ADSORPTIVE REMOVAL OF SODIUM DICLOFENAC

USING HYDROTHERMALLY PREPARED

ACTIVATED CARBON IMPREGNATED WITH ZnO

A PROJECT REPORT

Submitted by

BHUVANESHWARI G (181003012)
HRISHITHA SREE S (181003019)

in partial fulfilment for the award of the degree of

BACHELOR OF TECHNOLOGY
in
CHEMICAL ENGINEERING

Department of Chemical Engineering

Sri Sivasubramaniya Nadar College of Engineering
(An Autonomous Institution, Affiliated to Anna University)
Rajiv Gandhi Salai (OMR), Kalavakkam – 603 110

MAY 2022
 iii

ABSTRACT

The study of diclofenac sodium adsorption on an activated carbon

impregnated with ZnO surface was evaluated under various

circumstances which included adsorbent dose, initial concentration,

contact time and pH. X-ray diffractometer (XRD), Fourier-

transform infrared spectroscopy (FTIR) spectroscopy, scanning

electron microscope (SEM), and nitrogen physisorption

spectroscopy (BET) were used to evaluate AC/ZnO prepared in this

study. The adsorbent dosage ranged from 0.01g/L to 0.1 g/L at

25°C, and the initial diclofenac concentration was measured

between 50 mg/L to 250 mg/L and their effects were noted. . With

starting DS concentrations of 30 and 50 mg/L and a constant

adsorbent dose of 0.04 g/L , the contact time impact from 0 to 120

minutes was examined. pH values were altered from 2 to 12 to test

the pH impact. Besides, kinetic studies, thermodynamic studies and

adsorption isotherm models, carried out in this study are also

included. For diclofenac sodium adsorption on activated carbon, the

Freundlich isotherm model was shown to be the most accurate. For

sodium diclofenac adsorption on AC/ZnO, pseudo-first and pseudo-

 iv

second order models were used, with correlation coefficient values

of 0.932 indicating that the pseudo-second order model suited the

adsorption well. Kinetic studies revealed that this adsorption

proceeded quite quickly. Finally, the AC/ZnO composite retained

good adsorption characteristics after four consecutive cycles, with

removal efficiency exceeding 65% implying AC/ZnO is a cost

efficient and effective adsorbent for sodium diclofenac adsorption.

The results provided sufficient evidence to support AC/ZnO as a

promising adsorbent for removal of diclofenac in aqueous solution.

 v

ACKNOWLEDGEMENT

With deep sense of gratitude, I would like to express my sincere thanks

to Dr. Shiv Nadar, Founder of SSN Institutions for his valuable guidance

and blessings. I would like to express my sincere thanks to our

benevolent principal Dr. V.E. Annamalai, Principal of SSN College of

Engineering, and the management for providing support to carry out the

project successfully.

I would like to express my gratitude to Dr. K Sathish Kumar, Professor

and Head, Department Of Chemical Engineering, for his support and

guidance.

I owe my sincere thanks and regards to my project supervisor

Dr. Kilaru Harsha Vardhan, for his complete support, guidance and

encouragement throughout the project work. I express my thanks to all

the Project Review Committee members, for their timely advice. Finally,

I take this opportunity express our heartfelt gratitude to my family and

everyone who was a part of our project for everything they meant to us

during the critical time of project completion. I am honoured to

acknowledge the above-mentioned people who were instrumental in the

completion of the project.

BHUVANESHWARI G HRISHITHA SREE S

 vi

TABLE OF CONTENTS

CHAPTER TITLE PAGE

NO. NO.
ABSTRACT iii
LIST OF TABLES x
LIST OF FIGURES xi
LIST OF ABBREVIATIONS xiii

1 INTRODUCTION 1
1.1 Diclofenac sodium as an emerging contaminant 1
1.2 Adsorbent used for the removal of DCF 3
1.3 Hydrothermal Carbonization (HTC) 4
1.4 Schematic of the research 5

2 REVIEW OF LITERATURE 6
2.1 Adsorptive removal of diclofenac sodium from 6
aqueous solution onto sycamore ball activated
carbon – isotherms, kinetics, and
thermodynamic study

2.2 Efficient adsorption of diclofenac sodium from 6

aqueous solutions using magnetic amine-
functionalized chitosan

2.3 Diclofenac removal from water by adsorption 7

 vii

using activated carbon in batch mode and fixed-

bed column: isotherms, thermodynamic study
and breakthrough curves modelling

2.4 Removal of emerging contaminants from the 7

environment by adsorption

2.5 Superior adsorptive removal of eco-toxic drug 8

diclofenac sodium by Zn–AlLDH⋅xBi2O3 layer
double hydroxide composites

2.6 Adsorptive removal of diclofenac by graphene 8

oxide: Optimization, equilibrium, kinetic and
thermodynamic studies

2.7 Computational and experimental studies on the 8

efficient removal of diclofenac from water using
Zn Fe-layered double hydroxide as an
environmentally benign absorbent

2.8 Effect of ZnO loading to activated carbon on 9

Pb(II) adsorption from aqueous solution

2.9 Agro waste derived bio chars impregnated with 9

ZnO for removal of arsenic and lead in water
 viii

2.10 Enhanced adsorptive removal of 10

sulfamethoxazole from water using biochar
derived from hydrothermal carbonization of
sugarcane bagasse

3 AIM AND OBJECTIVE 11

3.1 Aim of the project 11
3.2 Objectives 11

4 METHODOLOGY 12
4.1 Chemicals and Reagents 13
4.2 Preparation of adsorbent (HTC-AC / ZnO) 13
4.2.1 HTC-AC Preparation 13
4.2.2 Zinc Oxide (ZnO) preparation 14
4.2.3 HTC-AC/ZnO preparation 16
4.3 Characterisation Studies 17
4.4 Adsorption experiment 18
4.5 Adsorption isotherm 19
4.6 Kinetic Mechanisms 21

5 RESULTS AND DISCUSSION 22

5.1 Characterization of Adsorbent 22
5.1.1 FTIR Spectrum analysis 22
5.1.2 SEM/EDAX analysis 24
5.1.3 Nitrogen Physisorption (BET analysis) 28
5.1.4 XRD analysis 30
 ix

5.2 Adsorption influencing parameters on DCF 33

removal
5.2.1 Effect of adsorbent dosage 33
5.2.2 Effect of initial concentration 34
5.2.3 Effect of contact time 35
5.2.4 Effect of pH 36
5.3 Adsorption isotherm modelling 38
5.4 Adsorption Kinetics modelling 40
5.5 Regeneration Capacity of the adsorbent 43

6 DESIGN OF EQUIPMENT 44
6.1 Design of Decanter 45
6.2 Design of Adsorption column 52

7 CONCLUSION 57

REFERENCES 58
 x

LIST OF TABLES

TABLE TITLE PAGE

NO. NO.

1.1 Characteristics of Diclofenac Sodium 2

4.1 Isotherm models and non-linear equations 19

4.2 Adsorption Kinetics and non-linear 21

equations
5.1 FTIR analysis data 25

5.2 Nitrogen Physisorption analysis Data 29

5.3 Isotherm models and parameters 40

5.4 Kinetic models and parameters 42

6.1 Data of contaminants in effluent water 44

6.2 Summary of decanter Parameters 51

6.3 Summary of Adsorption Column Parameters 55

 xi

LIST OF FIGURES

FIGURE TITLE PAGE

NO. NO.

