IRON SLUDGE AND ITS APPLICATION IN THE PREPARATION OF

FENTON CATALYST

A SEMINAR REPORT
Submitted by

SNEHA RAPHEAL
AJC16CH058

In partial fulfillment for the award of the degree of

BACHELOR OF TECHNOLOGY
In
CHEMICAL ENGINEERING

Department of Chemical Engineering,

AmalJyothi College of Engineering, Kanjirappally

October, 2019
IRON SLUDGE AND ITS APPLICATION IN THE PREPARATION OF
FENTON CATALYST

A SEMINAR REPORT
Submitted by

SNEHA RAPHEAL

AJC16CH058

Department of Chemical Engineering,

AmalJyothi College of Engineering, Kanjirappally

October,2019
 DECLARATION
I undersigned hereby declare that the seminar report “Iron sludge and its application in the
preparation of Fenton catalyst”, submitted for partial fulfillment of the requirements for the
award of degree of Bachelors of Technology of the APJ Abdul Kalam Technological
University, Kerala is a bona fide work done by me under supervision of Asst. Prof. Nikhi
Maria Raju. This submission represents my ideas in my own words and where ideas or words
of others have been included; I have adequately and accurately cited and referenced the
original sources. I also declare that I have adhered to ethics of academic honesty and integrity
and have not misrepresented or fabricated any data or idea or fact or source in my submission.
I understand that any violation of the above will be a cause for disciplinary action by the
institute and/or the University and can also evoke penal action from the sources which have
thus not been properly cited or from whom proper permission has not been obtained. This
report has not been previously formed the basis for the award of any degree, diploma or
similar title of any otherUniversity.

Place :
Date : SNEHARAPHEAL

i
 DEPARTMENT OF CHEMICAL ENGINEERING
AMAL JYOTHI COLLEGEOFENGINEERING, KANJIRAPALLY

CERTIFICATE

This is to certify that the report entitled “IRON SLUDGE AND ITS APPLICATION IN
THE PREPARATION OF FENTON CATALYST” submitted by SNEHA RAPHEAL
(AJC16CH058) to the APJ Abdul Kalam Technological University in partial fulfillment of
the requirements for the award of the Degree of Bachelor of Technology in chemical
engineering is a bona fide record of the seminar carried out by her under my guidance and
supervision. This report in any form has not been submitted to any other University or
Institute for any purpose.

Miss Nikhi Maria Raju Prof. Dr. David. K. Daniel

Asst. Professor, CH Head of the Dept.

Guide Dept. of Chemical Engg.

 ACKNOWLEDGEMENT

I express my sincere gratitude to all those who helped me in the successful completion
of this seminar report. First of all I would like to thank God, The Almighty, who has been a
constant support in every walk of my life and the source of my strength for preparing this
seminar report.

I am thankful to the management of Amal Jyothi College of Engineering

Kanjirappally, for providing all facilities in completing the seminar successfully.

I am grateful to Rev Fr. Dr. Mathew Paikatt, Manager, AJCE, for his constant
encouragement and support for this work.

I am much thankful to Dr. Z V Lakaparambil, Principal, Amal Jyothi College of

Engineering for providing the right ambience for carrying out this seminar successfully.

I acknowledge my deep sense of gratitude to Prof. Dr. David K Daniel , Head of the
Department, Department of Chemical Engineering, for his help for the successful completion
of this seminar.

I am deeply indebted to my Co-ordinator Miss Nikhi Maria Raju, Asst.Professor,

Department of Chemical Engineering, for her expert guidance and advice.

I thank all my teachers and friends for their great support and encouragement
throughout the seminar.

SNEHA RAPHEAL
 ABSTRACT

This work focuses on the different sources of iron sludge and its composition in the waste
water, recycling of chemical iron sludge. It draws a conclusion that scrap iron sludge can be
used in the fields of preparation of ironmaking raw material, iron oxide pigment, ferric salt
and new material, and put forwards that new prospect of cyclic utilization and application of
iron sludge in the preparation of iron catalyst used in the Fenton process. Also the Mariana
dam disaster shows waste can be change into resource. A simple and environmental friendly
strategy for recycling iron mining wastes involved the synthesis of a magnetic hybrid
(HbLM) material at ambient temperature. This study highlights the application of sludge iron
in the textile industry waste water treatment by the removal of dyes with 100%decoloration.
Different type of dyes like anionic, cationic dyes were experimented and optimum working
conditions noted .So this makes iron sludge develop in the direction of high added value from
low added value and bring favorable economic benefit and social benefit. The results obtained
in this work highlight the ability to combine the principles of green chemistry and industrial
symbiosis, with the development of new materials from abundant resources previously
considered to be waste.

iv
 TABLE OF CONTENTS
SI.No Content Page No.

1. Introduction 1

2. Iron sludge 3

3. Uses of iron sludge 5

3.1 Use iron sludge as raw material for 5
iron making

3.2 Use of iron sludge to prepare iron 5

oxide pigment

3.3 Use iron sludge to prepare ferric salt 8

3.4 Use iron sludge to prepare new material 10
4 Preparation of Fenton catalyst from iron sludge 12

4.1 Fenton process 12

4.2 Reuse of Fenton process sludge 13
4.3 Reuse of iron sludge from other sources 17
5
Case study- Mariana dam disaster 19

5.1 Preparation of the catalyst 19

5.2 Procedure 20

5.3 Characterization 20

6 Summary 23
7 Reference 24

v
 List of figures
SI. No Figure Name Page. No
2.1 Composition of iron sludge 4
4.1 Recycling of Fenton iron sludge 14
5.1 Synthesis of hybrid material 20
5.2 XRD pattern of HbLM 21
5.3 TG curve of HbLM 22
5.4 Infrared spectra of HbLM 22

