SORAN UNIVERSITY

FACULTY OF ENGINEERING
CHEMICAL ENGINEERING DEPARTMENT

Batch adsorption process for phenol

removal from phenol solution by using
walnut shell

Students: Supervised :
Omer maruf Prof.Dr. Ibtisam Kamal
Kubra edris
Kasar khanawdal
Ammr mahmood
 January / 2020

Contents
1.1 Introduction.....................................................................................................................................2
1.2 Green Adsorbents: Sources, Synthesis and Modification................................................................4
2.2 adsorption isotherms.......................................................................................................................7
2.3 types of adsorbent...........................................................................................................................7
2.4 Adsorption of phenols.....................................................................................................................8
2.5 Preparation of standard solutions & absorbance determination..................................................10
2.6 Preparation of the green bed........................................................................................................11
2.7 Batch adsorption Studies...............................................................................................................11
2.7.1 Effect of adsorbent dose.........................................................................................................11
2.8 Adsorption isotherms and models.................................................................................................12
Chapter three......................................................................................................................................14
3.1 Batch adsorbed design..................................................................................................................14
References...........................................................................................................................................18

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 Chapter one

1.1 Introduction
Organic contamination is the term used when organic compounds are high in amount. This
originates from domestic wastewater, municipal run-off, commercial wastewater and farm
wastewater Sewage treatment facilities and industry including food processing, pulp and
paper production Agriculture and aquaculture Dissolved oxygen can be devoured in Water to
receive at a higher rate than can be replenished during the organic contaminant
decomposition process, causing oxygen depletion and having severe implications for the biota
system. Wastewater with organic contaminants produces large amounts of suspended solids that
reduce the light available to photosynthetic organisms and change the characteristics from river bed
when it is deposited, rendering it an inappropriate environment for many invertebrates. Organic
pollutants include pesticides, fertilizers, hydrocarbons, phenols, plasticizers, biphenyls, detergents,
oils, fats, pharmaceuticals, proteins and carbohydrates. [1] Toxic organic contaminants lead our
climate to varying environmental problems. Common organic pollutants are called organic persistent
pollutants (POPs) [2]. Pops are aggregates of major concern because of their toxicity, persistence,
long-range transport capability and animal bioaccumulation. [3] Long distance travel and live
organisms persist. Organic persistent pollutants POPs are Mixtures and chemical compounds based on
carbon (twelve pollutants), comprising industrial chemicals such as Polychlorinated dibenzo-pdioxins
(PCDD / Fs) polychlorinated biphenyls (PCBs) And certain synthetic chlorinated pesticides (OCPs),
such as hexachlorobenzene (HCB) or dichlorodiphenyltrichloroethane (DDT), both enzo-p-dioxins
and furans (furans) .[4 ] Polychlorinated di benzene-dioxins PCDD / Fs are released Products
Released as goods in the community various processes, such as waste incineration or manufacturing
of metals. . [5] many of these chemicals, due to their persistence in the environment was used or
continues to be used in large amounts have the bioaccumulation and bio magnification capability [6].
Efficient methods have Drew considerable interest in extracting highly toxic organic compounds from
water. A variety of Processes as for example coagulation filtration precipitation zonation adsorption
exchange of ions Reverse osmosis and the advanced method of oxidation were used the reduction of
environmental pollutants from contaminated water and wastewater. Such approaches It was found to
be restrictive as they often require high costs of capital and operations On the other side Revision
exchange and osmosis are more desirable methods because it is possible to recover the pollutant
values together with their elimination from the effluents Because of their relatively high capital costs
And reverse osmosis of operating costs ion exchange and advanced oxidation processes do not appear
economically feasible The adsorption cycle by solid adsorbents shows potential as Most of the best
efficient methods for handling and eliminating organic pollutants in wastewater treatment among
possible water treatment techniques Due to simple nature, adsorption has advantages over the other
methods and can entail low investment in terms of both initial cost and required property. Commonly,