4.1 Flow of process 12

4.2 Hydro-char obtained from HTC 14
4.3 Zn (OH)2 prepared by co-precipitation 15
4.4 ZnO nano particles 16
4.5 Sonication of HTC-AC and ZnO 17
5.1 FTIR Spectrum for HTC-AC/ZnO 23
5.2.a) SEM- morphology for HTC – AC/ZnO 27

5.2.b) SEM- morphology for HTC – AC/ZnO 27

5.3 BET analysis - p/Po Vs Vads 29
5.4 Pore size distribution 30
5.5 XRD analysis data of HTC – AC 31
5.6 XRD analysis data of ZnO 32
5.7 XRD analysis data of HTC-AC/ZnO 33
5.8 Effect of adsorbent dosage 34
5.9 Effect of initial concentration 35
5.10 Effect of contact time 36
5.11 Effect of pH 37
5.12 Adsorption Isotherm fitting 39
5.13 Adsorption Kinetics fitting 42
 xii

6.1 Flow of process in waste water treatment 44

plant followed by adsorption

6.2 Schematic representation of Decanter 45

6.3 Flow of process in adsorption column 53
 xiii

LIST OF ABBREVIATIONS

ABBREVIATION FULL FORM

DCF Diclofenac

DCF-Na Diclofenac sodium

HTC Hydro-Thermal Carbonization

AC Activated Carbon

Zn(OH)2 Zinc hydroxide

ZnO Zinc Oxide

Zn(NO3)2 Zinc Nitrate

NaOH Sodium hydroxide

FTIR Fourier Transform Infra-Red

spectroscopy

XRD X-Ray Diffraction

BET Brunauer–Emmett–Teller

SEM Scanning Electron Microscope

EDAX Energy Dispersive X-Ray

HMF Hydroxymethylfurfural

JCPDS Joint Committee on Powder Diffraction

Standards

ICDD International Centre for Diffraction Data

UV Ultra Violet
 1

CHAPTER 1

INTRODUCTION

1.1. Diclofenac sodium as an emerging contaminant

Emerging contaminants are unregulated compounds even in the

most developed countries, and that can be hazardous to the surroundings and
human health (Esplugas et al., 2007). It includes compounds such as
pharmaceuticals and personal care products, plasticizers, food additives,
wood preservatives, laundry detergents, surfactants, disinfectants, flame
retardants, pesticides, natural and synthetic hormones (La Farré et al., 2008).
Among these compounds, the most commonly detected heterocyclic
aromatic product is the pharmaceutical contaminants. These pharmaceutical
contaminants are found in low concentrations in water and wastewater
treatment plants (i.e., ppb to ppm level). The main sources of
pharmaceutical wastes are effluents from pharmaceutical industries,
hospitals and municipal areas. The presence of pharmaceutical pollutants in
the environment can potentially destroy the aquatic ecosystem and endanger
human health. Hence, it is necessary to develop effective methods to
regulate their concentration in the environment (Al Aukidy M et al., 2012).
 2

Most commonly detected pharmaceutical contaminant is a Non-Steroidal

Anti-Inflammatory Drug (NSAID). These drugs are extensively used to
relieve inflammation and reduce pain caused by arthritis, migraine, gout and
other illnesses (Acuña V et al., 2015). Sodium Diclofenac is the most
commonly used NSAID and analgesic compound which is used to relieve
pain, reduce swelling and ease inflammation in conditions affecting the
joints, muscles and tendons. The characteristics of Diclofenac sodium is
listed in Table 1.1

Table 1.1 Characteristics of Diclofenac Sodium

PARAMETER CHARACTER/VALUE
Commercial Name Diclofenac Sodium, Voltaren,
Chemical Name 2-[(2,6-Dichlorophenyl)
amino] benzene- acetic acid
sodium salt
Odour/Colour/Nature Odourless/ White or Off-
white/Crystalline
Structure

Molecular Formula C14H10Cl2NNaO2

Molecular Weight 318.31 g mol-1
Solubility 50 mg mL-1 at 20°C
 3

However, diclofenac is not fully metabolized upon consumption,

and approximately 15% of the active compound is excreted and eventually
released to the environment due to incomplete removal by existing sewage
treatment plants. Hence, it has been detected in drinking and ground waters.
Presence of diclofenac in water leads to destruction of metabolic pathways
in microorganisms that are found in water and soil, destruction of entry of
sunlight into the water, damage to endocrine glands that are found in marine
organisms and terrestrial living bodies. Excessive consumption of
diclofenac leads to development of resistance within the host organisms.

There are many methods for the removal of diclofenac from

water, such as chemical oxidation, biodegradation, photo-degradation, Nano
filtration, reverse osmosis, and adsorption, but most of these methods are
accompanied by disadvantages such as energy consumption, formation of
toxic by-products. Among these techniques, adsorption is considered to be
simple, cheap, rapid, easy to operate, and an efficient method without any
generation of toxic by-products.

1.2. Adsorbent for the removal of DCF

Many adsorbents have been reported, such as carbon nanotubes,

activated carbon, metal organic frameworks, metal and metal oxides, Nano
composites, polymeric Nano-composites, microalgae strains, pyrite, clay
mineral, and resin. Carbon-based adsorbents such as Activated Carbon (AC)
from waste biomass were used to remove diclofenac. Among the most
 4

effective adsorbents, activated carbon has been widely used due to its
greater abundance large permeability, high pore volume, well-developed
internal porous structure, abundance of surface functional groups (polar
characteristics). ACs are efficient adsorbents for the elimination of various
organic pollutants in water treatment. The demand for activated carbon is
anticipated to increase due to the growing of strict regulations regarding the
maintenance of air quality and due to the increasing number of municipal
and industrial wastewater treatment plants. Activated carbon impregnated
with metal/metal oxides is proved to have a high adsorption capacity with
respect to high surface area. It is relatively cheap and is easily regenerated.

1.3. Hydrothermal carbonization

The current research focuses on fabrication of activated carbon

using a novel technology called Hydrothermal Carbonization (HTC). HTC
is called thermochemical conversion of waste biomass at normal
temperature and atomised pressure. Biochar developed using this procedure
has numerous amounts of oxygenated functional groups that assist in
holding the incoming pollutants. Additionally, pre-treatment of biomass is
not necessary, hence energy consumption would be limited in HTC. But
prolonged treatment of biomass in HTC may increase its energy requirement
but yield gained in this process would be comparatively high than other
processes (Zhou et al., 2017).
 5

Further it has other advantages like HTC operates in the water at

low temperature involving thermochemical conversion and the material
derived from HTC has uniform chemical and structural properties. One
limitation that should be noted is that material derived from HTC has very
less porosity unless and until it is subjected to additional heat treatment at
high temperature (Li and Shahabzi, 2015). Some of the waste biomass that
were reported are: sugarcane bagasse, rice husk, coconut shell, barley, wood
chips, sewage sludge, algae and bamboo waste.

1.4. Schematic of the research

This research primarily focuses on development of cost-effective

generation of carbon from bamboo waste using HTC. Secondly, HTC
derived carbon was impregnated with ZnO prepared using a sono-chemical
process. Thirdly, HTC derived AC/ZnO was tested in the laboratory as an
effective adsorbent in removing Diclofenac from water at optimised
condition. ZnO impregnation improved the microstructure of the AC and
increases the active sites to improve adsorption of toxic elements.
 6

CHAPTER 2

REVIEW OF LITERATURE

2.1 Adsorptive removal of diclofenac sodium from aqueous

solution onto sycamore ball activated carbon – isotherms, kinetics, and
thermodynamic study (Tarık Avcu. et al., 2021)

Adsorption of diclofenac sodium on a sycamore ball activated

carbon surface. At constant adsorption dosage content, the adsorption
temperature was found. The pH effect, kinetic and thermodynamics were
examined the study, was found to be exothermic, spontaneous, and feasible.
The results confirmed that sycamore ball activated carbon is an
economically suitable and effective adsorbent for sodium diclofenac
adsorption.