v
i
 Seminar Report, 2019

CHAPTER-1

INTRODUCTIO

In the technological process of preparing aromatic amino compounds with many aromatic
nitro compounds, iron powder is frequently used as the reducing agent. In the meantime, a
mass of industrial waste residue called iron sludge will be produced and it is a kind of
pollution source which is difficult to be degraded and disposed. In recent years, with the rapid
development of economy, the output of industrial waste residue especially iron sludge is
increasing with each passing day. There is a saying that "wastes are misplaced resources".
How to turn "waste" into wealth and improve resource utilization rate has become an urgent
demand for the development of society. Forefathers have made relevant explorations and
researches on the recycling aspect of iron sludge and already made some progress. This paper
is to make an introduction and summary of the application and progress of chemical iron
sludge.
Textile dyeing process produced large amounts of wastewater that are discharged into the
environment. These effluents usually contain several classes of toxic dyes that exhibit low
biodegradability and/or increased toxicity. Thus, effluents not only deteriorate the receiving
waters, but also pose significant threat to the aquatic life because of the oxygen deficiency
and formation of some toxic products by hydrolysis of dyes in the wastewater. Most of textile
dyes are designed to produce long-lasting colors and are resistant to mild oxidation
conditions. Therefore, stronger oxidation process is needed to degrade these structures. For
that purpose, advanced oxidation technologies (AOTs) were extensively investigated. These
processes rely on the generation of extremely active OH radicals, which are identified as
strong and non-selective oxidants of almost all organic compounds. As one of AOTs, Fenton-
like (Heterogeneous Fenton) process was used to generate the powerful hydroxyl radicals
from H2O2 in the presence of iron as Fe2+ or Fe3+, to decompose many organic compounds
including dyes .In case of Heterogeneous Fenton reaction, soluble Fe catalyst is replaced by
Fe-containing solids. This kind of Fenton reaction has been proved to be also effective in the
treatment of industrial wastewater containing non-biodegradable organic pollutants.

Department of Chemical Engineering, AJCE Page 1

 Seminar Report, 2019
Furthermore, this process has numerous advantages over classical homogenous

Department of Chemical Engineering, AJCE Page 2

Fenton catalysis; e.g. no iron sludge is generated and easy separation of the catalyst from the
treated stream .Various heterogeneous Fenton-like catalysts such as Fe2O3,S-doped Fe2O3 and
Fe3O4 were used for wastewater treatment. Unfortunately, a lot of these catalysts do not
exhibit favorable catalytic activity at neutral pH and the working pH values are usually
around 3. Therefore, acidifying the wastewater or inputting external energy into the reaction
system is a frequently used method to enhance their activity .So it is worth to use low cost
catalyst to reduce the overall cost of the treatment process while keeping reasonable
efficiency. In this study, the waste produced from steel industry was used as a catalyst in
heterogeneous Fenton oxidation process.
Steel is manufactured by the chemical reduction of iron ore, using an integrated steel
manufacturing process or a direct reduction process. In the conventional integrated steel
manufacturing process, the iron from the blast furnace is converted to steel in a basic oxygen
furnace (BOF). Steel can also be made in an electric arc furnace (EAF) from scrap steel and,
in some cases, from direct reduced iron. Three major waste streams are generated during steel
manufacturing, air emissions, wastewater and solid waste. The solid waste from the
conventional process, including furnace slag and collected dust, is generated at an average
rate ranging from 300 kg/t of steel manufactured to 500 kg/t. This waste is rich in iron and can
be used as a catalyst in heterogeneous Fenton process for wastewater treatment. The use of
iron-containing waste in the treatment of wastewater will hopefully reduce the cost of
wastewater treatment. This work focuses on the use of iron-containing waste instead of iron
salts as a catalyst in heterogeneous Fenton process using different kind of dyes as model
compounds for dye wastewater. [8]
 CHAPTER - 2

IRON SLUDGE
Iron-rich sludge is a problematic waste product of potable water treatment, mine
water/groundwater management and hydrometallurgical processing. Other major sources of
sludge are Iron and steel industries, machine manufacturing plants, battery manufacturing
units. The sludge is a highly hydrous bulk waste product that in addition to iron may contain
various proportions of organics and other metals. It is conventionally managed by discharge
to rivers or sewers or by retention in lakes, wetlands, tailings ponds or landfills. Figure 2.1
show the iron sludge composition obtained from JSC water treatment plant.
Another source of iron-rich sludge in lakes and wetlands arises from naturally occurring iron-
bearing groundwater. The ground water resources have iron content; the iron concentration in
87% of groundwater resources exceeds the permissible hygiene rates. Although iron does not
have a significant impact on human health, iron compounds should be removed from the
groundwater because when soluble ferrous (bivalent) iron compounds interact with oxygen,
insoluble ferric (trivalent) compounds, which fall into sediments, are formed. As a result, the
water's turbidity increases, it takes on an unpleasant metallic taste, and iron compounds give
the water a brownish color. Iron bacteria develop in the accumulated iron, and, as a result,
sludge is formed. During water pressure fluctuation in the system, more ferruginous
sediments come from water taps. Due to these aesthetic issues, the World Health Organization
recommends that the maximum permissible iron concentration in drinking water should not
exceed 0.3 mg/L. In drinking water treatment plants, these ions and compounds are efficiently
removed by aeration and filtration through granular media filters or by other conventional
technologies. The sludge formed from these plants are heavy metal sludge, it should be
treated before disposal. But it’s kind of pollution source which is difficult to degrade and
dispose. Because of increasing sludge production and tightening environmental legislation
particularly restrictions on landfill and water pollution (EU Council Directives, 1999 and
2000) – numerous attempts have been made by industry to reduce the environmental impact
of sludge and, where possible, to market or re-use the waste or itscomponents.[8]
 Seminar Report,2019

Figure 2.1The iron sludge composition obtained from JSC water treatment plant [8]
 Seminar Report, 2019

