KINETICS OF WET OXIDATION OF FORMIC ACID

BY

ANKITA ROY

YEAR: UG III SEC. : A2

ROLL NO. :001610301067

REG. NO. : 135735 OF 2016-2017

Submitted in the fulfilment of the requirement of Bachelor of Chemical

Engineering

Under the guidance of

DR. SHYAMAL ROY

DEPARTMENT OF CHEMICAL
ENGINEERING JADAVPUR UNIVERSITY

JUNE, 2019
 Dedicate tomy Parents

&

Respected Professors,

Who have helped me transform

into a better human being

2
 ACKNOWLEDGEMENT

I, Ankita Roy, would like to express my special thanks of gratitude to my teacher, Dr.Shyamal
Roy, Assistant Professor, Department of Chemical Engineering, Jadavpur University, who gave
me the golden opportunity to do this wonderful project on the topic “Advanced oxidation of
Formic Acid in Industrial effluents”, which also helped me in doing a lot of research and I came
to know about so many new things I am really thankful to him. Without his help and constant
support, compiling my work in form of this thesis would not have been possible and I would
always be thankful to him for his immense contributionin my development of a future Chemical
Engineer.

Secondly I would also like to thank my parents and friends who helped me a lot in finalizing this
project within the limited time frame.

(Ankita Roy)

Department of Chemical Engineering

Jadavpur University

3
 PREFACE

Advanced oxidation technologies (AOTs) involve the use of powerful oxidizing intermediates
(e.g., the hydroxyl radical ∙OH) that can oxidize and degrade primarily organic pollutants from
contaminated air and water. The term advanced is used because the chemical reactions involved
are essentially the same (except billions of times faster) as the reactions that would occur if these
pollutants were exposed in a natural environment. AOTs oxidize a broad range of contaminants,
including those that are not readily removed with other advanced technologies (e.g., reverse
osmosis or granular activated carbon).

Advanced oxidation processes (AOPs) utilizing powerful hydroxyl or sulfate radicals as a major
oxidizing agent were first proposed in the 1980s for potable water treatment. Later, AOPs were
broadly applied for treatment of different types of wastewaters because the strong oxidants can
readily degrade recalcitrant organic pollutants and remove certain inorganic pollutants in
wastewater. The objective of this study was to review the fundamentals of and recent advances in
the advanced oxidation processes for wastewater treatment. I tend to explore the regime of
advanced oxidation techniques and hope to come across a method which gives better results
while keeping the factors of economy and sustainability in mind.

4
 LIST OF CONTENTS

TOPICS PAGE NO.

ACKNOWLEDGEMENT 3
PREFACE 4
CONTENTS 5
LIST OF FIGURES 8
LIST OF TABLES 11
LIST OF ABREVIATIONS 13
ABSTRACT 14
CHAPTER 1: INTRODUCTION 21
CHAPTER 2:TYPES OF ADVANCED OXIDATION PROCESS 23

2.1 SONOLYSIS 23
2.2 OZONATION 25
2.3 O3 / H 2 O2 30
2.4 O 3/CATALYST 31
2.5 UV BASED AOP 31
2.6 UV/O3 PROCESS 34
2.7 FENTON’S PROCESS 37
2.8 HETEROGENEOUS PHOTOCATALYSIS 39
2.9 FENTON’S REACTION USING HETEROGENEOUS CATALYST 42
2.10 OTHER AOPS 44
CHAPTER 3: CATALYST PREPARATION METHODS 46
3.1 PRECIPITATION 48
3.2 GELATION AND FLOCULATION 50
3.3 HYDROTHERMAL TRANSFORMATION 52

5
 3.4 DECANTATION,FILTRATION,CENTRIFUATION AND WASHING 53
3.5 DRYING 54
3.6 CALCINATON 55
3.7 FORMING OPERATION 58
3.7.1 FORMING MICROGRANULES 59
3.7.2 FORMING GRAINS 60
3.7.2.1 EXTRUSION AND WET PRESSING 60
3.7.2.2 DRY TABLETTING 61
3.7.2.3 GRANULATION 63
3.7.2.4 DROP GRANULATION 63
3.8 SUPPORTED CATALYST 64
3.8.1 PRECIPITATION 66
3.8.2 IMPREGNATION 67
CHAPTER 4: EXPERIMENT 69
4.1 EXPERIMENTAL SETUP 69
4.2 CATALYST PREPARATION 70
4.3 FORMIC ACID REACTION 70
CHAPTER 5: RESULTS AND DISCUSSION 72
5.1 EFFECT OF TEMPERATURE AND OXYGEN PARTIAL PRESSURE 72

ON COD REDUCTION DURING NON-CATALYTIC WET OXIDATION

OF FORMIC ACID
5.2 EFFECT OF TEMPERATURE,OXYGEN PARTIAL PRESSURE AND 74

CATALYST LOADING ON CATALYTIC WET OXIDATION OF

FORMIC ACID

CHAPTER 6: CONCLUSION 77

APPENDIX A 78
6
APPENDIX B 79

REFERENCES 81

LIST OF FIGURES

FIGURE FIGURE TITLE PAGE NO.

NO.
1. CLASSIFICATION OF ADVANCED OXIDATION 22

PROCESS
2-1 SCHEMATICS OF WORKING PRINCIPLE OF 25

SONOLYSIS (A)BULK INTERIOR (B)LIQUID

BUBBLE INTERFACE (C) BULK SOLUTION

2-2-1 TYPICAL REACTOR ASSEMBLY FOR 26

7
 OZONATION
2-2-2 OZONATION REACTION IN WATER MATRIX 27
2-6-1 SCHEMATIC REPRESENTATION OF A UV 35

CONSISTING OF TWO UV BANKS

2-8-1 SCHEMATIC REPRESENTATION OF 39

PHOTOCATALYSIS MECHANISM
2-10-1 OPERATIONAL FLOW DIAGRAM OF WAO 45

PROCESS
3-1-1 SUPERSATURATION DEPENDENCE ON 48

CONCENTRATION,TEMPERATURE AND PH
3-1-2 PROPERTIES OF COLLOIDAL PARTICLES 49
3-2-1 FORMATION GELS AND FLOCULANTS 51
3-2-2 GELATION OF SILICA:INFLUENCE OF PH ON 52

GELATION TIME AND SURFACE AREA

3-5-1 PORE VOLUME REDUCTION IN SILICA 54

HYDROGEL
3-5-2 EFFECTS OF DRYING TEMPERATURE ON THE 55

SURFACE AREA OF A SILICA HYDROGEL

3-6-1 ALUMINA MODIFICATION UPON 56

CALCINATION
3-6-2 EFFECT OF CALCINATION TEMPERATURE 57

ON THE PORE SIZE OF γ-Al2O3

3-7-2 SPRAY DRYER 60
3-7-4 THE RELATION BETWEEN PELLETABILITY, 62

CRYSTAL STRENGHT AND MELTING POINT

8
3-7-5 INFLUENCE OF PELLETING PRESSURE ON 62

BOHEMITE PORE SIZE DISTRIBUTION

3-7-6 PRODUCTION OF SPHERES BY ROTATING 63

DISH GRANULAR
3-7-7 PRODUCTION OF SPHERES BY DROP 64

COAGULATION
3-8-2 SUPPORT IMPREGNATION 68
3-8-3 FOUR LIMITING TYPES OF IMPREGNATION 68
4-1 SCHEMATIC DIAGRAM FOR EXPERIMENTAL 69

SET-UP OF WET OXIDATION

5-1-1 EFFECT OF TEMPERATURE AND OXYGEN 73

PARTIAL PRESSURE ON COD REDUCTION

DURING NON-CATALYTIC WET OXIDATION

OF FORMIC ACID
5-1-2 FIRST ORDER KINETICS PLOT OF WET 73

OXIDATION OF FORMIC ACID

5-1-3 ENERGY OF OXIDATION FOR NON- 74

CATALYTIC WET OXIDATION OF FORMIC

ACID
5-2-1 EFFECT OF TEMPERATURE,OXYGEN 75

PARTIAL PRESSURE AND CATALYST

LOADING ON COD REDUCTION OF FORMIC

ACID SOLUTION
5-2-2 ENERGY OF ACTIVATION FOR CATALYTIC 75

9
 WET OXIDATION OF FORMIC ACID
A-1 REACTOR DESIGN FOR SWOP SYSTEM 78

A-2 MICROGRANULES OBTAINED BY SPRAY 78

DRYING

LIST OF TABLES

TABLE TABLE TITLE PAGE NO.

NO.
1 MAJOR MECHANISMS FOR ORGANICS 19
REMOVAL DURING WASTE WATER

TREATEMENT BY DIFFERENT AOPS

2-2-3 VARIOUS CATEGORIES OF POLLUTANTS 28
DEGRADED BY OZONATION
2-5 VARIOUS CATEGORIES OF POLLUTANTS 33
TREATED BY PHOTOLYSIS
2-6-2 SELECTED POLLUTANTS REMOVED BY UV 36
TREATMENT
2-8-2 VARIOUS PHOTOCATALYSTS STUDIED FOR 41
DEGRADING VARIOUS POLLUTANTS
10
2-9-1 POLLUTANTS DEGRADED USING 43
FENTON/HETEROGENEOUS CATALYST
3-7-1 DIFFERENT TYPES OF CATALYST SHAPES 59
3-7-3 INFLUENCE OF STARTING MATERIAL ON 60
CHOICE OF GRAIN FORMING PROCESS
3-8-1 TYPICAL CATALYST SUPPORT 66
B-1 LIST OF SOME ORGANIZATIONS THAT HAVE 79
INCORPORATED SCOW PLANT FOR WATER

TREATEMENT
B-2 TYPICAL PORE DIFFUSION VALUES OF 80
DIFFERENT SUPPORT AND CATALYSTS

11
 LIST OF ABREVIATIONS

AOT ADVANCED OXIDATION TECHNOLOGY

AOP ADVANCED OXIDATION PROCESS
UV ULTRAVIOLET

COD CHEMICAL OXYGEN DEMAND

TOC TOTAL ORGANIC CARBON

EDC EDOCRINE DISRUPTION CHEMICALS

POP PRESISTANT ORGANIC POLLUTANTS

ROS REACTIVE OXYGEN SPECIES

MIB METHYLISOBOMEOL
THM TRIHALOMETHANES
NDMA N-NITODIMETHYLAMINES
FMP FILTERED MEDIUM PRESSURE LAMPS

TSS TOTAL SUSPENDED SOLIDS

NTA NITOTRIACETIC ACID

EDTA ETHYLENEDIAMINE TETRA ACETIC

ACID

12
 ABSTRACT

Chemical oxidation technologies have been used for many years to degrade a wide range of
pollutants in waste water and drinking water,advanced chemical oxidation typically involves the
use of chemical oxidants like ozone or hydrogen peroxide to generate highly unstable and
reactive species hydroxyl radical is one of the strongest oxidants known.It is non selective and
capable of rapidly degrading a number of organic compounds.

Advanced oxidation process are used to remove generally organic and sometimes inorganic
materials in water and wastewater by oxidation through reactions with hydroxyl radicals . In
real-world applications of wastewater treatment, however, this term usually refers more
specifically to a subset of such chemical processes that employ ozone (O3), hydrogen
peroxide (H2O2) and/or UV light.It is an in situ chemical oxidation process.

