Chapter one

1.1 Introduction
Organic pollution is the term used when large quantities of organic compounds. It originates
from domestic sewage, urban run-off, industrial effluents and agriculture wastewater. sewage
treatment plants and industry including food processing, pulp and paper making, agriculture and
aquaculture. During the decomposition process of organic pollutants, the dissolved oxygen in the
receiving water may be consumed at a greater rate than it can be replenished, causing oxygen
depletion and having severe consequences for the stream biota. Wastewater with organic
pollutants contains large quantities of suspended solids which reduce the light available to
photosynthetic organisms and, on settling out, alter the characteristics of the river bed, rendering
it an unsuitable habitat for many invertebrates. Organic pollutants include pesticides, fertilizers,
hydrocarbons, phenols, plasticizers, biphenyls, detergents, oils, greases, pharmaceuticals,
proteins and carbohydrates.[1] Toxic organic pollutants cause several environmental problems to
our environment. The most common organic pollutants named persistent organic [2] pollutants
(POPs). POPs are compounds of great concern due to their toxicity, persistence, long-range
transport ability and bioaccumulation in animals,[3] travel long distances and persist in living
organisms. POPs are carbon-based chemical compounds and mixtures (twelve pollutants) that
include industrial chemicals such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-
pdioxins and dibenzofurans (PCDD/Fs), and some organochlorine pesticides (OCPs), such as
hexachlorobenzene (HCB) or dichloro-diphenyl-trichloroethane (DDT), dibenzo-p-dioxins
(dioxins) and dibenzo-p-furans (furans).[4] PCDD/Fs are released to the environment as
byproducts of several processes, like waste incineration or metal production.[5] Many of these
compounds have been or continue to be used in large quantities and due to their environmental
persistence, have the ability to bioaccumulate and biomagnify.[6]
Efficient techniques for the removal of highly toxic organic compounds from water have drawn
significant interest. A number of methods such as coagulation, filtration with coagulation,
precipitation, ozonation, adsorption, ion exchange, reverse osmosis and advanced oxidation
processes have been used for the removal of organic pollutants from polluted water and
wastewater. These methods have been found to be limited, since they often involve high capital
and operational costs. On the other hand ion exchange and reverse osmosis are more attractive
processes because the pollutant values can be recovered along with their removal from the
effluents. Reverse osmosis, ion exchange and advanced oxidation processes do not seem to be
economically feasible because of their relatively high investment and operational cost. Among
the possible techniques for water treatments, the adsorption process by solid adsorbents shows
potential as one of the most efficient methods for the treatment and removal of organic
contaminants in wastewater treatment. Adsorption has advantages over the other methods
because of simple design and can involve low investment in term of both initial cost and land
required. The adsorption process is widely used for treatment of industrial wastewater from
organic and inorganic pollutants and meet the great attention from the researchers. In recent
years, the search for low-cost adsorbents that have pollutant –binding capacities has intensified.
Materials locally available such as natural materials, agricultural wastes and industrial wastes
can be utilized as low-cost adsorbents. Activated carbon produced from these materials can be
used as adsorbent for water and wastewater treatment. [7]
The adsorption technique has become more popular in recent years for wastewater treatment
owing to its efficiency in the removal of pollutants too stable for biological methods (Figure 1).
Dye adsorption is a result of two mechanisms (adsorption and ion exchange) and is influenced by
many factors such as dye/adsorbent interaction, adsorbent’s surface area, particle size,
temperature, pH and contact time. The main advantage of adsorption recently became the use of
low-cost materials, which reduces the procedure cost.

Figure 1.
Works published for “adsorption” and various environmental (Data after search in Scopus).(7.1)
However, following the economic boom in the 1970s—where the procedure cost was not such a
big problem (or had not been taken into account)—the economic crisis of the 2000s arose and led
researchers to turn their interest to other fields with lower procedure costs. Therefore, different
materials were tested as possible wastewater adsorbents. The selection for the most appropriate
adsorbent would be based on some major characteristic properties such as: (i) the low-cost along
with the satisfactory adsorption properties (capacity, reuse, industrial-scale use etc.) and (ii) the
environmentally-friendly nature of each adsorbent. It is fundamental to use only materials which
either have the lowest impact on environmental balance or are absolutely environmentally-
friendly (from abundant natural sources, biodegradable, non-toxic etc.). ,
 a new term will be introduced in this study, which is called “green adsorption”. Under this term,
it is meant that the low-cost materials originated from: (i) agricultural sources and by-products
(fruits, vegetables, foods); (ii) agricultural residues and wastes and (iii) low-cost sources from,
which most complex adsorbents will be produced (i.e., activated carbons after pyrolysis of
agricultural sources Therefore). These “green adsorbents” will be expected to be inferior
(regarding their adsorption capacity) than the super-adsorbents of literature (complex materials
as modified chitosans, activated carbons, structurally-complex inorganic composite
materials etc.), but their cost-potential makes them competitive.

1.2 Objective

By studying the literature survey and the previous works, the investigation on the removal of
phenol from waster by adsorption using walnut shell as adsorbent was carried out. The objectives
of the research work are as following.
 Collection of walnut shell
 Washed
 Crushed in a crusher (FRITSCH industry.8 6580 Idar Oberstein).
 Sieved into particule size of 0.1mm, using a sifter (Analysensieb-retsch-5657 HAAN W).
 Characterization of the prepared adsorbent.
 Preparation of synthetic wastewater.
 Batch studies for adsorption of phenol on the adsorbent.
 Optimization of operating parameters using design of experiments.
 Conduction of isotherm and kinetic studies and to calculate the adsorption capacity.

1.3 Methodology
The walnut shell (50 g) were initially powdered to remove any earthy matter. It is washed with
distilled water to remove all the dirt and impurities. It is dried in hot air oven (Serve well
instruments Private Limited H024DF) at 110°C for 1h to remove the moisture content. The 50 g
of sample was mixed with 95 mL of 0.1 M sulphuric acid for 15- 20 minutes. Then the mixture
was kept in a muffle furnace (Shital Scientific EMF-34) at 450oC for 1.5 h. After the heating
process, the mixture was cooled and mixed with distilled water in 2000 ml beaker and allowed to
settle for overnight. The process was continued and 0.1N Sodium hydroxide was added, till the
pH of the chemically treated carbon comes in the range of 6-7. Then it is once again dried in hot
air oven for 24 hour and ground to fine particles passing through 300 mesh sieves. Finally the
prepared powder was stored in air tight containers.
The batch experiments were conducted in 250mL conical flasks containing 200mL of phenol
solution of various initial concentrations. The equilibrium time for the phenol adsorption was
evaluated. The variation of operating parameters such as adsorbent dosage, pH and initial
concentration were optimized and studied. The kinetic studies were conducted under optimum
conditions. The flasks were agitated in the shaker and the samples were collected at regular
interval of time. The samples were filtered using vacuum pump and the remaining phenol
concentration was measured using UV spectrophotometer at a wavelength of 270 nm with the
help of calibration chart prepared. The isotherm studies were conducted by agitating the
solutions of different concentrations 40, 60, 80, 100, 120, 140, 160 and 180 mg/L till the
equilibrium time. At the end of equilibrium time, the concentration of the samples were
determined using UV Spectrophotometer.[7.1]