CHAPTER - 3
USES OF IRON SLUDGE

Industrial waste residue called iron sludge is a kind of pollution source which is difficult to be
degraded and disposed. In recent years, with the rapid development of economy, the output of
industrial waste residue especially iron sludge is increasing with each passing day. There is a
saying that "wastes are misplaced resources". How to turn "waste" into wealth and improve
resource utilization rate has become an urgent demand for the development of society.
Forefathers have made relevant explorations and researches on the recycling aspect of iron
sludge and already made some progress. Some of the iron sludge derived products are
discussed below:
3.1. Use iron sludge as raw material for iron making
Iron sludge has high iron content. The material cost is low and effect is quite good if iron
sludge is used as the raw material for iron making. Mingcheng Steel Factory in Jilin Province
uses iron scurf reduction method to produce aniline and ortho-toluidine and a mass of waste
residue of amino compounds is produced accordingly every year. The waste residue is also
named as "reduced iron". With the increasing demand for amino compounds, reduced iron is
becoming more and more. In order to protect the environment and eliminate the pollution, Li
et al make iron sludge turn into iron making material through processing steps such as
recycling of metal scrap iron, settling separation of iron sludge, centrifugal filtration,
deposition and solidification and the effect is satisfactory. Although the effect of iron sludge
as ironmaking material is pretty good, abrasion of machine is quite severe and production
efficiency is reduced because there are unreacted reduced iron particles in iron sludge when
the machine is running at high speed.
3.2 Use iron sludge to prepare iron oxide pigment
Ferric oxide series pigments are the first major colored inorganic pigment and the second
major inorganic pigment next to titanium dioxide. Comparing with international pigments in
the aspect of quality, domestic pigments lag far behind. Under such condition, Technique of
making use of iron sludge to prepare ferric oxide series pigments including iron oxide red iron
oxide black and iron oxide yellow has an extremely wide application because of advantages
such as simple process, complete chromatography and small noxiousness.
3.2.1Preparation of iron oxide red
The molecular formula of iron oxide red is α-Fe2O3 and its output takes up 80% of iron series
products. Iron oxide red is an important colored pigment and it is widely applied in coloring
of oil paint, construction and plastics because of superior light fastness, thermo-stability,
alkali-resistance and resistance of atmospheric influence, dirty air and all kinds of alkali. A
little iron oxide red can be used in magnetic materials and materials for elements of
electronics and telecommunication. There are two preparation methods for iron oxide red.
One dry method (known as high-temperature calcination) and the process is relatively simple.
The other one is wet method and there are comparatively more process routes. However,
reaction mechanisms of these two preparation methods are basically the same. Iron oxide red
up to standard can be produced by both of two methods. Traditionally, iron oxide red
produced by iron sheet and scrap iron has a good quality but the technological process takes
quite a long time. What is more, costs are high but competitive force is low. Thus, it is
necessary to find new raw materials to enhance productivity.
Yang et al have confirmed that industrial iron sludge can be used as raw material after
exploration to produce iron oxide red pigment under the circumstance of 60% sulphuric acid
concentration after acid-curing oxidization, 1:1.2 mass ratio for sulfuric acid and iron sludge,
800°C temperature, and 120 min reaction time. Moreover, the pigment meets the
requirements of coating and oil paint on pigment.
Zhou et al use scrap iron and industrial waste sulfuric acid after production of hydroquinone
as the raw material, adopt high temperature dry method to produce iron oxide red through
processing steps such as smashing, burdening, calcination, cooling and ball-milling. Its cost is
30% lower than that of conventional methods. Optimal technological condition is confirmed
after exploration. Mass fraction of H2SO4 is 70% to 80%, mass ratio between iron and sulfuric
acid is 1:0.85 to 1:1, calcination temperature is 900oC, and calcination time is 40to70min.
Cui et al use both acid solution oxidation method and dry method to produce iron oxide red
with the chemical scrap iron sludge as raw material. First, sulfuric acid is used to steep iron
sludge and then the solution is heated to 50 oC with slow stirring. Sulfate liquor in iron-
containing mixed valence is produced after sufficient reaction. And then processing steps such
as iron powder feeding, filtering and high-temperature calcination are conducted. At last, an
analysis of XRD and chemical property is made towards the product to determine the
productive rate of iron oxide red product reaches 98.11%. Besides ordinary iron oxide red,
Wang et al also produce high-purity iron oxide red. Industrial scrap iron sludge after
production of DSD acid is used as raw material. Iron sludge is dried, smashed and made into
serous fluid with water after stirring. And then sulfuric acid and a certain amount of oxidizing
agent are added. Reaction under the condition of 80 oC temperature lasts one hour. When pH
value of the solution is equal to 3, the reaction is stopped and filtration is done. And then
sodium carbonate solution is used to adjust the pH value to 5.0 to 6.0 and filtration is done
next. Sodium carbonate solution is added to the filter liquor and filtration goes on to get
ferrous carbonate filter cake. A little amount of sodium carbonate solution and deionized
water are used to wash up to ferrous carbonate filter cake. And then drying, calcination and
smashing are done to get highly purified iron oxide red. Use ration of iron sludge under
optimal technological condition is up to 97% which meets the requirements of HG/T2574—
1994 Standard for Superior Products on quality.
3.2.2 Preparation of iron oxide yellow
Iron oxide yellow is non-toxic and has good color and wide range of application. The
chemical formula of iron oxide yellow is Fe2O3.XH2O or α-FeOOH. Iron oxide yellow is a
kind of high value-added inorganic pigment with excellent light resistance and weather
fastness so it is quite popular in the fields of coating, rubber, plastics, stationery and medicine.
The preparation methods of iron oxide yellow include peptization method, oxidation style,
acid process and alkaline process. Huang et al use iron vitriol dreg of yellow sodium as raw
material to make α-FeOOH seed crystal at first and then add weak aqua ammonia to form
Fe(OH)2 coating α-FeOOH and finally produce a large number of iron oxide yellow after the
oxidization of α-FeOOH seed crystal. These pigments have pretty good mono-dispersity and
have no agglomeration. The optimum condition is confirmed through exploration into the
optimal technological condition for the preparation of transparent iron oxide yellow. Ferrous
sulfate concentration is 40%, alkali ratio is 0.25, 1 L vessel Q is 0.16 to 0.2 m3/h; seed crystal
content is 1%, initial ferrous concentration is 0.40 mol/L, pH value is controlled within 3 to 4,
air doss is 0.4 to 0.5 m3/h, and stirring rate is 700 to 800r/min.
Zhang et al use industrial iron sludge as raw material to prepare α-FeOOH through
processing steps such as acid leaching, de-oxidation, air oxidation and filtration, make an
analysis on the influence of factors such as n(NaOH):n(FeSO4) and surface active agent to
finalize that good products can be produced under conditions of n(NaOH): n(FeSO 4)=5,
temperature=30°C, and sodium dodecyl benzene sulfonate as the surface active agent and 1h
reaction time.
3.2.3 Preparation of iron oxide black
Iron oxide black is mainly used in mosaic floor, wall and artificial marble in construction
industry. Iron oxide black can be also used as the coloring agent in plastics industry and
rubber industry. Besides, it is applicable to industries of printing ink and oil paint, and it can
be used to make iron oxide purple, iron oxide red and α-Fe 2O3.Although iron oxide black
prepared by traditional method has high performance, the cost is increasing because more and
more raw material is consumed in preparation. Shi et al use scrap iron sludge produced in the
iron powder reduction process as raw material to generate iron oxide black, turn iron sludge
into iron sludge in solid phase and reduced iron powder which is not fully reacted after
composition and filter pressing, and produce pure iron sludge in solid phase through size
mixing, sieving, water scrubbing and filter pressing. Finally, iron oxide black produced after
drying has good quality meeting relevant national standard. Patent 102583577A introduces
the method of using by-product chemical iron sludge in aminophenol process to prepare iron