Chemical oxidation technologies have been used for many years to degrade a wide range of
pollutants in waste water and drinking water . These reactive species are the strongest oxidants
that can be applied in water and can virtually oxidize any compound present in the water matrix,
often at a diffusion controlled reaction speed. Consequently, ·OH reacts unselectively once
formed and contaminants will be quickly and efficiently fragmented and converted into small
inorganic molecules. Hydroxyl radicals are produced with the help of one or more primary
oxidants (e.g. ozone, hydrogen peroxide, oxygen) and/or energy sources (e.g. ultraviolet light) or
catalysts (e.g. titanium dioxide). Precise, pre-programmed dosages, sequences and combinations
of these reagents are applied in order to obtain a maximum •OH yield. In general, when applied
in properly tuned conditions, AOPs can reduce the concentration of contaminants from several-

13
hundreds ppm to less than 5 ppb and therefore significantly bring COD and TOC down, which
earned it the credit of “water treatment processes of the 21st century”.

The AOP procedure is particularly useful for cleaning biologically toxic or non-degradable
materials such as aromatics, pesticides, petroleum constituents, and volatile organic
compounds in wastewater.[4] Additionally, AOPs can be used to treat effluent of secondary
treated wastewater which is then called tertiary treatment.[6] The contaminant materials are
converted to a large extent into stable inorganic compounds such as water, carbon dioxide and
salts, i.e. they undergo mineralization. A goal of the wastewater purification by means of AOP
procedures is the reduction of the chemical contaminants and the toxicity to such an extent that
the cleaned wastewater may be reintroduced into receiving streams or, at least, into a
conventional sewage treatment.

Although oxidation processes involving ·OH have been in use since late 19th century (such as in
Fenton reagent, which, however, was an analytical reagent at that time), the utilization of such
oxidative species in water treatment did not receive adequate attention until Glaze. The possible
generation of ·OH “in sufficient quantity to affect water purification” and defined the term
“Advanced Oxidation Processes” for the first time in 1987. AOPs still have not been put into
commercial use on a large scale (especially in developing countries) even up to today mostly
because of the relatively high costs. Nevertheless, its high oxidative capability and efficiency
make AOPs a popular technique in tertiary treatment in which the most recalcitrant organic and
inorganic contaminants are to be eliminated. The increasing interest in water reuse and more
stringent regulations regarding water pollution are currently accelerating the implementation of
AOPs at full-scale. There are roughly 500 commercialized AOPs installations around the world
at present, mostly in Europe and the United States. Other countries like China are showing
increasing interests in AOPs.

Chemical principle:

1.Formation of hydroxyl radial

2.Initial attacks on target molecules by ·OH and their breakdown to fragments;

14
 3.Subsequent attacks by ·OH until ultimate mineralisation.

Fig 1.Proposed mechanism of the oxidation of benzene by hydroxyl radicals

The mechanism of ·OH production (Part 1) highly depends on the sort of AOP technique that is
used. For example, ozonation, UV/H2O2 and photocatalytic oxidation rely on different
mechanisms of ·OH generation:

● UV/H2O2:

H2O2 + UV → 2·OH (homolytic bond cleavage of the O-O bond of H 2O2 leads to
formation of 2·OH radicals)

● Ozone based AOP:

O3 + HO− → HO2− + O2(reaction between O3 and a hydroxyl ion leads to the formation of
H2O2 (in charged form))

O3 + HO2− → HO2· + O3−· (a second O3 molecule reacts with the HO2− to produce the
ozonide radical)

O3−· + H+ → HO3· (this radical gives to ·OH upon protonation)

HO3· → ·OH + O2

the reaction steps presented here are just a part of the reaction sequence.

● Photocatalytic oxidation with TiO2:

TiO2 + UV → e− + h+(irradiation of the photocatalytic surface leads to an excited

electron (e−) and electron gap (h+)
15
 Ti(IV) + H2O ⇌Ti(IV)-H2O (water adsorbs onto the catalyst surface)

Ti(IV)-H2O + h+⇌Ti(IV)-·OH + H+the highly reactive electron gap will react with water

Currently there is no consensus on the detailed mechanisms in Part 3, but researchers have cast
light on the processes of initial attacks in Part 2. In essence, ·OH is a radical species and should
behave like a highly reactive electrophile. Thus two type of initial attacks are supposed to be
Hydrogen Abstraction and Addition. The following scheme, adopted from a technical handbook
and later refined, describes a possible mechanism of the oxidation of benzene by ·OH.

The first and second steps are electrophilic addition that breaks the aromatic ring in benzene (A)
and forms two hydroxyl groups (–OH) in intermediate C. Later an ·OH grabs a hydrogen atom in
one of the hydroxyl groups, producing a radical species (D) that is prone to undergo
rearrangement to form a more stable radical (E). E, on the other hand, is readily attacked by ·OH
and eventually forms 2,4-hexadiene-1,6-dione (F). As long as there are sufficient ·OH radicals,
subsequent attacks on compound F will continue until the fragments are all converted into small
and stable molecules like H2O and CO2 in the end, but such processes may still be subject to a
myriad of possible and partially unknown mechanisms.

ADVANTAGES

AOPs hold several advantages that are unparalleled in the field of water treatment:

● They can effectively eliminate organic compounds in aqueous phase, rather than
collecting or transferring pollutants into another phase.
● Due to the remarkable reactivity of ·OH, it virtually reacts with almost every aqueous
pollutant without discriminating. AOPs are therefore applicable in many, if not all,
scenarios where many organic contaminants must be removed at the same time.
● Some heavy metals can also be removed in forms of precipitated M(OH)x.
● In some AOPs designs, disinfection can also be achieved, which makes these AOPs an
integrated solution to some water quality problems.
● Since the complete reduction product of ·OH is H2O, AOPs theoretically do not introduce
any new hazardous substances into the water.
16
Current shortcomings
It should be realised that AOPs are not perfect and have several drawbacks.

● Most prominently, the cost of AOPs is fairly high, since a continuous input of expensive
chemical reagents is required to maintain the operation of most AOP systems. As a result
of their very nature, AOPs require hydroxyl radicals and other reagents proportional to
the quantity of contaminants to be removed.
● Some techniques require pre-treatment of wastewater to ensure reliable performance,
which could be potentially costly and technically demanding. For instance, presence of
bicarbonate ions (HCO3−) can appreciably reduce the concentration of ·OH due to
scavenging processes that yield H2O and a much less reactive species, ·CO3−. As a result,
bicarbonate must be wiped out from the system or AOPs are compromised.
● It is not cost effective use solely AOPs to handle a large amount of wastewater; instead,
AOPs should be deployed in the final stage after primary and secondary treatment have
successfully removed a large proportion of contaminants.

Future
Since AOPs were first defined in 1987, the field has witnessed a rapid development both in
theory and in application. So far, TiO2/UV systems, H2O2/UV systems, and Fenton, photo-Fenton
and Electro-Fenton systems have received extensive scrutiny. However, there are still many
research needs on these existing AOPs.

Recent trends are the development of new, modified AOPs that are efficient and economical. In
fact, there has been some studies that offer constructive solutions. For instance, doping TiO2 with
non-metallic elements could possibly enhance the photocatalytic activity; and implementation of
ultrasonic treatment could promote the production of hydroxyl radicals.

17
 Table 1

Major mechanisms for organics removal during wastewater treatment by different AOPs

Oxidant for
AOP types advanced Other occurring mechanisms
oxidation
O3 OH· Direct O3 oxidation
Direct O3 oxidation
O3/H2O2 OH·
H2O2 oxidation
O3/UV OH· UV photolysis
UV/TiO2 OH· UV photolysis
UV photolysis
UV/ H2O2 OH·
H2O2 oxidation
Iron coagulation
Fenton reaction OH·
Iron sludge-induced adsorption
Iron coagulation

Photo-Fenton
OH· Iron sludge-induced adsorption
reaction

UV photolysis
Acoustic cavitation generates transient high temperatures
Ultrasonic
OH· (≥5000 K) and pressures (≥1000 atm), and produce H· and
irradiation
HO2·, besides OH·
Heat/persulfate SO4·− Persulfate oxidation
UV/persulfate SO4·− Persulfate oxidation
Fe(II)/persulfate SO4 ·− Persulfate oxidation

18
 Iron coagulation

Iron sludge-induced adsorption

OH−/persulfate SO4 ·−/ OH· Persulfate oxidation

CHAPTER 1

INTRODUCTION

19
The availability of the earth’s fresh water resources has drastically depleted or contaminated due
to improper water management, leading to thevulnerable situation. On the other hand the demand
for safe potable water is increasing day-byday due to the exponential growth of population and
inability of the traditional treatment . There are many traditional and contemporary purification
techniques available or practiced for delivering safe water as per the local standards and these
spans from basic filtration, adsorption to most advanced techniques; membrane separation and
advanced oxidation processes (AOPs). Amongst the contemporary, the latter one is recognized as
highly effective in delivery of safe drinking water free of organics, inorganics, and microbes.
Owing to strong reactive oxygen species generation ability of AOPs it was considered for
treating different types of water and wastewaters containing thevarious classification of
pollutants including endocrine disrupting chemicals (EDCs), persistent organic pollutants
(POPs), total organic carbon (TOC) and micropollutants. This AOPs is a broad classification
wherein consists of various techniques for the generation of reactive oxygen species and is
shown in Figure . In general, the realistic aim of any water purification techniques is to render
water that is free of toxic matters (organic, inorganic and biological). In this regard, AOPs are
characterized as best water treatment/purification processes that involve generation of hydroxyl
radical (*OH) in sufficient quantity to affect water purification at standard temperature and
pressure . The significant advantage of AOPs over all existing chemical and biological processes
is that they are totally “environmental-friendly” as they neither transfer pollutants from one
phase to the other(as in chemical precipitation and adsorption) nor produce massive amounts of
hazardous sludge. The first AOP based water purification/treatment in full scale was proposed in
early 1980s and followed by considerable achievements have been reported. Thus, the present
review will emphasize on the various aspects of AOPs for efficient water managemene

20
 Fig 1. Classification of advanced oxidation process

The enhanced degradation of various categories of pollutants by different AOPs has drawn
attention from various research communities. The AOP allows the in-situ generation of various
reactive oxygen species (ROS) via different process such as sonolysis, ozonation, UV, Fenton
processes, etc. These ROS are subsequently utilized towards the degradation of the various
categories of pollutants. The insights on the process parameters and degradation of different
AOPs have been conferred. Thus, the present article consolidates the significant works that was
reported by the various researchers for efficient water management.

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 CHAPTER 2

TYPES OF ADVANCED OXIDATION PROCESS

Advanced oxidation processes , in a broad sense, are a set of chemical treatment procedures
designed to remove organic (and sometimes inorganic) materials
in water and wastewater by oxidation through reactions with hydroxyl radicals (·OH).[1] In real-
world applications of wastewater treatment, however, this term usually refers more specifically
to a subset of such chemical processes that employ ozone (O3), hydrogen peroxide (H2O2) and/or
UV light.[2] One such type of process is called in situ chemical oxidation. The various AOPs are
given below.