2
The adsorption method is used to treat industrial wastewater from organic and inorganic
contaminants, and receives the researchers ' great attention. Recent years have intensified the hunt for
low-cost adsorbents with pollutant-binding capacities. Local products such as Agribusiness and
agricultural waste may be used as low-cost adsorbents. Activated carbon from those materials may
be Suitable As an adsorbent to treatment of water and wastewater[7 ] Due to its efficiency in
removing Too stable contaminants for the biological methods figure (1) the adsorption technique has
become more popular in recent years for treatment of wastewater Dye adsorption occurs from two
processes adsorption and exchange of ions and is affected by many factors such as dye / adsorbent
interaction The adsorbent PH Temperature and time of touch of surface particle size Recently, the
principal benefit of adsorption was the use of low-cost materials, which reduces the cost of the
procedure.

3
 Figure 1.Published works for "adsorption" and different environment (Data after Scopus search).(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. Consequently,
different materials have been evaluated as possible to adsorb wastewater Choosing the most
effective adsorption will be based on certain major characteristics such as: I low-cost and
satisfactory adsorption properties (capacity, reuse, industrial use and etc.). And (ii) each
adsorbent is environmentally friendly . It is important to use only products that have the
lowest effect on the quality of the atmosphere or are completely environmentally sustainable
(from sufficient natural sources, biodegradable, non-toxic etc.). , For this report, a new
concept, called "green adsorption," will be implemented. Under this term, low-cost materials
are meant to originate from: I agricultural sources and by-products (fruits, vegetables, foods);
(ii) agricultural residues and waste; and (iii) low-cost sources from which the most complex
adsorbents will be produced (i.e., activated carbons following agricultural pyrolysis) Such
"neutral adsorbents" are supposed to be lower (in terms of their adsorption capacity) than the
super-adsorbents of literature (complex materials such as modified chitosan’s, activated carbons,
inorganic composite materials that are structurally complex, etc.) But their ability for cost-
effectiveness makes them competitive.

1.2 Green Adsorbents: Sources, Synthesis and Modification

The use of abundantly available economical adsorbents has been investigated as an
alternative to current cost-intensive methods for the removal of threatening pollutants from
aqueous solutions. Different approaches to developing Cheaper, more effective solutions
have been studied, both to reduce the volume of contaminated wastewater emitted and to
increase the efficiency of the treated effluent Over the last years The emphasis was on
looking for eco-friendly adsorbents with high performance, no harmful by-products and low
cost. In this perspective, the use of renewable, agricultural, industrial and domestic materials
in recent years has gained broad attention due to their abundance of availability, eco-friendly
characteristics, high efficiency, lower sludge production, low cost and possession. These
materials are herein referred to as green or eco-friendly adsorbents.
The green adsorbents can also be synthesized via green synthesis route. Conventional
synthesis of adsorbents can involve expensive chemical and physical processes that utilize
toxic materials with potential hazards (Shah et al. 2015). The toxicity may arise from the
stabilizers, organic solvents and the reducing agents that are used during the synthesis.
Hence, to synthesize green adsorbents, there is widespread interest in using environment-
friendly green processes, benign and bio- inspired synthesis route. Recent studies have
demonstrated that green based synthesis of adsorbents using plants and microorganisms is an
environment-friendly alternative, inexpensive and safe (Ladino et al. 2017b). There are
criteria based on source, wastes, process and performance to consider when selecting green
adsorbents for green adsorption. Particularly, to achieve green adsorption, the adsorbents
need to be cost-effective, easy to process, abundant and environmentally friendly to dispose
of.

1.3 Methodology
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

4
  screening the shells and separation from impurities
 walnut shells were placed for 24 hours in the urban water in order to softening shell
 rinsed and were dried for 5 hours at 105oC in thermostatic oven
 Crushed by electric mill.
 screened with standard laboratory sieves into particle size of 0.38mm
 Preparation of synthetic wastewater.
 Batch studies for adsorption of phenol on the adsorbent.
 Optimization of operating parameters using design of experiments.
 Isothermal and kinetic experiments conducted and adsorption power measured.