oxide black. Iron oxide black is mainly produced by sieving and dehydration of iron sludge,
adding 2% to 5% MnCO3 and 2% NaCl to thermal treatment furnace, warming under the
protection of nitrogen, cooling, washing and drying. By means of this patent, about 1.6 ton
chemical iron sludge can be used to get about 1 ton pigments of iron oxide black, bringing
enterprises with obvious economic benefit. Patent CN1415551 adopts physical method to
carefully chooses iron sludge and prepare iron oxide black with 70% to 90% content after
rouging, drying and smashing. No pollution is caused and less cost is spent by this method so
that it has a certain market value.
3.3 Use iron sludge to prepare ferric salt
3.3.1 Preparation of solid polymeric ferric sulphate
Polymeric ferric sulphate (PFS for short) is a kind of efficient inorganic water depurator and
its general formula is [Fe2(OH)n(SO4)3-n/2]m, m=f (n). As an inorganic water depurator,
polymeric ferric sulphate has advantages such as good coagulation ability and high efficiency,
good water quality after purification and has good effect on disposing organic waste water in
meat-packing, tanning and printing. Su et al make a research on solid polymeric ferric
sulphate produced by raw materials of industrial iron sludge and sulfuric acid. Polymeric
ferric sulphate is prepared by experimental procedures including smashing, soaking,
neutralization, oxidization, and filtration. Solid matters produced by this method have high
production efficiency and low pollution. Di et al make use of ions co-precipitation principle
to change all Fe2+ in iron sludge into Fe3+, add polypropylene phthalein amine to get pure
ferric sulfate through filtration and cooling, and then distribute the ferric sulfate to a solution
with certain concentration, and finally get PFS sample after polymerization reaction, aging
and smashing.
3.3.2 Preparation of solid poly-silicate ferrite
Poly-silicate ferrite (PSF for short) flocculating agent is a kind of inorganic polymer
flocculating agent in compound type. It has advantages such as low toxicity, cheap price, no
waste emission and friendship with environment so that it has relatively high value in use. Ma
et al use iron sludge and sodium silicate as raw materials to prepare poly-silicate ferrite
through calcination and excitation. Optimal technological condition is determined through
exploration. Iron sludge calcining temperature is 800 oC, calcining time is 1h, sulfuric acid
concentration is 4 to 5mol/L, liquid-solid ratio (mass ratio) is 4:1, acid leaching time is 2h to
3h, acid leaching temperature is 100 oC, ratio of n (Fe) and n (Si) is 2:1, pH value of silicate
activation is 3.0, activation time of silicate is 25min, and aging time is 2h.
3.3.3 Preparation of ferrous sulfate
Ferrous sulfate is blue-green monoclinic crystal or particle with no odor and it has wide
application in the aspects of water flocculating purification, processing of industrial
wastewater, treatment of iron deficiency anemia and coloring agent. Li et al establish a new
method for preparation of a hydrated ferrous sulfate with scrap iron sludge and sulfuric acid
as raw materials through lab test and pilot plant test. This technique requires no pretreatment
for scrap iron sludge in the process of preparing ferric salt. Optional experimental condition is
determined through experiment. Sulphuric acid concentration is 22%, solid-to-liquid ratio is
0.25, extraction time is40min, extraction temperature is 85°C, melting temperature is 90°C to
95°C, pH value is 0.5 to 1, and reaction time is 30min.Zhang et al use scrap iron sludge as
raw material to prepare FeSO4.7H2O through processing steps such as acid leaching,
reduction and pH value adjustment. A conclusion is drawn through experiment that
FeSO4.7H2O has relatively good crystal in water-ethyl alcohol. Crystal ratio reaches 95%
when FeSO4 concentration is 1.41mol/L, ratio of V (ethyl alcohol) and V (water) is 1.5:1.0,
and reaction time is 20min. Optimal technological condition is determined. Temperature is no
higher than 30°C, pH value is 1.7 to 2.0, 1.7~FeSO4concentration is over 0.8mol/L, and ratio
of V (ethyl alcohol) and V (water) is 1.5:1.0. Products meet the standard of HG/T2935-
2000D.
3.3.4 Prepare ammonium ferric citrate
Ammonium ferric citrate has wide application in the aspects of food, medical and
meteorological analysis due to high iron content and good performance. Dong et al use iron
sludge as raw material to prepare ammonium ferric citrate and use sulfuric acid to remove
hazardous substances in iron sludge. Optional experimental condition is determined. Mass
fraction of sulphuric acid concentration is 35%, extraction temperature is 85 oC, solid-to-
liquid ratio is 0.1:1, and extraction time is 2h. Ferric hydroxide is prepared under conditions
of 80 oC reaction temperature and 1h reaction time. And then citric acid and ammonium
hydroxide is added to generate the sample. High-purity ferric citrate got through heating
concentration, drying and anhydrous ethanol soak meets the requirement of the country on
the quality of iron supplement agents.
3.4 Use iron sludge to prepare new material
The application research fields of iron sludge is expanding constantly from the field of
relatively mature preparation of ironmaking material, iron oxide pigment and ferric salt to that
of the preparation of iron based new material. Nanometer material, water treatment material
and also battery material are involved.
3.4.1 Prepare nanometer material
As a new-type material, nanometer iron oxide has wide application in the aspects of magnetic
memory material, magnetic liquid and function material due to its unique magnetism. At
present, solid phase method, vapor phase method, liquid phase precipitation method and oxy-
reduction precipitation method are frequently used to prepare nanometer iron oxide. Xu et al
use chemical iron sludge as raw material to get α-FeOOH through processing steps such as
reaction with sulfuric acid, suction filtration reduction and standardization, take α-FeOOH as
drive body and add defined amount of Fe2+ to adjust pH value to 9 to form precipitation
solution. Nanometer iron oxide is finally got through ebullition, 4h reflux, centrifugal
separation and drying. Optional experimental condition is determined through exploration.
Phase inversion temperature is 80 °C, inversion time is 2h, pH value is 9, and R is equal to
n(Fe3+)/n(Fe2+) and 1.75. Nitrogen protection is required in the earlier stage of preparation by
this method. There are disadvantages such as long reaction cycle, heterogeneous particles and
harsh reaction condition. Li et al use hydrogen peroxide as oxidizing agent to determine the
optional experimental condition through orthogonal experiment. pH value is 11, reaction
temperature is 75 oC, reaction time is 3h, and hydrogen peroxide dosage is 0.5ml. Under
such technological conditions, productive rate of nanometer iron oxide is up to 95.89%,
overcoming previous disadvantages.
3.4.2 Prepare water treatment material named sponge iron
Sponge iron is also named direct reduction iron (DRI) for short. Sponge iron becomes a kind
of popular new-type water treatment material due to advantages such as many micro- pore
and high activity and it has better reducing capacity than ordinary iron powder. At present,
domestic industrialization methods of production include down draft kiln method, cold
consolidation pellet rotary kiln method, one-step rotary kiln method and XSH-A method. Sun
et al use iron sludge generated in the process of producing DSD acid as raw material to
develop sponge iron, a kind of water treatment material. DSD acid is also named Maurer's
acid and it is a kind of important dye intermediate. Optimum condition for preparation of
conventional sponge iron is determined through experiment. Carbon charging rate is 27%,
reaction time is 16min, and reaction temperature is 1160 oC. Metallization ratio of iron sludge
for sponge iron prepared under such condition is over 90%.
3.4.3 Prepare materials for Li-ion batteries
LiFePO4 is regarded as an ideal anode material for lithium-ion battery due to its advantages
such as high-energy density, high security, long life and little pollution. Wu Z J et al use iron
sludge after recycling by carbon-thermal and magnetic separation to synthesize LiFePO 4/C.
Chang et al make use of dissolution-precipitation process to recycle iron in the state of
FePO4.2H2O from iron sludge and use FePO4.2H2O as raw material for synthesizing
LiFePO4/C. The experiment improves the electrochemical performance of LiFePO 4/C through
analysis of iron sludge by virtue of inductively coupled plasma (ICP) for short. X=2, i.e.,
FePO4.2H2O is calculated through thermogravimetric analysis (TGA for short) of
prepared FePO4.XH2O. Because LiFePO4/C produced by iron sludge as raw material contains
beneficial impurity elements such as Mg, Co, Cr and Ni, it has relatively high cycling stability
and rate capability. [4]
 CHAPTER - 4
PREPARATION OF FENTON CATALYST
FROM IRON SLUDGE

