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VIETNAM NATIONAL UNIVERSITY, HA NOI
VNU UNIVERSITY OF SCIENCE

FACULTY OF CHEMISTRY
Phm Nh Thy
OXIDATIVE DENATURATION OF ACTIVATED CARBON SURFACE

BY KMnO4 FOR IONS TREATMENT IN WATRER ENVIRONMENT
Hanoi, June 2015
Oxidative denaturation of activated carbons surface by KMnO4 for ion treatment in water environment
ACKNOWLEDGEMENTS
I would like to express my special thanks of gratitude to my
Supervisor Prof.Dr.Sci.Tran Hong Con for giving me the topic and his keen
guidance in preparing this report as well as our principals who gave me the
golden opportunity to do this wonderful project on the topic Research the
changing surface properties of activated carbon oxidized by KMnO4, 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 them.
Secondly I would also like to thank my parents and friends who
helped me a lot in finishing this project within the limited time.
I am making this project not only for marks but to also increase my
knowledge.
Ha noi, April 8, 2014
Pham Nhu Thuy
CONTENTS
ACKNOWLEDGEMENTS ......................................................................................1
CONTENTS ...............................................................................................................2
LIST OF FIGURES ..................................................................................................4
LIST OF TABLES ....................................................................................................5
INTRODUCTION .....................................................................................................6
Chapter 1.
Overview............................................................................................. 7
1.1.
Activated Carbon ........................................................................................... 7
1.2.
Porous Structure of Activated Carbon Surface ............................................ 9
1.3.
Chemical Structure of Activated Carbon Surface ...................................... 12
1.3.1.
Carbon-Oxygen Surface Groups...........................................................13
1.3.2.
Characterization of Carbon-Oxygen Surface Groups ...........................14
1.4.
Applications of Activated Carbons ............................................................ 16
Chapter 2.
Experiments and methods .............................................................. 18
2.1.
Research objective ....................................................................................... 18
2.2.
Equipment and chemical ............................................................................. 18
2.2.1.
Equipments ...........................................................................................18
2.2.2.
Chemical subtance ................................................................................19
2.3.
Material ........................................................................................................ 19
2.4.
Method of examining features of denatured activated carbon .................... 21
2.4.1.
Determination of KMnO4 consumption and total electrons exchanged

21
2.4.2.
Determination of acid groups in activated carbon and oxidized
activated carbon ..................................................................................................21

2.5.
Method for determination of ions in solution .............................................. 22

2
2.5.1.
Determination of ammonium concentration .........................................22
2.5.2.
Determination of Arsenic concentration ...............................................24
2.6.
Method of calculating the adsorption capacity of the material ................... 26
2.6.1.
Investigation of ion adsorption capacity ...............................................26
2.6.2.
Investigation of adsorption equilibrium time .......................................28
2.6.3.
Determination of the maximal adsorption ............................................29
Chapter 3.
Results and Discussion ....................................................................30
3.1.
Determination of KMnO4 consumption of activated carbon ....................... 30
3.2.
Preliminary determination of total acid center on activated carbons surface30
3.3.
Investigation of Arsenic adsorption capacity of the material ...................... 33
3.3.1.
Investigation of Arsenic adsorption equilibrium time ..........................33
3.3.2.
Determination of the maximal arsenic adsorption capacity .................34
3.4.
3.3.2.1.
Material AC-1 ................................................................................34
3.3.2.2.
Material AC-2 ................................................................................35
3.3.2.3.
Material AC-2(B) ...........................................................................36
3.3.2.4.
Material AC-2(A) ...........................................................................37
Investigation of ammonium adsorption capacity of the material ................ 38
3.4.1.
Investigation of ammonium adsorption equilibrium time ....................38
3.4.2.
Determination of maximal ammonium adsorption of material AC2(B)