1. SONOLYSIS

It involves efficient utilization of ultrasonic sound with a frequency range of 20 KHz -10
MHz13, 14. It does not utilize any hazardous chemicals asmediator’s and hence regarded aseco
friendly process. The organic molecules are degraded as a result of explosions of the cavitation
bubbles formed as a result of ultrasonic/hydrodynamics. The generated cavitation bubbles tend to
fluctuate in their size until get collapsed at their resonance size, leads to dissipation of the stored
energy causing the explosions. The formation of these cavitation bubbles highly dependents on
the ultrasound frequency. In general, lower frequencies leads to formation of lesser concentration
of active bubbles due to presence of high water vapor content in the collapsing bubbles.
However, high frequency leads to collision among the active bubbles which generates smaller
number of reactive species leading to lesser efficiency. The schematic of working principle of
Sonolysis is depicted in Figure 2-1. The explosion of these bubbles leads to degradation of the
pollutants via pyrolysis at extreme pressure and temperature (500–10,000 atm&3,000– 5000 K
respectively) subsequently leading to the generation of *OH by the dissociation of water
molecules. Thus formed *OH further reacts with the pollutants leading to their simplest form.
The degradation at the bubble-liquid interface is dominated by the *OH. Also, the migration of
free radicals from the bubble–liquid interface into the bulk liquid leads to secondary reactions in
22
it. It is facile sludge free process with no additional generation of secondary pollutants,
promoting it as one of the most preferred techniques over photolysis, photo-Fenton and Fenton
process, etc. Moreover, it has inherent ability to treat cloudy water and leads to the efficient
degradation of volatile and sparingly soluble organic matters causing high turbidity.
Nevertheless, its lower viability due to higher energy consumption and lesser mineralization
efficiency limitations directs towards intensifying with various other AOPs like photocatalysis
(sono-photocatalysis), photofenton (sono-fenton), ozonolysis (sono-ozonation), sonophotolysis,
etc.

The mineralization efficiency can also be enhanced by varying the operational parameters such
as initial substrate concentration, pH, catalyst loading and ultrasonic power. Among the
intensified,sonophotolysis involves the synergistic effects of UV irradiation and ultrasound
waves towards the mineralization of the pollutants in the absence of catalysts. Whereas, sono-
photocatalysis involves the use of UV irradiation and ultrasound waves in the presence of a
semiconductor photocatalyst. The synergistic effect of UV/ultrasonic waves leads to enhanced
generation of the reactive radicals leading to improved mineralization efficiency. The enhanced
generation was attributed to the formation of electron-hole pair as a result of excitation in the
semiconductor photocatalyst. Additionally, presence of photocatalyst improves the bubble
cavitation phenomenon resulting in enhanced migration of the reactive species towards the liquid
bulk region. Thus, intensification of the above process leads to increased concentration of the
free radicals as a result of ultrasound on the peroxide species. In case of sono-ozonolysis, the
mass transfer of the *OH and ozone are enhanced leading to in-situ generation of H2 O2 /HO*
(each O3 molecules degrades generating 2*OH) resulting effective mineralization of the
pollutants. The reactive species are generated as a consequence of cavitation phenomenon in
water and thermolysis of ozone. The mineralization can be further enhanced either by increasing
the pressure or adding peroxide. The combination helps in achieving efficiency levels > 80 %
within a pH range of 5.5 – 6.5.

23
 Fig 2-1 Schematics of working principle of Sonolysis (a) Bulk interior (b) Liquid-Bubble
interface (c) Bulk Solution.

2. OZONATION

Ozone iscategorized as strong oxidant and a powerful disinfectant after fluorine. Theoretically
ozone has been reported to oxidize both inorganic and organic pollutants but practically ozone is
highly selective towards pollutant. Hence ozoneis considered as an electrophile with high
selectivity in its reaction. Ozonation for water treatment is highly applicable for degrading
microbes, decolorization, micropollutants removal, non-protonated amines and taste and odor
removal. This technique is commercially implemented in European countries like Switzerland,
Germany and etc as an oxidizer and in wastewater treatment plants. Ozone generator, cooling
system for ozone generator, pre-treatment unit for dehydrating the air added into the Ozonator
and post-treatment reactor for removing excess ozone in the off-gas are the unitsrequired for
implementation of ozonation. The schematic of a typical ozone reactor is shown in figure 2-2-2.

24
 Fig 2-2-1. A Typical reactor assembly for Ozonation(A = Liquid circulation pump; B =
Ozone liquid analyzer; C = Ozone gas analyser)

AQUATIC PHASE REACTION OF OZONE

In water, ozone is wobbly and hence undertakes reaction with the elements of water
components. The ozone decomposition mechanism in water entangle complex sequence of atoms
and single electron transport with intermediate *OH formation and further involves the formation
of OH-, HO2, O2-, O3-, HO3, OH, O2 and HO4 entities as shown in Figure 2-3 . This ozone
decomposition process can be accelerated by escalating the pH or hydrogen peroxide
concentration. It is well known that Ozone is the predominant disinfectant in water while OH and
O3 both act as oxidants in the oxidation process in water with O 3 being highly selective and *OH
is being highly reactive. Hence ozonation can simultaneously be used for disinfection and
oxidation. In the inception ozone concentration in water decreases rapidly and then follows first-
order kinetics while in the second phase of ozone decrease through oxidation following second-
order kinetics.

25
 Fig 2-2-2. Ozonation reaction in water matrix

The half-life of dissolved ozone varies from seconds to hours depending upon the water pH,
alkalinity, natural organic matter content. Among the three the natural organic matter can react
with ozone or scavenge *OH i.e. directly or indirectly affecting ozone stability. 26 It has been
reported that ozone is potent to react with substances directly or indirectly with *OH even at
neutral pH as hydrogen peroxide, superoxide ions. Ozone, *OH or the blend of the two and
subsumed throughout the ozonation of organic and inorganic compounds. Ozone oxidation is
enhanced by electron donating groups like –CH3, O-, -OCH3 and is reduced by electron
withdrawing groups like –Cl, -NO2. Sulfidic groups and compounds containing amino groups
and double bond also exhibit high ozone reactivity while the reactivity with the saturated
compounds is low being accumulated during the ozonation process. Low reactivity is also
observed in the reaction of ozone with methyl and ethyl ether. Two electron oxidation liberating
oxygen atom from ozone is followed in ozonation for oxidizing inorganic compounds. The
oxidation potential decreases with protonation of species due to decrease in
nucleophilicity.Hence the Ozonation can be effectively applied to varieties of pollutants as
shown in the Table 2-2-3.

26
 Table 2-2-3: Various categories of pollutants degraded by ozonation

S.No. Category Pollutant

1) Microbial (cyanobacteria) product Microcystin-LR

Carbofuran
2) Pesticide
Dinoseb

Vinyl chloride
3) Solvent
Dichloroethenes

Nitrilotriacetate (NTA)

4) Ligands Ethylenediaminetetraacetate (EDTA)

Dichlorofenac

Carbamazepine

Benzafibrate

Diclofenac

Ibuprofen

Sulfamethoxazole
5) Pharmaceutical
Roxithromycin

Iopromide

17 α - ethinylestradiol

6) Olefins  

7) Deproteinated amines  

27
 Fe(II)

CN-
Mn(II)
Inorganic micropollutants

8) H2S

NO2-

INFLUENCES OF PROCESS CONDITION

Higher dosage of ozone at elevated pH with low bromide concentration increases the abatement
efficiency of micro-pollutants. While low alkalinity and low dissolved oxygen concentrations
decrease the oxidation capacity of the system.For active compounds like diclofenac,
sulfamethoxazole, carbamazepine, trimethoprim, hydrochlorothiazide, phenazone, tramadol,
metoprolol etc. with ozone and *OH are independent of pH change without variation in
degradation efficiency; however elevated pH readily converts O3 resulting in the abatement of
ozone-resistant.

LIMITATIONS OF OZONATION
Low oxidation by ozone is reported for chlorinated benzenes, geosmin, and methylisoborneol
(MIB), trihalomethanes (THMs) etc. Cryptosporidium paravum oocyst are a resistant microbe
against disinfection requiring higher amount ozone exposure and hence forms undesirable by-
products in drinking water Ammonia removal by ozone is slow as it possesses weak oxidation
potential It has been seen that the oxidation products produced by ozonation can have unknown
toxic matters however these are in low concentration as compared to parental compounds having
negligible antimicrobial and estrogenic activities. The toxic matter includes formaldehyde,
ketones, phenols, nitromethanes and carcinogens like bromates, N-nitrodimethylamine
(NDMA). Bromate a potential carcinogen formation occurs when ozone and *OH react with
bromide in the liquid phase. Apart from all the high costs of ozone as a reagent is a major
limiting factor in implementing ozonation.
28
 3. O3/H2O2
Ozone combined with hydrogen peroxide has emerged as a new dimension in water treatment
which can oxidize both inorganic and organic substances more effectively than standalone
process. The first studies for wastewater treatment by using O 3/H2O2 were performed by
simultaneous by Nakayama et. al., and Hango et.al. While, Brunet et.al. and Duguet et.al.,
performed for treating drinking water. Studies showed that H2O2 application in ozonation
enhanced the organic substance and Trihalomethanes (THM) precursor oxidation. Its addition
increases the ozone transfer rate follows a single electron transfer forming HO2- which initiates
the ozone decomposition cycle forming *OH. The H2O2 incorporation in ozonation especially
increases the color removing efficiency but treating drinking water, the oxidation of pesticides,
aromatic compounds, and chlorinated solvents mainly applies O3/H2O2, Benefits of
O3/H2O2 usage include shorter reaction time, allowing higher application of ozone doses and low
agglomeration of ozone at the reactor outlet. Process conditions like reaction time increment
after ozone addition, intensifying pH and applying hydrogen peroxide can enhance the oxidation
property of ozone. However, increase in reaction time and pH is not economically viable
however H2O2 being a low-cost reagent most commonly applied in drinking water treatment for
achieving higher efficiency. Ozone decomposition by H2O2incorporation is initiated by *OH and
superoxide formation. .In case of treating surface waters using conventional ozonation and
O3/H2O2 much difference was not observed in the transformation of ozone to HO*. But in case of
groundwater, containing para-chlorobenzoic acid (pCBA) the oxidation of it by conventional
ozone is 20% and was increased to 50 % by incorporating H 2O2 along with O3. Compounds like
geosmin and 2-methylisobrneol (MIB) produced by algae are also difficult to oxidize by ozone
as they contain saturated ring system. However, they are well suited to be treated by
O3/H2O2 having high oxidation rate constant .The Bromate formation is low in O3/H2O2 process
than the conventional ozonation.

4. O3/CATALYST

29
Homogeneous and heterogeneous catalyst addition in ozonation process also plays a key role in
enhancing the oxidation reaction. Metal oxides like Fe2O3, Al2O3-Me, TiO2-Me, MnO2,
Ru/CeO2 and metal ions like Fe2+, Fe3+, Mn2+, etc. have been used as catalysts.57 Successful
removal of chemical oxygen demand, organochlorides, and total organic carbon had been
achieved by combining iron and manganese. Combinations like O3/TiO2,
Ru/CeO2/O3,33 Al2O3/O3 showed better efficacy in removing total organic matters . Granular
activated carbon is also considered as a catalyst for the destruction of bio-refractory compounds.

5. UV BASES AOP
The UV treatment is generally applied as a tertiary for killing the microbes and degradation of
those aquatic organic compounds which can absorb UV light. On the absorption of UV light, the
electrons in the pollutant excite from the ground state to the excited state, (equation. 1) from
where the electrons are transferred to an oxygen molecule which converts both O 2 and the
pollutant molecule into a radical (equation. 2). The radical being a highly reactive species
oxidizes other molecules to acquire a stable form.