2.2 Efficient adsorption of diclofenac sodium from aqueous

solutions using magnetic amine-functionalized chitosan (Xue Xu Liang.
et al., 2018).

Preparation of a magnetic composite based on amine-

functionalized chitosan (AmCS) and Fe3O4 to remove diclofenac sodium.
 7

The fabricated AmCS_Fe3O4 composite was characterized. The composite

retained good adsorption characteristics after four consecutive cycles,
removal efficiency exceeding 70%

2.3 Diclofenac removal from water by adsorption using activated

carbon in batch mode and fixed-bed column: isotherms,
thermodynamic study and breakthrough curves modelling (De Franco.
et al., 2018)

This research focus on detection of emerging contaminants in

aquatic environment. Thermodynamic parameters evaluate the orientation
and feasibility of the adsorptive reaction diclofenac adsorption onto an
activated carbon batch. Studies revealed that the Freundlich equation is
suitable to describe the isotherms behaviour.

2.4 Removal of emerging contaminants from the environment by

adsorption (Carmalin Sophia A. et al., 2018)

Application of different adsorbents such as, activated carbons,

modified biochars, Nano adsorbents, composite adsorbents, and others are
being used for EC's removal from water and wastewater.
 8

2.5 Superior adsorptive removal of eco-toxic drug diclofenac

sodium by Zn–AlLDH⋅xBi2O3 layer double hydroxide composites
(Pooja Kumari et al., 2021)

Efficient removal of eco-toxic pollutant diclofenac sodium from

wastewater. low adsorption capacity, high cost of conventional adsorbents
limits their utility. Therefore, Bi2O3 loaded Zn–Al layered double hydroxide
heterostructures have been investigated as a potential adsorbent for DCF
removal. Due to high adsorption capacities, low cost and easy DCF removal
process, the materials could act as efficient adsorbents for removal of DCF
and other pollutants from wastewater.

2.6 Adsorptive removal of diclofenac by graphene oxide:

Optimization, equilibrium, kinetic and thermodynamic studies (Billie
Yan Zhang Hiew et al., 2018)

Research investigated the adsorption of diclofenac using

graphene oxide GO and its characterization. The diclofenac uptake by GO
was consistent with the Langmuir adsorption and pseudo-second-order
kinetic models. The results provided sufficient evidence to support GO as a
promising adsorbent for removal of diclofenac in aqueous solution.

2.7 Computational and experimental studies on the efficient

removal of diclofenac from water using Zn Fe-layered double
hydroxide as an environmentally benign absorbent (Heba A et al., 2019)
 9

Zn–Fe Layered double hydroxide was prepared by co-

precipitation method and characterised using different analytical
instruments. The efficiency of Zn–Fe LDH as adsorbent for the removal of
diclofenac sodium (DCF) from aqueous solution was investigated. The
simulation results have shown that diclofenac strongly interacts with Zn–Fe
LDH through a variety of hydrogen bonds, as well as metal complexion.

2.8 Effect of ZnO loading to activated carbon on Pb(II)

adsorption from aqueous solution (Yosuke Kikuchi et al., 2005)

Research investigated Loading zinc oxide on the activated carbon

exhibited some activated effects of enlarging the specific surface area due to
the increase in mesopore surface area, while a detrimental effect was
observed for the oxidation of activated carbon. The zinc oxide loading to the
activated carbon was found to be effectively used for the Pb(II) adsorption
whereas only a part of surface functional groups was used for the zinc oxide
particles and the oxidized activated carbon.

2.9 Agro waste derived bio chars impregnated with ZnO for
removal of arsenic and lead in water (Mondal et al., 2020)

This study aimed to impregnate ZnO on biochar derived from

agricultural residual biomass to improve its As(V) and Pb(II) adsorption
capacity. The ZnO impregnation of the biochars derived from both
precursors improves their adsorption capacities and, in most cases,
 10

accelerates the rate of adsorption of both pollutants. The best results were
obtained by corncob derived ZnO impregnated reaching a maximum
equilibrium adsorption capacity of 25.9 mg of As(V)/g and at least 25.8 mg
of Pb(II)/g.

2.10 Enhanced adsorptive removal of sulfamethoxazole from

water using biochar derived from hydrothermal carbonization of
sugarcane bagasse (G.Prasannamedha et al., 2020)

This research work primarily focussed on the production of

biochar from sugarcane bagasse through HTC followed by NaOH activation
at inert atmosphere for removing SMX from water. Immobilisation of SMX
on surface of ABC is due to charge assisted hydrogen bonding and π-π
interaction with graphitized carbon, showing maximum sorption capacity of
400 mg/g through spontaneous reaction. The results suggested that HTC
derived biochar had great adsorption affinity with respect to pH towards
SMX and could be employed as an effective sorbent in cleaning water
contaminants.
 11

CHAPTER 3

AIM AND OBJECTIVE

3.1 AIM OF THE PROJECT

To remove sodium diclofenac from pharmaceutical industry

effluents via adsorption using HTC-derived activated carbon impregnated
with ZnO as an adsorbent.

3.2 OBJECTIVES

 To characterise HTC-AC/ ZnO using FTIR, XRD, SEM and

BET analysis
 To conduct batch adsorption studies in laboratory conditions
 To find the adsorption capacity and the regeneration capacity of the
adsorbent.
 To design decanter and adsorption column
 12

CHAPTER 4

METHODOLOGY

Figure 4.1 Flow of process

 13

4.1. CHEMICALS AND REAGENTS

All chemicals such as zinc nitrate Zn (NO3)2, sodium hydroxide

NaOH, concentrated sulphuric acid H2SO4 with the highest purity were

purchased in analytic grade. The stock solution (100 mg L−1) of Diclofenac

sodium was prepared by dissolving 0.010 g in 100 mL double-distilled

water. All working solutions with desired concentration were prepared by
diluting the stock solution with distilled water.

4.2. PREPARATION OF ADSORBENT (HTC-AC / ZnO)

Raw untreated bamboo was procured from discarded bamboo

furniture at a local warehouse. The collected bamboo was then washed with
deionized water 3 to 4 times. To remove the moisture content, shade drying
was done for 3 days. The dried bamboo waste was crushed using a mixer
grinder. The powder was then sieved into different particle sizes using a
sieve shaker in the range of 160 µm.

4.2.1. HTC-AC PREPARATION

The dried bamboo waste was heated in an HTC autoclave

maintained at 250℃ for about 3 hours. The supernatant was decanted after
the char obtained from HTC had settled. The Hydrochar shown in Figure 4.2
obtained was subjected to alkali activation by immersing it in NaOH
 14

solution for 8-9 hours straight. By rinsing the activated hydrochar with
water (i.e., water washing), the basic pH was brought to a neutral pH. The
AC was allowed to dry in the hot air oven till all the moisture content was
removed.

Figure 4.2 Hydro-char obtained from HTC

4.2.2. ZINC OXIDE (ZnO) PREPARATION

Zn (OH)2 was formed by co-precipitation.

2 Zn (NO3)2 aq + 4 NaOH aq 2 Zn(OH)2 aq + 4 NaNO3 aq (4.1)

0.1N NaOH solution was prepared by dissolving 2 g of NaOH in 50ml of

water. 14.875 g of Zn (NO3)2 was dissolved in 50 ml of water to form a 1 M
 15

Zn (NO3)2 solution, which was taken in a 250mL beaker and kept at room
temperature. By continuous stirring at 120 rpm using a magnetic stirrer, the
prepared NaOH solution was added drop by drop using a burette. As a result, a
milky white solution was formed. When allowed to settle, a milky white sludge
was precipitated. This substantiated Zn (OH)2. which was shown in Figure 4.3.