39
3.4.2.1.
Material AC-2(B) ...........................................................................40
3.4.2.2.
Material AC-2(A) ...........................................................................41
CONCLUSION ........................................................................................................43
REFERENCES ........................................................................................................44
LIST OF FIGURES
Figure 1.1: the macropores (a), the mesopores (b) , and the micropores (c)[5]. ......11
Figure 1.2: The reactions of activated carbons with oxygen gas ..............................14
Figure 1.3: Functional groups of basic character: (a) chromene, (b) pyrone-like. ...16
Figure 1.4: Model of a fragment of an oxidized activated carbon surface. ..............16
Figure 2.1: Calibration curve of ammonium .............................................................23
Figure 2.2: Calibration curve of As ..........................................................................26
Figure 3.1: Titration curve of AC and denatured AC ...............................................32
Figure 3.2: The Arsenic adsorption equilibrium time ...............................................33
Figure 3.3: The Langmuir adsorption isotherm of AC-1 ..........................................34
Figure 3.4: The Langmuir adsorption isotherm of AC-2 ..........................................35
Figure 3.5: The Langmuir adsorption isotherm of AC-2(B).....................................37
Figure 3.6: The Langmuir adsorption isotherm of AC-2(A) ....................................38
Figure 3.7: The Ammonium adsorption equilibrium time ........................................39
Figure 3.8: The Langmuir adsorption isotherm of AC-2(B).....................................40
Figure 3.9: The Langmuir isotherm of AC-2(A) ......................................................41
LIST OF TABLES
Table 2.1: Chemical substances ................................................................................19
Table 2.2: The standard curve of NH4+ .....................................................................23
Table 2.3: The standard curve of arsenic ..................................................................26
Table 3.1: Consumption of KMnO4 for oxidation of activated carbon ....................30
Table 3.2: pH of original and oxidized activated carbon with corresponding volume
of NaOH 0.01M ........................................................................................................31
Table 3.3: The data of arsenic adsorption equilibrium time of material AC2(B) .....33
Table 3.4: The examination data of material AC-1 ..................................................34
Table 3.5: The examination data of material AC-2 ..................................................35
Table 3.6: The examination data of material AC-2(B) .............................................36
Table 3.7: The examination data of material AC-2(A) .............................................37
Table 3.8: The data of ammonium adsorption equilibrium time of material AC-2(B)
...................................................................................................................................39
Table 3.9: Langmuir examining results of material AC-2(B)...................................40
Table 3.10: Langmuir examining results of material AC-2(A) ................................41
INTRODUCTION
Exacting demands are being made upon existing water resources to meet the
requirements of a highly industrialized society. These demands can be expected to
mount in the future, for continuing population expansion and tech non-logical
development lead naturally to both more extensive and more intensive use of
available supplies of water, and ultimately to the pollution and degradation of the
quality of these waters. Much of the water currently available to a large segment of
society has been subjected to previous use. Indeed, multiple reuse of water is not
uncommon today; planned and deliberate reuse is expected to be an even more
significant factor in water resources management in the years ahead. Evidently, as
reuse practice increases, more stringent requirements will be placed on the
treatment of waters and wastewaters, and more effective removal of persistent
materials, which might otherwise build up to intolerable concentrations during
several reuse cycles, will be required.
To increase the efficiency of water treatment, there are many methods
including methods of surface modification of activated carbon with HNO3, halogen,
sulfured, N2,... In this research, I focus on oxidative denaturation of activated
carbon surface by KMnO4 for ions treatment in water environment.
Chapter 1. Overview
1.1.
Activated Carbon[3]
Activated carbon, also called activated charcoal, activated coal, carbon