P  → P*                                                            ...............................(1)

1. P* + O2 → P+* + O2-*                                                 .....................(2)

UV light can also result in the homolytic cleavage of the chemical bond of the pollutants
resulting in the formation of two radicals (equation. 3). UV light with a wavelength less than 190
nm can effectively break highly stable C-F bond whereas wavelength in the range 210-230 nm
can break C-Cl bond. The radicals formed can then react with oxygen (equation. 4) or may take
part in the further oxidation-reduction reactions with the other dissolve molecules.

R  → X → R* + X*                                        .................(3)

R* + O2 → RO2                                               ............................(4)
High energy UV lights with a wavelength smaller than 190 nm can photolyze water molecule to
form *OH (equation. 5), that subsequently oxidize other organic substrates.61
H2O + hv → 2HO*                                        ..........................(5)

30
Lamps like Mercury arc with different UV light emitting intensities are used for generation of
the UV radiation. These are generally of three types: Low pressure, medium and high-pressure
lamp. The former is monochromatic in nature and emit light of wavelength 253.7nm. Medium
and high pressure lamps emit a wide range of wavelengths in the UV region and penetrate deeper
because of their higher intensity and take less time for the completion of the treatment. The
limitation with the application of them is that they are energy intensive. Lamps like Pulse
radiation lamps and Excimer lamps were also utilized for generation of UV irradiation. The main
component of UV treatment system includes lamps, ballast and a reactor. Mercury arc lamps are
generally used as the UV lamps. Ballast is a support device, which mainly performs two
functions: first, they provide appropriate voltage for the reliable starting of the lamp; secondly,
they maintain a continuous current flow to the lamp, to prevent the lamps from short-circuiting.
Finally, the Reactor, they are of two types: contact and non-contact reactor. The contact reactors
are the one in which the UV lamps remain in submerged condition. The lamps are generally
enclosed within quartz sleeves in order to prevent them from damages. Non-contact reactors are
the one in which a transparent material is placed between the water sample and the lamps. The
lamps can be positioned either in perpendicular or parallel to the wastewater flow direction. The
major strength of this process is eco-friendly and shorter treatment time. It also does not require
the use chemicals; therefore, no residual products are left after the treatment. This technique has
been applied for the degradation of numerous organic compounds, including EDCs (Endocrine
disrupting chemicals) and various industrial solvents. It is an effective method for degrading
NDMA (N-nitrosodimethylamine) a well-known potent carcinogen and mostly found in
wastewater in trace amounts. Sakai et al (2012) found 222 nm Kr- Excimer - UV lamps to be a
better option for NDMA degradation in the place of low pressure (LP) and filtered medium
pressure lamps (FMP).68 Sanches et. al. 2010 utilized low-pressure UV lamps to check the
degradation of five pesticides viz: Alachlor, Atrazine, Diuron, Pentachlorophenol,
Chlorphenvinphos and Isoproturon. More than 50% of all the pesticides were completely
degraded by the conventional low-pressure mercury lamp except Isoproturon. The low quantum
yield of Isoproturon, in spite of having high molar absorption coefficient, can be a reason behind

31
its less degradation. Various categories of pollutants treated by UV photolysis are summarized in
Table 2-5.
Table 2-5: Various categories of pollutants treated by UV photolysis

Category Specific Pollutant

Trace Organic
NDMA(N-nitrosodimethylamine)
Chemical

Diclofenac, Antipyrine, Chlorotetracycline, Norfloxacin, Caffeine,

Dipyridamole, Diltiazem, Clofibric acid, Acetamiprid
Pharmaceuticals
sulfamethoxazole (SMX), oxytetracycline (OTC) and ciprofloxacin (CIP)

Ditrizoate

Pesticides Atrazine, Diuron, Alachlor, Pentachlorophenol, Chlorphenvinphos

Anabolic-androgenic
Boldenone
steroid

EDC Butylparaben

The limitations of the technique are the *OH formed by the action of UV, sometimes leads to the
partial degradation of the organic contaminants, leaving behind the intermediates concentration
in a higher level at the place of CO2 and H2O. The higher concentration of Total Suspended
Solids (TSS) and particulate material (e.g. humic compounds and iron) lags the treatment.
Further, it is energy intensive and expensive as compared to the other tertiary processes like
chlorination.

6. UV/O3 PROCESS
Treatment by combining UV and O3 is a well-established advanced oxidation technology. This
technique is more advantageous than the individual UV and O3 technologies since it combines

32
the advantages of both. The ultraviolet light coming in contact with the ozone (O 3) breaks it to
form *OH, through the following reaction steps5:
O3 + H2O + hv → H2O2 + O2                 .......................(6)
H2O2 + hv → 2OH*                        .......................(7)
2O3 + H2O2 → 2OH*                                    ...........................(8)
The *OH formed, then either completely mineralizes the organic substances to form CO 2 or H2O
or form some easily degradable intermediate substances. Being an unstable and reactive
molecule, O3 gas is generated in-situ in the experiment. Thus, the generated O 3 is then sparged
into the reactor in which UV lamps are installed. 6 These UV lamps are enclosed within Quartz
sleeves in the contact reactors, which ensure better transmission of UV. In the non-contact type
UV lamp and wastewater are separated by a transparent separator. Schematics of a UV reactor
configuration are shown in Figure 2-6.

Fig 2-6-1 : Schematic representation of a U.V consisting of two U.V banks

In most of the studies, it was found that the UV/O 3 treatment was successful in TOC and COD
reduction besides its pollutant degradation capacity.  In a study performed by Hassan et. al.
(2017), it was found that the color removal was higher for UV/O 3 in comparison to individual
treatment with O3. Tehrani et. al. (2010) studied the removal of Reactive Blue 19 dye through the
UV/O3 and O3 treatment. In their study, it was found that the UV/O 3 treatment was more

33
effective in COD removal than the O 3. It was also found that decolourization decreased as the
initial concentration of dye was increased.78 The factors which can affect the treatment includes:
pH, initial pollutant concentration, the turbidity of the solution, amount of O 3 dose, amount of
UV dose, types of UV lamps used for the process, reaction time, scavengers present in the
water. Table 2-7 enlists some selected pollutants removed effectively by UV/O 3 treatment

Table 2-6-2: Selected Pollutants Removed By UV/O3 Treatment

Category Specific pollutant

RB-19

DB-86

Dyes MV-40

Direct Yellow 50

Phenols 4-Chlorophenol

Ketoprofen
Pharmaceuticals
Caffeine

Pesticides Linuron

Other organic chemicals Nitrosopyrollidine

34
 Bisphenol A

7. FENTON’S PROCESS
The Fenton is one of the prominent AOP and the chemistry of reactions related to this includes
reactions of peroxides (H2O2) with Fe2+ to generate reactive oxygen species that can degrade the
organic as well as inorganic matter in aqueous phase. Fenton chemistry dates back to 1894 when
the activation of H2O2 by ferrous salts was reported for oxidizing tartaric acid by Henry
J.Fenton. In 1934 it was proposed by Haber and Weiss that there is a formation of *OH due to the
Fenton reaction. This *OH has an oxidation potential of 2.73V. Hence it is one of the most active
and powerful oxidants, which can be used in the degradation of most organic compounds
including emerging.

HOMOGENEOUS FENTON’S REACTION

The Fenton process is an easy and economical method to generate highly reactive oxygen species
for degrading contaminants. H2O2 is safe and easy to handle, comparatively cheap and easily
decomposes into water and oxygen. Similarly, iron is also cheaper and safe to use. This
mechanism of decomposition of H2O2 was later revised by Barb et al.. to introduce the chain
reactions of the Fenton process. The proposed mechanism which involves the breaking down of
H2O2 to produce *OH /free radical is a sequence of seven reactions in an acidic medium under
dark conditions. The reactions are as follows:

Fe2+ + H2O2 → Fe3+ + OH− + *OH                                      ..........................(9)

Fe3+ + H2O2 → Fe2+ + HO·2 + H+                                                     ...........................................(10)

*
OH + H2O2 → HO·2 + H2O                                                            .............................(11)

35
*
OH + Fe2+ → Fe3+ + OH−                                                                     ................................(12)

Fe3+ + HO·2 → Fe2+ + O2H+                                                        .................................(13)

Fe2+ + HO·2 + H+ → Fe3+ + H2O2                                                           ..............................(14)

HO·2 + HO·2 → H2O2 + O2                                                       ...................................(15)

*
OH, which is the required oxidant for degradation of the contaminants is produced by reaction
9. Reaction 10, therefore, becomes the rate-limiting reaction because it is slower than proceeding
by several orders of magnitude. The organic compounds (RH / R) can be oxidized by any one or
combinations of the following: (1) *OH, (2) abstraction of hydrogen (R*), (3) addition of
hydroxyl (*ROH).96

RH + *OH → H2O + R* → Further oxidation                     ..................(16)

R + *OH → *ROH → Further oxidation                                                     ..............................(17)

*
OH, can be scavenged by either Fe2+ or H2O2 as shown in equation 10 and 11. Hence
optimization of Fe2+ / H2O2 is to be carried for reducing the scavenging of ·OH. Whereas, the
produced Fe3+ precipitates to form ferric oxy-hydroxides as the pH increases from its optimum
generating an undesirable sludge giving problems in practical applications. Additionally, the
drawbacks of application of Fenton process for large-scale wastewater treatment include pH
dependency (effective only in the range of pH 2 to 5), generation of iron-based sludge, the
necessity of its expensive post-treatment and finally neutralizing the treated water before
disposal.9 Therefore, further research is required on modified Fenton processes such as photo
Fenton which can increase the reaction rate by light irradiation. Sometimes the use of chelating
agents provides optimum pH for Fenton reactions. Chelating ligands compete favorably with
hydroxide ion; hence increase the pH range over which compounds are soluble. The reaction
kinetics is as similar to Fenton oxidation at the optimum pH. Various chelators include Fe3+-CIP

36
chelate, deferioxamine, cyclodextrin, nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic
acid (EDTA) were adopted. However, additional research is required to identify chelating agents
that can increase the rate of oxidation, stability, and eco-friendliness.
Photo – Fenton Process
Irradiating Fenton reaction solutions with ultraviolet and visible light increases its reaction rate
and the efficiency towards waste degradation.9 The increase in efficiency is correlated to the
photochemistry of Fe3+ complexes [Fe3+(OH)-] + and [Fe3+(RCO2)-]2+ to dissociate into Fe2+. The
photochemistry of Fe3+ gives an advantage to Fenton processes because the reduced Fe 2+ reacts
with H2O2 forming *OH as per reaction 9.4 The photo-Fenton reaction reaches its optimum
around pH 2.8 and as the pH increases above this the Fe 3+ precipitates as oxyhydroxides and as
pH decreases below the optimum, the concentration of Fe(OH)2+ will decline.5 The Photolysis of
hydrogen peroxide takes place under UV light irradiation as shown (equation 18):
H2O2 + hν → 2HO*                                        ................................(18)
Although the quantum yield by photolysis of hydrogen peroxide shown in reaction 10 is good,
due to the weak absorption of light irradiation by H2O2, its activity in photo Fenton reactions is
not significant. Similar to Fenton, photo-Fenton has the drawbacks of high cost for sludge
processing and the requirement of narrow pH range, limits its application in waste/wastewater
treatment.
8. HETEROGENEOUS
PHOTOCATALYSIS
Heterogeneous photocatalysis is different compared to other treatment methods involving
oxidation and reduction simultaneously, with the use of light irradiation and a light absorbing
photocatalyst. Various compounds can utilize light irradiation to catalytically undergo photolysis
to produce redox reactions. These compounds usually have a band structure with empty
conduction and a filled valence band.8 Once light irradiation is incident on a semiconductor and
if the energy of photons exceeds the energy gap of the semiconductor, electrons are excited from
valence band to the conduction band leaving behind the holes. The activated electrons in the
valence band and holes in the conduction reacts with water generating *OH, superoxide (*O2-)
and peroxide radicals (*OOH). These radicals further degrade various pollutants to obtain
37
products such as CO2 and H2O. The mechanism of photocatalysis and degradation of
contaminants is illustrated in figure 2-8-1
. 