The Zn (OH)2 thus formed was found to be alkaline. In order to

neutralise, the precipitate was washed with water for about 3 to 4 times. After
that pH was checked and confirmed to be 7.2

2 Zn (OH)2 2 ZnO + 2 H2O (4.2)

Figure 4.3 Zn (OH)2 prepared by co-precipitation

 16

The white sludge was allowed to dry in a hot air oven overnight
and the dried Zn (OH)2 was taken in a crucible and was heated in a muffle
furnace at 450º for about 3 hours which resulted in the formation of ZnO as
shown in Figure 4.4.

Figure 4.4 ZnO nano particles

4.2.3. HTC - AC / ZNO PREPARATION

When AC was sonicated, the surface of the AC cracked, allowing

ZnO to settle on the crevices of the AC structure. This improves the quality
of adsorption. In this experiment, HTC - AC and ZnO were taken in the
ratio of 1: 0.5 and combined with 50 ml of ethyl alcohol and sonicated as
shown in Figure 4.5 for 30 minutes. The obtained sludge was dried in a hot
air oven once the mixture had settled. The dried substance was found to be
HTC- AC/ZnO
 17

Figure 4.5 Sonication of HTC-AC and ZnO

4.3. CHARACTERISATION STUDIES

The presence of surface functional groups on fabricated materials

and mechanistic interaction of HTC-AC and HTC-AC/ZnO was studied
using Fourier Transform Infrared (FTIR) Spectroscopy (Nicolet iS50 Make
Thermo Fisher Scientific). Surface morphology of HTC-AC/ZnO was
studied using a scanning electron microscope (SEM) operated at 10 KV X
3000 (JEOL/EO – JCM 6000 plus) prior to which materials were gold
sputtered. The chemical composition of the sample was quantified using
Energy dispersive x-ray spectroscopy (EDAX Joel 6390LA/OXFORD XMX
N). X-ray diffraction (XRD) patterns are recorded using the PAN-ALYTICAL
X’Pert PRO X-ray diffractometer with Cu Kα (λ = 1.540 Å) radiation in 2θ
range of 10–80◦ at a scanning rate of 10◦ min-1. BET surface area
measurements were made by measuring N2 adsorption at 77K using a
MICROMERITICS 2000 instrument. Pore volumes were subsequently
determined from the cumulative nitrogen adsorption by the BJH method.
 18

4.4. ADSORPTION EXPERIMENT

Adsorption studies were conducted by adding certain grams of

HTC - AC/ZnO to 50 ml of Diclofenac sodium (DCF) solution and it was
subjected to stirring at 120 rpm using HASTHA orbital shaker at 27oC for
90 minutes. at the speed of normal pH (6.1±0.1) while maintaining the room
temperature. The supernatant was collected in a syringe and filtered through
a 0.22 µm nylon membrane syringe filter before being taken for quantitative
analysis. Quantitative analysis of Diclofenac sodium was performed in a UV
visible spectrophotometer (LARK Li-UV-7000) at the maximum
wavelength of 275 nm.
Removal efficiency of adsorbent was calculated using equation (4.3)

C0 – Ct
Removal efficiency (%) =
C0
×100 (4.3)

Adsorption capacity of the adsorbent was calculated using equation (4.4)

C0 – Ct ×V (4.4)
Qt =
m

In these equations,
C0 - Initial diclofenac concentration (mg L-1),
Ct - Diclofenac concentration at any time (mg L-1),
Qe - Diclofenac adsorption capacity at equilibrium (mg L-1),
Qt - Diclofenac adsorption capacity at any time (mg L-1),
m - Mass of the adsorbent used (g),
V - Volume of DCF solution (L).
 19

Adsorption parameters like effect of pH, effect of adsorbent

dosage, effect of contact time and initial pollutant concentration were
carried out. In pH studies, solution pH was varied from 2 to 12 using 0.1 M
HCL and 0.1 M NAOH solutions. The effect of contact time was examined
by studying adsorption kinetics using 0.1 g L-1 of HTC-AC/ZnO in 100 mL
of DCF solution at pH 5.0 ± 0.1 in a room temperature.

4.5. ADSORPTION ISOTHERM

Adsorption isotherms are significant for the explanations of

adsorbate distribution between solid and liquid phases upon reaching
adsorption equilibrium (M.S. Naeem et al., 2018). In this study, three
adsorption isotherm models: Langmuir, Freundlich and Temkin isotherm
models were selected to explain diclofenac sodium adsorption mechanism
and diclofenac distributions on HTC-AC/ZnO surface and in aqueous
solution during the adsorption equilibrium. The non-linear mathematical
equations used for estimation of all adsorption isotherm parameters were
given in Table 4.1
 20

Table 4.1 Isotherm models and non-linear equations

ISOTHERM
MODEL EQUATION DESCRIPTION
Langmuir qm KL Ce qe - amount of DCF adsorbed at
qe =
Isotherm 1+KL Ce equilibrium (mg/g),
qm - maximum monolayer adsorption
capacity (mg/g),
KL - Langmuir adsorption constant
(L/mg)
Ce - equilibrium concentration of
DCF in the solution (mg/L)
Freundlich 1 KF - Freundlich constant (mg/g)
qe =KF Cne
Isotherm (L/mg)1/n
n - Freundlich exponent which is
used to measure the intensity of
adsorption.
If n =1 - linear , n>1 - physical
process, n<1 - chemical process
Temkin qe = ln(ACe ) B = RT/b - enthalpy of adsorption
Isotherm b - Temkin constant related to the
heat of adsorption (J/mol)
T - absolute temperature in (Kelvin)
R - universal gas constant (8.314
J/mol K),
A - binding constant (L/g)
 21

4.6. KINETIC MECHANISMS

If an adsorbent is planned to be utilized on industrial scales in

waste water treatment plants, high adsorption rate beside high adsorption
capacity is very significant parameter (A.M. Aljeboree et al., 2017). Kinetic
studies for diclofenac sodium adsorption on HTC-AC/ZnO were
accomplished between 15 and 120 min. Kinetic data obtained from
diclofenac sodium adsorption experiments were applied to pseudo-first
order kinetic and pseudo-second order kinetic models. The non-linear
equations for the kinetic models were given in Table 4.2.

Table 4.2 Adsorption Kinetics and non-linear equations

KINETIC EQUATIONS DESCRIPTION

MODEL

Pseudo first qt =qe (1-exp (-k1 t) ) k1 - pseudo-first order kinetic

order kinetics rate constant (min-1)
t - time (min)
qt - amount of DCF adsorbed
on the adsorbent at any time t
(mg/g)
Pseudo second q2e k2 t k2 -pseudo-second order kinetic
qt =
order kinetics 1+qe k2 t rate constant (g mg-1 min-1),
t - time (min)
 22

CHAPTER 5

RESULTS AND DISCUSSION

5.1 CHARACTERISATION OF ADSORBENT

For the HTC-AC/ZnO has been studied using FTIR, XRD,

SEM/EDS and BET analysis.