activates or an AC filter, is a form of carbon processed to have small, lowvolume pores that increase the surface area available for adsorption or chemical
reaction.[6]
Activated carbons in the form of carbonized wood charcoal have been used
for many centuries. The Egyptians used this charcoal about 1500 BC as an
adsorbent for medicinal purposes and also as a purifying agent. The ancient Hindus
in India purified their drinking water by filtration through charcoal. The first
industrial production of activated carbon started about 1900 for use in sugar refining
industries. This activated carbon was prepared by the carbonization of a mixture of
materials of vegetable origin in the presence of metal chlorides or by activation of
the charred material by CO2 or steam. Better quality gas-adsorbent carbons received
attention during World War I, when they were used in gas masks for protection
against hazardous gases and vapors.
Activated carbons are unique and versatile adsorbents, and they are used
extensively for the removal of undesirable odor, color, taste, and other organic and
inorganic impurities from domestic and industrial waste water, solvent recovery, air
purification in inhabited places, restaurants, food processing, and chemical
industries; in the removal of color from various syrups and pharmaceutical
products; in air pollution control from industrial and automobile exhausts; in the
purification of many chemical, pharmaceutical, and food products; and in a variety
of gas-phase applications. They are being increasingly used in the field of
hydrometallurgy for the recovery of gold, silver, and other metals, and as catalysts
and catalyst supports. They are also well known for their applications in medicine
for the removal of toxins and bacterial infections in certain ailments. Nearly 80%
(~300,000 tons/year) of the total activated carbon is consumed for liquid-phase
applications, and the gas-phase applications consume about 20% of the total
production.
Because the activated carbon application for the treatment of waste water is
picking up, the production of activated carbons is always increasing. The
consumption of activated carbon is the highest in the U.S. and Japan, which
together consume two to four times more activated carbons than European and other
Asian countries. The per capita consumption of activated carbons per year is 0.5 kg
in Japan, 0.4 kg in the U.S., 0.2 kg in Europe, and 0.03 kg in the rest of the world.
This is due to the fact that Asian countries by and large have not started using
activated carbons for water and air pollution control purposes in large quantities.
Carbon is the major constituent of activated carbons and is present to the
extent of 85 to 95%. In addition, activated carbons contain other elements such as
hydrogen, nitrogen, sulfur, and oxygen. These heteroatoms are derived from the
source raw material or become associated with the carbon during activation and
other preparation procedures. The elemental composition of a typical activated
carbon is found to be 88% C, 0.5% H, 0.5% N, 1% S, and 6 to 7% O, with the
balance representing inorganic ash constituents. The oxygen content of the activated
carbon, however, may vary between 1 and 20%, depending upon the source raw
material and the history of preparation, which includes activation and subsequent
treatments. The most widely used activated carbon adsorbents have a specific
surface area on the order of 800 to 1500 m2/g and a pore volume on the order of
0.20 to 0.60 cm3g-1. The pore volume, however, has been found to be as large as 1
cm3/g in many cases. The surface area in activated carbons is predominantly
contained in micro-pores that have effective diameters smaller than 2 nm.
Activated carbons are mainly and almost exclusively prepared by the
pyrolysis of carbonaceous raw material at temperatures lower than 1000C. The
preparation involves two main steps: carbonization of the raw material at
temperatures below 800C in an inert atmosphere, and activation of the carbonized
product between 950 and 1000C. Thus, all carbonaceous materials can be
8
converted into activated carbons, although the properties of the final product will be
different, depending upon the nature of the raw material used, the nature of the
activating agent, and the conditions of the activation process. During carbonization
most of the non-carbon elements such as oxygen, hydrogen, nitrogen, and sulfur are
eliminated as volatile gaseous products by the pyrolytic decomposition of the
source raw material. The residual elementary carbon atoms group themselves into
stacks of aromatic sheets cross-linked in a random manner. The mutual arrangement
of these aromatic sheets is irregular and, therefore, leaves free interstices between
the sheets, which may become filled with the tarry matter or the products of
decomposition or at least blocked partially by disorganized carbon. These
interstices give rise to pores that make activated carbons excellent adsorbents. The
char produced after carbonization does not have a high adsorption capacity because
of its less developed pore structure. This pore structure is further enhanced during
the activation process when the spaces between the aromatic sheets are cleared of
various carbonaceous compounds and disorganized carbon. The activation process
converts the carbonized char into a form that contains the largest possible number
of randomly distributed pores of various shapes and sizes, giving rise to a product
with an extended and extremely high surface area.
1.2.
Porous Structure of Activated Carbon Surface [3]

Activated carbons with a random arrangement of micro-crystallites and with
a strongcross-linking between them have a well-developed porous structure. They

have relatively low density (less than 2 gm/cm3) and a low degree of graphitization.
This porous structure formed during the carbonization process is developed further
during the activation process, when the spaces between the elementary crystallites
are cleared of tar and other carbonaceous material. The activation process enhances
the volume and enlarges the diameters of the pores. The structure of the pores and
their pore size distribution are largely determined by the nature of the raw material
and the history of its carbonization. The activation also removes disorganized
carbon, exposing the crystallites to the action of the activating agent and leads to the
9
development of a micro-porous structure. In the latter phase of the reaction, the