Fig 2-8-1: Schematic representation of photocatalysis mechanism.

The heterogonous photocatalyst materials consist of TiO2, ZnO, Fe2O3, WO3, SnO2, ZrO2,
CdSZnS, etc. Among them, TiO2 is the most extensively used heterogonous photocatalyst due to
its easy availability, cheapness and high chemical stability. The other classification of
photocatalyst also experimented for its applicability. Owing to the limitation of utilizing the
visible light the conventional photocatalyst materials were hybridized with suitable co-catalyst.
Table 2-8-2 shows the various hybridized heterogeneous photocatalysts utilized for waste
degradation.

38
 Table 2-8-2: Various photocatalysts studied for degrading different pollutants

Sl. Removal
Photocatalyst Pollutant
No. efficiency
Graphene oxide/WS2/Mg doped ZnO
1. Rhodamine B (RhB) 90% in 5 min
nanocomposite.
2. Pd-TiO2 photocatalyst Amoxicillin (AMX) 97.5% in 5h
3. Hexagonal WS2 platelets Rhodamine B 98% in 105min
Ag+, Fe3+ and Zn2+ intercalated cadmium(II)
4. 2-cholrophenol (2CP) 93% in 5h
metal organic frameworks
Reduced graphene oxide and Ag wrapped Bisphenol A (BPA) 69.1% in 5h
5.
TiO2

Graphene bridged 94.96% removal in

6. Tetracycline
Ag3PO4/Ag/BiVO4photocatalyst 60min

7. Magnetic biochar supported g-C3N4/FeVO4 methyl paraben (MeP) 98.4% MeP

and 2-cholrophenol (2- removal and

39
 90.7% 2-CP
CP)
removal

93% AMX
8. In-based MOF/graphene oxide Amoxicillin (AMX) removal, 80%
TOC removal

9. Magnetic RGO/ZnO/ZnFe2O4 composite Methylene Blue (MB) 98.64% in 60min

11. Fe3O4 nanoparticles and oxalate complex Phenol 97.61% in 3h

12. Copper zinc tin sulfide (CZTS) Methylene blue (MB)

50% in 45min
nanoparticles dye
13. Reticulated ZnO Acid Red 88 dye 79% in 180min

14. α-Fe2O3 nanosheets Bisphenol S 91% in 120min

63.48% AMX &

Amoxicillin (AMX), 2,4-
15. Ag/TiO2 photocatalyst 60.23% 2,4-DCP
dichlorophenol (DCP)
in 5h

9. FENTON’S REACTION
USING HETEROGENEOUS
CATALYST
In conventional Fenton process removal of dissolved iron from the treated water is one of the
biggest challenges which prompted the use of heterogeneous catalysts along with Fenton
process. The investigation has been carried out on the use of supported iron catalysts to decrease
sludge formation and to increase the pH range over which the Fenton reaction is effective. In
Heterogeneous catalysts supported Fenton process reactant molecules get adsorbed on the active
sites present on the surface of the catalyst. The products get desorbed after the reaction takes
place.  The use of goethite (-FeOOH), hematite (-Fe2O3), FeS2/SiO2, Ilmenite (FeTiO3) and
40
Titanomagnetite (Fe3TiO4) as heterogeneous Fenton catalysts has been studied by various
researchers.1 The advantage of an ideal heterogeneous catalyst is its ability to separate from
water and function in wide range of pH.  Various pollutants degraded using Fenton/
Heterogeneous catalysts are tabulated in table 2-9-1.

Table 2-9-1: Pollutants degraded using Fenton/ Heterogeneous catalysts

Sl. Fenton/ Heterogeneous

Pollutant Removal Efficiency
No catalysts
Photo-Fenton/ magnetite and
1. Bisphenol A (BPA) BPA = 70% in 11h
EDDS

Bioelectro-Fenton /carbon felt COD = 60%, 5-fluorouracil =

2. cathode /boron-doped diamond Pharmaceutical wastewater 88%, caffeine = 43% in
anode 3days

Ciproflaxacin = 99% in 60
3. Fenton/ FeS2/SiO2 Ciproflaxacin
min

4. Fenton/ ferric sludge Landfill leachate BOD7 = 99%, COD = 86%

Micropollutants from
5. Photo-Fenton Micropollutants = 40%
municipal wastewater

Rhodamine B (RhB), acid

Fenton with graphene modified RhB = 99%, ARG = 98.5%,
6. red G (ARG),
iron sludge as catalyst metronidazole = 91.8%
metronidazole

7. Photo Fenton oxidation with Paracetamol Paracetamol removal =

zeolite as catalyst ~99%, TOC removal = 60%
41
 in 5h

10. OTHER AOPs

The above discussed processes are the most prominence among the AOPs with practical
applicability. Apart there are few like wet air oxidation (WAO), supercritical wet oxidation
process (SWOP) process and electron beam radiation. Off this WAO utilizes the molecular
oxygen or air as oxidizer in high pressure and temperature environment. This extreme condition
allows the generation of free radicals that decomposes the waste. Thus temperature and pressure
are the controlling factor for WAO process. Most of the organic acids excluding acetic and
propionic acid are converted to CO2 at high temperature. Figure 2-10-1 depicts the simple
functionalities of wet oxidation.

Huge operational expenditure and investment is required to maintain a WAO system as it

handles an extreme reaction environment. Figure A-1 illustrates Reactor design adopted for
WAO system.

SWOP employs supercritical condition refers to the extreme temperature and pressurized
condition, where water changes its polarity and became a non-polar solvent to get miscible with
the organic part. In supercritical condition, water can be mixed with the oxygen creating a
homogeneous mixture which is perfect medium for organic degradation. When organic
compounds and oxygen are dissolved in water above the critical point they are immediately
brought into intimate molecular contact in a single homogeneous phase. With no interface
transport limitations at sufficiently high temperatures, the kinetics is fast and the oxidation
reaction proceeds rapidly to completion. This supercritical water oxidation (SCOW) is also
referred as hydrothermal oxidation (HTO). This process uses hydrogen peroxide in a
homogeneous mixture to oxidize the toxic effluents above the critical point of water. If the
organic material is in solid phase it requires the heterogeneous catalytic SCOW. It is most
42
efficient method in case of environmental remediation as complete removal of oxidisable
material can be achieved by this process. Till date inorganic substances like ammonia or
cyanides can also be converted to CO2, H2O, and N2. SCOW consists of four steps, starting
from pressurizing the reagent, reaction, salt separation and depressurization. Wastewater and
oxidant are mixed and fed in the SCOW reactor. The oxidants are normally heated before
reaction and this reaction condition allows the exothermic reaction between the waste and
oxidant. The heat energy obtained in the oxidation reaction helps to activate the reagent
optimally to oxidizable condition. After the treatment the salt precipitation is visible inside the
reactor, because of reduced salt solubility. Though the process requires high energy, this demand
can be recovered by utilization of this hot stream for preheating or energy production. A number
of works that study in depth the organic reactions in SCW, focusing on the influence of the
properties of water and in the kinetics modelling, has been developed over the last few years.
The table B-1 consists of the list of some organizations that have incorporated SCOW plant for
water treatment. Figure A-1shows the schematics of a SWOP process for water/wastewater
treatment while the table B-1 lists the organization that incorporated the same.

Fig 2-10-1: Operational flow diagram of WAO process

43
 CHAPTER-3
CATALYST PREPARATION METHODS
Solid catalysts are highly sophisticated products derived from chemicals by means of several
different procedures. The catalytic properties of heterogeneous catalysts are strongly affected by
every step of the preparation together with the quality of the raw materials. The choice of a
laboratory method for preparing a given catalyst depends on the physical and chemical
characteristics desired in the final composition. It is easily understood that the preparation
methods are also dependent on the choice of the base materials and experience shows that
several ways of preparation can be considered, even for a given selection of the base material.
This variety of possibilities might seem to confirm that making a catalyst is a ‘black art’ . In the
recent past, however, some generalities have become discernible in catalyst preparation and it
may now be claimed that a catalyst preparation science is being built. Despite the variety of
possibilities of preparing catalysts we must consider that most of them can be reduced to a series
of elementary steps, or unit operations, which present quite strongly marked analogies from one
catalyst to another, and may therefore be described in a general way. Such unit operations can be
classified by

(1) The chemical and physical transformations which are implied.

(2) The scientific laws which govern such transformations based on fundamental inorganic
chemistry.

(3) The operation variables such as temperature, pressure, pH, time, concentration.

(4) The general characteristics of the products of the operation.

44
(5) The type of the required apparatus.

Most catalyst formulations involve a combination of some or even all these operations.
However, even though the preparation procedures differ considerably from one catalyst to
another, three broad categories can be introduced to classify the catalysts with respect to the
preparation procedure:

1. Bulk catalysts and supports;

2. Impregnated catalysts;

3. Mixed-agglomerated catalysts.

Bulk catalysts are mainly comprised of active substances. Important examples include
silicaalumina for hydrocarbon cracking, Zn-Cr oxide catalyst for the conversion of CO-H,
mixtures to methanol, iron-molybdate for methanol oxidation. The supports are prepared by
similar procedures (e.g. aluminas, silicas, silica aluminas).

Unit operations in catalyst preparation

1. Precipitation

2. Gelation

3. Hydrothermal transformation

4. Decantation, filtration

5. Washing

6. Drying

7. Calcination

8. Forming operation

9. Impregnation ,

10. Crushing and grinding centrifugation

45
11. Mixing

12. Activation

1. PRECIPITATION
The aim of this step is to precipitate a solid from a liquid solution. While each intermediate in the
preparation chain can be considered the precursor of the following one, precipitation gives rise to
the basic precursor, because it really creates the imprint or latent image of the final solid that
subsequent operations will progressively reveal. Precipitation occurs in three steps:
supersaturation, nucleation and growth. Pertinent parameters producing supersaturation are
shown in Fig. 3-1-1. Solubility curves are functions of temperatures and pH. In the
supersaturation region the system is unstable and precipitation occurs with any small
perturbation. The supersaturation region can be approached either by increasing the
concentration through solvent evaporation (A to C), lowering the temperature (A to B) or
increasing the pH (which moves the solubility curve to D and A into the supersaturation region).
This last approach is quite usual in the preparation of hydroxides and sulfides. Particles within
the supersaturation region develop in a two-stage process: nucleation and growth. Nucleation
may proceed spontaneously (homogeneous nucleation) or be initiated with seed materials
(heterogeneous nucleation). These are solid impurities such as the dust or the rough edges of the
vessel surface. The rate of nucleation can be accelerated by deliberate addition of seed nuclei.
The growth process depends on concentration, temperature, pH and ripening.

46
 Fig 3-1-1. Supersaturated dependence on concentration, temperature and pH.

The size of the precipitated crystal diminishesas their equilibrium solubility diminishes (i.e. as
supersaturation increases), as Ostwald ripening is slowed down by the reduced transfer rate
between the suspended particles . Most precipitates are crystalline precipitates. Depending on the
precipitation conditions it is possible to obtain amorphous solids. If the supersaturation is very
high, the aggregation rate can exceed the orientation rate and the solid obtained is amorphous.
However, by ripening in the presence of the mother liquor, the amorphous solid can become
crystalline. Precipitation can be performed starting from either ‘true’ solutions or colloidal
solutions (~01s). Fig.3-1- 2 shows the characteristics of such solutions .