5.1.1 FTIR SPECTRUM ANALYSIS

The Figure 5.1 represents the FTIR spectrum indicating the

functional group present in HTC-AC/ZnO. Variations could be seen in the
surface functional groups that were formed during the series of chemical
reactions in a controlled atmosphere. Bamboo contains complex blends of
polysaccharides (hemi-cellulose, cellulose and lignin) that are rich in O-H
and C=O in its carbon skeleton. After heat treating under forced conditions,
the so formed biochar was analyzed for dissimilarities in structural elements
in the IR spectrum between 4000 and 400 cm−1.
 23

The intensity of spectra at 3564 cm-1 was mildly broad that

correspond to the OH stretching vibrations was due to the lower degree of
carbonisation
Transmittance (%)

Figure 5.1 FTIR Spectrum for HTC – AC

A short peak at 2788 cm-1 was due to stretching vibrations of the

carbonyl aliphatic C-H group. This suggested that AC had an aliphatic C
group that could be produced by aromatization which was achieved by
dehydrogenation of existing cyclic compounds. The intensity around 1521
cm−1 that corresponds to aromatic ring stretching vibrations which was due
to the formation of aromatic rings during the hydrothermal reaction.
 24

The intensity of spectra at 1069 cm−1 was broad and shallow

corresponding to the fingerprint region and possessing C=O group that were
formed by dehydrogenation of one or more saccharide molecules, thus the
presence of carbonyl groups. Table 5.1 shows the analysis data of FTIR

Table 5.1 FTIR analysis data

Wavenumber (cm-1) 3564 2788 1521 1069

Functional group OH C-H Aromatic group C=O

5.1.2. SEM/EDAX ANALYSIS

Figure 5.2 a) and 5.2 b) shows the morphology and structure of

HTC-AC impregnated with ZnO. It could be observed that HTC produced
hydro-chars are sphere shaped structures. This suggests that produced
carbon showed spherical shape or aggregates of spheres with a smooth
surface. The sizes of the spheres were found to be in the range of a few
microns. Most of the spheres were agglomerated to form clusters,
this indicated the accumulation of hydrolyzed products from polymers that
were found in bamboo. These products were proposed to consist of poly
aromatic structures carrying hydrophilic functional groups on its surface and
hydrophobic groups in the core (less reactive functional groups). The poly
aromatic structures were formed due to major reactions like dehydration and
aromatization of polymers. It was proposed that the accumulated poly
 25

aromatic structures could be humins that were formed as intermediates

during HTC reaction and the analysis were consistent with the FTIR study.
Inside HTC, bamboo was hydrolyzed to glucose thereby yielding
Hydroxymethyl Furfuraldehyde HMF due to intense heat. HMF via
rehydration leads to the formation of 2,5-Dioxo-6-HydroxyHexanal DHH
which reacts with the same HMF. As a result of this reaction, aldol
addition/condensation nuclei are formed that agglomerate as secondary char
shows the morphology of AC.

Compared to a non activated sample, this showed a slight

variation in this surface. AC exhibits near uniformly scattered spheres with
small average diameter range from 195 nm to 298 nm. Though the sphere
shape is maintained its surface seems to show a roughness thereby yielding
a disturbance on them. The variation is due to activating with NaOH which
is an effective activating agent for carbon materials. NaOH is responsible
for the reduction and oxidation reaction in carbon materials for separating
and degrading the graphitic layers. The activated sample shows minute and
random pores that are formed due to the evolution of H2, CO2, and CO.

These pores may provide a suitable channel for DCF interaction

with the carbon surface allowing access to its pores and its functional
groups. In general chemical activation enhances the adsorption capacity by
providing additional surface area filled with interactive functional groups.
Here, HTC derived biochar were activated using NaOH, which can dissolve
unbroken cellulose and lignin and promote related chemical reactions in the
 26

thermal activation process. The interaction of alkali and carbon promotes

increased surface area for effective adsorption.

Here, AC is a base matrix where ZnO particles were randomly

distributed around the surface of AC. A bright white light is refracted which
might be due to the presence of Zinc metal oxide. The incorporation of ZnO
in the carbon matrix partially blocked the porosity of the AC surface. It is
reported that ZnO did not enter the inner microporosity of the AC during
incorporation process but remained on the outer surface. It has a rough
surface which could be due to the presence of pores or the availability of
ZnO on AC matrix

EDAX for AC/ZnO was taken and it shows that carbon and
oxygen were major atoms that are present in the hydrochar with a very low
level of silica. Silica was found in the spectra due to the interaction of char
with crucible material during activation inside the tubular furnace. Presence
of C and O as major elements in the AC denoting the availability of carbon
and oxygen-rich hydrophilic functional groups on its surface which are
responsible for holding DCF through ionic interaction of hydrochar.
 27

Figure 5.2.a) SEM- morphology for HTC – AC/ZnO

Figure 5.2.b) SEM- morphology for HTC – AC/ZnO

 28

5.1.3. NITROGEN PHYSISORPTION (BET ANALYSIS)

Table 5.2 Nitrogen Physisorption analysis Data

SURFACE AVERAGE TOTAL MICRO MESO PORE

AREA PORE PORE PORE VOLUME
DIAMETER VOLUME VOLUME

m2g-1 nm cm3g-1 cm3g-1 cm3g-1

89.124 2.848 0.153 0.008 0.145

BET surface area analyser was used to analyse the active surface
area and porosity generated after activation of HTC-AC/ZnO with NaOH.
Figure 5.3 shows the type of BET isotherm followed. From the Vads Vs P/Po
plot (Figure 5.3) it is obvious that HTC-AC/ZnO displayed a combined
type II and IV adsorption-desorption isotherm. The HTC-AC/ZnO was
noticed with a BET surface area of 89.124 m2 g-1. The total pore volume was
0.153 cm3 g-1 which included a micropore volume of 0.008 cm3 g -1
and the
mesopore volume of 0.145 cm3 g-1. The average pore size was found to be
2.848 nm, a meso porous material (2–50 nm). The pore volume and average
pore diameter indicates the presence of a higher amount of mesoporous
structure than micropore structure. Additionally, the hysteresis loop and
broad condensation step in medium-to-high, flatter region in the middle and
relative pressure (p/P° = 0.1–1.0) indicated predominant occurrence of
 29

mesopores and macropores in HTC-AC/ZnO. The formed pores were

responsible to capture the contacting DCF onto the HTC-AC/ZnO surface
adsorption active sites.

Figure 5.3 BET analysis - p/Po Vs Vads

 30

Figure 5.4 Pore size distribution

5.1.4. XRD ANALYSIS

HTC-AC

The crystalline structure of HTC-AC, ZnO and HTC-AC-ZnO

were analysed by XRD. The results were presented in Figure 5.5, 5.6 and
5.7 respectively.

XRD pattern for prepared HTC-AC is shown in Figure 5.5. AC

derived from HTC shows a broad peak in the range of 20–30° with
approximately θ = 23.53°. The peak did not have any graphitic structure.
 31

Hence the XRD pattern around 23.53° can be assigned as an amorphous

state of carbon. From Figure 5.5, it could be witnessed that the intensity of
peak at 23.53° is greater than the intensity at 42.59°. This high peak
intensity is due to a stack of parallel aromatic layers whereas low peak
intensity is due to the regular arrangement of an individual layer segment.
Intensity (a.u.)

Figure 5.5 XRD Analysis of HTC – AC

Zinc Oxide (ZnO)

Comparing this with standard data, it was observed that all the
peaks were matched with the standard data of hexagonal phase of zinc oxide
(JCPDS card no. 36-1451). The diffraction peaks of ZnO occurred at 2θ =
33.23 °, 34.52 °, 36.43 °,47.62 °, 56.71 ° 63.03 ° and 68.12 ° with the
highest peak occurred at 36.12 ° as shown in Figure 5.6.This indicated that
there was no impurity appeared in ZnO as well as other phases of ZnO,
 32

suggesting the high purity of ZnO. The width of XRD peaks are related to
crystallite size. Scherrer equation was used for calculating the average
crystallite diameter

Intensity (a.u.)