widening of existing pores and the formation of large pores by burnout of the walls
between the adjacent pores also takes place. This causes an increase in the
transitional porosity and macro-porosity, resulting in a decrease in the micro-pore
volume. According to Dubinin and Zaverina, a micro-porous activated carbon is
produced when the degree of burn-off is less than 50% and a macro-porous
activated carbon when the extent of burn-off is greater than 75%. When the degree
of burn-off is between 50 and 75%, the product has a mixed porous structure and
contains all types of pores.
Activated carbons are associated with pores starting from less than a
nanometer to several thousand nanometers. Dubinin proposed a classification of the
pores that has now been adopted by the International Union of Pure and Applied
Chemistry (IUPAC). This classification is based on their width (w), which
represents the distance between the walls of a slit-shaped pore or the radius of a
cylindrical pore. The pores are divided into three groups: the micropores, the
mesopores (transitional pores), and the macropores.
Micropores have molecular dimensions, the effective radii being less than 2
nm. The adsorption in these pores occurs through volume filling, and there is no
capillary condensation taking place. The adsorption energy in these pores is much
larger compared to larger mesopores or to the nonporous surface because of the
overlapping of adsorption forces from the opposite walls of the micropores. They
generally have a pore volume of 0.15 to 0.70 cm3/g. Their specific surface area
constitutes about 95% of the total surface area of the activated carbon. Dubinin
further suggested that for some activated carbons, the microporous structure can be
subdivided into two overlapping microporous structures involving specific
micropores with effective pore radii smaller than 0.6 to 0.7 nm and the super
micropores showing radii of 0.7 to 1.6 nm. The micropore structure of activated
carbons is characterized largely by the adsorption of gases and vapors and, to a
smaller extent, by small-angle x-ray scattering technique.
10
Mesopores, also called transitional pores, have effective dimensions in the 2

to 50 nm range, and their volume usually varies between 0.1 and 0.2 cm3/g. The
surface area of these pores does not exceed 5% of the total surface area of the
carbon. However, by using special methods, it is possible to prepare activated
carbons that have an enhanced mesoporosity, the volume of mesopores attaining a
volume of 0.2 to 0.65 cm3/g and their surface area reaching as high as 200 m2/g.
These pores are characterized by capillary condensation of the adsorbent with the
formation of a meniscus of the liquefied adsorbate. The adsorption isotherms show
adsorption desorption hysteresis is which stops at a relative vapor pressure of 0.4.
Besides contributing significantly to the adsorption of the adsorbate, these pores act
as conduits leading the adsorbate molecules to the micropore cavity. These pores
are generally characterized by adsorption-desorption isotherms of gases, by mercury
porosimetry, and by electron microscopy.
Macropores are not of considerable importance to the process of adsorption
in activated carbons because their contribution to the surface area of the adsorbate is
very small and does not exceed 0.5 m2/g. They have effective radii larger than 50
nm, and frequently in the 500 to 2000 nm range, with a pore volume between 0.2
and 0.4 cm3/g. They act as transport channels for the adsorbate into the micro- and
mesopores. Macropores are not filled by capillary condensation and are
characterized by mercury porosimetry.
Figure 1.1: the macropores (a), the mesopores (b) , and the micropores (c)[5].
Thus, the porous structure of activated carbons is tridisperse, consisting of
micro-, meso-, and macropores. Each of these groups of pores plays a specific role
in the adsorption process. The micropores constitute a large surface area and
11
micropore volume and, therefore, determine to a considerable extent the adsorption

capacity of a given activated carbon, provided that the molecular dimensions of the
adsorbate are not too large to enter the micropores. Micropores are filled at low
relative vapor pressure before the commencement of capillary condensation. The
mesopores, on the other hand, are filled at high relative pressures with the
occurrence of capillary condensation. The macropores enable adsorbate molecules
to pass rapidly to smaller pores situated deeper within the particles of activated
carbons. Thus, according to Dubinin, the pattern of porous structure in activated
carbons constitutes macropores opening up directly to the external surface, the
transitional pores branching off from the macropores, and the micropores in turn
branching off from the transitional pores.
1.3.
Chemical Structure of Activated Carbon Surface [3]

The crystalline structure of a carbon has a considerable influence on its
chemical reactivity. However, the chemical reactivity at the basal plane sites is
considerably lower than at the edge sites or at defect positions. Consequently,
highly graphitized carbons with a homogenous surface consisting predominantly of
basal planes are less reactive than amorphous carbons. Grisdale and Hennig
observed that the oxidation rates of carbon atoms at the edge sites were 17 to 20
times greater than at the basal plane surface. Similarly, intercalation reactions that
involve dimensional changes to the carbon structure are possible only with highly
graphitized carbons because of their high degree of order.
Activated carbons are almost invariably associated with appreciable amounts
of oxygen and hydrogen. In addition, they may be associated with atoms of sulfur,
nitrogen, and halogens. These heteroatoms are derived from the starting material
and become a part of the chemical structure as a result of imperfect carbonization,
or they become chemically bonded to the surface during activation or during
subsequent treatments. There is also evidence that the carbon can adsorb certain
molecular species such as amines, nitrobenzene, phenols, and several other cationic
species.
12
1.3.1. Carbon-Oxygen Surface Groups

