FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

A project report submitted in partial fulfilment of the requirements for the award of the degree of
Bachelor of chemical Engineering

BATCH ADSORPTION PROCESS FOR PHENOL

REMOVAL FROM AQUEOUS SOLUTION USING
WALNUT SHELL ASH

BY

KASAR KHANAWDAL
AMMR MAHMOOD
OMAR MAROUF
KUBRA EDRIS

SUPERVISOR
PROF. Dr. IBTISAM KAMAL

28 / MAY / 2020
IN THE NAME OF MERCIFUL AND COMPASSIONATE ALLAH

COPYRIGHT BY

KASAR KHANAWDAL
AMMR MAHMOOD
OMAR MAROUF
KUBRA EDRIS

©2020

ii
APPROVAL PAGE
I certify that this Dissertation entitled “BATCH ADSORPTION PROCESS FOR PHENOL
REMOVAL FROM AQUEOUS SOLUTION USING WALNUT SHELL ASH” was
prepared by “KASAR KHANAWDAL, AMMR MAHMOOD, OMAR MAROUF, KUBRA
EDRIS” has met the required standard for submission in partial fulfillment of the requirements
for the award of Bachelor of Chemical Engineering at Soran University.

Approved By;

Signature:

……………………………………………………….

Supervisor:

……………………………………………………….

Date :

iii
DECLARATION
I certify that this project report entitled “BATCH ADSORPTION PROCESS FOR PHENOL
REMOVAL FROM AQUEOUS SOLUTION USING WALNUT SHELL ASH” has been
performed by us under the supervision of Prof. Dr. Ibtisam Kamal. No part of this project report
was presented for another degree or diploma elsewhere at any institution to the best of our
knowledge. I also declare that, as required by this rules and conduct, I have fully cited and
referenced all material and results that are not original to this work.

Students name:

KASAR KHANAWDAL MHE

AMMR MAHMOOD MIRO

OMAR MAROUF SAEED

KUBRA EDRIS RASUL

iv
ACKNOWLEDGEMENTS
In the name of Allah, the Most Gracious, the Most Merciful. Praise be to Allah, the Lord of the
Worlds; peace and blessings of Allah be upon the noblest of the Prophets and Messengers. First,
we would like to thank our parents and all family members for their open mindedness and
endless support. They are always close to our heart. We wish to express our sense of gratitude to
our supervisor Prof. Dr. Ibtisam Kamal and who have been a constant source of guidance to us
throughout our study. We wish to thank them for his valuable time and resources, to make this
thesis a success. Furthermore, special thanks to the academic, management and technical staff in
Faculty of Engineering. We wish to thank everyone who has helped us throughout our four
years‟ period at University of Soran, especially Prof. Dr. Ibtisam Kamal regarding to her help
guiding us to study in Soran. We thank all Soran people whom we met for their openness
friendship and hospitality. We express our indebtedness to Kurdistan Ministry of Higher
Education and Scientific Research and Soran university for giving us the permission for this
study.

v
 BATCH ADSORPTION PROCESS FOR PHENOL REMOVAL FROM AQUEOUS
SOLUTION USING WALNUT SHELL ASH

ABSTRACT
Phenol is an important chemical which is used in the manufacture of many products such as
dyes, synthetic resins, pesticides, tanning materials, perfumes and medicinal products, lubricants,
essential oils, solvents, etc. It is very toxic even present as traces in industrial wastewater
effluents. It may constitute a potential pollution source of ground waters and hence it has to be
eliminated. Amongst the numerous techniques of contaminant removal, adsorption using solid
materials (adsorbents) is a simple, useful and effective process. The adsorbent may be of
mineral, organic or biological origin. In this work the elimination of phenol from aqueous
solutions was carried out by adsorption onto walnut shell ash as green adsorbent using the batch
adsorption mode. The result of the current project demonstrated that walnut shell ash shows good
capability for removal of phenol from aqueous solutions in the batch experiments. Walnut shell
ash was found to be capable of removing up to 85% of the phenol from aqueous solutions with
initial concentrations of phenol in aqueous solution between 10- 100 microgram/L during 125
minute. Also, Langmuir model was identified as the more appropriate adsorption isotherm model
for the equilibrium modeling of adsorption process compared to the Freundlich model. The
adsorption rate driving force of phenol seemed to follow Zero-order kinetics which provides
information about phenol uptake rate and time required for adsorption process.

Keywords: Batch adsorption, Phenol solution, Low cost green adsorbent, Walnut shell ash,
Material balance.

vi
Table of Contents
APPROVAL PAGE .................................................................................................................. iii
DECLARATION ...................................................................................................................... iv
ACKNOWLEDGEMENTS.........................................................................................................v
ABSTRACT ............................................................................................................................. vi
List of Figures .............................................................................................................................x
List of Tables ............................................................................................................................ xi
List of Abbreviations................................................................................................................ xii
CHAPTER ONE .........................................................................................................................1
1.1 Introduction ...........................................................................................................................2
1.2 Green Adsorbents: Sources, Synthesis and Modification .......................................................4
1.3 Structure of Phenol ...............................................................................................................5
1.4 Methodology .........................................................................................................................7
1.5 Project Objective ...................................................................................................................7
CHAPTER TWO ........................................................................................................................8
2.1 Various Adsorbents used for Adsorption of Phenol................................................................9
2.2 Adsorbents Classification .................................................................................................... 11
2.3 Control Adsorbent Performance .......................................................................................... 12
2.4 Process Selection ................................................................................................................. 13
2.4.1 Technologies for Removal of Phenolic Compounds ...................................................... 13
2.4.1.1 Biodegradation....................................................................................................... 13
2.4.1.2 Chemical Method................................................................................................... 14
2.4.1.3 Physical Methods ................................................................................................... 14
2.5 Adsorption Process .............................................................................................................. 14
2.6 Batch Process ...................................................................................................................... 15
CHAPTER THREE................................................................................................................... 17
3.1 Preparation of Standard Phenol Solutions & Absorbance Determination.............................. 18
3.2 Preparation of the Green bed ............................................................................................... 18
3.2.1 Characteristics of the Adsorbent ............................................................................... 19
3.3 Batch adsorption Studies ..................................................................................................... 21
3.3.1 Effect of Adsorbent Dose .............................................................................................. 21

vii
 3.3.2 Effect of Contact Time .................................................................................................. 22
3.4 U.V. Spectrophotometer ..................................................................................................... 23
3.5 Adsorption Kinetics ............................................................................................................. 23
3.5.1 Pseudo Zero Order ........................................................................................................ 23
3.5.2 Pseudo First Order ........................................................................................................ 24
3.5.3 Pseudo Second Order .................................................................................................... 24
3.6 Adsorption Isotherm ............................................................................................................ 24
3.6.1 Langmuir Isotherm Model ............................................................................................ 24
3.6.2 Freundlich Isotherm Model ........................................................................................... 25
CHAPTER FOUR ..................................................................................................................... 26
4.1 Preparation of Standard Solutions & Absorbance Determination ......................................... 27
4.2 Effect of Adsorbent Dose .................................................................................................... 28
4.3 Effect of Contact Time ........................................................................................................ 28
4.4 Adsorption Kinetics ............................................................................................................. 29
4.4.1 Pseudo Zero Order ........................................................................................................ 30
4.4.2 Pseudo First Order ........................................................................................................ 30
4.4.3 Pseudo Second Order .................................................................................................... 31
4.5 Adsorption Isotherm ............................................................................................................ 32
CHAPTER FIVE ...................................................................................................................... 35
5.1 Plant Layout ........................................................................................................................ 36
5.2 Equipment Design ............................................................................................................... 36
5.2.1 Peristaltic Pumps .......................................................................................................... 36
5.2.2 Batch Adsorber Design ................................................................................................. 37
5.2.2.1 Design of Batch Adsorption from Isotherm data..................................................... 38
5.2.3 Chemical Regeneration ................................................................................................. 40
5.2.4 Adsorbent Regeneration and Economics ....................................................................... 40
5.3 Control Process ................................................................................................................... 41
5.3.1 Peristaltic Pump ............................................................................................................ 41
5.3.2 Batch Adsorber Control ................................................................................................ 43
CHAPTER SIX ......................................................................................................................... 45
6.1 Matrial Balance ................................................................................................................... 46
6.1.1 Material Balance for Phenol based on Effect of Adsorbent dose .................................... 47

viii
 6.1.2 Material Balance for Phenol based on Effect of Time .................................................... 50
6.2 Energy balance .................................................................................................................... 53
6.2.1 Isothermal ..................................................................................................................... 53
CHAPTER SEVEN................................................................................................................... 54
7.1 Cost Estimation ................................................................................................................... 55
7.1.1 Amortization Cost of investment (AC) .......................................................................... 55
7.1.2 Operating Cost (OC) ..................................................................................................... 56
CHAPTER EIGHT ................................................................................................................... 58
8.1 Environmental Pollution ...................................................................................................... 59
8.2 Effect Phenol of Environmental ........................................................................................... 60
8.3 Effect Phenol of Health ....................................................................................................... 61
8.4 The Role of Adsorption on Environment ............................................................................. 61
8.5 Conclusions ......................................................................................................................... 63
8.6 Future Perspectives ............................................................................................................. 63
References ................................................................................................................................ 64

ix
List of Figures
Figure 1.1 Published works for "adsorption" and different environment (Data after
Scopus search). ...........................................................................................................................3
Figure 1.2 Structure and dimensions of phenol . ..........................................................................5