2 Theta (degree)

Figure 5.6 XRD analysis for ZnO

HTC – AC / ZnO

The XRD pattern of HTC-AC/ZnO shown in Figure 5.7 consists

of more peaks as compared to ZnO and AC with 2θ = 24.03 °, 31.70 °,
34.51 °, 36.38 °, 47.49 °,56.72 °, 62.98°, 67.99°,72.85° and 77.37°. There
were two stronger peaks formed at 24.03 ° and 36.98 ° where the peak at
24.03 ° indicated the presence of AC while the peak at 36.98 ° represented
the presence of ZnO. This is clearly due to the incorporation of ZnO onto
the surface of AC. HTC – AC/ZnO exhibits hexagonal wurtzite structure
(ICDD 891397).
 33

Intensity (a.u.)

Figure 5.7 XRD analysis data of HTC-AC/ZnO

5.2. ADSORPTION INFLUENCING PARAMETERS ON DCF

REMOVAL

5.2.1. EFFECT OF ADSORBENT DOSAGE

The quantitative removal of DCF-Na from aqueous solution

using HTC – AC/ZnO was studied with respect to change in adsorbent
dosage. The dosage of adsorbent varied from 0.02 to 0.1 g L-1.The
experiment was conducted at optimum pH (5.4) and temperature (303K).
Optimization of the mass of adsorbent was conduction in 50 mg L-1
concentration of DCF solution. It could be witnessed from Figure 5.8 that
maximum removal of 60.694% was observed in 0.04 g L-1 of adsorbent. As
 34

the dosage of adsorbent was increased, lower adsorption was found which
could be due to the availability of more adsorption sites at higher dosage. As
a result, increased surface active sites in the adsorbent induce the formation
of aggregation of particles thereby exposing limited active sites for efficient
adsorption (Prasannamedha, G et al., 2021)

Figure 5.8 Effect of Adsorbent dosage

5.2.2. EFFECT OF INITIAL CONCENTRATION

The concentration of DCF solution was varied from 50 to 250 mg

L-1. As the concentration increases, adsorption was lower which might be
 35

due to the competitive adsorption of sorbate molecules. It was clear that

more diclofenac ions can reach the empty accessible surface of AC / ZnO,
as DCF concentration in solution increases. An increase in C0 typically
increased the Qe likely due to the greater concentration driving force to
overcome the mass transfer resistance for DCF between the liquid and solid
adsorbent. The relation between concentration and removal efficiency was
represented in Figure 5.9

Figure 5.9 Effect of initial concentration

5.2.3. EFFECT OF CONTACT TIME

At constant initial concentration (50 mg L-1,), the effect of

contact time on DCF adsorption by HTC-AC/ZnO was investigated from 15
 36

to 120 min using constant HTC-AC/ZnO amount along with constant

stirring rate (120 rpm). The results shown in Figure 5.10 obviously indicate
fast DCF adsorption rate on HTC-AC/ZnO because of high vacant
accessible sites on HTC-AC/ZnO in first 60 minutes, and then slow
increases in DCF adsorption with progressive contact time are seen until
DCF adsorption equilibrium due to the active site saturation (Liang, X. X et
al., 2019).

Figure 5.10 Effect of contact time

5.2.4. EFFECT OF pH

The solution pH is a significant aspect influencing adsorption. pH

effect was investigated by varying the pH from 2 to 12 using a benchtop pH
 37

meter (Orion StarTM A211) with a constant HTC-AC/ZnO quantity (0.5g

L-1) and initial sodium diclofenac concentration (50 mg L-1) at 25oC
adsorption temperature. The ideal pH (4.5) was chosen for two reasons:
first, for DS cannot dissolve entirely at pH 2 or 3; and second, since the
carboxyl groups on DS are easily dissociated and turn negative, causing
them to react with the positive HTC-AC/ZnO species at high pH (> 4.2).
The charges of the adsorbent surface and the ionization of the adsorbate
might be modified by the pH of the solution. Protonation (–COOH) occurs
when the pH of the solution is lower than the pKa value of the adsorbate.
While deprotonation occurs, when the pH exceeds the pKa value (–COO).

Figure 5.11 Effect of pH

 38

5.3. ADSORPTION ISOTHERM MODELING

The adsorption process in liquid phase adsorption is influenced

by the affinity of the adsorbate and the concentration of the adsorbent. Thus,
the well-known two-parameter models, Langmuir (Langmuir, 1918),
Freundlich (Freundlich, 1906), and Temkin (Temkin and Pyzhev, 1940)
isotherms were chosen to examine the interaction between adsorbent and
adsorbate and to understand the adsorption dynamics of DCF with HTC-
AC/ZnO with respect to the time isotherms. Non-linear isotherm models
were used to fit experimental equilibrium isotherm data and build up the
adsorption system. For experimental purposes, the standard dosage of
adsorbent was added to the DCF solution of concentration varying from 5 to
50 mg L−1 in a volume of 100 mL at an optimum temperature of 303 K. The
accuracy of fitting the models was evaluated based on reduced chi-square
coefficient (χ2 red), chi-square coefficient (χ 2), non-linear coefficient r2,
adjusted R2, residual sum of squares (RSS) calculated from nonlinear
regression analysis.

The mechanism of an adsorption process can be studied utilizing

equilibrium adsorption isotherms. The obtained data were tested with the
help of 3 isotherm models, Langmuir (Langmuir, 1918), Freundlich
(Freundlich, 1906), and Temkin (Temkin and Pyzhev, 1940). The
Freundlich isotherm has a higher regression coefficient than any of the other
2 isotherm models. Correlation Coefficient (R2) described that adsorption of
DCF-Na on HTC-AC/ZnO matched with Freundlich isotherm. Hence
 39

sorption of DCF follows multilayer adsorption on the heterogeneous surface

on the adsorbent. Therefore from the Figure 5.12 it is evident that the most
accurate model opted is Freundlich which signifies the multilayer adsorption
of DCF-Na onto the HTC-AC/ZnO surface without any interaction between
the adsorbed molecules. This might be due to either the heterogeneous
nature of the adsorbent surface or the uneven distribution of pores (i.e.
meso-pores and macropores) present within. Isotherm models and
parameters calculated were given in Table 5.3

Figure 5.12 Adsorption Isotherm fitting

 40

Table 5.3 Isotherm models and parameters

Isotherm Parameters Values

model
KL (min-1) 4.70075
qm (mg/g) 21.14836
Langmuir R2 0.70042
Reduced chi- 10.15177
square
Kf (min-1) 15.3603
n 7.84362
Freundlich R2 0.97846
Reduced chi- 0.7298
square
B (J/mol) 1.43421
A(L/g) 141327.41

Temkin R2 0.89869
Reduced chi- 3.43315
square

5.4. ADSORPTION KINETICS MODELLING

Adsorption kinetics describes the rate of adsorbate uptake on

adsorbent at constant pressure with respect to time. The parameters
calculated from adsorption kinetics were helpful in understanding
 41

adsorption rate over a period of time that helps in predicting the type of
adsorption process occurred. The reaction mixture of 100 mL DCF-Na
solution with varied concentrations of HTC-AC/ZnO was used to conduct
the adsorption kinetic studies. The contact time was varied from 15 to 120
min at the preferred optimum condition maintaining an initial DCF
concentration of 50 mg L−1. To evaluate the mechanism of the kinetics of
DCF on HTC-AC/ZnO two kinetic models were used for interpretation of
the obtained experimental data. The models used to determine the
adsorption rate are: Pseudo-first order (Lagergren, 1898), pseudo second-
order (Ho and Makay, 1999) were used. Upon comparing, PSO fitted the
best and it implies the chemisorption mechanism.