Carbon-oxygen surface groups are by far the most important surface groups
that influence the surface characteristics such as wettability, polarity, and acidity,
and physico-chemical properties such as catalytic, electrical, and chemical
reactivity of these materials. In fact, the combined oxygen has often been found to
be the source of the property by which a carbon becomes useful or effective in
certain respects. For example, the oxygen has an important effect on the adsorption
capacity of carbons for water and other polar gases and vapors, on their ageing
during storage, on the adsorption of electrolytes, on the properties of carbon blacks
used as fillers in rubber and plastics, on the lubricating properties of graphite as
well as on its properties as a moderator in nuclear reactors. In the case of carbon
fibers, these surface groups determine their adhesion to plastic matrices and
consequently their composite properties. According to Kipling, the atoms of oxygen
and hydrogen are essential components of an activated carbon with good adsorptive
properties, and the surface of such materials is to be considered as a hydrocarbon
surface modified at some points by oxygen atoms.
Although the determination of the number and nature of these surface
chemical groups began more than 50 years ago, the precise nature of the functional
groups is not entirely established. The estimations obtained by different workers
using varied techniques differ considerably because the carbon surface is very
complex and difficult to reproduce. The surface groups cannot be treated as
ordinary organic compounds because they interact differently in different
environments. They behave as complex structures presenting numerous mesomeric
forms, depending upon their location on the same polyaromatic frame. Recent
electron spectroscopy for chemical analysis (ESCA) studies have shown that
irreversible transformation of surface groups occurred when classical organic
chemistry methods were used to identify and estimate them. It is Thus, expected
that the application of more sophisticated techniques such as FTIR, XPS, NMR
13
spectroscopy, and radiotracer studies will contribute significantly to a more precise

knowledge about these surface chemical groups.
1.3.2. Characterization of Carbon-Oxygen Surface Groups
Carbons have great tendency to extend this layer of chemisorbed oxygen,
and many of their reactions arise because of this tendency. For example, carbons are
capable of decomposing oxidizing gases such as ozone and oxides of nitrogen,
chemisorbing oxygen. They also decompose aqueous solutions of silver salts,
halogens, ferric chloride, potassium and ammonium persulphate, sodium
hypochlorite, potassium permanganate, potassium dichromate, sodium thiosulphate,
hydrogen peroxide, and nitric acid. In each case, there is chemisorption of oxygen
and the formation of carbon-oxygen surface compounds. Carbons can also be
oxidized by heat treatment in air, CO2, or oxygen. The reaction of activated carbons
with oxygen gas at temperatures below 400C predominantly results in the
chemisorbtions of oxygen and the formation of carbon-oxygen surface compounds,
whereas at temperatures above 400C the decomposition of the surface compounds
and the gasification of the carbon are the predominating reactions.
Figure 1.2: The reactions of activated carbons with oxygen gas