Figure 2.1 Conventional adsorbents for the removal of pollutants from wastewaters [22,32,34] 11
Figure 2.2 Non-conventional adsorbents for the removal of pollutants from wastewaters
[22,32,34] ................................................................................................................................. 12
Figure 2.3 Schema depicting the relationships between the three components of an adsorption
system [22] ............................................................................................................................... 15

Figure 3.1 The prepared walnut shell and ash ............................................................................ 19

Figure 3.2 The equipment and glassware used (a) Whatman no.1 filterpaper and Erlenmeyer
flask .......................................................................................................................................... 20

Figure 4.1 Calibration curve for phenol solution ........................................................................ 27

Figure 4.2 Typical UV-Visible spectrum for a phenol solution .................................................. 27
Figure 4.3 Effect of adsorbent dosage on the adsorption of phenol by walnut shell ash. ............. 28
Figure 4.4 Adsorption percentage of phenol onto walnut shell ash vs. time ............................... 29
Figure 4.5 Pseudo-zero-order kinetics ....................................................................................... 30
Figure 4.6 Pseudo-first-order kinetics for the ............................................................................. 31
Figure 4.7 Pseudo-second-order kinetics for .............................................................................. 31
Figure 4.8 Langmuir Isotherm Adsorption ................................................................................. 33
Figure 4.9 Freundlich Isotherm Adsorption ............................................................................... 33

Figure 5.1 Plant layout of the batch adsorption .......................................................................... 36

Figure 5.2 Peristaltic pumps ...................................................................................................... 37
Figure 5.3 Single-stage batch-adsorber design ........................................................................... 39
Figure 5.4 Peristaltic Pump Control Schematic .......................................................................... 41
Figure 5.5 Open loop voltage mode. .......................................................................................... 42
Figure 5.6 Velocity loop mode. ................................................................................................. 42
Figure 5.7 Flow (and Velocity) Loop Mode .............................................................................. 43
Figure 5.8 Schematic of batch adsorption sydtem ...................................................................... 44

x
List of Tables
Table 1.1 The Main Physical Properties of Phenol.......................................................................6

Table 2.1 Comparison of adsorption capacities of adsorbents for Phenol. .................................. 10

Table 3.1 Calibration curve for phenol solution ......................................................................... 18

Table 3.2 Characteristics of the prepared activated walnut shell ash. ......................................... 19
Table 3.3 Adsorbent dose versus % phenol removal .................................................................. 21
Table 3.4 Contact time versus % phenol removal ...................................................................... 22

Table 4.1 Kinetics Adsorption of walnut shell ash. .................................................................... 29

Table 4.2 Comparison of Adsorption Rate Kinetics. .................................................................. 32
Table 4.3 Isotherm Adsorption data. .......................................................................................... 33
Table 4.4 Isotherm Parameters for adsorption. ........................................................................... 34

Table 6.1 Removal based on weight of adsorbent . .................................................................... 47

Table 6.2 Result of material balance of phenol effect of adsorbent dose. ................................... 50
Table 6.3 Phenol removal based on Contact time....................................................................... 50
Table 6.4 Result of material balance of phenol effect of content time ........................................ 53

xi
List of Abbreviations

FTIR………………………………………………... Fourier Transform Infrared Spectrometry

TEM………………………………………………….Transmission Electron Microscopy
UV…………………………………………………...Ultra Violet
AC……………………………………………………Activated Carbon
WS……………………………………………………Walnut Shell
EPA…………………………………………………..Environmental Protection Agency
POP …………………………………………………..Persistent Organic Pollutants
BLDC…………………………………………………Brushless DC
PWM …………………………………………………Pulse Width Modulation
FOC …………………………………………………..Field Oriented Control
DS …………………………………………………….Diffusion Coefficient
PI controller……………………………………………Proportional Integral controller

xii
CHAPTER ONE

INTRODUCTION

1
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 persistent organic
pollutants (POPs) [2]. Pops are an aggregate of major concern because of its toxicity continues
for 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, for example
polychlorinated dibenzo-pdioxins (PCDD / Fs), (PCBs) of polychlorinated biphenyls and some
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 Its success in the world 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

2
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,
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 adsorbents to low cost. 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 (1.1)
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.

Figure 1.1 Published works for “adsorption” and different environment (Data after Scopus search). [8]

3
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 (i) 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 : Agricultural and fruit-grown food sources ii agricultural residues and waste and
iii low-cost sources from which the most complex adsorbents are produced I e (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. [8]

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. [9-11] 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

4
with potential hazards [12]. 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. Latest studies have shown the green based synthesis of adsorbents using plants
and microorganisms is an environment-friendly alternative, inexpensive and safe [13]. 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 Structure of Phenol

The monohydroxy derivative of benzene is known as phenol. [63]. Phenol is recovered from coal
tar, and considerable amounts are manufactured synthetically. It is a colourless or white solid
when it is pure; however, it is usually sold and used as a liquid. It has the chemical formula as
C6H6O and the molecular weight of 94,144 g /mol,The phenol odor threshold is 0 04 ppm with a
solid, very sweet odor that is very water-soluble and very inflammable. The vapour pressure for
phenol is 0,41 mm Hg at 25 0C, and it has a log octanol / water partition coefficient (Log KOW )
of 1,46. Chemical structure of phenol is 5 illustrated in Figure 1.2., and physical properties are
given in Table 1.1.

Figure 1.2 Structure and dimensions of phenol [64].

5
 Table 1.1 The Main Physical Properties of Phenol [64].

Properties Values
Molecular weight (g/mol) 94.144
Molar volume (cm3/mol) 90
Boiling point (oC) 182
Melting point (oC) 43
Auto ignitition temperature (oC) 715
Solubility in water (mg/L) 50-100 @ 19 oC
Liquid density (g/cm3) 1.06
pH of aqueous solution 6
Molecular diffusivity in water (cm/sec) 6.0 x 10-4
Vapour pressure (mm Hg) 0.41 @ 25 oC
Relative vapour density 3.24 (air=1)
Air-water partition coefficient, Kaw(25 oC) 2.5 x 10-5
Dipole moment (debyes) 1.450007
Polarizability, i 0.89
Liquid surface tension (dynes/cm) 36.5 @ 55 oC
Excess free energy (kJ/mol) 10
Excess enthalpy (kJ/mol) [S/D] * 1/8
Excess entropy (J/mol K) [S/D]* -9/-2
Acidity constant, pKa(25 oC) 9.90
Fraction in neutral form at pH 7 0.998
[S/D]* saturated/dilute solution

Phenol is used as a raw chemical in the manufacture of plywood, furniture, automotive and
appliance industries, and in the processing of nylon, epoxy resins. In addition, it becomes a
disinfectant, slime-killing agent, and an additive in medicines. Biphenol and is another field of
phenol use. [65].

6
1.4 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

 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
 Were impregnated with an acid solution. The activated shells were carbonized in an
ashing furnace at 500 Co for 60 min, and then used as the green adsorbent bed in the
project.
 Preparation of phenol solution.
 Batch studies for adsorption of phenol on the adsorbent.
 Optimization of operating parameters using design of experiments.
 Isothermal and kinetic experiments conducted and adsorption capacity measured.

1.5 Project Objective

The main aim of the current projectis to provide a descriptive information about using materials
available locally as adsorbents for removing phenolic compound from aqueous solutions. Other
objective includes:
1. Preparation of the green bed (walnut shell ash).
2. Using the green bed as adsorbent to remove phenol from aqueous solution in batch process.
3. Studying the effect of adsorbent dose and contact time on adsorption capacity.
4. Process Design and material balance calculations.
5. Process Control, economic and environmental aspects.

7
 CHAPTER TWO

LITETURE REVIEW
AND
PROCESS SELECTION

8
2.1 Various Adsorbents used for Adsorption of Phenol
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.
Bunch adsorption reads were completed for assessing the appropriateness of plum pieces as an
adsorbent for the expulsion of phenol from squander water by Juang et al.[14] The activation
temperature and time tested were in the ranges 750-9000C and 1-4 h, respectively and the
adsorption capacity was 257.4mg/g.
The potential of jute stick carbon to remove phenol from aqueous solution was evaluated by
Mustafa et al. [15] It was justified that the extent of removal was dependent on concentration of
phenol, contact time, pH, and quantity of adsorbent. The Freundlich isotherm was seen as
proficient for the adsorption framework and evacuation was 8 mg/g.
The capability of nutshells of Sterculia alata, a woodland waste to get ready actuated carbons by
zinc chloride enactment to expel phenol from fluid arrangement was assessed Mohanty et al.[16]
Trials were done at various impregnation proportions, carbonization temperature and time. The
most extreme take-up of phenol was found at pH 3.5 and adsorption limit was 2.8 mg/g.
The FTIR examines shows that the cooperation of the particular utilitarian gatherings in
adsorption association, while SEM contemplates imagined the development of the adsorbed
white layer on the phenol surface. The relevance of shells, seed coat, stone and pieces of
different horticultural items as adsorbents for the expulsion of harmful poisons from water has
been explored. The feasibility initiated carbon from almond shell, hazelnut shell, pecan shell and
apricot stone for the evacuation of phenol has been researched by Ayguun et al. [17] and
discovered that the adsorption limit of 70.4, 100, 145 and 126 mg/g was gotten for almond shell,
pecan shell, hazelnut shell and apricot stone separately. It was discovered that the impregnating
operators and initiating specialists had influence on phenol removal.
The seeds of some agricultural by products have been explored as effective adsorbents. The
adsorption of phenol on palm seed coat initiated carbon was assessed by Rengaraj et al. [18] the
adsorption limit of palm seed coat initiated carbon was 18.3mg/g for the particle size of 0.5 mm.
In comparison with commercial activated carbon palm seed coat carbon, has a lower ash content
which indicates more carbon content.