4.1 Fenton process

H.J.H Fenton discovered in 1894 that several metals have a special oxygen transfer properties
which improve the use of hydrogen peroxide. Actually, some metals have a strong catalytic
power to generate highly reactive hydroxyl radicals (HO•). Since this discovery, the iron
catalyzed hydrogen peroxide has been called Fenton's reaction. Nowadays, the Fenton's
reaction is used to treat a large variety of water pollution such as phenols, formaldehyde,
BTEX, pesticides, rubber chemicals and so on. This process may be used to wastewater,
contaminated soils and sludge with the following actions:
Organic pollutant destruction, toxicity reduction, biodegradability improvement, BOD/COD
removal ,odor and color removal, destruction of resin in radioactive contaminated sludge.

In the Fenton process, H2O2 reacts with Fe2+ to generate strong reactive species. The reactive
species produced are traditionally recognized as hydroxyl radicals, the classical Fenton
radical mechanisms primarily involve the following reactions:

Fe2+ + H2O2 → Fe3+ + HO•+OH-------------------------------------------------(1)

------------------------------------------------
Fe3+ + H2O2 → Fe2+ + HOO•+H+ (2)

2 H2O2 → HO• + HOO•+ H2O--------------------------------------------------(3)

OH- is generated from Eq. 1through electron transfer. However, OH- produced can be
scavenged by either of Fenton reagents as shown in Eqns. 2 and 3. Therefore, the optimal
molar ratio of iron ion to hydrogen peroxide needs to be experimentally determined for
minimization of the unwanted scavenging. Although Eq. 2 indicates that the produced
Fe3+from Eq. 1 can be reduced to Fe2+, the iron cannot be a catalyst in the Fenton system
because the rate constant in Eq. 2 is several orders of magnitude less than that in Eq. 1.
Consequently, Fe3+ forms iron sludge at typical water and wastewater treatment conditions.
The sludge needs to be separately disposed of, thus increasing the treatment complexity and
operational costs. Of note, the generation of hydroxyl radicals during the Fenton reaction is
the most effective only at an acidic pH condition. As a result, the application of Fenton
reaction for wastewater treatment is restricted in practice.
Based on the classical Fenton treatment scheme, three modified Fenton processes are
proposed, including the Fenton-like system, photo-Fenton system, and electro-Fenton system.
In the Fenton-like reaction, Fe2+ is replaced by ferric ion (Fe3+), namely, the series of reactions
in the Fenton system are initiated from Eq. 2 in the Fenton-like system, rather than from Eq. 1
in the traditional Fenton treatment. In the photo-Fenton reaction, UV irradiation is applied
with the traditional Fenton system with a major purpose of enhancing the UV- induced
reduction of dissolved Fe3+ to Fe2+. In the electro-Fenton reaction, either or both of the Fenton
reagents may be generated through electrochemical method.

Ferrous sulphate is commonly used as Fenton catalyst in the Fenton reaction. The catalyst for
Fenton reaction can be obtained from iron sludge, which is another use of the iron sludge. This
sludge can be from different sources.