1.4 Objective
The main aim of this analysis is to provide a description of information on the use of
materials available locally as adsorbents for removing phenolic compounds. Therefore a
comparative analysis of some local adsorbents is provided in this paper based on recent
publications, and their removal output is recorded.

5
 Chapter two
2.1 Adsorption by green adsorbents
Recently, a great deal of interest in the research for the remotion of big alloy metals and dyes
from industrial effluent has been focused on the use of green adsorbents in particular from
natural sources, Agrarian residuals and waste, especially lignocellulose biomass, and low-
cost sources from which activated carbon adsorbents are produced. High adsorption ability
for methylene blue and safrarine dye was documented by McKay and co-workers using some
green adsorbents including tea wood bark, rice husk, cotton waste, hair and bituminous coal.
[106] The adsorption capacities for Safranine dye were found to be 1119, 838, 875, 190 and
120 mg/g and for methylene blue were 914, 312, 277, 158 and 250 mg/g for tea wood bark,
rice husk, cotton waste, hair and bituminous coal, Severally In another Topic ferrero
examined methylene blue adsorption on ground shells of hazelnuts[107]. It was notice that
adsorption capacities of methylene blue for hazel nut shells was 41.3 mg/g, Which was five
times the respective amount of activated carbon obtained from the same material reported
Look into the remotion of chrome(VI) from aqueous solution with batch adsorption
techniques using dissimilar low-cost adsorbents. To assess the adsorption efficiency for
Chrome (VI), he used some low-cost adsorbents such as clarified sludge, rice husk ash,
activated alumina, fuller soil, fly ash, sighted dust and neem bark. Such adsorbents showed
low adsorption potential of 26.31, 25.64, 25.57, 23.58, 23.86, 20.70 and 19.60 mg / g for
clarified sludge, rice husk ash, activated alumina, fuller dirt, fly ash, saw dust and neem bark.
[108] Azolla treated with Magnesium chloride (Mgcl2) adsorption values of cadmium (Cd),
lead (Pb), zinc (Zn), and copper (Cu) were approximately 33, 29, 40 and 24 mg / g severally
With increased concentration of magnesium chloride mgcl2 these values increase through
better ion swap conduct between metals and magnesium mg2 + ions on the azolla cell walls..
When azolla was treated with hydrogen peroxide h2o2 no remarkable effect was observed on
the heavy metal removal the maximum alloy removal was therefore noted for the treatment of
2m magnesium chloride mgcl2 azolla with 8 mm hydrogen peroxide h2o2 the Overall
adsorption potential for copper ii cui ii zinc ii zn ii cadmium ii cd ii and lead ii pb ii was 228
86 62 and 48 mg / g in another subject adsorption of bivalent heavy metal ions specially cu2+
zn2+ co2+ ni2+ and pb2+ onto acid and alkali treated annadurai And co-workers carried out
banana and orange peels[109]

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2.2 adsorption isotherms
The analysis of adsorption isotherms that define how an adsorbent interacts with the
adsorption. The isotherm provides an interrelationship concentration of phenol in solution
and an adsorbed volume of phenol on the solid phase where both processes are in equilibrium
[9].The Langmuir, Freundlich Temkin, BET, Redlich-Peterson and Dubinin-Radushkevich
Isothermic models (D-R) were used in explain the relationship between the phenol adsorbed
value and its concentration of equilibrium in solutions . [10] Reported the R2 values for linear
form of Langmuir and isotherms Freundlich are 0.988 and 0.992, respectively. According to
R2 values, the Freundlich isotherm best represents the equilibrium adsorption of phenol on
neutralized red mud. This is because various active sites or heterogeneous mixtures of many
minerals on neutralized red mud have various affinities with the phenol molecule [11,
12].The well-known Freundlich, on phenol from industrial wastewater using olive mill Waste
Langmuir isothermic equations [13] were applied for effects of adsorption of the equilibrium.
The ultimate-? Toted isothermic adsorption models [14] were found to be in the following
order: Freundlich > Redlich– eterson > Langmiur > Temkin for temperature range 25-45 ° C.