9
The roots of the agricultural materials were found to be potential adsorbents for water treatment.
The root of an Indian plant Hemidesmus indicus has been used as raw material in the preparation
of ash activated carbon by chemical activation with sulphuric acid by Srihari and Das28 for the
sorption of phenol from aqueous solutions. The adsorption limit was 16.10 mg/g and the
adsorption information followed pseudo-first request, pseudo-second request model and pore
dissemination model.
Hazelnut Bagasse carbon activated with zinc chloride was examined for the removal of phenol
from water by Karabacakoglu et al. [19]. The results showed that the removal efficiency
increased with increase in adsorbent dose and phenol concentration. Freundlich and Langmuir
adsorption isotherms were applied to the experimental data. The adsorption capacities of 97.36,
91.32 and 99.27 mg/g were found at (25, 35 and 45 0C ) respectively. As shown in table 2.1

Table 2.1 Comparison of adsorption capacities of adsorbents for Phenol.

Adsorption
Adsorbent Solute
capacity (mg/g)
Plum kernels Phenol 257.4
Jute stick Phenol 8
Nutshells of Sterculia alata Phenol 2.8
Almond shell Phenol 70.4
Hazelnut shell Phenol 100
Walnut shell Phenol 145
Apricot stone Phenol 126
Palm seed coat Phenol 18.3
Hazelnut Bagasse carbon Phenol (25 0C) 97.36
Hazelnut Bagasse carbon Phenol (35 0C) 91.32
Hazelnut Bagasse carbon Phenol (45 0C) 99.27

10
2.2 Adsorbents Classification
Solid materials used as adsorbents can take a broad range of chemical forms and different
geometrical surface structures. This is reflected in the range of their applications in industry, or
helpfulness in laboratory practice.

Adsorbents can be usually classified in five categories:

1) Natural materials such as sawdust, wood, fuller‟s earth or bauxite.

2) Natural materials treated to develop their structures and properties such as activated
carbons, activated alumina or silica gel.

3) Manufactured materials such as polymeric resins, zeolites or aluminosilicates.

4) Agricultural solid wastes and industrial by-products such as date pits, fly ash or red mud.

5) Biosorbents such as chitosan, fungi or bacterial biomass.

Another simplified classification, introduced by Crini [22,32,34] , can be used as follows:

conventional and non-conventional adsorbents.

Figure 2.1 Conventional adsorbents for the removal of pollutants from wastewaters [22,32,34]

11
 Figure 2.2 Non-conventional adsorbents for the removal of pollutants from wastewaters [22,32,34]

2.3 Control Adsorbent Performance

In an adsorption-oriented process, separation is defined as a system that transforms a mixture of
substances into two or more products that differ from each other in composition. The process is
difficult to achieve because it is the opposite of mixing, a process favored by the second law of
thermodynamics. For many separation processes, the separation is caused by a mass separating
agent, the solid material or adsorbent [24,30,31]. Consequently, the performance of any
adsorptive separation or purification process is directly determined by its quality. So, the first
important step to an efficient adsorption process is the search for a solid material with high
capacity, selectivity, and rate of adsorption.
In principle, as adsorption is a surface phenomenon, any porous solid having a large surface area
may be an adsorbent [24] Other requirements to be taken into account in choosing a material are
based on the following criteria: low cost and readily available, suitable mechanical properties,
high physical strength (not disintegrating) in solution, a long life, able to be regenerated if
required, etc. The information from the writing show that the control of adsorption exhibitions of

12
a strong material in fluid stage adsorption relies upon the accompanying elements: (I) the source
and nature of the strong, for example, its physical structure (e.g. particle size, specific surface
area, porosity), chemical nature and functional groups (e.g. surface charge, pH at the point of
zero charge), and mechanical properties; (ii) the activation conditions of the raw solid (e.g.
physical treatment, chemical modification); (iii) the influence of process variables used in the
contacting system such as contact time, initial pollutant concentration, solid dosage and stirring
rate; (iv) the chemistry of the pollutant(s) (for instance, for a dye molecule, its pKa, polarity, size
and functional groups); and finally, (v) the solution conditions, referring to its pH, ionic strength,
temperature, presence of multi-pollutant or impurities, and its variability [22, 23,32,33]

2.4 Process Selection

2.4.1 Technologies for Removal of Phenolic Compounds

Among the unit operations in water and waste water treatment, adsorption technique remains
widely preferred due to its simplicity of design and operation. Other conventional processes for
removing phenolic compounds include extraction, steam distillation, bacterial and chemical
techniques, oxidation with ozone/hydrogen peroxide [35], ion-exchange [36], electrochemical
oxidation [37], reverse osmosis [38] and photo catalytic degradation [39].
The various disadvantages associated with those techniques are
1) Treated effluent quality not satisfactory
2) High cost of operation
3) Used of large amount of chemicals for oxidation processes, ion-exchange etc. becoming
source of secondary pollution
4) Difficulty in regeneration causing disposal problems.
In fact, there is no single process capable of adequate treatment, mainly due to the complex
nature of the effluents. Therefore, in practice, a combination of different processes is often used
to achieve the desired water quality in the most economical way.[30]

2.4.1.1 Biodegradation

Biodegradation involves the use of microorganisms, for example, microbes, yeasts, green growth
and parasites which can amass and corrupt diverse kind of pollutants. In any case, their

13
application is frequently limited on account of specialized limitations. Natural treatment requires
an enormous land zone and is obliged by affectability toward diurnal variety also harmfulness of
certain synthetic concoctions and adaptability in plan and operation. With current traditional
biodegradation forms, natural treatment is unequipped for acceptable phenol removal.

2.4.1.2 Chemical Method

Chemical methods for phenol reduction like coagulation, flocculation, precipitation-flocculation

with Fe (II)/Ca(OH)2, electro kinetic coagulation, ordinary oxidation by oxidizing operators are
regularly costly and despite the fact that phenols are expelled, collection of concentrated muck
makes a removal issue. Optional contamination issue may likewise emerge because of
unnecessary concoction use. Propelled oxidation process includes the utilized of exceptionally
ground-breaking oxidizing specialists, for example, hydroxyl radicals. In spite of the fact that
these techniques are proficient for the treatment of waters tainted with contaminations, they are
exorbitant and financially ugly.

2.4.1.3 Physical Methods

Physical methods like membrane-filtration filtration is likewise connected with the hindrance of
layer fouling and cost of occasional substitution must be remembered for any examination of
their financial reasonability. With inexhaustible writing information, fluid stage adsorption is one
of the most popular methods for the removal of pollutants from wastewater since proper design
of the adsorption process will produce a high quality treated effluent. It is an attractive
alternative for water treatment; especially if the adsorbent is inexpensive it does not require an
additional pre-treatment step before application.[30]

2.5 Adsorption Process

Adsorption is a process of separation during which the substances of a fluid, liquid or gas, bind
to the exterior and interior surfaces of a solid material called the adsorbent.
The separation is based on the selective adsorption (i.e. thermodynamic and/or kinetic
selectivity) of the contaminants by an adsorbent owing to specific interactions between the
surface of the adsorbent material and the adsorbed contaminants: simple mass transfer from the
liquid phase towards the solid phase [20].

14
This surface phenomenon is a manifestation of complicated interactions among the three
components involved, i.e. the adsorbent, the adsorbate and the wastewater (e.g. effluent,
synthetic solution or water).
Figure 2.2 shows a schematic adsorption model for the three components and their interactions.
Generally, in this ternary system, the affinity between the adsorbent and the adsorbate is the
main interaction force controlling adsorption [21-23]. However, the affinities between the
adsorbate and the solution, the adsorbent and the solution, and the contaminant molecules can
also play a major role in adsorption. In aqueous solution, hydrophobic compounds have low
solubility and tend to be pushed to the adsorbent surface. It is reasonable to expect that
adsorption capacity will be dependent upon the interaction forces between the three adsorption
components.

