1.

Introduction

Various treatment technologies have been used for the reduc- tion of COD, which is a major
contaminant in petroleum refinery and industrial wastewater. These techniques include
filtration, ion exchange, coagulation/flocculation, reverse osmosis and electro- dialysis.
Adsorption provides an attractive alternative treatment, especially if the adsorbent is
inexpensive and readily available. Adsorption of COD has been previously studied to
evaluate the overall adsorption behavior in wastewaters. Considerable effort has been
devoted to the production of low cost adsorbents using less expensive and readily available
materials. The use of acti- vated carbon (AC), as an absorbent, has proven to be effective in a
wide range of applications, including the removal of both organic and inorganic pollutants
from wastewater. The versatility of high surface area, porous structure and surface
adsorption capac- ity, which can be appropriately modified by physical and chemical
treatments, are among the reasons for the use of such adsorbent. However, the cost of
commercially available AC is relatively high and therefore great attention has been focused
on the pro- duction of low-cost AC of properties comparable to those of the commercially
available. In order to achieve this target, agricultural waste was considered as a promising
raw material for generat- ing AC capable of removing various pollutants including COD from
industrial wastewater. Mohan et al. investigated the adsorption effectiveness of AC from
different raw materials for COD removal, and reported reduction percentages of up to 74%
using AC from coconut shell fiber and rice husk. Recently, date-pits (DP) have received
considerable attention as a lignin origin for preparing AC. In addition to producing AC
from inexpensive raw material, using DP is considered a waste minimization process. DP
consti- tute approximately 10% of the total weight of dates making them the largest
agricultural by-product in palm growing countries, including the UAE. Therefore, finding
ways to use this agricultural by-product profitably will benefit date farmers substantially
and offers a useful alternative for its disposal or current use as animal feed .
Several studies have examined different activation processes of DP and the possibility of
using the produced AC in wastewa- ter adsorption treatment. DP-AC was prepared by
physical and chemical activation In addition, physical activation of DP has been carried out
in different reactor configurations including fluidized bed The adsorption effectiveness of
DP-AC of alu- minum was evaluated and compared to that of commercial BDH-AC Generally,
the effectiveness of DP-AC was found to be compa- rable to that of BDH-AC, and was even
preferable under certain conditions, such as low Al concentrations and low pH.
The objective of the present work is to explore the viability of using DP-AC, locally
prepared by physical activation, as a low cost adsorbent for the reduction of COD from
petroleum refinery wastewater. Equilibrium and kinetics studies were carried out to
determine the mechanisms of the adsorption process.
1.1. Adsorption isotherms
Adsorption is a process that results in the removal of a solute from a solution and concentrating it at
the surface of the adsorbent, until the amount of the solute remaining in the solution is in equilibrium
with that at the surface. This equilibrium is described by expressing the amount of solute adsorbed
per unit mass of adsorbent, qe, as a function of the concentration of solute remaining in solution, Ce.
An expression of this type is termed adsorption
isotherm. Many theoretical and empirical models have been developed to represent the various
types of adsorption isotherms. At present, there is no single model that satisfactory describes all
mechanisms and shapes. Langmuir and Freundlich equations are examples of such models that are
commonly used to describe adsorption isotherms in water and wastewater treatment applications.
The Langmuir isotherm assumes uniform and constant binding of the sorbate on the surface of the
adsorbent, which is usually described by:
1.2. Adsorption kinetics
The adsorption kinetics can be described by diffusion through the adsorbent, such as
film, pore and surface diffusions, and poresurface adsorption or any combination of
these four steps. In order to examine the controlling mechanism of an adsorption
process and to determine the minimum necessary time to achieve equilibrium,
several kinetics models such as the pseudo-first order, Elovich’s, pseudo-second
order and intraparticle diffusion models can be used. Brief descriptions of these
models are given in the following sections.
2. Experimental methods
2.1. Preparation of DP-AC
DP-AC was prepared from raw DP granules, obtained from Al-Saad Date Processing
Factory, Al-Ain, UAE. The granules were washed, dried, grinded and screened. The
collected granules were carbonated and activated to produce DP-AC. The
carbonization is performed in a tube furnace (Thermolyene, USA) which has been
initially purged with a flow of nitrogen for 10 min. After that, the furnace was heated
at a rate of 10 ◦C/min up to 600 ◦C and then kept at this temperature for 4 h. After
cooling to room temperature, the material is considered carbonized, but still inactive.
After weighing the inactive carbon, it was activated in the same tube furnace at
a temperature of 900 ◦C using a flow of carbon dioxide instead of nitrogen. The
resulting AC was then degassed under vacuum (Shel Lab, USA) for about 2 h before
use. The main surface characteristics of the prepared DP-AC and commercially
available DBH-AC were determined using a surface area analyzer (Micromeritics,
Model ASAP-2010) and presented in Table 1. 2.2. COD batch adsorption Batch
adsorption equilibrium experiments were carried out by contacting a specified
amount of adsorbent with 50 ml wastewater sample, of a known initial COD
concentration, in a sealed glass bottle. The bottle was kept on a shaker (WSB-30,
Korea) at different temperatures for 24 h to reach equilibrium. At regular intervals,
samples were withdrawn and the COD was measured usingUVSpectrophotometer
(DR-5000, Germany). TheCODuptake was determined as a function of time, using
20 g/L DP-AC and BDHAC, contacted with refinery wastewater samples obtained
from a local petroleum refinery. Wastewater samples of three different initial
concentrations, namely, 3490, 1662 and 950 (±0.5) mg/L were tested. In addition,
the experiment was carried at different values of temperature and pH to determine
their effects. After 24 h, the samples were filtered and the final COD was determined.
Adsorption efficiencies of the prepared DP-AC were compared to those of
commercial BDH-AC. The uptake, q, was then calculated from the difference
between the initial and the final COD 2.3. Regeneration Regeneration is an important
aspect in evaluating the capacity and practicality of any adsorbent. The regeneration
of activated carbon has been meticulously examined in the literature and many
researchers have successfully regenerated activated carbon using different
methods. These included the utilization of pyrolysis [14], steam [15], water under
sub-critical conditions [16], surfactants [17], direct ozonation [18],microwave [19],
electrochemical methods [20,21] wet peroxide oxidization [22] bio-regeneration [23],
and ultrasound [24]. Although the results depended on the application and the type
of wastewater treated, in most cases the activated carbon was fully regenerated and
reused for many cycles. These studies have confirmed that activated carbon can be
easily regenerated and that the cost associated with the regeneration process can
be substantially reduced. In the present study, the regeneration of activated carbon
was not addressed and will be thoroughly examined in a future study that evaluates
the continuous adsorption of COD in a packed bed column.
4. Conclusions
The kinetics and equilibrium of the adsorption of COD were examined using two
types of adsorbents, namely commercial BDH and locally prepared date-pit (DP)
activated carbons. The adsorption effectiveness of DP-AC was found to be
comparable to that of the commercial BDH-AC and the equilibrium data for both
were almost equivalent. For both adsorbents, kinetic data were best fitted by the
pseudo-second order model, and the equilibrium data followed the Langmuir
isotherm. Modeling the adsorption mechanisms indicated that mass transfer was
dominant for low COD content; whereas for high concentrations the intrinsic reaction
kinetics is the dominant mechanism. Overall, the study revealed that DP-AC is a
promising alternative for the highly expensive activated carbon currently available
commercially. In addition, the utilization of DP-AC can provide an excellent disposal
option for the date palm industry.