47
 Fig 3-1-2. Properties of colloidal particles

Particles which show little or no attraction for water form hydrophobic colloids. These are easily
flocculated and the resulting colloidal precipitates are easily filtered (e.g. arsenic trisulfide, silver
chloride). Particles which show a strong affinity to water form hydrophilic colloids. These are
very difficult to flocculate and the resulting jellylike mass is difficult to filter. Hydrophilic
colloidal solutions can be prepared from many inorganic compounds, such as silicic acid and the
hydrous oxides of aluminum and tin.

Precipitation procedures can be used to prepare either single component catalysts and supports or
mixed catalysts. The main purpose in the latter case is the intimate mixing of the catalyst
components that can be achieved either by the formation of very small crystallites or by the
formation of mixed crystallites containing the catalyst constituents. Hydroxides and carbonates
are the preferred precipitated intermediates for the following reasons :

(1) The solubility of these salts of transition metals are very low. Consequently, very high
supersaturations can be reached, leading to very small precipitate particle sizes.

(2) Hydroxides and carbonates are easily decomposed by heat to oxides of high area without
leaving potential catalyst poisons (as, for example, the sulfur left by sulfates calcination).

48
(3) Safety and environmental problems arising from the calcination of hydroxide and carbonates
are minimal.

During coprecipitation care must be taken in order to avoid independent or consecutive

precipitations. Besides, the pH should be adjusted and kept constant during the operation: this
can be done by mixing the starting solution continuously, instead of adding one solution to the
other

2. GELATION AND FLOCCULATION

Hydrophilic colloidal solutions are formed of micelles that remain separated because of electrical
charges on their surfaces and in the surrounding solution. These charges create repelling forces
which prohibit coagulation of the micelles. Such micelles are produced via chemical reactions of
polymerization and polycondensation. For instance, a silica sol can be obtained starting from
sodium silicate and a mineral acid by polycondensation of the intermediate silicic acid.

Fig3-2-1. Formation of gels and flocculates

The reticulation of these micelles gives rise to a hydrogel, a three-dimensional network that
imprisons molecules of water. The mechanism of a hydrogel formation is reported in Fig. 3-2-1.
The point at which this process, also called gelation, occurs depends on the concentration of
micelles, the temperature, the ionic strength of the solution and especially on the pH. For silica
sols the gelation time ranges from a few minutes to a hundred hours while the pH varies from 2
to 7 . The density of the gel will increase with the concentration of the original salts in the
solution and with the gelation rate. Co gel can be obtained by gelation of sols containing two or

49
more species (Si0,/A1,03, SiO,/Cr,O,). The starting sol can also be obtained by hydrolysis of
alkoxides such as tetraethyl orthosilicate. This is the first step in the well known sol-gel process
largely used to produce homogeneous ceramics, glass and composites . The sol-gel process can
also be successfully applied for catalysts preparation . Sol-gel methods have several promising
advantages over precipitation. In general, sol-gel synthesis offers better control over surface area,
pore volume and pore size distribution.

Besides the number of alkoxides commercially available allows the formulation of quite a
number of cogel with high uniformity and stability. The flocculation of a sol can be obtained
through the neutralization of the micelle charges (Fig. 3-2-2). The micelles thus coagulate into
flocculates that more or less precipitate well. Hydrophilic sols generally give jellylike flocculates
that contain large amounts of water (e.g. the amorphous flocculate of Al(OH),). Such flocculates
are denser than hydrogels, but in both cases the elementary solid particle has the dimensions
of the original micelles. The surface area of the final solid depends on the original micelle size
and also on the ripening and drying conditions.

Fig 3-2-2. Gelation of silica: Influence of pH on gelation time(Upper Curve) and surface
area(Lower Curve).

3. HYDROTHERMAL TRANSFORMATION

50
For hydrothermal transformations we usually consider the modification of precipitates, gels or
flocculates, induced by temperature, under aging or ripening in the presence of the mother liquor
(usually water). These transformations are usually carried out at rather low temperatures (loo-
300°C). They involve textural or structural modifications of the solid that can be summarized as
follow:

(1) small crystals + large crystals;

(2) small amorphous particles + large amorphous particles;

(3) amorphous solid -+ crystalline solid;

(4) crystal 1 + crystal 2;

(5) high porous gel + low porous gel (Aging or syneresis of a gel ).

All such transformations obey the laws of thermodynamics and thus proceed in a direction
corresponding to a decrease in free energy of the system. Increasing interest has been devoted in
the last decades to the hydrothermal synthesis of zeolites and molecular sieves, which is a
particular application of the hydrothermal transformations. In most ripening treatments
hydrothermal transformations usually occur within a liquid phase. However they can also be
performed in an atmosphere of steam, such as the steam stabilization procedure of Y zeolites.

The variables of these types of operations for a given solid are: pH, temperature, pressure, time
and concentration. When a hydrothermal transformation is distinct from other operations, it is
carried out in specific reactors. In other instances the hydrothermal transformations are carried
out during other unit operations such as precipitation, washing, drying, extrusion.
4. DECANTATION, FILTRATION, CENTRIFUGATION AND
WASHING
Decantation, filtration and centrifugation are well known unit operations, the aim of which is the
separation of the solid phase from the mother liquor. Washing of the solids is then required to
remove the mother liquor completely and to eliminate impurities.

51
The separation of the mother liquor is quite easy for crystalline precipitates, difficult for
flocculates and of no use for hydrogels. The selection of the separation method will also depend
on the particle size of the solids.

A satisfactory but time-consuming method is decantation. Washing is carried out simultaneously

with it. The slurry is added to a large volume of distilled water and the suspension is thoroughly
mixed. Upon standing, particles settle down. When a definite interface is visible, water is
removed by decantation and the process repeated till the desired purity is reached. When
washing flocculates, problems may arise as the purified flocculate takes longer to settle with
each washing, since removal of counter-ions reverts the flocculate to sol. This is the well known
phenomenon called peptization. Care must be taken not to wash too much or allow settling times
to become too long. When washing is completed the solid is filtered. If the particles are too small
and the settling time too high, filtration or centrifugation must be used. Again care must be taken
not to wash too much with water, otherwise the flocculates peptize and pass through the filter.

Washing can also be applied to exchange certain undesirable or useless ions for others that are
easily decomposable by calcination. For this purpose a proper salt solution in water will be used
instead of distilled water. High temperatures (e.g. 100°C) can increase the efficiency by
increasing the exchange rate. For example the exchange of Na+ for NH,f is used to obtain the
ammonium form of a zeolite, which is transformed into the acidic form by calcinations.

5. DRYING
Drying is described as the elimination of the solvent (usually water) from the pores of a solid.
This is a routine procedure for crystalline solids but becomes critical for flocculates and even
more for hydrogels that can contain up to 90% of water. Therefore we will discuss only the
drying of such gels.

The removal of water can result in a certain collapse of the structure. Care must be taken to
properly control the drying operations if high porosity is desired.

Initially drying occurs through evaporation of moisture from the outside surface of hydrogel. The
water loss rate is constant and the mass transfer is controlled by temperature, relative humidity,

52
flow rate of air over the surface and size of the gel particles. This process continues until the
moisture content is reduced to about 50%. Then the gel mass begins to shrink. The material so
obtained is called xerogel.

Fig 3-5-1. Pore volume reduction in silica hydrogel.

The subsequent moisture loss occurs with a declining rate, in which evaporation is controlled by
capillary forces. The saturation point decreases as pores become smaller and evaporation slows
until water is forced into larger pores by concentration gradients. If evaporation occurs but
removal of moisture is blocked by smaller pores, an internal pressure of steam develops and the
structure collapses, with loss of pore volume and surface area. The pore volume loss on drying of
a silica hydrogel is reported in Fig. 3-5-1 . High temperature gradients should be avoided in order
to reduce such effects. The effect of temperature is shown in Fig.3-5-2. Gel breakage is reduced
by lowering the drying temperature, increasing the relative humidity of the drying medium or
reducing airflow through the gel bed . Vacuum drying at lower temperatures is an advisable
laboratory procedure.

53
 Fig 3-5-2. Effect of dryng temp on surface area of a silica hydrogel

Dried xerogels contain 25-30% of water, encapsulated in fine pores or chemically bound to the
oxide. In this moist state it is sometimes easier to form the material into pellets or extrudates.
This is sometimes done for convenience provided subsequent calcination does not weaken or
damage the particles.

Large capillary stresses can be avoided by operating at temperatures higher than the critical
temperature of water or by vaporizing the water under vacuum at temperatures ranging from -50
to - 5°C . The solid structure undergoes only a small modification by retaining the textural
properties of the wet gel and leading to a highly porous dry solid called aerogel.

6. CALCINATION
Calcination is a further heat-treatment beyond drying. As with drying, this unit operation can be
located before or after the forming operation, depending on the case. We will refer in the
following to calcination in air, typically at temperatures higher than those used in the catalytic
reaction and catalyst regeneration. Other thermal treatments, such as reductions or sulfidations,
are performed in special atmospheres, so they will be designated as activation operations. The
latter are usually performed in the industrial reactor at the start-up of the unit. Therefore they are
not considered to be preparation procedures. Several processes occur during calcination: loss of
the chemically bonded water or CO,, modification of the texture through sintering (small crystals
or particles which turn into bigger ones), modification of the structure, active phase generation

54
and stabilization of mechanical properties. Alumina is a good example with which to
demonstrate all these features. Fig. 3-6-1 outlines the principal decomposition sequences that
occur upon heating the aluminum hydroxide .

Fig 3-6-1. Alumina modification upon calcination

Upon calcination of bohemite above 3OO”C, a series of phase changes occur, simultaneously
with loss of hydroxyl groups and hence of water. These result in the formation of a series of
oxides (q-, y- and &phases), known as pseudo y-alumina, good for binder and catalysts support,
and therefore useful ingredients in catalyst preparation . Above 1000°C monoclinic Ɵ- Al2O3
forms, transforming into hexagonal α-Al2O3 at 1200°C. These are anhydrous, low surface area
oxides and are not suitable for porous supports. They are used in applications where mechanical
strength is required. Changing the calcination temperature, even when phase transitions are
avoided, can affect the pore size distribution. In Fig. 3-6-2 is reported the effect of the
calcination temperature on a y-alumina : increasing the temperature results in a collapse of
micropores and in the increase of the mean pore size.

55
 Fig 3-6-2. Effect of calcination temperature on the pore size of y-Al2O3

By calcining a xerogel various types of sintering can result with two extremes:

(1) sintering at constant pore radius and

(2) sintering at constant pore volume.

The first is the case of a xerogel with covalent bonds (silica and silica-alumina), calcined in dry
air. The textural modification results in a contraction of the untouched xerogel around pinpoints
of crystallization. The overall pore volume reduces.

The second case is typified by ferric hydroxide, a xerogel with ionic bonds, which retains its pore
volume, even in dry air, by calcination and sintering. The particles get bigger and the pore size
increases.

Between the two extremes the intermediate cases are observed. Thus calcining a xerogel with
covalent bonds in the presence of steam results in a sintering at constant pore volume. The
addition of a specific agent can affect the sintering. For instance the addition of sodium to silica
lowers the sintering temperature. A substance which inhibits the sintering is called textural
promoter.

