ĐẠI HỌC QUỐC GIA HÀ NỘI
TRƯỜNG ĐẠI HỌC KHOA HỌC TỰ NHIÊN
---------------------------
Cao Việt
EVALUATION OF STERILIZATION POSSIBILITY IN WATER
ENVIRONMENT OF ACTIVATED NANO MnO2 COATED ON CALCINED
LATERITE
CHUYÊN NGÀNH: QUẢN LÝ CHẤT THẢI VÀ XỬ LÝ VÙNG Ô NHIỄM
(CHƯƠNG TRÌNH ĐÀO TẠO QUỐC TẾ)
LUẬN VĂN THẠC SĨ KHOA HỌC
GIÁO VIÊN HƯỚNG DẪN: PGS.TS. TRẦN HỒNG CÔN
Hà Nội - 2011
Table of contents
Abbreviation ....................................................................................................................i
List of Figures ................................................................................................................ ii
List of Tables ................................................................................................................ iii
Chapter 1......................................................................................................................... 1
INTRODUCTION .......................................................................................................... 1
1.1 Water situation in general ...................................................................................... 1
1.2 Water sterilization .................................................................................................. 3
1.2.1 Boiling ............................................................................................................. 4
1.2.2 Chlorine ........................................................................................................... 5
1.2.3. Ozone ............................................................................................................. 5
1.2.4 Ultraviolet light ............................................................................................... 6
1.2.5 Hydrogen peroxide .......................................................................................... 7
1.2.6 Solar disinfection ............................................................................................ 7
1.2.7 Photocatalysis on semiconductors .................................................................. 7
1.2.8 High speed water sterilization using one-dimensional nanostructures ........... 7
1.3 Nanotechnology ..................................................................................................... 8
1.4 Manganese dioxide............................................................................................... 10
1.5 Laterite ................................................................................................................. 11
Chapter 2....................................................................................................................... 13
OBJECTIVES AND RESEARCH METHODS ........................................................ 13
2.1 Objectives ............................................................................................................. 13
2.2 Materials and Research methods.......................................................................... 13
2.2.1 Material and instruments ............................................................................... 13
2.2.2 Research methods ......................................................................................... 14
2.2.2.1 Synthesis of nano MnO2 adsorbents .......................................................... 14
2.2.2.3 Investigation of sterilizing capability of nano MnO2 adsorbents............... 15
Chapter 3....................................................................................................................... 17
RESULTS AND DISCUSSION .................................................................................. 17
3.1 Synthesis of nano MnO2 adsorbents .................................................................... 17
3.2 Investigation of sterilizing capability of nano manganese dioxide ...................... 23
3.2.1 Investigation in static condition .................................................................... 24
3.2.2 Investigation in dynamic condition ............................................................... 28
3.3 Mechanism of sterilization of MnO2 coated on calcined laterite in water ........... 33
3.3.1 Investigation the influence of Mn2+ in sterilizing capability ........................ 33
3.3.2 Examine the mechanism of sterilization of MnO2 ........................................ 35
Chapter 4....................................................................................................................... 38
CONCLUSION ............................................................................................................. 38
REFERENCES ............................................................................................................. 40
Abbreviation
MD
Manganese Dioxide
UV
Ultraviolet
DNA
Deoxyribonucleic Acid
SODIS
Solar Disinfection
CNT
Carbon Nanotube
AgNWs
Silver Nanowires‟
TEM
Transmission Electron Microscopy
SEM
Scanning Electron Microscope
EPA
Environmental Protection Agency
E. coli
Escherichia coli
BRM
Bacteria removing material
MPN
Most probable number
EBCT
Empty Batch Contact Time
i
List of Figures
Figure 1: Nanoscale materials ........................................................................................ 10
Figure 3: Coating process............................................................................................... 18
Figure 4: MnO2 nanoparticles with the magnification of 40000 times .......................... 19