The qe values calculated from pseudo-second order model are

quite close to the experimental qe values. Also, the correlation coefficient
values calculated for pseudo-second order model were determined to be
higher than those calculated for pseudo-first order model, indicating that
pseudo-second order model is best fitting model for sodium diclofenac
adsorption on HTC-AC/ZnO. In addition to decreasing the number of
available adsorption sites as the adsorption progresses, the decrease in the
concentration of sorbate molecules can take place at the same time. If there
is a linear correlation between these two effects, the adsorption kinetics can
follow the PSO model. Thus, the suitability of PSO model should be
carefully checked when it is used to describe the adsorption of high-
molecular-weight adsorbate on larger adsorbent particles. However, most of
the adsorbents used are tiny particles or powders, and the molecular weights
 42

of adsorbates are not high enough (e.g. Phenols and heavy metal ions). The
PSO model is thus suitable for common adsorption systems. Parameters
calculated using kinetic models were given in Table 5.4

Figure 5.13 Adsorption Kinetics fitting

Table 5.4 Kinetic models and parameters

Sample Pseudo first order Pseudo second order

Co (mg/L) 50 Co (mg/L) 50
qe (mg/g) 31.90 qe (mg/g) 36.88
HTC- k1 (min-1) 0.068 k2 (min-1) 0.002
AC/ZnO R2 0.90367 R2 0.93197
Reduced 1.94354 Reduced 2.75206
chi-square chi-square
 43

5.5. REGENERATION CAPACITY

Hydrochar is a simple and cost-effective material that may be

used on a laboratory scale to produce carbon compounds from waste
biomass. Reusability studies examine if a certain adsorbent is cost-effective
and suitable for industrial use. For cost reductions, the frequency of HTC-
AC/ZnO renewal and its performance after each regeneration are critical.
(Prasannamedha, G et al., 2021). A competitive adsorbent should be
reusable and recyclable for industrial applications, and it should be able to
significantly lower the cost of sorbents through repeated sorption-desorption
cycles. Organic solvents such as benzene, acetone, water, ethanol,
acetonitrile and methanol had been used to extricate the adsorbents on
activated carbon. Adsorption principle based on similarity and integration
(Dai, Y et al., 2019). DCF HTC-AC/ZnO was stirred with 50 ml of various
solvents. This adsorption-desorption cycle was carried out three to five
times (Suresh, S et al., 2013). The effective regeneration of HTC-AC/ZnO
was eminent while ethanol was used (Zafar, M. N et al., 2019). After five
times of repeated administration, the adsorption efficiency was around 63
percent. The porous structure and textural changes in ZnO-AC were most
likely responsible for the drop in removal effectiveness after five cycles
(Zbair, M et al., 2018). The preparation of HTC-AC/ZnO required little
energy and cost, and the regeneration procedure likewise required little cost
and energy. As a result, it may be inferred that the sorbent employed can be
used in large-scale enterprises.
 44

CHAPTER 6

DESIGN OF EQUIPMENT

The design of equipment has to be chosen on the basis of one of

the equipment that was used in the process of removal of diclofenac sodium

from the wastewater. The Figure 6.1 shows flow of process in the waste

water treatment plant followed by adsorption using an adsorption column

AC

Figure 6.1 Flow of process in the waste water treatment plant followed
by adsorption

A- fermented wastewater AC- adsorption Column

B- Decanter C- filtrator D- thermal Treatment plant
 45

6.1. DESIGN OF A DECANTER

Inlet flow= 125700 kg hr-1 Light phase m

DECANTER
(L)=37,400 kg hr-1
Heavy phase m
(H)= 12,620 kg hr-1

Figure 6.2 Schematic representation of decanter

Table 6.1 Data of contaminants in effluent water

Component Density Mole Souders’ Molecular

fraction index weight
Toluene 851.5 0.738 296.4 92
Nitrogen - 0.0021 74.0 14
Water 992.6 0.0008 35.1 18
Para-xylene 851 0.2589 346 106.16
Meta-xylene 848.9 0.0001 346 106.16
Ortho-xylene 725.5 0.002 342 106.16
 46

Your plant needs to separate immiscible liquids and your boss decided that
you should design a decanter. The mixed feed enters the decanter and
spends enough time for the liquids to separate and settle. Make suitable
assumptions. Design a decanter and find all the geometric properties of the
decanter. (Use the data given for you.) (Ayhan D et. al., 2017)

STEP 1

Densities (ρ) of a mixture of n liquids it can be simply calculated by average

the pure component densities, weighting each on by the mass fraction of the
component:
n
ρ= i=1 (xi. ρi)
The density of the mix:
Where,
xi is the mole fraction
ρi is the density of each component, kg m-3
Given the data of density and mole fraction
ρm (L)=(0.738×851.5 + 0.0008×992. 6 + 0.2589×851 + 0.0001×848.9+ 0.0002×725.5)
ρm(L) = 849.8 kg m-3
ρm(H) = 992. 6 kg m-3

STEP 2

For organic liquid mixtures a modified form of Souders’ equation can be

used; using a mol fraction weighted average value for the viscosity constant
for the mixture, and the average molecular weight.

x1. I1 + x2.I2
log(log 10 μm) = ρm( )×10−3 − 2.9
x1.M1 + x2.M2
 47

μm = viscosity of mixture,
ρm = density of mixture,
x1, x2 = mol fraction of components,
M1, M2 = molecular masses of components.
I1, I2 = Souders’ index,

{849.8 [
(0.738×296.4) + (0.021×74)+( 0.0008×35.1)+(0.2589×346)+(0.0001×346)+ (0.0002×342)
(0.738×92)+(0.021×14)+(0.0008×18)+( 0.2589×106.16)+( 0.0001×106.16)+( 0.0002×106.16)

]*10-3}-2.9

μm (L) = 0.5147 m. N.s. m-2

And also as the heavy phase is water, the viscosity of heavy phase is:
μm (H) = 0.6652 m. N.s. m-2
From fig 1 it is evident that:
m (L)= 37,400 kg hr-1 and
m (H)= 12,620 kg hr-1
The volumetric flow rate Q is given by: m 1
Q= * m3 s-1
ρm 3600
Q (L) = 0.0122 m3 s-1
Q (H) = 0.0035 m3 s-1

STEP 3

Drop settling velocity is estimated from Stokes' Law using Newton's basic
drag equation: g.(ρd -ρc ).D2
d
Ud =
18 μc
 48

Where,
Ud = settling (terminal) velocity of the dispersed phase droplets with
diameter d,
Dd =drop diameter, m
g = the acceleration of gravity= 9.81 m.s-2
ρd = density of the dispersed phase, kg .m-3
ρc = density of the continuous phase, kg .m-3
μc = viscosity of the continuous phase, N.s.m-2

ρm(H) = ρd = 1014.5 kg.m-3 ρm(L) = ρc = 849.8 kg.m-3

μm(H) = μd = 0.1317 m.N.s.m-2 μm(L) = μc = 0.5147 m.N.s.m-2
Q(H) = Qd = 0.0035 m3.s-1 Q(L) = Qc = 0.0122 m3.s-1

According to Walas, 150 μm is a common drop diameter for the design of

decanters.
Taking, Dd = 150 μm
2
9.81.(1014.5-849.8).(150*10-6 )
Ud =
18 (0.0122*10-3 )
= 0.1655 ×10−2 m.s-1