2.3 types of adsorbent

Adsorbent Types Similar adsorbent types are categorized into natural adsorbents and
synthetic adsorbents. The natural adsorbents include coal, clays, and crystals of clay, zeolites,
and ores. Adsorbent Types Similar adsorbent types are categorized into natural adsorbents
and synthetic adsorbents. The natural adsorbents include coal, clays, and crystals of clay,
zeolites, and ores. Such, in many situations, are natural materials are relatively cheap; Supply
abundant and with significant potential to modify and ultimately improve their adsorption
capabilities. Synthetic adsorbents are adsorbents Constructed from farm produce and
household waste , industrial waste, sewage sludge, and polymer adsorbent content.--
Adsorbent Will have its own characteristics ,for example porosity porous structure and the
design of its adsorbent surfaces . Many waste materials used include fruit waste coconut
shells scrap bark tyres, and other tannin-rich materials sawdust rice husk petroleum waste
fertilizer waste fly ash sugar industry waste furnace slag chitosan and seafood wastese,Algae
and seaweed, peat moss, clay, red mud, zeolites, rocks and sediments, minerals, etc.
Activated carbons as an adsorbent to organic pollutants represent a complex process in their
adsorption, and considerable complexity still exists The key cause of this problem is the vast
number of variables involved. These include, for example, electrostatic, dispersive and
chemical interactions, solute intrinsic properties (e.g., solubility and constant ionization),

7
adsorbent intrinsic properties (Such distribution of pore size), the solution properties
(especially pH), and system temperature.[15] Both Carbon granular activated gac and carbon
powdered pac activated carbons are typical adsorbents that are used to remove unwanted
odor, color, taste, . Other organic and inorganic impurities resulting from domestic and
industrial wastewater due to their large surface area, non-polar micro-porous structure and
economic viability. The key constituent of activated carbon is the carbon that accounts for up
to 95 percent of the mass weight In addition, active carbons contain other Atomic heteroes
like hydrogen, nitrogen, sulfur, and oxygen. Throughout activation and other preparation
procedures, and these are extracted from the source raw material or become correlated with
carbon. [16, 17]Putra et al. [18] Investigated pharmaceutical effluent removal of Amoxicillin
(antibiotic) using bentonite and activated carbon as adsorbents the test took place at different
pH-values. Then models from Langmuir and Freundlich were used to compare the
equilibrium data on which both models equally well match the results. While chemisorption
is the bentonite's dominant adsorption mechanism, both physic sorption and chemisorption
have played an important role in adsorption to activated carbon. The study investigated
methane adsorption on granular activated carbon (GAC). The results showed that the
Effectiveness of adsorption decreased with reduced temperature or increased methane
absorption by GAC. Interactions between the methane molecules and the surface of carbon
increase the density of adsorbed methane in respect to the density of compressed gas. The
effect that the porosity and the surface chemistry of the activated carbons have on the
adsorption of two VOC (benzene and toluene) at low concentration (200 ppm) was also
studied. The results show that the volume of narrow micro pores (size <0.7 nm) seems to
govern the adsorption of VOC at low concentration, especially for benzene adsorption. AC
has the highest adsorption capacities in oxygen surface groups with low content .Among the
AC tests, those prepared with hydroxides by chemical activation Show higher adsorption
capacity for VOC.

2.4 Adsorption of phenols

Since 1860, phenol has been in production, with its basic use as an antiseptic. During late
19th century and thereafter the use of phenol has been further extended to the synthesis of
dyes, aspirin, plastics, pharmaceuticals, and petrochemical and pesticide chemical industries.
In fact, by 2001, the global phenol production has reached an impressive 7.8 million tons.[19]
Among the different organic pollutants in wastewater, phenols are considered as priority
pollutants since they are harmful to plants, animals and human, even at low concentrations.