Figure 5: MnO2 nanoparticles with the magnification of 60000 times .......................... 20
Figure 6: MnO2 nanoparticles with the magnification of 100000 times ........................ 21
Figure 7: Creation of adsorbent coating by nano MnO2 particles (100k) ...................... 22
Figure 8: Creation of adsorbent coating by nano MnO2 particles (200k) ...................... 22
Figure 9: Shaking equipment for static condition investigation .................................... 23
Figure 10: Column device for dynamic condition investigation ................................... 24
Figure 11: Samples in contact time‟s influence experiment .......................................... 25
Figure 13: Samples in BRM/water ratio‟s influence experiment .................................. 27
Figure 14: Samples in BRM/water ratio‟s influence experiment .................................. 28
Figure 15: Model of column device ............................................................................... 29
Figure 16: Samples in flow rate in BRM column‟s influence experiments ................... 30
Figure 17: Influence of flow rate on bacteria sterilizing in BRM column..................... 30
Figure 18: Samples in the experiments .......................................................................... 32
Figure 19: Influence of column height on bacteria sterilizing in BRM column ............ 32
Figure 21: Influence of Mn2+ in sterilizing capabilities ................................................. 35
ii
List of Tables
Table 1: Influence of contact time on bacteria sterilizing .............................................. 24
Table 2: Influence of the ratio of BRM and water on bacteria sterilizing ..................... 27
Table 3: Influence of flow rate on bacteria sterilizing in BRM column ........................ 29
Table 4: Influence of column height on bacteria sterilizing in BRM column ............... 31
Table 5: Influence of Mn2+ in sterilizing capabilities .................................................... 34
iii
Chapter 1: Introduction
Chapter 1
INTRODUCTION
1.1 Water situation in general
Water is one of the world‟s most essential demands for human life, and the
origin of all animal and plant life on the planet. Civilization would be impossible
without steady supply of fresh and pure water and it has been considered a
plentiful natural resource because the sensitive hydrosphere covers about 75% of
the Earth's surface. Its total water content is distributed among the main
components of the atmosphere, the biosphere, oceans and continents. However,
97% of the Earth's water is salty ocean water, which is unusable for most human
activities. Much of the remaining 3% of the total global water resource, which is
fresh-water, is locked away in glaciers and icebergs. Approximately 20% of the
freshwater resources are found as groundwater, and only 1% is thought to be
easily accessible surface water located in biomass, rivers, lakes, soil moisture,
and distributed in the atmosphere as water vapor. [1]
In the process of rapid development of science and technology, the demand for
pure water is increasing to serve multifarious purposes in different types of
industries. Global water consumption raised six folds in the past century, double
the rate of population growth. In addition, the boom in world‟s population during
recent decades, has contributed to the dramatically rising demand of pure water
usage for both household and industrial purposes. The high population density
and industrialization speed have triggered the hydrosphere to be polluted with
inorganic and organic matters at a considerable rate. Moreover, to satisfy the
food demand, a number of harmful chemicals such as pesticides and herbicides
1
Chapter 1: Introduction
are used in order to improve the productivity in agricultural production, which
also causes the scarcity of clean resources. [1]
The contamination of ground water (mostly by toxic metal ions due to both
natural and anthropogenic reasons) is also one of concerning issues on clean
water. It is necessary to assess the quality of water used in industry, household
activities and drinking purpose. Understanding of the importance of clean water
in human life, many countries has gradually adjusted their environmental
regulations more stringently to reserve clean water resources. With the purpose
of overcoming the water pollution problems, and to meet the stricter
environmental regulations, scientists and researchers have focused on improving
exist water purification processes and approaching to alternative water treatment
technologies as well, so as to increase the efficiency of those decontamination
methods. It is surveyed that human awareness about the seriousness of water
pollution has enhanced over the world. People have also started realizing that
water is not an unlimited resource, hence it needs to be protected and smartly
used.
An ideal water treatment process should have the capability to mineralize
completely all the toxic organic components without leaving behind any harmful
by-products and to recover all toxic metals from wastewater. In broader
classification, biological, mechanical, thermal, chemical or physical treatments,
or their combinations may be applied to purify contaminated water. The choice
of the proper water treatment processes depend on the nature of the pollutants
presenting in water, and on the acceptable contamination level in treated water.