Classification based on the iron sludge source

It can be classified into two:
1.Sludge generated from Fenton process.
2. Sludge generated from paper mills, industrial waste water etc

4.2 Reuse of Fenton process sludge

We can reuse the Fenton process sludge itself for the production of the Fenton catalyst. The
sludge can be from a homogenous Fenton process or from the heterogeneous Fenton process.
Production of heterogeneous catalyst is more advantageous. [6]
Basic steps followed in the reuse of sludge is shown in the figure 4.1
Figure 4.1 Basic steps followed in the reuse of sludge [6]

4.2.1 Graphene modified iron sludge derived from homogeneous Fenton process as an
efficient heterogeneous Fenton catalyst for degradation of organic pollutants
30 mg of graphene was dispersed in 100 mL of deionized water under ultrasonic shaking for
30 min. Then, FeSO4.7H2O (25 mmol) with molar ratio of H2O2/Fe2+ equaling to 20:1 was
slowly added into the solution. The reactants were stirred for another 60 min. After that, the
resulting composite was filtered, washed and then dried in an oven at 100 °C for 4 h. Fenton
activity of the Fe-G catalyst was evaluated using rhodamine B (RhB), acid red G (ARG) and
metronidazole as model pollutants .A series of Fe-G composites with different graphene
weight ratios were synthesized using iron sludge as the iron precursor. A low graphene
loading (0.5-2 wt %) in the composite could significantly enhance the heterogeneous Fenton
activity of iron sludge. Under the optimal conditions, the Fe-G-1 composite exhibited much
higher catalytic activity for degradation of RhB. The as-prepared catalyst showed wide pH
operating range (3.03-9.44), excellent stability and was efficient for the degradation of acid
red G and metronidazole as well, making itself a promising candidate as a heterogeneous
Fenton catalyst for water treatment. The mesoporous structure, enhanced adsorption ability as
well as the promoted =Fem/=Fen cycle of the composite are responsible for its enhanced
catalytic property. It has 98% production rate. iron sludge existed as goethite (FeOOH)
particles entrapped inside in the graphene sheet acted as the catalyst.[3]
 RSC Advances
Seminar Report, 2019

4.2.2 Synthesis of Cu2O-CuFe2O4 micro particles from Fenton sludge and catalytic
degradation of phenol

The synthesis of a heterogeneous Fenton catalyst, namely Cu2O-CuFe2O4, for the reuse of
iron incorporated in Fenton sludge. In comparison to CuFe 2 O4, much higher phenol
catalytic degradation was found for Cu2O-CuFe 2 O4, indicating the key role of Cu2O in
Fenton reaction. The rapid electron transfer built up galvanic cell between Cu + and Fe3+,
which favored the formation of relatively excess Fe 2+species. The highly reactive Fe2+ species
interaction with adsorbed H2O2 gave abundant HO- radicals for phenol degradation .The
higher Fenton catalytic activity of Cu2O-CuFe2O4 could be attributed to the synergetic effect
+ 2+
between CU /CU and Fe2+/Fe3+ redox pairs. The as prepared Cu2O-CuFe2O4 was stable,
recoverable and reusable, offering a promising potential as a heterogeneous Fenton catalyst.
CuFe2O4 micro particles were prepared by co-precipitation technique, i.e., CuSO4.5H2O was
dissolved into ultrapure water and then the prepared CuSO 4 solution was mixed with Fenton
sludge at Fe/Cu molar ratio of 2 : 1. Thereafter, sodium hydroxide solution (5 mol L -1) was
added into the mixture of Fenton sludge and CuSO4 drop by drop under continuous stirring to
raise the pH value to 10.0. The mixture was stirred continuously at temperature of 65 °C for 2
h. The obtained precipitate was then separated by centrifugation and washed with ultrapure
water until the pH value of the filtrate reached 7.0. The resulting product was kept in an oven
at temperature of 105 °C for 3 h to make it dry and then finally sintered at 850 °C for 3 h
under nitrogen atmosphere. The formation of CuFe2O4microparticles could be described by
eqn (1)-(3):

Fe +3(OH-) →Fe(OH)3----------------------------- (1)

Cu2++2(OH-) →Cu(OH)2---------------------------------- (2)
2Fe(OH)3 + Cu(OH)3→CuFe2O4+4H2O----------------(3)

Synthesis of Cu2O-CuFe2O4micro particles:

Cu2O-CuFe 2 O4micro particles were prepared through modified hydrothermal technique. In
this case, CuSO4.5H2O solution and Fenton sludge were mixed together at Fe/Cu molar ratio
of 1:1. Sodium hydroxide solution (5 mol L -1) was added drop wise into the mixture of
Fenton sludge and CuSO4 under continuous stirring to raise the pH
 Seminar Report, 2019

value to 10.0 to get colloidal suspension. After this, 0.97 g gallic acid was blended with the
suspension. The obtained mixture was sonicated for 15 min and then was poured into a 200
mL Teflon-line stainless steel autoclave. The closed autoclave was then allowed to keep at
200°C for almost 12 h and finally cooled normally to room temperature. During hydrothermal
process the gallic acid attached with chemical substances as organic ligands. The obtained
product was separated and washed several times with ultrapure water, then dried at 105 °C
and finally sintered at 850 °C for 3 h under nitrogen atmosphere. The calcination temperature
was chosen as 850°C because higher temperature causes lower reactivity and lower
temperature favors severe leaching from catalysts. Moreover, for comparison purpose, the
Cu2O micro particle was synthesized in a similar way by using CuSO4.5H2O individually as a
precursor material. [2]

4.2.3 Reuse of homogenous Fenton sludge from detergent industry as Fenton catalyst for
the removal of organic pollutants from wastewater

Fenton sludge obtained from detergent industry contains 37% of iron .The sludge is dried,
calcined and milled to get the catalyst. To know the efficiency of the catalyst prepared it is
treated with olive mill water.500 mL glass reactors were used to carry the reaction. Inside
them, 300 mL of the simulated effluent were poured and the required amount of catalyst was
added. Magnetic stirring was employed in order to maintain the bulk as homogeneous as
possible. The pH maintained at 3.0. The mixture was left for one hour before the addition
H2O2 to evaluate contaminants removal by catalyst adsorption. The desired volume of H 2O2 at
the concentration of 244 mM, was slowly poured into the reactor and only then the Fenton's
reaction started to take place. At certain time intervals (30, 60, 90 and 120 min), samples
were withdrawn to a vacuum filtration system (funnel, kitassato and air pump) using a 0.45
pm pore diameter quantitative filter paper to remove the solid catalyst from the liquid phase.
Right after the filtration, the pH of the sample was raised until a value of above 10 using
NaOH of 3M concentration in order to stop the reaction by quenching the remaining
hydrogen peroxide. Then the samples were named and stored at 4 °C until being forwarded to
analysis. Higher baking temperatures presented more activity (superior TPh, COD and TOC
removals) and less adsorption. Although the catalyst baked at 1000 °C reached very good
removals (almost 100% of TPh, more than 50% of COD and around 45% of TOC), the iron
leaching is too high (172.0 mg.L-1 for the catalyst dose of 2.0 g.L-1). Also, the BOD5/COD
ratio is reduced to less than half of the initial simulated effluent (around 0.19 for the treated
samples while the synthetic solution has a 0.42 ratio). Since these two last parameters (iron
leaching and BOD5/COD ratio) are major preoccupation for the Fenton catalysts due to
environmental concerns, an optimum of 500oC is used.[6]