8
The major sources of phenolic are steel mills, petroleum refineries, pharmaceuticals,
petrochemical, coke oven plants, paints, coal gas, synthetic resins, plywood industries and
mine discharge. The wastewater with the highest concentration of phenol (>1000 mg/L) is
typically generated from coke processing. Phenolic compounds are also emanated from resin
plants with a concentration range of 12–300 mg/L. Environmental Protection Agency (EPA)
has set a limit of 0.1 mg/L of phenol in wastewater. The World Health Organization (WHO)
is stricter on phenol regulation. It sets a 0.001 mg/L as the limit of phenol concentration in
potable water. Adsorption of phenolic compounds from aqueous solutions by activated
carbon is one of the most investigated of all liquid-phase applications of carbon adsorbents.
[20] Several adsorbents were used treatment wastewater and removal of phenols. The
adsorption isotherms for mono-, di-, and trichlorophenols from aqueous solutions on wood-
based and lignite-based carbons were investigated. The adsorptive capacity for 2, 4-DCP was
found to be 502 mg/g and Freundlich model gave a best fit the experimental data [21].
Zagorsk et al. [22] studied the kinetics of adsorption of phenols on GAC. They observed that
60% to 80% of the adsorption occurs within the first hour of contact followed by a very slow
approach to the final maximum equilibrium concentration. In another study, the extent of
adsorption of 2, 4-dichlorophenol was found to be a function of ph. The presence of surface
functional groups also affected the adsorption of phenols onto activated carbon. The presence
of dissolved oxygen on activated carbon increased the adsorptive capacity for phenolic
compounds this increase in adsorptive capacity was attributed to the oligomerization of the
compounds through oxidative coupling reactions [23]. Hamdaouia et al. [24] studied and
modeled the adsorption equilibrium isotherms of five phenolic compounds from aqueous
solutions onto GAC. The five compounds selected were Phenol (Ph.), 2-chlorophenol (2-CP),
4-chlorophenol (4-CP), 2, 4-dichlorophenol (DCP), and 2, 4, 6-trichlorophenol (TCP). They
also observed that the interaction of phenolic compounds with activated carbon surface
occurred in localized monolayer adsorption type, i.e. adsorbed molecules are adsorbed at
definite, localized sites. Uptake of phenols increased in the order Ph. < 2-CP < 4- CP < DCP
< TCP, which correlated well with respective increase in molecular weight, cross-sectional
area, and hydrophobicity and decrease in solubility and pka. Sawdust, a very low cost
adsorbent was used, after carbonization, for the removal of phenol from industrial waste
waters. The equilibrium adsorption level was determined as a function of the solution pH,
temperature, contact time, adsorbent dose and the initial concentration. The adsorption
maximum for phenol using sawdust was 10.29 mg/L.[25] Adsorbents, carbonaceous
materials, activated carbon (AC), bagasse ash (BA) and wood charcoal (WC), were used for

9
removal of phenol from water.[26]The results showed the removal efficiencies for phenol–
AC, phenol–WC and phenol–BA, approximately 98%, 90% and 90%, respectively. Removal
efficiency of phenol slightly increased when the pH of adsorption system decreased. Yapper
and yilmar. [27] Reported the adsorptive capacity of some clays and natural zeolite materials
found in Turkey for the removal of phenol. They found that calcanei hydrotalcite was the best
among the studied adsorbents in which adsorbed 52% of phenol from a solution of 1000
mg/L phenol at the adsorbent/phenol ratio of 1:100 while the others adsorbed only 8% of
phenol. Also, silica gel, activated alumina, AC, fitrasorb 400 and hisir 1000 adsorbent were
examined as adsorbents for the removal of phenol from aqueous solution. They found that
hisir 1000 was the best among the tested materials [28]. Das and Pataki utilized blast furnace
flue dust (BFD) and slag to investigate [29] phenol adsorption through batch experiment.
Bromophenols (2-bromophenol, 4-bromophenol and 2, 4- dibromophenol) considered as one
of toxic organic phenol. Industrial wastes was used as low cost adsorbent for the removal of
these pollutants.