In conclusion, the calcination operating variables for a given gel are time and temperature and
the presence of steam

7. FORMING OPERATIONS
56
Forming operations are applied to obtain suitably sized particles of catalyst to be used in the
reactor. Therefore, forming and shaping of supports and catalysts is an important step in the
preparation procedure of a catalyst. A catalyst particle shape and dimension should promote
catalytic activity, strengthen the particle resistance to crushing and abrasion, minimize bed
pressure drop, lessen fabrication cost and distribute dust build-up uniformly. Unfortunately, these
objectives are not easily achieved. Indeed, several are mutually exclusive. For instance, a smaller
particle size increases activity but also increases bed pressure drop. The best operational catalyst,
therefore, has the shape and size that, in the end, represent the optimum eco nomic trade-off .
The selection of the shape and size is driven by the type of reactor. Table 3-7-1 gives a rough
survey of the different shapes and the reactors in which they are used. For a given reactor the
shape and the size of the catalytic particles will depend on the hydrodynamic and on heat and
mass transfer limitations. Here we will describe the different techniques for shaping the catalysts
into the shape.

Two extreme types of shaping can be distinguished , depending on whether the desired products
are powder microgranules or grains of the size order of one to several millimeters.

Table 3-7-1. Different types of catalyst shapes

7.1 FORMING MICROGRANULES

Crushing and grinding are of no use to produce microgranules for such a purpose. Actually the
powder so obtained has a broad particle size distribution, with a lower limit of few microns. Such
a powder is not usable in fluidized beds because of its poor mechanical resistance. Spray drying
57
is a suitable technique to produce microspherical materials. In a spray dryer a hydrogel or a sol is
sprayed through nozzles into a heated zone. Depending on the temperature, either drying or both
drying and calcination occur as the drops fall. Examples of catalyst produced by this procedure
are: catalytic cracking catalysts (silica-alumina doped with X or Y type zeolites) ; titanium
silicalite catalyst ; silica gel.

The process itself is more art than science There is hardly any information in the a Ipen
scientific literature . Important process parameters are the viscosity of the liquid, the solid
content of the suspension, the film-forming characteristics, the type of atomizer, the temperature,
the gas velocity. In Fig. 3-7-2 is reported the scheme of a spray dryer. Appendix A-2 shows two
different kinds of particles obtained by different feeds.

Fig 3-7-2. Spray dryer

7.2 FORMING GRAINS

The raw materials comprise a calibrated powder or paste with suitable rheological properties.
Table 3-7-3 summarizes the methods used for making grains according to the nature of the
original charge.

58
 Table 3-7-3. Influence of starting material on choice of grain foring process

7.2.1 EXTRUSION AND WET PRESSING

Extrusion is the most commonly applied shaping technique for catalysts and catalyst supports. A
wet paste is forced through a die. As the ribbon of the extrudate paste emerges from the die it is
cut to the desired length by a proper device. Usually catalyst mixes of powdered oxides made by
precipitation do not by themselves have the necessary mouldability and plasticity even when the
optimum water content is added. They behave rather like sand.

Besides, quite a number of such materials need a binder to produce extrudates with good
mechanical behavior. So in the formulation of the paste different additives can be used:
compounds for improving the rheological behavior of the paste (clays or starch); binders
(aluminas, clays); peptizing agents to deagglomerate the particles (acetic acid, nitric acid);
combustible materials to increase the macroporosity (the so called pore formers like carbon
black, starch). Extruding equipment can be classed in one of two categories: press extruders (for
wet pressing) and screw extruders. The operating variables include: mixing time, additives
content, water content, paste aging, extrusion temperature. The quality of the extrudates will also
depend on the drying and calcining procedure.

Special shapes such as trilobates, rings, hollow cylinders can be obtained by using proper dies.
Monolith or honeycomb supports are also manufactured by extrusion of a thick inorganic dough
through a special die. Such unusual support form is used in automobile catalytic converters,
where a very low pressure drop is required to minimize power loss from the engine.

7.2.2 DRY TABLETTING

59
In this shaping process a dry powder is pressed between two punches in a tabletting press. The
production of strong particles by tabletting requires that the particles of the tablet feed be
subjected to a reasonably uniform triaxial pressure and that under this pressure they are crushed
together to form a dense bed which then welds at points of contact. At the tabletting stresses
capable of being generated by normal machines, the requirement of welding implies that a
sufficient fraction of the material has adequate ductility. A very crude relationship exists between
ductility, melting point, elastic modulus and Moh’s scale of hardness, This is shown in Fig. 3-7-
4.

Fig 3-7-4. The relation between pelletability, crystal strength and melting point

Additives such as lubricants (mineral oil, talc, graphite, various stearates) and binders (bohemite,
clays) are added to give the powders proper qualities. For example, when tabletting untablettable
material such as Cu2O, Al2O3 , a sufficient quantity of hydroxide or carbonate precursor is left in
the tabletting feed (e.g. CuCO,, Al(OH),) to act as binder. The tabletting pressure heavily affects
the porosity of the tablet. This is shown in Fig. 3-7-5 for the tabletting of bohemite.

Compared to other shaping methods tabletting is quite an expensive method. Tabletting is widely
used as preliminary forming method in order to prepare samples for catalyst testing in fixed bed
microreactors, starting from powders. Depending on the reactor diameter the pellets are then
crushed and sieved to a suitable particle size (reactor to particle diameter ratios of 5- 10).

60
 Fig 3-7-5. Influence of pelleting pressure on bohemite pore distribution.

7.2.3 GRANULATION
Granules are particles with more or less spherical shape. The diameter of these particles ranges
between 2 to 30 mm. The principle of the shaping method is best described by the snowball
effect . A round dish (see Fig. 3-7-6) rotating on an inclined axis is used. Small particles are fed
into the dish. At the same time a cohesive slurry is sprayed onto the particles. The particle
surface becomes wet and granules begin to grow. The small particles rotating develop layer by
layer into larger, more or less spherical particles. After drying, the green spheres are calcined to
obtain higher mechanical strength. Sometimes some binder and cement are used to make the
layers adhere better.

Fig 3-7-6. Production of spheres by rotating dish granulator

7.2.4 DROP COAGULATION

61
Drop coagulation results from sols suspended in an immiscible liquid, by simultaneous gelation,
ripening and forming. Fig. 3-7-7 illustrates the principle of the method. In the form of droplets
the aqueous sol is forced, through a sparger in a water-immiscible solvent, the temperature of
which is raised to around 100°C. The surface tension created on the droplets permits the
formation of gel spheres that are than ripened and dried. The gelation can also be induced by
increasing the pH . During drying a contraction of the bead without deterioration is observed as
long as the diameter is not too large. Accordingly, this method is suitable for producing beads
such as alumina beads used as support (Appendix A-3).

Fig 3-7-7. Production of spheres by drop coagulaton

8 SUPPORT CATALYST
Supported catalysts are often applied because they combine a relatively high dispersion (amount
of active surface) with a high degree of thermostability of the catalytic component.

The preparation of supported catalysts aligns all the unit operations toward dispersing an active
agent on a support, that may be inert or catalytically active. The wetting of the support with a
solution or a slurry of the active phase precursors is the operation that characterizes such a
preparation. The other operations (drying, washing, calcination, forming) are ruled by the same
laws, depend on the same parameters.

62
The function of a support is, quite simply, to enable the formation of a large particle or tablet of
catalyst composed of very small readily sinterable crystals of catalyst which are prevented from
coalescing by being separated from each other by the support component. The support
component clearly has to be much more resistant to sintering than the catalytic species. Two
methods of utilizing support are common . Firstly, a support may be used as a form of refractory
surface on which the catalyst crystals are dispersed; rather like putting small drops of mercury on
a table top. Secondly, the support may be used in the form of more finely divided refractory
crystals than the catalytic species, positioned between particles of such species so that they are
kept out of contact - rather like dust which can be used to stop a heap of mercury drops from
coalescing. With the first method, the volume of support is considerably greater than the volume
of catalytic species, consequently this method is normally employed with precious metal. The
preferred preparation procedure for such catalysts is impregnation on a preformed support.

Preparation procedures for the second type of catalysts usually start from powders of support or
support precursors (e.g. precipitation of active species on powder support). Then a forming
operation will follow.

SUPPORT SELECTION

The selection of a support is based on its having certain desirable characteristics. Principally they
are:

1. Inertness.

2. Desirable mechanical properties, including attrition resistance, hardness and compressive

strength.

3. Stability under reaction and regeneration conditions.

4. Surface area. High surface area is usually, but not always, desirable.

5. Porosity, including average pore size and pore size distribution. High area implies Fine pores,
but relatively small pores (for example < 5 nm) could become plugged during impregnation,
especially if high loading is sought.

63
6. Low cost. Of a wide variety of possible materials, only three of them possess a good
combination of the characteristics mentioned: alumina, silica and activated carbon. Alumina is
the most widely used industrially.

Table 3-8-1 reports the main characteristics of some typical supports . Materials with low
surface area are generally useful in supporting very active catalytic components in reaction
where further side reactions may affect activity and selectivity. Examples of catalysts prepared
with low surface area supports are: FischerTropsch cobalt catalyst on diatomaceous earth and
ethylene oxide silver catalyst on pumice . Supports with high surface area are widely used in
precious metal catalyst preparation.

Table 3-8-1. Typical catalyst support

8.1 PRECIPITATION

In precipitation, the reaction of the type:

64
Powders or particles are slurred with an amount of salt sufficient to give the required loading.
Enough alkali solution is added to cause precipitation, the powder is then treated with the same
operations already discussed for bulk catalyst preparation. When preformed support is used
forming operations are avoided.

Two process are involved in the deposition:

(1) precipitation of solution in bulk and pore fluid;

(2) interaction with the support surface.

Best results occur when the OH groups of thesupport interact with the metal. For example,
silanols group of silica interact with Ni(NO,),, resulting in a surface hydrosilicate formation,
rather than hydroxide deposition.

Rapid nucleation and growth in the bulk solution must be avoided, since it produces a deposition
only outside the support porosity. An effective method to obtain a uniform precipitation is to use
urea rather than conventional alkalis. Urea dissolves in water but decomposes very slowly at
90°C giving a uniform concentration of OH- in the bulk and in the pores. So precipitation takes
place homogeneously over the support surface.

The precipitation is the preferred deposition route for loading higher than lo-20%. Below this
value, impregnation is usually practiced.

8.2 IMPREGNATION
The impregnation method involves three steps:

(1) contacting the support with the impregnating solution for a certain period of time,

(2) drying the support to remove the imbibed liquid and

(3) activating the catalyst by calcination, reduction or other appropriate treatment.

Two methods of contacting may be distinguished, depending on the total amount of solution.
Two methods of contacting may be distinguished, depending on the total amount of solution.

65
 (1) With excess of solution. The support is placed on a screen and dipped into an excess
quantity of solution for the time necessary for total impregnation. The solid is then
drained and dried. This operation can be done continuously as shown in Fig. 16a. In such
an operation the composition of the batch solution will change and the release of debris
can form a mud which makes it difficult to completely utilize the solution.
(2) With repeated application of solution. A more precise control is achieved by this
technique, termed dry impregnation or impregnation to incipient wetness. The support is
contacted with a solution of appropriate concentration, corresponding in quantity to the
total known pore volume or slightly less. This operation can be performed continuously
as shown in Fig. 3-8-2b. The catalyst is kept in motion in a rotating cylinder or drum, and
is sprinkled as required with a solution of salt by sprayers. The disadvantage is the poorer
distribution of the precursors.

