Trans. (cm) 20.0
E.C. (Amho) 1068 1465 and 1400 cm  1 are assigned to a CUO
T.S. (mg/l) 890 stretching vibration of carboxylate groups which
TDS (mg/l) 715 are metal dependent and depend on the heating
TSS (mg/l) 175 process during alkali treatment. The bands at 1740
TFS (mg/l) 555
and 1662 cm  1 are due to ketonic and aldehydic
TVS (mg/l) 335
CMO stretching frequencies. This interpretation is in
Chemical parameters a good agreement with the elemental analysis
pH 7.42 described in Table 1.
Oxygen studies
DO (mg/l) 0.0
3.3. Treatment of wastewater samples
BOD (mg/l) –
COD (mg/l) 24.4
Major anions The samples of the SOBLE drain contain the
CO3 (mg/l) 0.0 agriculture and sewage wastewaters at El-Menofiya,
HCO 3 (mg/l) 767.23 Governorate, Egypt. The wastewater samples ob-
SO4 (mg/l) 130.2
tained have the specifications shown in Table 3.
S  (Ag/l) –
CL  (mg/l) 114.35 The initial concentrations of heavy metals in
Major cations SOBLE drain (cf. Table 4) are higher than the permis-
Ca2 + (mg/l) 84.96 sible levels according to the Egyptian Environmental
Mg2 + (mg/l) 26.35 Regulations [20]. So, we used the two prepared
Na + (mg/l) 75.32
sorbents to check their applicability for metal removal
K + (mg/l) 6.82
Nutrient salts in wastewater treatment of this drain. As shown in
NO2 (Ag/l) 397.58 Fig. 3, the percent removal by S-1 or S-2 for the six
NO3 (Ag/l) 798.75 heavy metals in question is almost 100% and the final
NH3 (mg/l) 2.539 concentration of any metal after treatment was insig-
SiO2 (mg/l) 12.36
nificant at (V/M ratio = 16.66).
PO34  (Ag/l) (T RP) 380.113
TP (Ag/l) 543.60

3.2. FTIR studies Table 4

The concentration of heavy metals before and after treatment

In order to gain better insight into the surface Metal Permissible Initial Concentration after
ions levela concentration treatment, Ce (Ag/l)
functional groups available on the surface of S-1 and C0 (Ag/l)
S-2 sorbents, FTIR spectra for the prepared sorbents, S-1 S-2
3+
with the original rice husk (Rh), are recorded as Fe 1.0 9740 0.0 0.0
shown in Fig. 2. All spectra display three bands, Mn2 + 0.5 540 0.0 0.0
Zn2 + 1.0 100 0.05 0.0
around 3400, 1080 and 460 cm  1. The broad band Cu2 + 1.0 30 0.01 0.0
around 3400 cm  1 is attributable to the existence of Cd2 + 0.01 10 0.0 0.0
surface hydroxyl groups, and chemisorbed water Pb2 + 0.05 15 0.0 0.0
[18]. The siloxane band appears around 1080 a
According to the Egyptian Environmental Affairs Agency,
cm  1 due to SiUOUSi formation and the sharp Law #4, 1995.
 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731 1729

Fig. 3. The percent removal of the six metals of Soble drain after treatment by sorbent 2.

Let us say we wanted to treat 100,000 l at 9740 Ag/l sorbent 1 or sorbent 2 within 4 h of contact between the
of Fe and 540, 100, 30, 10, 15 Ag/l of Mn, Zn, Cu, Cd wastewater and any sorbent. The two sorbents are
and Pb, respectively. This would require c 6 kg of capable to remove all above-mentioned metals at the

Fig. 4. PAH of the condensed liquor produced during activation of sorbent 2 by gas chromatography analysis.
1730 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731

same time in a complex matrix under these circum- species, it seems that some nonelectrostatic force
stances and can reach the permissible levels according called ‘‘specific adsorption’’ was involved in the
to Egyptian Law. process of adsorption [22]. The possible adsorption
mechanism include the following:
3.4. Comparative cost
SO þ M2þ ! SOMþ
Comparing between the two sorbents (S-1 and S-
2), we can conclude that sorbent S-2 has some
SO þ MOHþ ! SOMOH
disadvantages: (i) the condensed liquor contains some
polycyclic aromatic hydrocarbons (PAH) which are
SOH þ M2þ ! SOMþ þ Hþ
carcinogenic and highly toxic. (Fig. 4); (ii) the sample
preparation is more difficult and needs especial
SOH þ MOHþ ! SOMOH þ Hþ
equipment and (iii) in spite of the fact that sorbent
1 costs tenfolds higher than sorbent 2 as indicated in
Table 5, the former can be a friendly material to the where SO  denotes negatively charged surface, SOH
environment. denotes neutral surface and M denotes metal ions.
Besides, two major types of chemical bindings
3.5. Sorption mechanisms can be responsible for the adsorption of various
metal ions onto the activated carbon (S-2) surface:
The ion-exchange reaction on the silica surface is covalent bonding and hydrogen bonding [23]. The
accomplished through the substitution of protons of covalent bonding results from the sharing of free
the surface silanol groups by the metal ions from electron pairs between the surface oxygen atom and
solution, as follows [21]: the metal atom or the formation of an OUM
bonding.
Mnþ þ xðZSiOHÞ X MðZSiOÞðnxÞþ
x þ xHþ

where Mn + = metal ion with n + charge, USiOH =

silanol group on the SiO2 surface and xH + = number
of protons released.
This cation-exchange mechanism is expected in S-
1 and S-2 as the two sorbents contain large amounts of
silica in the ash contact. Also, since electrostatic
attraction was not possible between positively charged
adsorbent surface and positively charged metal ion