There are two main purposes of water treatment study – the reduction of
contaminant level in the discharged stream to meet environmental standards, and
2
Chapter 1: Introduction
the purification of water to ultrapure water in order to be able to use in
semiconductor, microelectronic and pharmaceutical industries. Moreover, the
cost or effectiveness of the water treatment processes also plays a significant role
in choosing a particular one. Biodegradation, adsorption in activated carbon, air
stripping, incineration, ion-exchange, coagulation-precipitation, membrane
separation, thermal and catalytic oxidation, oxidation by permanganate, chlorine,
ozone and hydrogen peroxide are widely applied in conventional water treatment
processes for organic and inorganic pollutant containing water. Besides
advantages, each process has their own shortcomings which are being improved
gradually via new technologies. [1, 2]
1.2 Water sterilization
Water sterilization technology is useful in various ways for our daily life. For
example, it is used in water and sewerage systems treatment. Methods
commonly used for sterilization include chemicals, heat, ultraviolet (UV)
radiation, and ozone. Chemicals (chlorine, peroxide, etc.) are utilized extensively
for sterilization because of their simplicity; however, they probably form
unexpected effects, such as modifying the quality of the target. In addition,
sterilization by chlorine usually generates odorous substances and bio-hazardous
materials. [2]
It is not totally accurate to assess whether water is of an appropriate quality only
by visual examination. Simple procedures such as boiling or the use of a
household activated carbon filter are not sufficient for treating all the possible
contaminants that maybe present in water from an unknown source. Even natural
spring water – considered safe for all practical purposes in the 1800s – must now
be tested before determining what kind of treatment, if any, is needed. Chemical
3
Chapter 1: Introduction
analysis, while expensive, is the only way to obtain the information necessary for
deciding on the appropriate method of purification. [3]
Simple techniques for treating water at home, such as chlorination, filters, and
solar disinfection, and storing it in safe containers could save a huge number of
lives each year.
Sterilization is accomplished both by filtering out harmful microbes by and also
adding disinfectant chemicals in the last step in purifying drinking water. Water
is disinfected to kill any pathogens which pass through the filters. Possible
pathogens include viruses, bacteria, including Escherichia coli, Campylobacter
and Shigella, and protozoa, including Giardia lamblia and other cryptosporidia.
In most developed countries, public water supplies are required to maintain a
residual disinfecting agent throughout the distribution system, in which water
may remain for days before reaching the consumer. Following the introduction
of any chemical disinfecting agent, water is usually held in temporary storage often called a contact tank or clear well to allow the disinfecting action to
complete. [4]
1.2.1 Boiling
Boiling is an easy, cheap and common way to eliminate contaminations and
microorganisms in developing countries, but this method is only practical for
small amounts. When the water has boiled for 5 – 10 min all the pathogens have
been killed and the water is safe to drink. [2]
The main disadvantage of this method is that it requires a continuous source of
heat and appropriate equipment.
4
Chapter 1: Introduction
1.2.2 Chlorine
Chlorine is most effective against pathogens and not as much for turbidity; it will
function relatively effectively up to 20 NTU [2]. If chlorine were combined with
other methods such as rapid sand filtration the turbidity would decrease.
Chlorine Bleach can be used to purify water with the dosage of 1 part of bleach
and 10 parts of water and wait for 30 min, or longer if the solution still looks
cloudy [3]. It is important to note that chlorine bleach does not kill
Cryptosporidium and may not kill Giardia, a pathogen and a parasite that both
give diarrheal diseases [5]. It is difficult to determine the correct chlorine dosage,
too much gives an unpleasant taste and people will be reluctant to drink it, but a
too small dosage will not kill the germs [4].
The drawback of this method is that it the storage of chlorine and its use must
need careful handling, large chlorine residual may cause bad taste.
1.2.3. Ozone
Ozone (O3) is an unstable molecule which readily gives up one atom of oxygen
providing a powerful oxidizing agent which is toxic to most waterborne
organisms. It is a very strong, broad spectrum disinfectant that is widely used in
Europe. It is an effective method to inactivate harmful protozoa that form cysts.