Figure 2.3 Schema depicting the relationships between the three components of an adsorption system [22]

2.6 Batch Process

When studying adsorption from solutions on materials it is convenient to differentiate between
adsorption from dilute solution and adsorption from binary and multicomponent mixtures
covering the entire range of mole fractions. To judge by the number of papers published annually
on adsorption from dilute (single) solution, this subject is more important than adsorption from
binary mixtures. It is also important to consider the modes of contacting the solid adsorbent and

15
the wastewater when applying the adsorption system to both industrial large scale treatments and
laboratory scale [24-26]. There are several types of contacting systems available to obtain
experimental data and for industrial applications, including batch methods, fixed-bed type
processes, pulsed beds, moving mat filters and fluidized beds. However, the two most frequently
used systems applied in solid/liquid adsorption processes are the batch-type contact and fixed-
bed type processes. Adsorption forms for cleaning of wastewaters can be completed either
irregularly in cluster reactors or persistently in fixed-bed reactors or columns. Batch methods are
also widely used because this technology is cheap and simple to work and, therefore frequently
preferred for little and medium size procedure applications utilizing straightforward and
promptly accessible blending tank hardware. Effortlessness, entrenched test techniques, and
effectively interpretable outcomes are a portion of the principle reasons every now and again
evoked for the broad utilization of these strategies. Another interesting advantage is the fact that,
in batch systems, the parameters of the solution/ effluent such as contact time, pH, strength ionic,
temperature, etc. can be controlled and/or adjusted. [26-29]

16
 CHAPTER THREE

EXPERMENTAL PART

17
3.1 Preparation of Standard Phenol 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
microgram /L The absorbance of the solutions was determined by UV-Visible spectrophotometer
between 200 and 750nm. The standard calibration curve is then plotted.
Table 3.1 Calibration curve for phenol solution

Conc.
Exp. no. Absorbance
microgram/ml

1 2 0.20

2 4 0.41

3 6 0.62

4 8 0.74

5 10 0.96

6 12 1.22

3.2 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 was dried for 5 hours
at 105 Co 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 impregnated with an acid solution. The activated shells were carbonized in an ashing
furnace at 500 Co for 60 min, and then used as the green adsorbent bed in the project.

18
 collect shell milled

walnut shell powder walnut shell ash

Figure 3.1 The prepared walnut shell and ash

3.2.1Characteristics of the Adsorbent

The adsorbent must have good mechanical properties such as strength and resistance to attrition
and it must have good kinetic properties, that is, it must be capable of transferring adsorbing
molecules rapidly to the adsorption sites. An adsorbent material must have a high internal
volume, which is accessible to the components being removed from the solvent. Surface area and
the distribution of area with respect to pore size are two very important factors in determining
extent of adsorption. The nature of the intra particle surface area markedly influences the types
of adsorption process.

Table 3.2 Characteristics of the prepared activated walnut shell ash.

Parameter Value

Bulk density (kg/m3) 792

C% 52.65

O% 32.22

19
 Si% 1.56

P% 0.97

Specific surface area (m2/g) 765

Average pore diameter (nm) 46.6

Porosity % 32.9

pH 3.3

Iodine no. (mg/g) 622

Ash content % 4.4

*The full characterization is supported by Iraqi South Oil Company, Nahran Omer Laboratories

Figure 3.2 The equipment and glassware used (a) Whatman no.1 filterpaper and Erlenmeyer flask
(b) Beaker and shaker (c) Graduated cylinder (d) Phenol (e) Funnels.

20
3.3 Batch adsorption Studies
3.3.1 Effect of Adsorbent Dose

Batch adsorption equilibrium experiments were carried out by contacting a known amount of
walnut shell ash 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 concentrations 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 Whatman 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 in table 3.3.

(3.1)

Where:

Co = the initial phenol concentration in solution (microgram phenol/ml);

Ce = the equilibrium phenol concentration in solution (microgram phenol/ml).

Table 3.3 Adsorbent dose versus % phenol removal

Exp. Adsorbent dose

% Removal
No. (g/100ml)

1 1 53.7

2 1.5 65.4

3 2 77.5

4 2.5 82.2

5 3 88.4

21
 6 4 88.1

7 5 88.5

3.3.2 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 Whatman no.1 filterpaper. The samples were analysed by U.V. spectrophotometer.
The percentage removal was calculated as percentage reduction in the absorbance, shown in
table 3.4.

Table 3.4 Contact time versus % phenol removal

Time (min) Removal %

1 25 35.3

2 50 51.3

3 75 65.6

4 100 77.8

5 125 88.4

6 150 88.4

7 200 88.5

22
3.4 U.V. Spectrophotometer
A (U.V. Spectrophotometer) measures the amount of light absorbed at each wavelength of the
U.V. and visible regions of the electromagnetic spectrum. In a standard U.V. Spectrophotometer,
a beam of light is split; one half of the beam (the sample beam) is directed through a transparent
cell containing a solution of the compound being analyzed; and one half (the reference beam) is
directed through an identical cell that does not contain the compound but contains the solvent.
U.V. Spectrophotometry is a powerful technique to obtain useful information about optical
properties of nanostructure and their size [72].

3.5 Adsorption Kinetics

The adsorption kinetics is the rate of adsorption of a fluid by the adsorbent in a time period. The
adsorption kinetics of a substance can be determined by measuring the change in the
concentration of the adsorbed agent, and analyzing the k value (slope), and plotting the data on
the graph. Many kinetic models describe the order reactions of the adsorption system based on
concentration and capacity of the adsorbent. This kinetic equation has three commonly used
types of reaction kinetics, which are zero, one and two reaction order kinetics [40].

3.5.1 Pseudo Zero Order

A reaction is said to have a zero order if the magnitude of the reaction rate is not affected by any
change in the concentration of the reactant. This means that any increase in reagent concentration
will not affect the magnitude of the reaction rate. The linear equation of the zero reaction order is
expressed by the following equation.
(3.2)
Where:
CAo = the initial phenol concentration in solution (microgram/ml);
CA = the equilibrium phenol concentration in solution (microgram/ml).
k = kinetics constant (min-1)
t = time (minutes)

23
3.5.2 Pseudo First Order

The first-order reaction is a reaction whose velocity depends only on one of the substances which
reactor is proportional to one of the forces of the reactant. The linear equation of one reaction
order is given by the following equation [40]:
(3.3)
Where:
CAo = the initial phenol concentration in solution (microgram/ml);
CA = the equilibrium phenol concentration in solution (microgram/ml).
k = kinetics constant (min-1)
t = time (minutes)

3.5.3 Pseudo Second Order

The second-order reaction is a reaction whose speed is directly proportional to the product of the
concentration of the two reactants or directly proportional to the square of the concentration of
one of its reactants. If the adsorption mechanism is a second order reaction in which the
adsorption rate is directly proportional to the two concentrations of followers. The rate of the
kinetics of a two order reaction can be expressed by the following equations [40]:

(3.4)

We defined parameters before.

3.6 Adsorption Isotherm

The aim of adsorption isotherm is to connect the concentration adsorbate in large quantities and
the amount adsorbed on the interface [41]. There are several isotherm equations available for
analysing experimental adsorption equilibrium parameters; the most common are Langmuir and
Freundlich models.

3.6.1 Langmuir Isotherm Model

The Langmuir isotherm model is based on the assumption that there are a limited number of
active sites distributed homogeneously through the surface of the adsorbent. This active site has

24
the same affinity for the adsorption of single-layer molecules and there is no interaction between
the adsorbed molecules [42]. The linear form of the Langmuir equation can be expressed as
follows

(3.5)

(3.6)

Where:
V = the volume of solution (100 ml);
W = the mass of walnut shell (g);
Ce = concentration of solute at equilibrium (microgram/ml).
qe = number of adsorbed solute per unit mass of adsorbent (µgram/g) at equilibrium.
qm = maximum adsorption capacity (µgram/g).
b = a constant related to the affinity of the binding sites (ml/mg).

3.6.2 Freundlich Isotherm Model

The Freundlich isotherm model applies to adsorption on heterogeneous surfaces by an interaction

between the adsorbed molecules, and not limited to the formation of a single layer (monolayer).
This model assumes that the concentration of adsorbate increases, the concentration of adsorbate
on the surface of the adsorbent also increases; the adsorption energy exponentially decreases at
the completion of adsorption [43]. The equation for the Freundlich model is as follows:

(3.7)

Where:
Kf = Freundlich constant
1/ n = Heterogenity factors related to capacity and intensity of adsorption.

25
 CHAPTER FOUR

RESULT AND DISCUSSION

26
4.1 Preparation of Standard Solutions & Absorbance Determination

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

Figure 4.1 Calibration curve for phenol solution

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

The concentration of the adsorbate in the residual solutions was subsequently analyzed UV-
Visible spectrum at the λmax values of 270 for phenol.

Figure 4.2 Typical UV-Visible spectrum for a phenol solution

27
4.2 Effect of Adsorbent Dose
Figure 4.3 shows the effect of adsorbent dosage on the adsorption capacity of walnut shell ash
for phenol uptake. It is obvious that by increasing the adsorbent dosage, the adsorption capacity
(qe, mg/g) decreased and the adsorption percentage increased as depicted in Figure 4.3. This
might be due to the fact that all active sites were entirely exposed at lower doses, while only a
fraction of the active sites were exposed at higher doses [55, 56]. Thus, a higher adsorbent
dosage may cause aggregation, which decreases the total surface area of adsorbent, leading to a
decrease in adsorption [57, 58]. And qe (that we found in isotherm section) is number of
adsorbed solute per unit mass of adsorbent (µgram/g) at equilibrium.