In the case of oxidations in the solution phase, the major reaction is the
formation of the surface compound, although some gasification may also take place
depending upon the strength of the oxidative treatment and the severity of the
experimental conditions. The formation of carbon-oxygen surface compounds using
different activated carbons and carbon black, and using various oxidative treatment
in gaseous and solution phase, has been studied by a large number of investigators
14
and has been very well reviewed. Thus, we merely point out that carbons have a
tendency to pick upon oxygen, at least to some extent under all conditions.
Carbons have an acid-base character. This fact has encouraged many
investigators to devote their research effort to understand the cause and mechanism
by which a carbon acquires an acid or a base character. Several theories (e.g., the
electrochemical theory of Burstein and Frumkin, the oxide theory of Shilov and his
school, the chromene theory of Garten and Weiss, and the pyrone theory of Voll
and Boehm, have been proposed to explain the acid-base character of carbons.
These theories and the related work have been elaborately reviewed and critically
examined in several review articles. It is now well accepted that the acid-base
character of carbons is developed as a result of surface oxidation and depends on
the history of formation and the temperature of oxidation.
Three types of carbon-oxygen surface groups (acidic, basic, and neutral)
have been recognized. The acidic surface groups are very well characterized and are
formed when carbon is treated with oxygen at temperatures up to 400C or by
reaction with oxidizing solutions at room temperature. These surface groups are
thermally less stable and decompose on heat treatment in vacuum or in an inert
atmosphere in the temperature range of 350 to 750C evolving CO 2. These acidic
surface groups render the carbon surface hydrophilic and polar in character and
have been postulated to be carboxylic, lactone, and phenolic groups.
The basic surface oxygen groups are much less characterized and are
obtained when a carbon surface, freed of all surface oxygen groups by heat
treatment in vacuum or in inert atmosphere at 1000C, and after cooling to room
temperature, is contacted with oxygen gas. Garten and Weiss proposed a pyronetype structure for basic surface groups, which has also been referred to as a
chromene structure. This structure has a heterocyclic oxygen-containing ring with
an activated = CH2 or = CHR (R is an alkyl group) group. According to Voll and
Boehm, the oxygen atoms in the pyrone-like structure are located in two different
rings of a graphitic layer. Out of the two differently bonded oxygen atoms on the
15
basic surface sites, one decomposes into CO2 and CO at 900C and the other at
1200C.
Figure 1.3: Functional groups of basic character: (a) chromene, (b) pyronelike.
The neutral surface oxygen groups are formed by the irreversible
chemisorption of oxygen at the ethylene type unsaturated sites present on the carbon
surface. The surface compound decomposes into CO2 on heat treatment. The
neutral surface groups are more stable than the acidic surface groups and start
decomposing in the temperature range 500 to 600C and are removed completely
only at 950C.
Figure 1.4: Model of a fragment of an oxidized activated carbon surface.
1.4.
Applications of Activated Carbons [3]

Activated carbons are excellent and versatile adsorbents. Their important
applications relate to their use in the adsorptive removal of color, odor, taste, and
other undesirable organic and inorganic impurities from drinking waters; in the
16
treatment of urban ground and industrial waste water; solvent recovery; air
purification in inhabited spaces such as restaurants, food processing, and chemical
industries; for the removal of color from various types of sugar syrups, oils, and
fats; in thepurification of many chemical, food, and pharmaceutical products; in
respirators forwork under hostile environments; and in a variety of other gas-phase
applications. They are increasingly being used in the field of hydrometallurgy for
the recovery of gold, silver, and other inorganics, and as catalytic and catalyst
supports. Their use in medicine and health applications to combat certain types of
bacterial ailment and for the removal of certain toxins is well known. These
applications of activated carbon are of interest to most economic sectors and
concern areas as diverse as the food, pharmaceutical, chemical, petroleum, mining,
nuclear, automobile, and vacuum industries. Nearly 80% of the total activated
carbon is consumed for liquid-phase applications, where both the granulated and
powdered forms of activated carbon are used. For gas-phase applications,
granulated carbon is usually the choice. However, with the commercial production
of fibrous activated carbons in the form of fibers and fabric, these materials may be
in preference, especially for water treatment processes, because they produce low
hydrodynamic resistance to flow and can easily be molded into any shape in the
adsorption equipment.
17
Chapter 2. Experiments and methods

2.1.
Research objective
First, activated carbon was modified by using oxidizing agent KMnO4/
H2SO4 at the difference concentration of acid and KMnO4 at room temperature in