2.5 Preparation of standard solutions & absorbance determination

A stock solution of phenol compound was prepared by dissolving special amounts it in water.
This solution was diluted as required to obtain standard solutions containing 2,4,6,8, 10 and
12 mg/L The absorbance of the solutions was determined by UV-Visible spectrophotometer
between 200 and 750nm. The standard calibration curve is then plotted.
1.4
1.2
1
Absorbance

0.8
0.6
0.4
0.2
0
0 2 4 6 8 10 12 14
Conc. microgram/ml

Calibration curve for phenol solution

Typical UV-Visible spectrum for a phenol solution is shown in the figure below.

10
2.6 Preparation of the green bed
Walnut shell was collected from household waste of Erbil Province gardens and mainly from
Erbil city. After screening the shells and separation from impurities, in order to softening
Walnut shells, walnut shells were placed for 24 hours in the urban water, rinsed and were
dried for 5 hours at 105 C in thermostatic oven. The dry shells were milled using electric mill
and then were screened with standard laboratory sieves. Particles with an average particle
size of 0.38 mm were used as the adsorbent bed in our project.

2.7 Batch adsorption Studies

2.7.1 Effect of adsorbent dose

Batch adsorption equilibrium experiments were carried out by contacting a known amount of
walnut shell powder with 100 mL wastewater sample in a sealed glass bottle. Set of eight
samples each contain 100 ml of effluent was taken in a 300 ml beaker and certain amount of
adsorbent was added to it. The concentration of the solutions were (0.5, 1, 1.5, 2, 2.5, 3, 4, 5,
g/100ml). The samples were kept on a shaker (200rpm) at a constant temperature for 24 h to
reach equilibrium. The samples were withdrawn and filtered with Whitman no.1 filter paper.
The samples were analysed by U.V. spectrophotometer for absorbance. The percentage
removal was calculated as percentage reduction in the absorbance. The batch studies were
carried out at ambient temperature. All experiments were carried out in duplicates and the
average values were reported.

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 100
90
80
70

% Removal
60
50
40
30
20
10
0
0 1 2 3 4 5 6
Adsorbent dose (g/100ml)

2.7.2 Effect of contact time

For carrying out batch operation, and to study the effect of contact time, set of seven samples
each contain 100 ml of effluent was taken in a 300 ml beaker and identical amount of
adsorbent was added to each sample. Each sample was kept on a shaker (200rpm) at a
constant temperature for definite time (25, 50, 75, 100, 125, 150, and 200 minute). The
samples were withdrawn and filtered with Whitman no.1 filter paper. The samples were
analysed by U.V. spectrophotometer. The percentage removal was calculated as percentage
reduction in the absorbance.

100
90
80
70
60
% Removal

50
40
30
20
10
0
0 1 2 3 4 5 6 7 8 9
Contact time ( minute)

2.8 Adsorption isotherms and models

An adsorption isotherm is the presentation of the amount of solute adsorbed per unit weight
of adsorbent as a function of the equilibrium concentration in the bulk solution at constant
temperature. Langmuir and Freundlich adsorption isotherms are commonly used for the
description of adsorption data. The Langmuir equation is expressed as:

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/ 1/ /, Ce qe bXm Ce Xm = + (2)

Where Ce is the equilibrium concentration of solute (mmol L−1), qe is the amount of solute
adsorbed per unit weight of adsorbent (mmol g−1 of clay), Xm is the adsorption capacity
(mmol g−1), or monolayer capacity, and b is a constant (L mmol−1). The Freundlich
isotherm describes heterogeneous surface adsorption. The energy distribution for adsorptive
sites (in Freundlich isotherm) follows an exponential type function which is close to the real
situation. The rate of adsorption/desorption varies with the strength of the energy at the
adsorptive sites. The Freundlich equation is expressed as:

1/, logqe logk nlogCe = + (3)

Where k (mmol g−1) and 1/n are the constant characteristics of the system [90].

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 Chapter three

3.1 Batch adsorbed design

In batch adsorbers, the adsorbent is in contact with the adsorbate solution until the
equilibrium is reached. Batch adsorber design for single-solute adsorption is therefore very
simple and requires only combining the material balance with the isotherm equation. The
material balance equation for the batch reactor is the same as used for the determination of
isotherms.