It also works well against almost all other pathogens. Ozone is made by passing
oxygen through ultraviolet light or a "cold" electrical discharge. To use ozone as
a disinfectant, it must be created on-site and added to the water by bubble
contact. Some of the advantages of ozone include the production of fewer
dangerous by-products (in comparison to chlorination) and the lack of taste and
odor produced by ozonization. Although fewer by-products are formed by
ozonation, it has been discovered that the use of ozone produces a small amount
5
Chapter 1: Introduction
of the suspected carcinogen bromate, although little bromine should be present in
treated water. Another of the main disadvantages of ozone is that it leaves no
disinfectant residual in the water. Ozone has been used in drinking water plants
since 1906 where the first industrial ozonation plant was built in Nice, France.
The U.S. Food and Drug Administration has accepted ozone as being safe; and it
is applied as an anti-microbiological agent for the treatment, storage, and
processing of foods. [6]
The disadvantage of this method is the high cost for operation.
1.2.4 Ultraviolet light
Ultraviolet light is very effective at inactivating cysts, as long as the water has a
low level of colour so the UV can pass through without being absorbed.
Ultraviolet light works against viruses, bacteria, pathogens and other potentially
harmful particles by modifying and even destroying their nucleic acids and
disrupting their deoxyribonucleic acid (DNA). When employed in a UV filter,
UV light can have two effects on these microorganisms. It can either eliminate
their ability to reproduce, or can kill them outright, a more desirable outcome
where water purification is concerned.
The main disadvantage to the use of UV radiation is that, like ozone treatment, it
leaves no residual disinfectant in the water. Because neither ozone nor UV
radiation leaves a residual disinfectant in the water, it is sometimes necessary to
add a residual disinfectant after they are used. This is often done through the
addition of chloramines, discussed above as a primary disinfectant. When used
in this manner, chloramines provide an effective residual disinfectant with very
few of the negative aspects of chlorination. [6]
6
Chapter 1: Introduction
The main disadvantages of this methods is the low efficiency and the dependent
on water turbidity.
1.2.5 Hydrogen peroxide
Hydrogen peroxide (H2O2) works in a similar way to ozone. Activators such as
formic acid are often added to increase the efficacy of disinfection. It has the
disadvantages that it is slow-working, phytotoxic in high dosage, and decreases
the pH of the water it purifies. [6]
1.2.6 Solar disinfection
One low-cost method of disinfecting water that can often be implemented with
locally available materials is solar disinfection (SODIS). It partially relies on the
ultraviolet radiation that is part of sunlight. Unlike methods that rely on
firewood, it has low impact on the environment. [6]
1.2.7 Photocatalysis on semiconductors
The processes of heterogeneous photocatalysis on semiconductors, developed
during the last twenty years, were firstly regarded as potential methods for
hydrogen photoproduction from water. However, even at the very beginning of
their development, some papers appeared which dealt with photooxidation of
organic and some inorganic (e.g. CN- ions) compounds. For more than ten years
the interest of scientists has turned into application of the heterogeneous
photocatalytic methods to water detoxification. [6]
1.2.8 High speed water sterilization using one-dimensional nanostructures
One-dimensional nanostructures have been extensively explored for a variety of
applications in electronics, energy and photonics. Most of these applications
involve coating or growing the nanostructures on flat substrates with
architectures inspired by thin film devices. It is possible, however, to make
7
Chapter 1: Introduction
complicated
three-dimensional
mats
and
coatings
of
metallic
and
semiconducting nanowires, as has been recently demonstrated in the cases of
superwetting nanowire membranes and carbon nanotube (CNT) treated textiles
and filters. Silver nanowires‟ (AgNWs) and CNTs‟ have unique ability to form
complex multiscale coatings on cotton to produce an electrically conducting and
high surface area device for the active, high-throughput inactivation of bacteria
in water. [6]
1.3 Nanotechnology
Nanotechnology is the science of the small; the very small. It is the use and
manipulation of matter at a tiny scale. At this size, atoms and molecules work
differently, and provide a variety of surprising and interesting uses.