order to modify the activated carbons surface from hydrophobic surface to
hydrophilic surface, from reducing surface to oxidized surface and have ability to
adsorb ion (material AC1).
Then, we titrate modified activated carbon by NaOH to determine total of
acid site on modified activated carbon.
In order to alter the activated carbons surface, we mobilized MnO2, Fe(OH)2,
Al(OH)3 into the surface of activated carbon after being modified to enhance the ion
adsorption ability of activated carbon (material AC-2). After that, the material AC-2
will be divided into 3 parts, the first part is submerged into the NaOH 0.5M solution
to form the alkaline form, the second part is submerged into H2SO4 0.5M solution to
make materials AC-2 has acidic form. In this study, we mainly focus on the
treatment of arsen in the form of AsO4- and cation NH4+ in aqueous solution based
on the adsorption, ion exchange.
2.2.
Equipment and chemical
2.2.1. Equipments
Hood, oven
A laboratory shaker
50.00ml, 100.00 ml volumetric flask.
10.00ml, 5.00ml, 20.00ml, 50.00ml pipet.
20ml glass tube.
100ml, 50ml, 25ml beakers.
18
filter paper.
flask.
2.2.2. Chemical subtance
Table 2.1: Chemical substances
No
Name
Quality
Activated
TraBac Joint Stock Company, size
carbon
0.51mm
NaOH
Chinese, PA.
HCl
Chinese, 35%, PA
KI
Chinese, 10%, PA
SnCl2
Chinese, saturated, PA
HgBr2
Chinese, PA.
Pb(CH3COO)2
Chinese, PA.
KNaC6H4O4
Chinese, PA.
KMnO4
Chinese, 0.025M, PA.
H2SO4
Chinese, 0.1M, PA.
2.3.
Material
AC-1:
Oxidating completely total activated carbons surface by 0.025M
KMnO4/H2SO4 solution until the oxidation process completes and the amount of
KMnO4 excess (color of solution is violet)
19
The resulting mixture was separated, the solution was titrated by H2C2O4 to
find out the remaining amount of KMnO4. The solid part was washed by acid HCl
(pH=3) to clean out MnO2 (if it exists), then the activated carbon was washed by
distilled water to clean out SO42- and Cl- (check by BaCl2 solution and AgNO3
solution). After that, it was dried in the oven at temperature of 1100C. At this
temperature, if acid remains, it will be decomposed totally. The resulting sample is
the totally oxidized activated carbon, called AC-1 material.
AC-2:
Weighing of 5g FeSO4.7H2O (1% Fe in comparing to activated carbon), 1.7g
MnSO4.2H2O (the ratio between Fe and Mn is 2:1), 2.46g Al2(SO4)3, after that,
dissolving this mixture in 110ml of water. Adding 99g of AC-1 to this solution and
vacuuming from 1 to 2 hours.
The resulting mixture was precipitated NaOH/ H2O2 solution until the pH is
6-8 (note that the solution should not be too alkaline because MnO2, Al2O3 could be
dissolved). The mixture is annealed in 8 hours, then it washed by distilled water to
clean out SO42- (check by BaCl2 solution) and. After that, it was dried at
temperature of 1000C to obtain the material AC-2.
AC-2(B) and AC-2(A):
Mashing material AC-2 in NaOH solution with the concentration in range
from 0.1-1M (in this experiment, the concentration of NaOH solution is 0.5M) in 1
hour. Washing the material until the pH was 7-8. Then it was dried naturally or
dried at temperature of 60oC. The obtaining material had alkaline form (Material
AC-2(B)).
Similarly, to create the material having acid form material AC-2(B), the
material AC-2 was masked in H2SO4 solution with concentration of 0.5M in 1 hour.
Washing this material until pH was 6 and ion SO42- was cleaned out. The obtaining
material was dried naturally or dried at temperature of 60oC.
20
2.4.
Method of examining features of denatured activated carbon
2.4.1. Determination of KMnO4 consumption and total electrons exchanged

Take 1g activated carbon and add a 120mL of the 0.025M KMnO4 solution,
shake it in 3 hour. Then, titrate the excess potassium permanganate by using the
standard oxalic acid solution. The end point is the point at which color change from
violet to colorless. Repeat 3 times and calculate total electrons exchanged.
Formula for total electrons exchanged:
electron exchanged =electron donor = electron acceptor
2.4.2. Determination of acid groups in activated carbon and oxidized
activated carbon
On the surface of activated carbon, there are weak and strong acid functional
groups that attend to the process of making surface complex and exchanging with
the ions in the wastewater. Therefore, the determination of the number of acid
functional groups on the surface of activated carbon plays an important rule in
assessing ion adsorption ability of resulting activated carbon.
There are 2 methods to determine the total number of acid centers on the
surface of activated carbon and oxidized activated carbon.
The first method is neutralizing by the excess amount of NaOH 0.018M. The
remaining alkali is titrated by 0.021M HCl solution with phenolphthalein indicator.
However, this method can cause error because the activated carbon can adsorb
phenolphthalein indicator.
The total mole of acid group per gram is determined by the below formula:
( ) 103
=
(/)
Where:
21
V volume of NaOH solution used to neutralize (ml)