Although adsorption kinetics is rapid due to the small particle size, equilibrium may not be
achieved within the contact time provided. Generally, the rate of adsorption depends not only
on the particle size but also on further factors such as adsorbent type, adsorbate properties,
and process conditions (e.g. adsorbate concentration, adsorbent dose, mixing conditions). On
the other hand, often the contact time in practical treatment processes cannot be extended
arbitrarily due to technical or economic restrictions. In the case of short contact times without
establishment of equilibrium, the simplified model approach only based on mass balance and
isotherm equation leads to an overestimation of the removal efficiency. This can be
compensated by an empirical safety margin to the estimated adsorbent dose. Alternatively,
short-term isotherms, with the same contact time as in the practical treatment process, can be
determined. These short-term isotherms then have to be used in the adsorber design instead of
the equilibrium isotherms.
For the following discussion, the establishment of equilibrium will be assumed. Thus, the
adsorber design requires only considering the material balance and the isotherm. Depending
on the kind of adsorbent addition (all at once into one reactor or consecutively in different
portions into different reactors), it can be distinguished between single-stage and multistage
adsorption processes. In water treatment plants, adsorption in slurry adsorbers is most
frequently carried out as a single-stage process.

3.1.1Design of batch adsorption from isotherm data

Generally the sorption process proceeds through varied mechanisms such as external mass
transfer of solute onto sorbent followed by intraparticle diffusion. Unless extensive
experimental data are available concerning the specific sorption application, determining the
rate-controlling step is impossible. Therefore, empirical design procedures based on sorption
equilibrium conditions are the most common method for predicting the adsorber size and
performance. Sorption equilibrium is a dynamic concept achieved when the rate at which
molecules adsorb onto a surface is equal to the rate at which they desorb. The physical
chemistry involved may be complex and no single theory of sorption has been put forward to
explain all the systems. Fortunately, engineering requires only the data under equilibrium
conditions. Previously sorption isotherm relations were used to predict the design of single-
stage batch-sorption systems [91, 92–94]. A schematic diagram is shown in Fig. 3.1. The
design objective is to reduce the phenol solution of volume V (L) from an initial
concentration of C0 to C1 (mg/L). The amount of adsorbent is M and the solute loading
changes from q0 (mg/g) to q1 (mg/g). At time t = 0, q0 = 0 and as time proceeds the mass
balance equates the phenol removed from the liquid to that picked up by the solid. The mass
balance equation for the sorption system in Fig. 3.1 can be written as

V (C0 −C1) =M (q0 −q1) =Mq1.

Under equilibrium conditions,

14
C1→Ce and q1→qe.

Since the sorption isotherm studies confirm that the equilibrium data for phenol onto walnut
shell particle fitted well in a Langmuir isotherm, a Langmuir isotherm equation can be used
for q1 in equation batch adsorber design.

Fig. 3.1. Single-stage batch-adsorber design

3.2 Chemical Regeneration

[95] Investigated chemical regeneration as an alternative method to thermal regeneration in
which chemical reagents (solvent) are applied to the exhausted carbon. When an adsorbent is
chemically regenerated by treating with methanol, acetone, ethanol and benzene, the amount
of adsorbate removed has been found to be a function of the accessibility of the organic
regenerate and the adsorbate carbon surface interactions. The desorption or extraction of
adsorbate is a simple and inexpensive method. However, the regeneration efficiency (defined
as the ratio of the adsorption capacity after to before regeneration) of this method is usually
below 70% and about 1015% of the AC pores are blocked by the solvent [96-98].
Moreover, contaminant materials are not destroyed, and the purification step for reuse of the
solvent is expensive. For these reasons, chemical regeneration is not widely used in practice.

15
However, the significant advantages of chemical / solvent regeneration of adsorbent include
[99]:
 Due to no adsorbent (carbon) loss during regeneration, the cost of carbon attrition is
avoided
 Due to the fact solvent regeneration can be done rapidly in situ, unloading,
transporting and repacking of adsorbents are eliminated.
 Is possible to recover valuable adsorbates (solute)
 Solvent can be reused easily by proper subsequent treatments such as distillation.
 No degradation of the adsorbent surface or pore structure.