The prefix of nanotechnology derives from „nanos‟ – the Greek word for dwarf.
A nanometer is a billionth of a meter, or to put it comparatively, about 1/80,000
of the diameter of a human hair. Nanotechnology should not be viewed as a
single technique that only affects specific areas. It is more of a „catch-all‟ term
for a science which is benefiting a whole array of areas, from the environment, to
healthcare, to hundreds of commercial products.
Although often referred to as the 'tiny science', nanotechnology does not simply
mean very small structures and products. Nanoscale features are often
incorporated into bulk materials and large surfaces.
Nanotechnology is already in many of the everyday objects around us, but this is
only the start. It will allow limitations in many existing technologies to be
overcome and thus has the potential to be part of every industry:
Health and medicine - With advances in diagnostic technologies, doctors will
be able to give patients complete health checks quickly and routinely. If any
8
Chapter 1: Introduction
medication is required this will be tailored specifically to the individual based on
their genetic makeup, thus preventing unwanted side-effects. As a result, the
health system will become preventative rather than curative.
Society and the environment - Renewable energy will become the norm. For
example, solar cells based on quantum dots could be as much as 85% efficient.
Wind, wave, and geothermal energy will also be tapped more effectively using
new materials and stored or delivered more efficiently through advances in
batteries and hydrogen fuel cells. New ambient sensor systems will allow us to
monitor our effect on the environment and take immediate action, rather than
“waiting to see”. Nanotechnology will also help us clean up existing pollution
and make better use of the resources available to us.
New materials - Nanomaterials such as quantum dots, carbon nanotubes and
fullerenes will have applications in many different sectors because of their new
properties. So quantum dots can be used in solar cells, but also in
optoelectronics, and as imaging agents in medical diagnostics. Carbon nanotubes
can be used in displays, as electronic connectors, as strengthening materials for
polymer composites, and even as nanoscale drug dispensors. Fullerenes can be
used in cosmetics, as “containers” for the delivery of drugs, in medical
diagnostics, and even as nanoscale lubricants.
9
Chapter 1: Introduction
Figure 1: Nanoscale materials
Nanoscale materials and devices hold great promise for advanced diagnostics,
sensors, targeted drug delivery, smart drugs, screening and novel cellular
therapies. [7]
The future of nanotechnology has great potential. However, it also has the
potential to change society more than the industrial revolution. It will affect
everyone and so should be developed for everyone.
1.4 Manganese dioxide
Manganese dioxide (MnO2) occurs naturally as the mineral pyrolusite, which is
the main ore of manganese and a component of manganese nodules.
In the past decades, Manganese dioxide have been exploited for heavy metal
removal from aqueous media, i.e., heavy metal ions [8], arsenate [9], and
phosphate [10] from natural water has attracted considerable attention, because it
would significantly mediate the fate and the mobility of the target pollutants in
water [11, 12]. For example, Kanungo et al. [12] and Kanungo et al. [13] studied
10
Chapter 1: Introduction
the sorption of Co(II), Ni(II), Cu(II), and Zn(II) ions on manganese dioxide
particles in the presence of different electrolytes. They found that these toxic
metals can be effectively trapped by manganese dioxide through electrostatic
forces and formation of inner-sphere complexes. The specific properties of
manganese dioxide render it a potential sorbent for heavy metal ion removal
from contaminated water.
Manganese dioxide has high oxidation potential so it can disrupt the integrity of
the bacterial cell envelope through oxidation (similar with Ozone, Chlorine…).
1.5 Laterite
Laterites are residual products, which are formed during prolonged mechanical
and chemical weathering of ultramafic bedrocks at the surface of the earth [14].
It was found that laterite‟s profiles depend on the conditions of weathering
intensities, geotectonic zones and the parent rock‟s compositions. Laterite is used
to describe soils, ferruginous materials, weathering profiles, and chemical
compositions, which are based on SiO2, Al2O3, and Fe2O3 [15]. Laterite is
categorized as soil which contains up to 60.3% iron [16] and is available in many
tropical regions, such as India, Vietnam, Philippines and China [17-19].