100 80
90 70
80
60
70
%Removal 50
% Removal

60
qe

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

Figure 4.3 Effect of adsorbent dosage on the adsorption of phenol by

walnut shell ash.

4.3 Effect of Contact Time

Gaining the equivalency period of attraction is required to define the numerous component
points of the isotherms and its kind. While adsorption is a surface process of converting of the
contaminants from a fluid bulk to solid surface. The period between phases can be defined as
limiting factor. The analysis composes to put in contact, a volume of 100ml of a solution of
phenol (2 to 10 microgram/ml) with different weight of walnut adsorbent ash (g/100ml) prepared
at the laboratory. The mixture is put in agitation at 200rpm and ambient temperature then we
follow the variations of the concentration of the liquid phase with the time. Results obtained for

28
our organic pollutant, which is the phenol are represented on the figure 4.4. According to the
figure represented we notice that equilibrium is practically reached at the end of 125 minutes.
The results obtained show the existence of two phases; the first rapid and the second slow one.
This relates to the great availability of the free active sites of the adsorbent at the beginning of
the experiment and which becomes weak as one advance in time.

100
90
80
phenol adsorption (%)

70
60
50
40
30
20
10
0
0 50 100 150 200 250

Contact time ( minute)

Figure 4.4 Adsorption percentage of phenol onto walnut shell ash vs. time

4.4 Adsorption Kinetics

The adsorption kinetics is the rate of adsorption of a fluid by the adsorbent in a time period. The
adsorption kinetics of a substance can be determined by measuring the change in the
concentration of the adsorbed agent, and analyzing the k value (slope), as we seen the
experimental data and the estimated parameters of kinetics study are listed in table (4.1) and
plotting the data on the graph.

Table 4.1 Kinetics Adsorption of walnut shell ash.

Exp, Time Pseudo Zero Order Pseudo First Order Pseudo Second
CAo
no. (min) (CA) (ln(CAo/CA)) Order (1/CA)

1 50 2 1.026 0.667479 0.974659

2 75 4 2.624 0.421594 0.381098

3 100 6 4.656 0.253603 0.214777

29
 4 125 8 7.072 0.123298 0.141403

5 150 10 8.82 0.125563 0.113379

6 200 12 10.62 0.122168 0.094162

4.4.1 Pseudo Zero Order

Based on Table 4.1, the rate of zero-order adsorption kinetics can be seen in Figure 4.5. The
graph shows the concentration value (C A) of the phenol in the wastewater versus the stirring time
is obtained zero-order kinetics rate based on equation (3.2). The optimum value of (R2)
approaches 0.9714.

12
10
y = 0.0674x - 2.0578
y=0.0674x − 2.0578 R² = 0.9714
8
CA

6
Comparison between them 4
x=t 2
So (K = −0.0674) 0
R² = 0.9714 0 50 100 150 200 250
time (min)
Figure 4.5 Pseudo-zero-order kinetics
For the adsorption of phenol onto walnut shell ash

4.4.2 Pseudo First Order

Based on Table 4.1, the rate of first-order adsorption kinetics can be seen in Figure 4.6. The
graph shows the value of (ln(CAo / CA)) versus stirring time. It obtains first order kinetics rate
based on equation (3.3). At the first-order, the value of R2 approaches 0.728.

30
 0.8
y = −0.0035x + 0.6928
0.7 y = -0.0035x + 0.6928
0.6 R² = 0.728
0.5
Comparison between them

ln(CAo/CA)
0.4
x=t 0.3
0.2
So (K = 0.0035)
0.1
R² = 0.728 0
-0.1 0 50 100 150 200 250
time (min)
Figure 4.6 Pseudo-first-order kinetics for the
adsorption of phenol onto walnut shell ash

4.4.3 Pseudo Second Order

Figure 4.7 shows the value of (1/C A) versus stirring time. The rate of second-order kinetics is
determined based on equation (3.4). In the second order, the value of R2 obtains 0.6184.

1.2
y = −0.0049x + 0.893 1
y − 0.893 = −0.0049x 0.8 y = -0.0049x + 0.893
R² = 0.6184
0.6
1/CA

0.4

0.2
Comparison between them 0
x=t 0 50 100 150 200 250
-0.2
time (min)
So (K = −0.0049)
Figure 4.7 Pseudo-second-order kinetics for
R² = 0.6184 the adsorption of phenol onto walnut shell ash

From Figure (4.5, 4.6, 4.7), kinetic adsorption rate in this research follows on the zero-order with
maximum R2. The adsorption of phenol onto walnut shell ash is greatly represented by the
pseudo-zero-order kinetics. The applicability of zero-order to the adsorption data of phenol onto
walnut shell ash indicates that the concentration of both adsorbent and phenol are not involved in
the rate determining step and the adsorption process may be chemisorption. Similar trends were
shown for the adsorption of methylene blue onto coconut‟s activated carbon [54]. So, the value
of adsorption constant (k) of this research is (-0.0674 min-1).

31
Because of (R2) from the figure (4.5) is the highest one so reaction is zero order and K value is
(K = − 0.0674)

Table 4.2 Comparison of Adsorption Rate Kinetics.

Kinetic order R2 K

Pseudo-zero-order 0.9796 − 0.0674

Pseudo-first-order 0.8744 0.0035

Pseudo-second-order 0.6925 − 0.0049

4.5 Adsorption Isotherm

To know the maximum capacity of phenol adsorption which can be absorbed by walnut shell ash
occurs by using the equation of Langmuir and Freundlich isotherms.

First we find (qe) for all the experimental.

(3.6)

Where:
V = the volume of solution (100 ml);
W = the mass of walnut shell (g);
Ce = concentration of solute at equilibrium (microgram/ml).
qe = number of adsorbed solute per unit mass of adsorbent (µgram/g) at equilibrium.
According for exp. No.1

qe=64.93333 µgram/g

We did the same for all experiment then tabulate data, As we seen the experimental data and the
estimated parameters of isotherm study are listed in table (4.3) and plotting the data on the graph.

32
Table 4.3 Isotherm Adsorption data.

Co Adsorbent Ce qeq
Time (Ce / qe) log (Ce) log qe
(min) (µgram/ml) (gr) (µgram/ml) (µgram/g)

50 2 1.5 1.026 64.93333 0.015801 0.011147 1.812468

75 4 2 2.624 68.8 0.03814 0.418964 1.837588

100 6 2.5 4.668 53.76 0.086607 0.668013 1.730459

125 8 3 7.072 30.93333 0.228621 0.849542 1.490427

150 10 4 8.82 29.5 0.298983 0.945469 1.469822

200 12 5 10.62 27.6 0.384783 1.026125 1.440909

The Langmuir isotherm equation based on equation (3.5) is performed to determine the
adsorption capacity as shown in table 4.4 using an adsorption isotherm curve prepared by
plotting the phenol concentration in equilibrium (Ce) versus the amount of the precipitated
phenol (Ce/qe). Langmuir's isotherm equation curve is shown in figure 4.8.

2 0.45
y = 0.0403x - 0.0586
1.8 0.4
R² = 0.9718
1.6 0.35
1.4 0.3
1.2 0.25
log(qe)

Ce/qe

1 0.2
y = -0.4231x + 1.9067
0.8 0.15
R² = 0.7812
0.6 0.1
0.4 0.05
0.2 0
0 -0.05 0 5 10 15
0 0.5 1 1.5
log(Ce) Ce
Figure 4.9 Freundlich Isotherm Adsorption Figure 4.8 Langmuir Isotherm Adsorption

Figure 4.9 is a Freundlich isotherm model for the adsorption of phenol wastewater using walnut
shell ash. The graph representing the linear plot of the (Log Ce versus Log qe) based on equation
(3.7). The value of KF and 1/n (Table 4.4) were determined from the intercept and the slope
respectively. Although, the value of R2 (0.7812) of Freundlich is slightly lower than the value of
R2 (0.9718) of Langmuir isotherm. Therefore, Freundlich model is still a good model to describe
the adsorption data. The results of Langmuir and Freundlich implies that the adsorption of

33
phenol onto walnut shell ash show a complex mechanism involving both monolayer and
heterogeneous surface condition. The value of (qm, b and R2) are presented in Table 4.4. The
high value of R2 as 0.9718 indicated minimal deviation from the fitted equation showing that the
adsorption data would follow Langmuir equation. The data in Table 4.4 indicated that the
maximum adsorption capacity (qm) of walnut shell ash for phenol was calculated as 24.814 mg/g.

Table 4.4 Isotherm Parameters for adsorption.

Freundlich isotherm model Langmuir isotherm model

KF 1/n R2 R2 qm b

80.67 −0.4231 0.7812 0.9718 24.814 − 0.688

34
 CHAPTER FIVE

EQUIPMENT DESIGN
AND
CONTROL PROCESS

35
5.1 Plant Layout

Figure 5.1 Plant layout of the batch adsorption

5.2 Equipment Design

5.2.1 Peristaltic Pumps

Peristaltic pumps, also known as tubing pumps, are a type of positive displacement pump. A
tubing pump can pump a variety of fluids and is a critical and reliable part of processes ranging
from chemical transfer to pharmaceutical processing to wastewater treatment. The peristaltic
pump features a unique design a drive system turns a set of rollers which compress and release
flexible tubing as they rotate. This squeezing action creates a vacuum that draws fluid through
the tubing. The flexible tubing is the only wetted part offering multiple advantages.