4.3 Reuse of iron sludge from other sources

4.3.1 Use of paper mill sludge-derived heterogeneous Fenton catalyst for the
degradation of methylene blue
The hydrous sludge was dewatered naturally at room temperature in a ventilated place. The
dewatered paper mill sludge sample was heated to 400 °C in a muffle furnace in air for 2 h to
obtain the catalyst designated as PMS-400. The paper mill sludge-derived catalyst was
prepared as follows: 10 g of dewatered sludge was added to 50 mL 0.5 M FeSO 4-7H2O
solution and stirred for 6 h at room temperature and then recovered via centrifuging and dried
in air at 105 °C overnight. Finally, the Fe-loading sludge was calcined in air at 400 °C for 2h,
and the paper mill sludge-derived Fe-loading nanocomposite was designated as PMS-Fe-400.
we synthesized a paper mill sludge-derived low cost and high stable catalyst (PMS-Fe-400)
via a facile and simple method. The XRD results illustrate that a-Fe 2O3 nanoparticles were
observed in PMS-Fe-400. Under best conditions (1 g/L of catalyst, 2 mL/L of 3% H 2O2, 50
mg/L of MB), 93.3% discoloration and 78% mineralization were achieved within 80 min.[5]

4.3.2 Reutilization of iron sludge as heterogeneous Fenton catalyst for the degradation
of Rhodamine B

All reagents were analytical grade and used without further purification. Deionized water was
used throughout the experiment. In a typical procedure, FeSO4.7H2O (2mmol) was added into
100 mL of deionized water, then 50 mL of H2O2 (30 wt%) was added dropwise into the above
solution and iron sludge was formed. The reactants were stirred for 1 h and then filtered,
washed and dried at 100 °C. Finally, the obtained sample was calcined at 400, 600 and 800 °C
for 3 h, respectively. The final samples were labeled as Fe-x, where x denoted the heating
temperature. For the viewpoint of practical application, cationic dye rhodamine B (RhB) and
anionic dye acid red G (ARG) were selected as model pollutants. FeSO47H2O (25 mmol) was
added into 100 mL of RhB and ARG solutions (2000 mg/L), respectively, then 50 mL of
H2O2 (30 wt%) was slowly added into the solution. The reactants were stirred for 1 h. The
iron sludge was formed during the Fenton degradation of RhB or ARG. The mixture of the
products was filtered, washed, dried at 100 °C and further calcined at 600 °C for 3 h. The
final products were labeled as Fe-600-R and Fe-600-A, respectively. In order to investigate
the effect of sulfur in the Fe2O3, FeCl24H2O other than FeSO47H2O was used to synthesize
Fe2O3 under the same conditions and the obtained sample was named as Fe-600-C. The
calcination at 600 oC, the iron sludge (Fe-600) exhibited much enhanced catalytic
performance (99%) toward rhodamine B (RhB) in comparison with iron sludge without
calcination (10%) in the presence of H2O2. The mesoporous structure of Fe-600 could
facilitate its adsorption and immobilization of RhB, and the self-doped lattice sulfide played
an important role during the Fenton degradation process. Moreover, the Fe-600 exhibited
excellent heterogeneous Fenton degradation efficiency of acid red G and methylene blue as
well. [7]
 CHAPTER – 5
CASE STUDY- MARIANA DAM DISASTER

The Mariana dam disaster occurred on 5 November 2015, when an iron ore tailings dam in
Mariana, Minas Gerais, Brazil, suffered a catastrophic failure, resulting in flooding that
destroyed the village of Bento- Rodrigues and killed 19 people. From this disaster 34 million
m3 of iron ore sludge attained 663 km of land before reaching the ocean. Even though, this
sludge that comes from an adversity it can be applied as a low cost resource to wastewater
treatment. This iron mining waste can be employed in the synthesis of magnetic hybrid
materials and using them as iron catalysts in Fenton's or Fenton's-like reactions.

5.1 Preparation of the catalyst

Synthesis of the cobalt ferrite/NOM hybrid materials: HbLM was synthesized from iron mine
tailings collected from the Rio Doce in Mariana/MG- Brazil waterway according to the
methodology developed previously. The inorganic precursors were CoCl2.6H2O (analytical
grade) and iron salts (mentioned above), which were dissolved in 150 mL of NOM-rich
water, using cobalt/iron/NOM concentrations of 7.0/13.9/0.024 g L -1. The pH of the medium
was then gradually adjusted to pH 9.0 with aqueous 1.0molL -1NaOH, after which the system
was maintained under agitation for 30 min. After gel formation, the system was heated at 100
°C to remove water and obtain a xerogel. The resulting material was washed with deionized
water, dried in an oven at 60 °C, and homogenized. Figure.5.2 illustrates the scheme of the
synthesis of the hybrid material and shows the simplicity of the route, which was performed
in a few steps. It is also possible to visualize the high response of the magnetic hybrid when
subjected to a magnetic field (neodymium magnet).
 Seminar Report, 2019

Figure 5.2 The scheme of the synthesis of the hybrid material [1]

5.2 Procedure
Heterogeneous EF experiments were performed at a batch system In the cell, was inserted
130 mL of 25 mL-1 AB29 dye in 0.050 M of Na2SO4 .Differents concentrations of HbLM (0
- 1.0 g L-1) were tested. A boron-doped diamond (BDD) material and a carbon-PTFE screen
were used as anode and diffusion cathode, respectively with an electroactive area of 3 cm 2 .
The cathode was fed with an air pump at 300 mL min- for H2O2 electrogeneration. Both
electrodes were connected to a power supply. The color decay of the solution was followed
by an UV-spectrophotometer.
By using UV –spectrophotometer absorbance of the mixtures were analysed. 25 mg L-1 AB29
diazo dye by adsorption, electrochemical oxidation with H2O2eletrogeneration (EO-H2O2) and
heterogeneous EF-HbLM at 33.3 mA cm-2in order to verify the catalyst effect was compared.
0.25 mg L-1of the HbLM demonstrated low adsorption power. On the other hand, at the end
of the treatment time, the EO-H2O2 removed 62% of color, while heterogeneous EF achieved
total decolorization, after 20 min of electrolysis.