3.3 Adsorbent regeneration and economics

Regeneration, or desorption is an important and necessary process when the adsorbent used is
expensive or if it is not always available in large quantities. Usually, this process is achieved
by changing the conditions in the adsorbent to bring about a lower equilibrium loading
capacity by increasing the temperature or decreasing the partial pressure. From an economic
view point, the sorbent can be considered effective if it can be easily regenerated and reused
as many times as possible without alteration of its performance. There are several methods
used for regeneration of adsorbent loaded with organic pollutants materials. In practice, the
choice of one type of regeneration process versus another depends on many factors, such as
cost, time, consumption and regeneration efficiency. [100]

16
 Chapter four

4.1 Material balance

Mat. Balance calculations: Typical calculations
In put = out put
Basis: 100 ml phenol solution
According to exp. No.2 wt. of adsorbent (bed) =1g/ 100ml
Initial conc. of phenol solution= 2 microgram/ml
Phenol in solution = 2* 100 = 200 microgram/100 ml
Phenol out = 200 microgram * 0.537 (% removal) = 107.4 microgram (not adsorbed)
Mat. Balance for phenol
Phenol in- phenol out = 200-107.4= 92.6 microgram

In put = out put

Basis: 100 ml phenol solution
According to exp. No.3 wt. of adsorbent (bed) =1.5g/ 100ml
Initial conc. of phenol solution= 4 microgram/ml
Phenol in solution = 4* 100 = 400 microgram/100 ml
Phenol out = 400 microgram * 0.654 (% removal) = 261.6 microgram (not adsorbed)
Mat. Balance for phenol
Phenol in- phenol out = 400-261.6= 138.4 microgram

In put = out put

Basis: 100 ml phenol solution
According to exp. No.4 wt. of adsorbent (bed) =2g/ 100ml
Initial conc. of phenol solution= 6 microgram/ml
Phenol in solution = 6* 100 = 600 microgram/100 ml
Phenol out = 600 microgram * 0.775 (% removal) = 465 microgram (not adsorbed)
Mat. Balance for phenol
Phenol in- phenol out = 600-465= 135 microgram

17
In put = out put
Basis: 100 ml phenol solution
According to exp. No.5 wt. of adsorbent (bed) =2.5g/ 100ml
Initial conc. of phenol solution= 8 microgram/ml
Phenol in solution = 8* 100 = 800 microgram/100 ml
Phenol out = 800 microgram * 0.822 (% removal) = 657.6 microgram (not adsorbed)
Mat. Balance for phenol
Phenol in- phenol out = 800-657.6= 142.4microgram

In put = out put

Basis: 100 ml phenol solution
According to exp. No.6 wt. of adsorbent (bed) =3g/ 100ml
Initial conc. of phenol solution= 10 microgram/ml
Phenol in solution = 10* 100 = 1000 microgram/100 ml
Phenol out = 1000 microgram * 0.884 (% removal) = 884 microgram (not adsorbed)
Mat. Balance for phenol
Phenol in- phenol out = 1000-884= 116 microgram

In put = out put

Basis: 100 ml phenol solution
According to exp. No.7 wt. of adsorbent (bed) =4g/ 100ml
Initial conc. of phenol solution= 12 microgram/ml
Phenol in solution = 12* 100 = 1200 microgram/100 ml
Phenol out = 1200 microgram * 0.881 (% removal) = 1057.2 microgram (not adsorbed)
Mat. Balance for phenol
Phenol in- phenol out = 1200-1057.2= 138.4 microgram

exp. No. wt. of Initial conc. of Phenol in phenol Mat.

adsorbent phenol solution solution out balance for
( bed) =g/ microgram/ml microgram/100 phenol
100ml ml (In-out)

18
1. 1 2 200 107.4 92.6
2. 1.5 4 400 261.6 138.4
3. 2 6 600 465 135
4. 2.5 8 800 657.6 142.4
5. 3 10 1000 884 116
6. 4 12 1200 1057.2 142.8

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