Furthermore, laterite adsorbs other ion and heavy metals, such as fluoride (F),
cesium (Cs), mercury (Hg II) and lead (Pb) [20-22]; in water treatment, laterite
has been found to be effective and feasible as an adsorbent in removing some
heavy metals in contaminated groundwater.
When laterite heated to 420-900oC, the removal capacity is even better.
Expanded laterite has special properties such as high porosity (and consequently,
low density), it is chemically rather inert, non-toxic, thus it can be used as
excellent filter aid and as a filler in various processes and materials.
11
Chapter 1: Introduction
Because of it low specific surface area and acidic surface, expanded laterite was
found to be of limited use as an adsorbent for bacterial removal on its own, but it
can be utilized as an appropriate carrier material. On the other hand,
nanoparticles MnO2 have a large surface area and high oxidation potential which
make them excellent candidates for the bacterial removal in general.
12
Chapter 2: Objectives and Methodology
Chapter 2
OBJECTIVES AND RESEARCH METHODS
2.1 Objectives
When materials possess nanoparticle size, they will have special
properties in chemical, physical, adsorption and electrode, etc. Therefore, the
research objectives are addressed as follows:
- To synthesize MnO2 nanoparticles coated on calcined laterite;
- Analyzing of MnO2 nanoparticles formation portion and its physical structure;
- To investigate the sterilization possibilities of created material;
- To examine the mechanism of sterilization of MnO2 coated on calcined laterite
in water.
2.2 Materials and Research methods
2.2.1 Material and instruments
All chemicals were reagent grade and they were used without further
purification. Laterite ore was taken from coal and baked at 900 oC. Potassium
permanganate (KMnO4), ethanol, sodium hydroxide (NaOH, 98%), and
hydrogen peroxide (H2O2) were made in China. Agar was purchased from Ha
Long company, endo agar from Merck. Petri disks, distilled water and others
instruments which were used in the experiment, taken from Faculty of Chemistry
lab equipment.
For structural characterization, the samples were taken to use Transmission
Electron Microscopy (TEM) operated at 80kV. Surface analysis was done using
Scanning Electron Microscope (SEM) (Hitachi S-4800) in National Institute of
Hygiene and Epidemiology.
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Chapter 2: Objectives and Methodology
2.2.2 Research methods
2.2.2.1 Synthesis of nano MnO2 adsorbents
According to Environmental Protection Agency (EPA) [23], particles are
classified regarding to size: in term of diameter, coarse particles cover a range
between 10,000 and 2,500 nanometers. Fine particles are size between 2,500 and
100 nanometers. Ultrafine particles, or nanoparticles are sized between 100 and
1 nanometers. Therefore, our goal is to create particles which have the size
between 100 and 1 nanometers.
The MnO2 nanoparticles were synthesized using potassium permanganate
(KMnO4) as a precursor using a slight modification of method [24] in the
following way: stirring vigorously a 100ml water:ethanol (1:1, v/v) solution
using magnetic stirrer at room temperature for 10 min, and then the solution was
added 5ml of KMnO4 0.05M, stirring steady then put slowly H2O2 until brown
black color appears (around 10ml H2O2 10%). Finally, colloidal nano MnO2
solution was taken for analyzing of nanoparticles formation portion and coating
on calcined laterite.
To synthesize laterite/MnO2, the dried calcined laterite, which was grained with
size of 0.1 – 0.5 mm diameter, was poured into MnO2 nanoparticles solution
with the volumetric portion of solid and liquid was 1/1. The soaking time was 8
to 24 hours. Then the liquid phase was drained off. Solid phase was washed out
of dissolved ions and dried to get bacterial removing material (BRM).
2.2.2.2 Structural characterization
For structural characterization, the samples were taken to use Transmission
Electron Microscopy (TEM) operated at 80kV. TEM is a microscopy technique
whereby a beam of electrons is transmitted through an ultra thin specimen,
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