 Why Choose a Peristaltic Pump?

Fluid contacts only the flexible tubing; creating a contamination-free pump system that is easy to
clean and maintain. Peristaltic pumps are self-priming and non-siphoning, and handle peristaltic
and high viscosities.
Gentle, low-shear pumping action makes a tubing pump ideal for handling live cells, large
proteins, suspensions, and other shear-sensitive fluids. Our tubing pumps offer flow rates as low
as 0.00001 mL/min to 42 LPM and are able to generate pressures up to 10 bar (150 psi). We

36
carry over 20 tubing formulations to ensure compatibility with an extensive variety of fluids.
From low cost fixed speed pumps to advanced controlled models suitable for critical metering
and dispensing applications. [80]

Figure 5.2 Peristaltic pumps

5.2.2 Batch Adsorber 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.

(5.1)

Where:
qo = the sorption capacity of walnut shell at the start of the process (mg phenol on lg walnut shell
at time 0 (= 0 for fresh walnut shell);
qeq= the sorption capacity of phenol on adsorbent (microgram adsorbed phenol g−1 adsorbent) at
equilibrium
L = the volume of solution (dm3);
m = the mass of walnut shell (g);
Co = the initial phenol concentration in solution (mg phenol dm−3);

37
Ce = the equilibrium phenol concentration in solution (mg phenol dm−3).

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.

5.2.2.1 Design 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 [44-47].

38
A schematic diagram is shown in Fig. 5.3. 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. 5.3 can be written as

V (C0 −C1) =M (q0 −q1) =Mq1 (5.5)

Under equilibrium conditions,

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.

(5.6)

Figure 5.3 Single-stage batch-adsorber design

39
5.2.3 Chemical Regeneration

[48] 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 [49-51]. 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. However, the significant
advantages of chemical / solvent regeneration of adsorbent include [52]:
 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.

5.2.4 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. [53]

40
5.3 Control Process
5.3.1 Peristaltic Pump

Peristaltic pumps are commonly used to deliver larger amounts of liquid to a site where the
liquid is needed. A typical peristaltic pump (Figure 5.4 ) consists of a pump housing, a spinning
rotor driven by a motor/encoder, typically 3 or 4 rollers, and a flexible section of tubing. The
rollers compress the tubing while rotating thereby moving pockets of liquid from intake to outlet.
The advantage of peristaltic pumps is that only the tubing is in contact with the liquid. The
disadvantage is that the discrete pockets create an unsteady flow rate, resulting in difficulty
delivering small, precise volumes of liquid. In higher-end peristaltic pumps, a Brushless DC
(BLDC) motor with a quadrature encoder and Hall sensors is typically used. A BLDC
motor/encoder lends itself well for a more sophisticated controls approach as shall be discussed
in this paper.

Figure 5.4 Peristaltic Pump Control Schematic

41
Figure 5.5 through 4 illustrate several methods of controlling the pump motor in a peristaltic
pump. The simplest controller (Figure 5.5) applies a voltage to the motor without any form of
feedback. The motor speed will depend on the applied voltage. Clearly this control gives no
consideration the actual delivery velocity of liquid or the velocity of the motor as a result of the
tubing compression and will thus result in the largest flow variations. In addition, stopping the
pump is imprecise, resulting in an unpredictable amount of liquid being delivered. For large
volumes of liquid this may not matter since there are many pump rotations involved, but for
smaller volumes this effect becomes important. Figure 5.6 demonstrates a control mode wherein
encoder signals are fed back to a velocity control loop which is regulated by a velocity set point
and Hall signals are fed back to a current control loop. The velocity loop outputs a torque
command to a current loop (PI controller) and a Field Oriented Control (FOC) scheme which
generates a PWM signal as an input to the amplifier. When one of the rollers starts compressing
the tubing (or starts releasing it) the velocity changes and the torque delivered by the motor is
changed as well, resulting in a more even rotor rotation. Depending on how “stiff” the controller
is this will result in a fairly even velocity of the rotor and thus in even liquid delivery. Figure 5.7
is an enhanced version of the controller in Figure 5.6, wherein a flow compensation loop is
added to the control scheme. This result in a system wherein the increases and decreases in flow
from the rollers compressing the tubing is part of the feedback in the control system, thereby
making the system stiffer than the controller in Figure 5.6 that is not aware of the actual flow rate
changes.

Figure 5.5 Open loop voltage mode.

Figure 5.6 Velocity loop mode.

42
 Figure 5.7 Flow (and Velocity) Loop Mode

However, in such a system, the reaction speed of the flow sensor has to be faster than the actual
changes in flow. This can be accomplished with turbine-based sensors as well as non-contact
sensors such as ultrasonic sensors. This controller, by measuring the actual flow rate, gives a
more robust compensation mechanism particularly at low velocities.[80]

5.3.2 Batch Adsorber Control

Phenol adsorption processes investigated in this study were operated on both batch and fixed bed
basis. Batch experiments were conducted to evaluate the film transfer coefficient (kf) and the
solid phase diffusion coefficient (DS) on walnut shell ash of phenol at various temperatures.
Batch kinetic experiments were conducted in a rectangular vessel made of plexiglass. The
dimensions of the vessel were 34 cm x 30 cm x 36 cm which are L, B, and H, respectively. Wall
thickness was 0.68 cm. A steel impeller was located at the center of the vessel and 7 cm from the
bottom. A temperature-controller was used to regulate the temperature of the solution. The
schematic of experimental facilities are illustrated in Figure 5.8. The rate experiments were
normally conducted for duration of 50 to 200 minutes.[81]
A solution of 24 liters was prepared from tap water passed through a three carbon columns to
remove suspended and organic matter. The depth of each solution from the bottom was about
23.5 cm. In no experiments were crystals of solute directly introduced into the vessel. In all
cases, stock solutions with the desired concentration were made up. The impeller was maintained
at a speed of 200 rpm to agitate the solution to reach equilibrium within the vessel. A fixed
amount of solution was withdrawn to determine the initial concentration after the impeller ran
steadily. A predetermined amount of carbon was poured abruptly into the reaction vessel at
which moment the time started counting. Samples were withdrawn from the vessel with a pipet

43
to analyze concentration at selected time intervals. Particles with an average particle size of 0.38
mm were impregnated with an acid solution. The activated shells were carbonized in an ashing
furnace at 500 Co for 60 min, and then used as the green adsorbent bed in the project. The
weight of the walnut shell ash used was (1, 1.5, 2, 2.5, 3, 4, 5) gr/100ml. The solution was
preheated, if necessary, to the desired temperature. A temperature controller was used to keep the
temperature at a constant value. For a step change in temperature, solution was held constant in
the first hour followed by the use of a heater or dry ice for an increase or decrease in
temperature. To decrease temperature, approximate 1.5gr of dry ice was introduced into the
vessel, and it took 20 minutes to bring down the temperature from 35° to 25°C. For constant
temperatures, at temperature of 25°, was carried out for single solute studies and The temperature
at which an adsorption process is conducted will affect both the rate of adsorption and the extent
to which adsorption occurs. Adsorption rate parameters generally increase with increased
temperature and decrease with decreased temperature. The extent of adsorption will increase
with a decrease in the lower temperature and decrease with an increase in the higher temperature
due to being en exothermic nature of the adsorption reaction.[82]

Figure 5.8 Schematic of batch adsorption sydtem

44
 CHAPTER SIX

MATERIAL BALANCE
AND
ENERGY BALANCE

45
6.1 Matrial Balance
Material balance is the basis of the process that is needed to be designed. Martial balance is the
mathematical tool to determine the quantities of raw materials are required for producing a
targeted product. Balances and calculations the quantities to control the stream flow and
compositions, it will control the process conversation and increase the productivity and avoid
process problems or shutdowns. The general material balance equation can be written as;
Input + Generation –Output –Consumption = Accumulation

In case of study reactive state process (continuous process) , when there is no accumulation or
depletion of material , the general equation is written as ;
Input + Generation –Output –Consumption = 0

Input + Generation = Output +Consumption

If there is no chemical reaction, there is no means for a material to be generated or consumed ,

then the equation is written in the form of ;
Input – Output = Accumulation

46
6.1.1 Material Balance for Phenol based on Effect of Adsorbent dose

Table 6.1 Removal based on weight of adsorbent .