STEP 4

Determining the Decanter diameter

π.D2L
AL = ……….(6.1)
8

L
………..(6.2)
AL
 49

Combining (6.1) and (6.2)

8. L
π.D2L
D
π. L
4
The hydraulic diameter is given by : Rh(L)
2+π
4.ρL l
h(L)
The Reynolds number for light phase is given by: Re(L)=
.μL
8.ρL VL
Re(L)= 8.ρ VL
.(2+π)DL .μL L
e(L)=
.(2+π)DL .μL

Similarly the Reynolds number for heavy phase is given by: Re (H) =
8.ρH VH
.(2+π)DH .μH

Assuming Re(L) and Re(H) ≤ 10,000

8.ρL VL
Now, e(L)=
.(2+π)DL .μL

For light phase,

8×849.8×0.0122
10,000=
(2+π)×0.5147×DL ×10-3
DL=3.1341 m
Similarly for heavy phase,
DH=4.1949 m
 50

STEP 5

To calculate the residence time Rt

A value of 10 per cent of the decanter height is usually taken for design
purpose.
HD = 0.1 (D)
=0.1 x (4.2672)
HD =0.4267m

HD
Rt =
UD
0.4267
=
0.1655×10-2

Rt= 258 seconds = 4.3 minutes

STEP 6

To calculate the length of the decanter

8× H
VH = 2
π×D

8×0.0035
=
π×(4.2672)2

=0.4865 x 10-3 m.s-1

The total decanter length is L = Ls + LD
Where,
Ls is the settling length, m
LD is the dispersion length, m
VH ×D
To find the settling length, Ls =
2×UD
 51

0.4895×10-3 ×4.2672
Ls =
2×0.1655×10-2

Ls=0.6311 m

To find the dispersion length L =

D
2× H × t
Interfacial area Ai =
HD

Ai= 42.3248 m2
42.3248
LD=
4.2672

LD=10.581m
Thus, the total decanter length is
= 0.6311 m + 10.581 m
L= 11.2123 m
Checking length to diameter ratio
11.2123
= = 2.628
4.2672

Gravity decanters normally are specified with a length-to-diameter ratio

must greater than 2 to maximize the phase boundary between the two settled
layers (Perry R. H., 2008). In this case, a length-to-diameter ratio of is 2.63
which is satisfied this condition.

STEP 7

To know the decanter geometry

1) Total area
At =2×L×√r2 -h2

At =2×11.2123×√2.13362 -11.21232
At= 246.7827 m2
 52

2) Inlet diameter
di = 260 G0.53 ρ-0.37

Where , G is the flow rate, kg s-1

Gi = = 34.9167 kg s-1

di= 260(34.9167)0.53 (6.683)−0.37

di = 846.33 mm
3) Outlet diameter do(L) = 260 G0.53 ρ-0.37
G= 34.9167 kg s-1
do(L)= 74.12 mm
4) Outlet diameter do(H) = 260 G0.53 ρ-0.37

G= 3.5056 kg s-1
do(H)=39.35mm

Table 6.2 Summary of decanter Parameters

Droplet settling velocity uD 0.1655 x10-2 m.s-1
Decanter diameter D 4.2672 m
Decanter length L 11.2123 m
Area of interface Ai 42.3248 m2
Height of the dispersion band HD 0.4267 m
Residence time Rt 4.3 minutes
Inlet diameter di 846.33 mm
Light phase outlet diameter ( ) 74.12 mm
Heavy phase outlet diameter ( ) 39.35 mm
 53

6.2. DESIGN OF ADSORPTION COLUMN

Problem Statement

To design an adsorption column for removal of DCF from

wastewater having inlet concentration Co= 200 mg/L at the rate of
150m3/day. The allowable level of DCF concentration at the outlet of the
column is to be 10mg/L using the adsorbent material Activated Carbon.

Figure 6.3 Flow of process in adsorption column

Given data:
Q= 50L/hr
Column diameter= 9cm
Column depth (packed bed) = 175 cm
Packed bed material density= 1140 kg/m3
Plant diameter= 2.846 m
Vbreakthrough= 8400 L
 54

Vexhaustion= 9500 L
qc =150 mg of DCF/ g of adsorbent
Pilot plant data (from literature Juan C. Moreno-Piraj et al., Design and
Construction of Equipment to Make Adsorption at Pilot Plant Scale of
Heavy Metals)
Amount of packing material required as per Langmuir adsorption isotherm
and is given by,
q Cc x 0.143
= …………..( 3)
2.275 1+0.143Cc
Cc= 200-10=190 mg/L
DCF load = 190 mg/L x 150000 L/day = 28.52 kg/day
Vbreakthrough is generally taken as the condition where 90%of the bed is
saturated.
100⁄
90
Packing material required= 28.52 kg/day x
q

For calculating q, Langmuir isotherm is used:

0.325 x 200
From (6.3), q=
1+28.6

mg of DCF
q = 2.195
g of adsorbent

Adsorbent required:
100
= 28.52 x g of adsorbent per day
90 x 2.195

= 12.98 x 106 g of adsorbent per day

Rate of filtration of the plant:
Rate= Q/A
 55

50 L/hr
=
π x rx r

= 7.863 m3 hr -1
Area of packed column:
From (2), A= Q x Rate
150
A= = 0.794 m2
7.863

Empty bed contact time of pilot plant:

V
T=
3.14 x 0.092 x 0.1754
=
50

= 1.77 m
Mass of adsorbent required:
m = Volume x Density
= 1.77 x 3.14 x 1.005x (1.005/4) x 1140
= 1601.7 kg of adsorbent required.
Determined of qc
Fraction of capacity left unused:
Total capacity= 9500 x 200 = 1900000 mg
DCF removed from breakthrough= 200 x 8400
= 1680000 mg
1.9-1.68 x 100
Unused =
1.9

Unused fraction of capacity= 11.57 %

Breakthrough time for packed column:

DCF loading = 200 mg/L x 150 m3/day x 1000 L/m3
= 30 x 106 g/day
 56

DCF loading
Adsorbent consumption rate=
qc

30 x 106
=
150

= 200 kg/day
Amount of adsorbent consumed= mass of adsorbent x fraction used
= 1601.7 x (1-0.115)
= 1416.268 kg of adsorbent used.
Breakthrough time = adsorbent used/ consumption rate
= 1416.268/ 200
= 7.08 days

Table 6.3 Summary of Adsorption Column Parameters

Parameters Values Units

Area of the packed column 0.794 m2
Height of packed column 1.77 m
Column diameter 9 cm
Column depth (packings) 175 cm
 57

CHAPTER 8

CONCLUSION

HTC-AC/ZnO was successfully prepared for effective

elimination of DCF from Aqueous solution. The synthesized HTC-AC/ZnO
were characterized by Fourier transform infrared spectroscopy (FT-IR) and
scanning electron microscopy (SEM) The removal efficiency of DCF was
found to increase with decrease in Equilibrium pH indicating acidic nature
of the adsorption process. Different isotherms such as, Langmuir,
Freundlich and Temkin were studied at particular temperatures and it was
found that the adsorption characteristics was well predicted by Freundlich
adsorption isotherm with a multilayer capacity. The kinetics of the
adsorption was found to follow the pseudo second order kinetics at various
initial concentrations and temperatures. Adsorption experiments over ZnO
and the HTC carbonaceous materials showed that their adsorption capacities
are adequate for the removal of this emerging contaminant present in water,
with ZnO being less effective than activated carbons. The results obtained
could be extended to chemically similar compounds, with the subsequent
potential application in the treatment of water contaminated with Diclofenac
Sodium.
 58

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