5.3 Characterizations
5.3.1 XRD
X-ray diffraction measurements were performed at room temperature using a diffractometer
with Co K α radiation, in continuous scan mode in the range from 10° to 80°, with a scan
speed of 1° min-1. The crystal structures obtained were identified by comparison to ICSD
(Inorganic Crystal Structure Database) standards. Figure 5.2 shows the XRD patterns of
HbLM. The noisy baselines of the diffractogram indicated a low degree of crystallinity, due
to the presence of NOM in the structures of the materials, since they were not subjected to
 Seminar Report, 2019

calcination. However, the most intense diffraction peaks of the samples were in good
agreement with the CoFe 2 O4diffraction data available in ICSD card #192031, this result
showed that this phase was formed in both samples, evidencing the efficiency of the proposed
route using iron ions recovered from wastes as precursors.

Figure5.2 XRD patterns of HbLM [1]

5.3.2 TGA
Thermogravimetric curves were obtained with a Shimadzu Model TGA-50 instrument,
under an atmosphere of nitrogen, using a flow rate of 40 mL min -1 and heating at a rate of 10
°C min-1 in the temperature range 26-900 °C. The thermogravimetric (TG) curves of HbLM
hybrids (Figure 5.3) revealed four different stages of mass loss totaling approximately 20%.
These stages were mainly associated to the breakdown of the various structures composing
the NOM present in the water used in the synthesis. In the first stage, a loss of approximately
6% was related to dehydration of the sample at 100-120 °C. The second stage was extended to
just below 400 °C, with a loss of around 12%, associated to the decomposition of
carbohydrates and phenolic, carboxylic, and carbonyl species, as well as thermal dehydration
of hydroxylated aliphatic structures. The third stage was extended from 400 to 520 °C for
HbLM . The final stage occurred in the temperature range of 550-800 °C. The mass loss
between 400 and 500 °C has been reported to be due to the dissociation and breakdown of
polyunsaturated material and elimination of hydrogen by cracking reactions of the
heterocyclic structures. From 500 to around 800 °C, mass losses are associated to the
combustion of aromatic structures and the cleavage of C-C bonds. The final mass loss was
also associated to the decomposition of silicate, derived from the sludge extraction solution
employed in the synthesis.
 Figure 5.4 FTIR spectra of the
hybrid material [1]

Figure 5.3 Thermogravimetric curve of the hybrid material [1]

5.3.3 FTIR
Infrared spectra were acquired using a Varian Model 640 IR instrument (in transmission
mode) in the range 400-4000 cm-1, with a resolution of 4 cm-1.Figure 5.4 illustrates the
infrared spectra of HbLM. The spectra showed a broad band at around 3400 cm -1, attributed
to the stretching of O-H groups, indicating the presence of water, alcohols, phenols, and/or
carboxylic acids. A band at 1626 cm -1 could be attributed to aromatic C=C bonds and
asymmetric stretching of COO-, and a band at 1525 cm-1 to symmetric stretching of COO-,
which are characteristic of NOM . These results were in agreement with the XRD analyses
and revealed the presence of NOM in the structures of the hybrids. An absorption band at
around 596 cm-1 could be attributed to the Fe-O bond characteristic of ferrites , a band at
around 990 cm-1 could be attributed to the Si-O bonds of silicate impurities derived from the
tailings sludge from which the iron ions were extracted.[1]
 CHAPTER-6

SUMMARY
In this report, we discussed about the iron sludge derived from different sources like ground
water resources, iron and steel industries, water treatment plants etc. Iron sludge is heavy
metal sludge. Proper treatment of the sludge leads to the reduction in the sludge formation.
Reutilization of iron sludge developed a direction of high added value from low added value
and brings favorable economic benefit and social benefit. So in this paper preparation of
various iron containing products from the iron sludge were discussed. And also its application
in the preparation of Fenton catalyst from different sources of iron sludge was found out.
There is a saying that "wastes are misplaced resources". How to turn "waste" into wealth and
improve resource utilization rate has become an urgent demand for the development of
society. The ability to combine the principles of green chemistry and industrial symbiosis,
with the development of new materials from abundant resources previously considered to be
waste was discussed. The sustainable use of iron sludge can be achieved by means of a
circular economy and, especially, biotechonomic principles for the extraction of resources in
the production of secondary material utilizations. A circular economy can be treated as a
"panacea" to save the planet's finite resources, as the current linear economy, which is based
on a "take-cook-exclude everything" approach, creates large amounts of waste.
 CHAPTER-7

REFERENCE

1 A.J. dos Santos, G. da Costa Cunha, D.R.S. Cruz, et al.,2019, Iron

mining wastes collected from Mariana disaster: Reuse and application as
catalyst in
a heterogeneous electro-Fenton process, Journal of
Electroanalytical Chemistry
2
Muhammad Faheem, Xinbai Jiang, Lianjun Wang, Jinyou Shen C
,2018,Synthesis of Cu2O-CuFe2O4 microparticles from Fenton sludge and
its application in the Fenton process: the key role of Cu 2O in the catalytic
degradation of phenol
3
Sheng Guo, Na Yuan, Gaoke Zhang, Jimmy C. Yu,2016,
Graphene modified iron sludge derived from homogeneous Fenton
process as an efficient heterogeneous Fenton catalyst for degradation
of organic pollutants
4 Wang Hongmin and Liu Manman,2016, Application and Progress of
Chemical Iron Sludge

Guoqiang Zhou, Feifang, Ziwen Chen, Yuefeng He, Hail Sun

5 ,HuixiangShi, 2015, Facile synthesis of paper mill sludge-derived
heterogeneous catalyst for the Fenton-like degradation of methylene
blue
6
Guo-min Cao , Mei Sheng, Wen-fengNiu, Yu-lei Fei, Dong Li,2009,
Regeneration and reuse of iron catalyst for Fenton-like reactions.

7 Sheng Guo, Zhixiong Yang, Zhipan Wen, Hussain Fida, Gaoke Zhang,
Jinyi Chen,2018, Reutilization of iron sludge as heterogeneous Fenton
catalyst for the degradation of Rhodamine B: Role of sulfur and
mesoporous structure
8 Ramune Albrektiene, Karolis Karaliunas, Kristina Baziene
,2019,Sustainable Reuse of Groundwater Treatment Iron Sludge for
Organic Matter Removal from River Neris Water