Initial conc. of phenol wt. of adsorbent

Exp. No. % removal
solution (microgram/ml) (bed) (g/100ml)

1 0.5 32.1

2 2 1 53.7

3 4 1.5 65.4

4 6 2 77.5

5 8 2.5 82.2

6 10 3 88.4

7 12 4 88.1

Assumptions:
 No chemical reaction
 No phenol loss
 No phenol consumption
 Steady state Material balance at constant time (50 minute)

In put − out put = phenol adsorbed

Basis: 100 ml phenol solution

According to exp. No.2 wt. of adsorbent (bed) =

Initial conc. of phenol solution= 2 microgram/ml

In put = 2 × 100ml = 200 microgram

Phenol adsorbed = 200 microgram × 0.537 (% removal) = 107.4 microgram (adsorbed)

47
In put − Phenol adsorbed = output

Output = 200 − 107.4= 92.6 microgram

According to exp. No.3 wt. of adsorbent (bed) =

Initial conc. of phenol solution= 4 microgram/ml

In put = 4 × 100ml = 400 microgram

Phenol adsorbed = 400 microgram * 0.654 (% removal) = 261.6 microgram (adsorbed)

In put − Phenol adsorbed = out put

Output = 400 − 261.6= 138.4 microgram

According to exp. No.4 wt. of adsorbent (bed) =

Initial conc. of phenol solution= 6 microgram/ml

In put = 6 × 100ml = 600 microgram

Phenol adsorbed = 600 microgram × 0.775 (% removal) = 465 microgram (adsorbed)

Mat. Balance for phenol

In put − Phenol adsorbed = out put

Output = 600 − 465= 135 microgram

According to exp. No.5 wt. of adsorbent (bed) =

Initial conc. of phenol solution= 8 microgram/ml

In put = 8 × 100ml = 800 microgram

48
Phenol adsorbed = 800 microgram × 0.822 (% removal) = 657.6 microgram (adsorbed)

Mat. Balance for phenol

In put − Phenol adsorbed = out put

Output = 800 − 657.6 = 142.4microgram

According to exp. No.6 wt. of adsorbent (bed) =

Initial conc. of phenol solution= 10 microgram/ml

In put = 10 × 100ml = 1000 microgram

Phenol adsorbed = 1000 microgram × 0.884 (% removal) = 884 microgram (adsorbed)

Mat. Balance for phenol

In put − Phenol adsorbed = out put

Output = 1000 − 884= 116 microgram

According to exp. No.7 wt. of adsorbent (bed) = Initial conc. of phenol

solution= 12 microgram/ml

In put = 12 × 100ml = 1200 microgram

Phenol adsorbed = 1200 microgram × 0.881 (% removal) = 1057.2 microgram (adsorbed)

Mat. Balance for phenol

In put − Phenol adsorbed = out put

Output = 1200 − 1057.2 = 142.8 microgram

49
Table 6.2 Result of material balance of phenol effect of adsorbent dose.

exp.
In put out put Phenol adsorbed
No. (microgram) (microgram) (microgram)

2. 200 92.6 107.4

3. 400 138.4 261.6

4. 600 135 465

5. 800 142.4 657.6

6. 1000 116 884

7. 1200 142.8 1057.2

6.1.2 Material Balance for Phenol based on Effect of Time

Table 6.3 Phenol removal based on Contact time.

Initial conc. of phenol solution Contact time ( minute) % removal

Exp. No.
(microgram/ml)

1 2 50 51.3

2 4 75 65.6

3 6 100 77.8

4 8 125 88.4

5 10 150 88.4

6 12 200 88.5

50
Assumptions:
 No chemical reaction
 No phenol loss
 No phenol consumption
 Unsteady state

In put − out put = phenol adsorbed

Basis: 100 ml phenol solution

According to exp. No.1 Time(at steady state) = 50 min

Initial conc. of phenol solution= 2 microgram/ml

Input = 2 × 100ml = 200 microgram

Phenol adsorbed = 200 microgram × 0.513 (% removal) = 102.6 microgram (adsorbed)

Input − Phenol adsorbed = output

Output = 200 – 102.6= 97.4 microgram

According to exp. No.2 Time = 75 min

Initial conc. of phenol solution= 4 microgram/ml

Input = 4 × 100ml = 400 microgram

Phenol adsorbed = 400 microgram * 0.656 (% removal) = 262.4 microgram (adsorbed)

Input − Phenol adsorbed = output

Output = 400 – 262.4= 137.6 microgram

According to exp. No.3 Time = 100 min

Initial conc. of phenol solution= 6 microgram/ml

51
Input = 6 × 100ml = 600 microgram

Phenol adsorbed = 600 microgram × 0.778 (% removal) = 466.8 microgram (adsorbed)

In put − Phenol adsorbed = output

Output = 600 – 466.8= 133.2 microgram

According to exp. No.4 Time = 125 min

Initial conc. of phenol solution= 8 microgram/ml

Input = 8 × 100ml = 800 microgram

Phenol adsorbed = 800 microgram × 0.884 (% removal) = 707.2 microgram (adsorbed)

Input − Phenol adsorbed = output

Output = 800 – 707.2 = 92.8 microgram

According to exp. No.5 Time = 150 min

Initial conc. of phenol solution= 10 microgram/ml

Input = 10 × 100ml = 1000 microgram

Phenol adsorbed = 1000 microgram × 0.884 (% removal) = 884 microgram (adsorbed)

Input − Phenol adsorbed = output

Output = 1000 − 884= 116 microgram

According to exp. No.6 Time = 200 min

Initial conc. of phenol solution= 12 microgram/ml

Input = 12 × 100ml = 1200 microgram

52
Phenol adsorbed = 1200 microgram × 0.885 (% removal) = 1062 microgram (adsorbed)

In put − Phenol adsorbed = output

Output = 1200 − 1062 = 138 microgram

Table 6.4 Result of material balance of phenol effect of content time

exp.
In put out put Phenol adsorbed Volume Ce
No. (microgram) (microgram) (microgram) (ml) (µgram/ml)

1. 200 97.4 102.6 100 1.026

2. 400 137.6 262.4 100 2.624

3. 600 133.2 466.8 100 4.668

4. 800 92.8 707.2 100 7.072

5. 1000 116 884 100 8.84

6. 1200 138 1062 100 10.62

6.2 Energy balance

6.2.1 Isothermal

Heat transfer resistance can be neglected. The Isothermal option ignores the energy balance.
Fluid and solid temperatures are set to the same, constant value. The separating of the
concentration front is due entirely to axial dispersion and mass transfer resistance [83].

53
 CHAPTER SEVEN

COST ESTIMATION

54
7.1 Cost Estimation
Despite the success of the adsorption process in the removal of phenol pollutants, there is a lack
of studies that dealt with the economic aspects. In this section, real aqueous solution samples
were collected from at Erbil City, Kurdistan. The company produced a daily discharge of 100 m3
containing phenol concentration of 150 ± 50 microgram L-1. Batch tests were conducted based
on the optimum environmental condition of pH: 7, and adsorbent dosage: 21 g L-1, as obtained
previously. The contact time was selected as 125 min because the design criteria of a large-scale
treatment facility entail shorter contact time, which can decrease the sizing of units. The total
cost of the adsorption process (TC) was estimated by considering the amortization cost of the
investment (AC) and operating cost (OC);

TC = AC + OC (7.1)

7.1.1 Amortization Cost of investment (AC)

The AC was assumed as the sum of the installation (construction) items and the required
mechanical and electrical facilities [59]. The total treated volume describes the number of
batches conducted for a particular working duration. Hence, the treatment unit capacity (V c, in
m3) can be computed based on the ratio of the working hours per day (t w: assuming 8 h d-1) to the
treatment time in each batch (t t: assuming 125 min), as seen in Eq. (7.2).

Vt t
Vc   t
D tw (7.2)

Where:

Vc: treatment unit capacity (m3).

Vt: the total treated volume on a yearly basis (assuming 30000 m3 yr-1).

D: the number of operating days (i.e., 300 d yr -1).

tw: working hours per day (h d-1).

tt: treatment time in each batch (min).

55
The amortization of investment per m3 of wastewater was calculated by Eq. (7.3) [60].

C p  Vc
AC 
L  Vt (7.3)

Where:

Cp: the cost per cubic meter of the treatment unit (i.e., assumed as 10000 $ m-3 based on quotes
from local contractors).

L: the lifecycle of the adsorption unit (assuming 10 yr).

The AC per year (ACannual) was estimated by Eq. (7.4).

 1  i L i 
AC annual  AC  

 1  i   1 
L
(7.4)

Where

i: annual interest rate (assuming of 4%).

Based on the yearly wastewater discharge of 30000 m3, the units volume could be approximately
10 m3 resulting in AC of 0.34 $ m-3. This value was equivalent to 29% of the TC.

7.1.2 Operating Cost (OC)

The OC included the adsorbent material with a lifespan of 2 yr, water and chemicals supply, and
energy consumption. The labour expenses were not involved in this study for simplification
because the adsorption process does not require intensive manpower.

The costs of adsorbent and utilized chemicals, namely (Creactant), were calculated from the dosage
(Ci in kg m-3) multiplied by the unit price (Pi in $ kg-1). Based on a cost survey from local

56
suppliers and administrative databases in the period of 2014–2018, the Pi of CAC material
(including the collection of raw material, cleaning, and activation) and chemicals were 0.6–0.7
and 0.40–0.45 $ kg-1, respectively.

The energy cost (EC, in $ m-3) was calculated by Eq. (7.5), based on the power required for
pump, regeneration, batch adsorber, and equipment operation.