Table 5
The estimated costs of 1 kg of prepared sorbents (1 and 2)
No. Item Costs (pt.)
Sorbent 1 Sorbent 2
1 Raw material 35 30 The hydrogen bonding results from the long-range
(transportation included) force between surface oxygen atom and the hydrogen
2 Commercial KOH (kg) 504 216 atom of the hydrated metal ions. Covalent bonding
3 Commercial HCl (l) 3920 Nill
4 Power consumption Nill 144
produces inner-sphere complexes; whereas hydrogen
(4 h
1.8 kW
20 pt.) bonding produces outer-sphere complexes. Under the
5 Water 10 10 currently available experimental results, it is not
6 Personnel 20 20 possible to differentiate the exact nature of these
Total 4489 420 two adsorption mechanisms.
 A.A.M. Daifullah et al. / Materials Letters 57 (2003) 1723–1731
References
[1] W.H. Bassett, Clays’s Handbook of Environmental Health,
Chapman & Hall, London, 1992.
[2] S.H. Gharaibeh, D. Schuller, R. Gels, B. Hollmann, Belastung
der umgebung der Akeider Muellkipe in Nord Jordanien durch
schwermetalle und organohalogenverbindungen, Wasser und
Boden 8 (1994) 54 – 57.
[3] British Medical Association, Guide to Pesticides, Chemicals
and Health, Edward Arnold, London, 1992, pp. 25 – 49.
[4] Deutsche Gesellschaft fuer Technische Zusammenarbeit
(GTZ), Abwassertechnologie, Springer-Verlag, Berlin, 1984.
[5] P.W. Lankford, W.W. Eckenfelder, Toxicity Reduction in In-
dustrial Effluents, Van Nostrand-Reinhold, New York, 1990.
[6] D.H. Kim, M.A. Anderson, Photoelectrocatalytic degradation
of formic acid using a porous TiO2 thin film electrode, Envi-
ronmental Science and Technology 28 (1994) 479.
[7] A.A.M. Daifullah, B.S. Girgis, Removal of some substituted
phenols by activated carbon obtained from agricultural waste,
Water Research 32 (4) (1998) 1169 – 1177.
[8] S.K. Banerjee, M.D. Mathew, Carbonisation of jute, an agri-
cultural waste, Agricultural Waste 15 (1985) 225 – 229.
[9] S.J.T. Pollard, F.E. Thompson, G.L. McConnachie, Micropo-
rous carbons from Moringa oleifera husks for water purifica-
tion in less developed countries, Water Research 29 (1995)
337 – 347.
[10] T. Wigmans, Industrial aspects of production and use of acti-
vated carbons, Carbon 27 (1989) 13 – 22.
[11] K.G. Mansaray, A.E. Ghaly, Energy Sources 20 (1998)
653 – 663.
1731
[12] A.M.M. El-Azab, PhD thesis, Cairo University, 1992.
[13] HP Environmental Solutions Catalog, Hewlett Packard, 1995/
1996.
[14] NORIT Testing Methods, Norit N.V., Holland, Special publi-
cation.
[15] C.H. Tessmer, R.D. Vidic, L.J. Uranowski, Impact of oxygen-
containing surface functional groups on activated carbon ad-
sorption of phenols, Environmental Science and Technology
31 (1997) 1872 – 1878.
[16] S.A. Stout, W. Spackman, International Journal of Coal Geol-
ogy 8 (1987) 55.
[17] D.W. McKee, Fuel 62 (1983) 170.
[18] B. Stuart, Modern Infrared Spectroscopy, Wiley, Chichester,
UK, 1996.
[19] G. Socrates, Infrared Characteristic Group Frequencies, Wiley,
Chichester, 1980.
[20] Egyptian Environmental Affairs Agency, Law #4, 1995.
[21] H.H. Tran, F.A. Roddick, J.A. O’Donnell, Comparison of
chromatography and desiccant silica gels for the adsorption
of metal ions—I. Adsorption and kinetics, Water Research
33 (13) (1999) 1992 – 1997.
[22] C. Namasivayam, K. Ranganathan, Removal of Cd(II) from
wastewater by adsorption on ‘‘Waste’’ Fe (III)/Cr(III) hydrox-
ide, Water Research 29 (1995) 1737 – 1744.
[23] M.O. Corapcioglu, C.P. Huang, The adsorption of heavy met-
als onto hydrous activated carbon, Water Research 21 (9)
(1987) 1031 – 1044.