Fig 3-8-2. Support impregnation process(a) with excess solution (b)impregnation to

incipent wetness

For both techniques the main operating variable is the temperature which affects both the
precursor solubility and the solution viscosity and, as a consequence, the wetting time. In Fig. 3-
8-3 are shown four limiting types of impregnation profiles. A proper control of the operating
conditions during impregnation and drying determines the impregnation profile of the final
catalyst.

66
 Fig 3-8-3. Four limiting types of impregnation or activity profiles. Hatched areas in the
cross sections of slabs and pellets (top and middle rows) indicate the regions where active
components are deposited. The bottom row shows schematic examples of impregnation or
activity profiles

CHAPTER 4

EXPERIMENT

1. EXPERIMENTAL SET UP

67
 Fig 4-1. Schematic diagram of the experimental setup for wet oxidation: CW, cooling
water; CY, gas cylinder; δ, sample con- denser; GS, gas sparger/liquid sampling device; H,
electric heater; PI, pressure indicator; R, reaction vessel/autoclave; RD, rupture disk; S,
sample outlet; SI, speed indicator; T, thermowell; TI, temperature indicator; TIC,
temperature indicator and controller

Since oxidation of formic acid is difficult, their oxidation to CO2 and H2O becomes the rate
controlling step in the oxidation process. Since we are interested from an environmental point
of view, the results are presented in terms of COD of the final stream.

2. CATALYST PREPARATION
The steps of catalyst preparation are as follows:

1. Amount of metal salt is taken stoichiometrically.

68
 2. 50cc distilled water + calculated amount of salt is taken in a beaker.
3. The mixture is stirred for 30 mins at room temperature.
4. 20 gm alumina(Al2O3)/Silica/TiO2/Mixed oxides such as Alumina-SiO2 gel or Al2O5-
CeO2 mixed oxide or Alumina-titanium oxide was added in the beaker solution.
5. It was stirred for 4 hrs at room temperature.
6. Then the solution was dried overnight for 12 hrs at 100⁰C.
7. Calcination at 550⁰C was done for 4 hrs.
8. Catalyst was ready.
9. After the catalyst was ready, it was reduced with hydrogen for 6 hrs at 25⁰C.
3. FORMIC ACID REACTION
The reaction for oxidation of formic acid can be represented as

HCOOH + 1/2O2 → H2O + CO2

In the present investigation, oxidation was carried out from an environmental engineering point
of view, and therefore results are given in terms of COD. The kinetics of noncatalytic oxidation
was carried out in the temperature range 150-240°C and oxygen partial pressure range of 0.345-
1.380MPa. Owing to the high diffusivity of oxygen in the gas phase and its low solubility in
water, the gas phase mass transfer resistance was estimated to be negligible in the range of
operating temperatures used for oxidation studies.

The liquid phase mass transfer resistance depends upon the level of turbulence in the liquid
phase, and hence the effect of speed of agitation on the rate of the reaction may be deemed as the
barometer to indicate the presence of liquid phase mass transfer resistance.

The effect of speed of agitation on the rate of reaction was studied in the range 6.3 -14.5 rps.
The liquid side mass transfer resistance was completely eliminated at an impeller speed of 14.5
rps. Thus it was ensured that the reaction was kinetically controlled under the experimental
conditions employed.

69
 CHAPTER 5

RESULTS AND DISCUSSIONS

The main alternating variables in my project were

1. Effect of temperature and oxygen partial pressure change on COD reduction during non-
catalytic wet oxidation of formic acid.
2. Effect of temperature, oxygen partial pressure and catalyst loading on COD reduction
during catalytic wet oxidation of formic acid.
In the present investigation, oxidation was carried out from an environmental engineering point
of view, and therefore, results are given in terms of COD. The kinetics of non-catalytic oxidation
was carried out in the temperature range 150-240 °C and oxygen partial pressure range 0.345-
1.380 MPa. In order to ascertain the absence of a mass transfer resistances (kGa and kLa), it was
decided to study the destruction of COD as a function of speed of agitation by varying the
impeller speed in the range 6.3-14.5 rps. It was observed that the rate of oxidation was
independent of impeller speed, indicating the absence of liquid phase mass transfer resistance.
The high oxygen partial pressures employed and the low solubility of oxygen meant the absence
of gas phase mass transfer resistance. All subsequent measurements were carried out at an
impeller speed of 14.5 rps.

1. EFFECT OF TEMPERATURE AND OXYGEN PARTIAL

PRESSURE ON COD REDUCTION DURING NON-CATALYTIC
WET OXIDATION OF FORMIC ACID:
The effect of temperature and oxygen partial pressure on COD reduction during non-catalytic
wet oxidation is shown in Figure 5-1-1 . The COD reduction was 12.92% at 150 °C and 0.69
MPa oxygen partial pressure. However, about 95% COD reduction was observed at 240 °C.
Over the entire temperature range studied, the reaction was found to obey first-order kinetics
with respect to COD (m = 1) though other orders were also tried. The reaction kinetics could be
well explained by having m= 1, i.e., order with respect to substrate (formic acid (COD)) as 1.

70
 Fig 5-1-1. Effect of temperature and oxygen partial pressure on COD reduction during
noncatalytic WO of formic acid: ( g) 150°C, 0.69 MPa; ( 0) 200 °C, 0.69 MPa; ( 4) 210 °C,
0.69 MPa; ( )225 °C, 0.35 MPa; ( 9) 225 °C, 0.69 MPa; ( 2) 225 °C, 1.38 MPa;(]) 240 °C,
0.69 MPa.

The first-order kinetics plot is shown in Figure 5-1-2. The effect of oxygen partial pressure on
COD reduction was studied over the range of oxygen partial pressures 0.345-1.380 MPa at 225
°C. The order with respect to oxygen was found to be 0.86. This, therefore, indirectly presents
evidence for a free radical mechanism.

Fig 5-1-2.. First-order kinetics plot for wet oxidation of formic acid: (0) 210 °C, 0.69 MPa; (
4) 218 °C, 0.69 MPa; ( )) 225 °C, 0.69MPa; (g) 225 °C, 0.345 MPa; ( +) 225 °C, 1.38 MPa.

71
The Arrhenius plot showing ln k vs 1/T is exhibited in Figure 5-1-3. The energy of activation
was found to be 28.94 kcal/(g mol), confirming the absence of diffusional resistance. Based on
experimental findings, the global rate equation for noncatalytic wet oxidation of formic acid is
given by

r1 = 4.712 × 1010 exp[-14565/T][COD]1 [O2] 0.86

Fig 5-1-3. Energy of activation for noncatalytic wet oxidation of formic acid.

2. EFFECT OF TEMPERATURE, OXYGEN PARTIAL PRESSURE AND CATALYST

LOADING ON CATALYTIC WET OXIDATION OF FORMIC ACID.

Catalytic oxidation of formic acid using cupric sulfate (CuSO4) was studied in the temperature
range 150- 180 °C and oxygen partial pressure range 0.345-1.035 MPa. The effect of
temperature, oxygen partial pressure, and catalyst loading on COD reduction is shown in Figure
5-2-1.

72
 Fig 5-2-1. Effect of temperature, oxygen partial pressure and catalyst loading on COD
reduction of formic acid solution: ( 0) 150°C, 0.690 MPa, 6.888 × 10-4 kmol/m 3; (4) 165
°C, 0.345 MPa, 6.888×10-4kmol/m3;()) 165°C,0.690MPa,6.888×10-4kmol/m3;
(g)165°C,1.380MPa,6.88×10-4kmol/m3;(+) 180 °C, 0.690MPa,6.888×10-4kmol/m3;(×) 165
°C,0.690MPa,1.252×10-4kmol/m3;(9) 165 °C,0.690MPa,3.131×10-4kmol/m3.

For the catalyst loading of 6.888 × 10-4 kmol/ m3, a maximum COD reduction of 97% was
achieved at 180 °C in 1.5 h. In this interesting case, we have observed that the order with respect
to COD is 1.5 and first order with respect to O2. The higher order with respect to COD (formic
acid) may be due to a formic acid-Cu complex forming during oxidation. The Arrhenius plot for
catalytic WO of formic acid is shown in Figure 5-2-2.

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 Fig 5-2-1.Energy of activation for catalytic wet oxidation of formic acid.

The energy of activation was found to be 22.5 kcal/(g mol). This value confirms the absence of
mass transfer resistance. Kinetic data for the catalytic wet oxidation of formic acid within the
range of above variables could be correlated by the expression

r2 = 1.752 × 1012 exp[-11302/T][COD]1.5[O2] 1 × [CuSO4] 0.44

It was possible to achieve complete oxidation of formic acid (in terms of COD) within 3 h using
6.888 × 10-4 kmol/m3 catalyst loading at 180 °C. Thus the homogeneous copper catalyst was
found to be effective at lower temperatures

74
 CHAPTER 6.

CONCLUSION
The wet oxidation of formic and acetic acids catalyzed by cupric sulfate was proved to be an
effective technique to meet the discharge standards with respect to COD and concentration of
individual acids as well. The noncatalytic wet oxidation of formic acid was found to obey first-
order kinetics with respect to substrate COD, whereas, in the case of catalytic oxidation the
data could be well fitted to m = 1.5. Wet oxidation of acetic acid was found to obey first-order
kinetics with respect tosubstrate COD and it was found to be oxidized directly into carbon
dioxide and water. The use of homogeneous CuSO4 catalyst may be very effective in destroying
organic molecules via wet oxidation because it is effective in destroying formic and acetic acids
that are formed in wet oxidation.

We, therefore, postulate that since homogeneous “CuSO4” can destroy acetic acid, it could be a
very effective catalyst in wet oxidation of any organic substrate. Almost complete destruction of
phenol (COD) was possible during catalytic wet oxidation in the presence of homogeneous
cupric sulfate .

The wet oxidation of formic and acetic acids catalyzed by cupric sulfate was proved to be an
effective technique to meet the discharge standards with respect to COD and concentration of
individual acids as well.

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 APPENDIX A

A-1: REACTOR DESIGN FOR A-2: MICROGRANULES

SWOP SYSTEM OBTAINED BY SPRAY DRYING
(a)TITANIA (b)SILICA-
ALUMINA

A-3: ALUMINA SPHERES

OBTAINED BY DROP
COAGULATION

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 APPENDIX B

Table B-1 : List of some organizations that have incorporated SCOW plant for water
treatment

Compound Treated Effluent Removal efficiency

ETH Zurich
Methanol TOC rem. 99.9%
(Switzerland)

ITC-CPV Karlsruhe
Ethanol, Na2SO4, Paper mill waste TOC rem. 99.9%
(Germany) effluents

Sandia’s EER Isopropyl alcohol No Na2SO4 deposits in the

(USA) Military smokes and dye formulations transpiring wall

Isopropyl alcohol

Pine Bluff Arsenal Sugar and Na2SO4

TOC rem. 99.9%
(USA) Solutions Military smokes and dye

formulations

U.S. Navy/Army’s
Dugway Proving TOC rem.> 99.9%
Naval wastes (Cl- and Fl- containing)
Ground Facility (Trials for Blue Grass
(71 h) Chemical weapons (231 h)
chemical weapons destruction)
(Utah, USA)

CEA (France) Methanol TOC rem.   99.9%

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Table B-2: Typical pore diffusion values of different support and catalyst

78
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