E  PE  t w  D
EC 
Vt (7.5)

where,

E: is the consumed power (kW).

PE: is the unit price of power energy (i.e., 0.24 $ kWh-1).

Maintenance cost was assumed as 2% of the AC [31]. Hence, the total operating cost

including consumed materials, power, and maintenance was calculated by Eq. (7.6)

2
OC  Creac tan t  EC  AC (7.6)
100

Results showed that the reagent cost was Creactant = 0.70 $ m-3, corresponding to 59.2% of TC. In
addition, the reactant cost was higher than the energy cost and the resulting OC was 0.84 $ m -3.
Similarly, Alalm et al. [60] found that the variation of OC was mainly depended on the dosage
and type of chemicals in a fixed bed adsorber employed for the treatment of pesticides industry
wastewater. Thus, the total cost including amortization and operating costs was estimated as 1.18
$ m-3. In addition, the phenol concentration in the treated effluent was not detected, suggesting a
removal efficiency of approximately 89%. This result indicated that WS ash could be used as a
low-cost and efficient material for the adsorption of phenol. However, further studies should be
conducted using a large-scale application for the adsorption process under a continuous mode of
operation; i.e., and that will be the focus of our future work.
57
 CHAPTER EIGHT

ENVIRONMENT ASPECTS

58
8.1 Environmental Pollution
The result of deteriorating environmental situation in various countries and regions where
environmental pollution is the most intense climate is warming, ozone layer is depleting,
desertification. According to the definition adopted by the UN organization, “pollution are
exogenous chemical substances encountered on a suitable place
The impact of economic and other activities on the environment may be different in character:
direct (immediate) and indirect synergy. From the are usually described in terms of which we
have already pointed out: degradation, devastation, endangering the environment, in different
time periods. It is possible to perceive the effects of pollution in air, water, soil, wildlife, human
health, and so on. We can speak of long-termed and short-termed effects of pollution. It can be
very important to understand the concept of the working environment, if it is connected with the
concept of environmental protection in the context of discussions on environmental management.
This can be done for many reasons. First, because of the connection of the working environment
as part of the environment, there are connections and processes related to the operation and are
of importance to the issue of the environment. There are several provisions in the law on safety
and health at work and other regulations governing this area, which are directly relevant to the
understanding of the relationship between the working environment and the environment. It is
necessary to know not only the notion of working environment but also to bear in mind the
definition of a number of other terms such as “hazardous materials”, “danger”, “dangerous
phenomenon”, “risk”, “risk assessment”, and so on. According to this law work environment
defines the working environment in which the work is performed under specific operating
conditions in the workplace, working procedures and relationships in the work process.
Unfavorable changes in the environment caused by human activities, causing a change in the
inflow of energy, radiation levels physico-chemical and microbiological composition of
environmental pollution can be defined. The harmful effect of pollution, their effect is
manifested in the anatomical and morphological structure, metabolism, growth process, at all
levels of cellular organization, from the molecular to the cellular level, through individual and
population to biocenosis and ecosystems.[79]

59
8.2 Effect Phenol of Environmental
Pollution of environment is one of the main problems facing humans today. Recently, the
problem of environmental pollution has increased exponentially and reached worrying level in
terms of its impact on the life of human beings. Among the contaminants that have harmful
effects in animals and humans are considered the toxic organic compounds. As mentioned
earlier, dissolved phenolic compounds that are present in industrial wastewater cause pollution of
groundwater and owing to its harmful effect these compounds generate a serious problem in this
type of water resources. Exposure to this type of chemical reagents, once they enter into human
body can cause damage to the nervous and respiratory systems, kidney and blood system.
Phenolic compounds have been classified as the top 45th in the list of priority hazardous
substances by the Agency for Toxic substances and Disease Registry, USA, which require
immediate treatment before disposal in the environment [61]. Consequently, removing organic
compounds or reducing their concentrations to the permitted levels by environmental standards
represents a big challenge.

Phenolic compounds are priority contaminants with high toxicity even at low concentrations.
These compounds are present in industrial effluents, where increase biochemical and chemical
oxygen demands resulting in detrimental effects on the environment. Some of them are highly
toxic as well as carcinogenic and can remain in the environment for a long time due to their
stability and bioaccumulation. Owing to the high toxicity of phenolic compounds, treatment of
the organic wastewater has an important effect on the lives of human beings [62].

Many phenolic compounds can be removed efficiently by conventional treatments such as

extraction, distillation, chemical oxidation, electrochemical oxidation and adsorption among
others. On the other hand, some advanced treatments use less chemical reagents compared to the
conventional processes, but they have the disadvantage of having high energy costs. Within the
advanced treatments are as follows: Fenton, ozonation, wet air oxidation and photochemical
method. Biological treatments have certain advantages compared to physicochemical treatments;
among these advantages may be mentioned: environmentally friendly and energy saves.
However, it has the disadvantage that cannot treat high concentration of contaminants. One of
the best ways to treat phenolic compounds under mild conditions is the enzymatic treatment,
which uses different enzymes such as peroxidases, laccases and tyrosinases [67]. Thus, there is a

60
need to treat waste contaminated with phenolic compounds before discharge. The adsorption
method is used in this project

8.3 Effect Phenol of Health

Phenol has acute and chronic effects on human health. Inhalation and dermal exposure to phenol
is highly irritating to skin, eyes, and mucous. These invers effects also known as acute (less than
14 days-exposure) effects of phenol. The other acute health effects are headache, dizziness,
fatigue, fainting, weakness, nausea, vomiting and lack of appetite at high levels. Effects from
chronic exposure (longer than 365 days) include irritation of the gastrointestinal tract. Phenol
also can change blood pressure and can cause liver and kidney damage. Nervous system is
affected negatively for long time exposures (EPA, 2002). Environmental Protection Agency
(EPA) has classified phenol as a Group D, not classifiable as to human carcinogenicity. Animal
studies have not shown tumors resulting from oral exposure to phenol, while dermal studies have
reported that phenol applied to the skin may be a tumor promotor and/or a weak skin carcinogen
in mice.[69]

8.4 The Role of Adsorption on Environment

Adsorption method for removal of phenols from water is effective from low concentrations to
high concentrations, depending on the economics and recycling the required secondary material,
adsorbent. Activated carbon (AC) is the most used in industry as adsorbent. Various proposals
have been designed with the aim of controlling, reducing and in some cases, eliminate pollutants,
so check these environmental problems, which have caused this part of chemistry. It is organized
in several sub-areas within which it is worth mentioning green chemistry, area that aims to
synthesize and prepare chemical type substances not only to achieve a healthy environment by
removing pollutants with direct or indirect deleterious effects on humanity or at least minimize
them, but that will decrease the existing pollution. For the control of pollutants, a broad type of
materials has been synthesized and prepared. Materials such as catalysts[73], carbon foams,
activated carbon cloth [74]. Clays pillared clays, foams ceramics, zeolites [75], aerogels,

61
xerogels [76], among other special materials, have been used to reduce and control the
environmental pollution generated by the chemical industry [77]. Within these solids, which
have been the most used are the activated carbons due to their chemical and textural features,
including: large surface area, volumes and diameters of pores controllable through the process of
preparation, as well as its surface chemistry. The adsorption is one of the processes that is using
to design experiments that subsequently, according to the results, can be scaling to an industrial
level. Physical chemistry is a phenomenon that offers good results for the elimination of a wide
variety of pollutants and offers significant advantages over other types of techniques used for the
control of the environment such as high removal of the treated effluent, low cost of operation and
low sensitivity to the toxic. These adsorption processes with activated carbon have a great
advantage over other conventional treatment systems such as phytoremediation, electrochemical
treatment, microbial isolates, coagulation flocculation, biosorption, among others and it is the
regeneration of the material to be used again in the same system for several more cycles,
minimizing in this way the environmental impact that the activated carbon can have once used
and giving the possibility to recover also the retained pollutants and reintroduce them in the same
productive processes [78,84].

62
8.5 Conclusions
The conclusion could be withdrawn from the results of the work in current project are:

1. The experimental results demonstrated that walnut shell ash shows good capability for
removal of phenol from aqueous solutions.

2. The adsorption rate increases by increasing the amount of the adsorbent due to increasing the
contact surface area.

3. At higher concentrations of phenol, a decrease in adsorption rate was observed. The optimum
adsorption capacity of 24.814 mg/g is obtained when applying 3 g walnut shell ash for removal
of phenol from 100 mL of solution containing 8 microgram/ml of phenol with duration of 125
minutes.

4. It was observed that, walnut shell ash is capable of removing more than 88.4% of the phenol
from aqueous solutions with initial concentrations of phenol between 2 to 12 microgram/ml.

5. The adsorption isotherms results show that Langmuir model is more appropriate for the
equilibrium modelling of adsorption process compared to the Freundlich model.

6. The adsorption rate driving force of phenol seemed to follow Zero-order kinetics which
provides information about phenol uptake rate and time required for adsorption process.

8.6 Future Perspectives

1. Studying the effect of pH, particle size of the ash and temperature on adsorption process.

2. Studying the adsorption process using other green adsorbents.

3. Studying the adsorbent regeneration using different chemicals.

63
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