C0, C concentration of original and equilibrated NaOH solution (M)
respectively.
m weight of activated carbon (g).
The second method is titrating method by alkali, measuring pH with glass
electrode. This method has higher accuracy. Steps of this method are as follows:
weighing 1g of activated carbon and put to a flask. Pouring each volume of 0.01M
NaOH solution and then shaking in 15 minutes in order to neutralize the acid center
with the strong alkali, after that measuring pH. Continuing these steps until the pH
is nearly unchanged.
The total number of acid centers is determined by the below formula:
a=V.C.10-3.R /m. (*)
Where:
C concentration of original NaOH solution (M) .
m weight of activated carbon (g).
V the volume of NaOH solution used to neutralize (ml)
R - Avogadro number
2.5.
Method for determination of ions in solution
2.5.1. Determination of ammonium concentration

Ammonium concentrations in water are determined by color measurement
method with Nessler reagent.
General principle: In the alkaline environment, NH4+ reacts with Nessler
reagent and become a complex with the color from yellow to brown, depended on
the concentration of ammonium in the solution.
22
The limiting factors: Iron hinders the determination, and it is eliminated by

signet salt or comlexon(III). When the organic compounds, alcols, aldehyt, cloramin
which can react with Nessler reagent exist in solution, they need to be distilled to
separate ammoniac before determining. If water is muddy, it should be processed by
solution ZnSO4 25%.
Determining method: Take 5 ml of sample, add 0.2 ml of Segnete and 0.5 ml
of Nessler. After 10 minutes, measure the optical adsorption at the wavelength of
420 nm.
Building ammonium standard curve: Create the ammonium solution with
concentration of 5mg/l from the ammonium solution with concentration of 1g/l.
Pour distilled water and 5mg/l ammonium solution into the test tube with the
corresponding amount as shown in the below table:
Table 2.2: The standard curve of NH4+
V NH4+ (ml)
4.5
V H2O (ml)
0.5
1.4
y = 0.1848x + 0.2698
R = 0.9983
1.2
Abs
1
0.8
0.6
0.4
0.2
0
0
5
C(g/ml
Figure 2.1: Calibration curve of ammonium

23
2.5.2. Determination of Arsenic concentration

1. Arsenic standard solution
Dissolve 1.32 g of As2O3 ( PA ) in 10 mL H2O which was dissolved 4 g
NaOH , using 6M HCl solution transferred to weak acidic ( pH 5-6 ) , after which
the flask 1000ml distilled water added to As a solution outlined 1g / L ( 1000ppm ) .
Get a 5 mL 1000 ppm As for 1000ml flask and dilute norms we obtain a
solution Arsenic 5 ppm (5000 ppb). Liquid phase is finished bottled polyethylene.
2. 10 % KI solution
Weighing 10g of KI and dissolving it with 30 ml of distilled water in a cup.
Pouring this solution into 100ml flask which is rinsed by distilled water. Rinsing the
cup 3 times and then adding water to reach the outline norm, then shaking. The
obtaining KI solution was stored in a color bottle to avoid the light, with sealed
buttons.
3. SnCl2 solution
Putting 20 tin beads into 100 ml of 1:1 HCl solution and storing this mixture
in a glass bottle with sealed buttons. After 48 hours, obtaining SnCl2 solution.
During the experiment, if the tin is dissolved, adding some beads to remain SnCl2
solution.
4. Paper impregnated with Pb(CH3COO)2
Weigh 10 g of Pb(CH3COO)2 and dissolved in 100ml of distilled water.
Liquid phase are completed on filter paper impregnated, dried naturally. The paper
is cut to the size of 60 80 mm and stored in colored glass jars, sealed.
5. Mercury-impregnated paper
Dissolve 4g HgBr2 (PA) in 100 ml of ethanol 95 %. Liquid phase are
completed on filter paper impregnated with crude not contain arsenic. Let it dry
naturally. HgBr2 impregnated paper cut to size 3x150 mm and stored in colored
glass jars, sealed
24
6. 1:2 HCl solution

The 1:2 HCl solution is diluted from the condensed HCl solution with the
ratio between condensed HCl and distilled water of 1:2. Liquid phase completed in
containers sealed glass button.
The principle of the method
After the samples were acidified, AsH3 gas generated by the reaction of
arsenite with hydrogen newborn ( Zn + HCl in the reactor ) will draw up , go
through the jar wrapped with lead acetate impregnated paper, and then reacted with
HgBr2 on impregnated paper , impregnated paper HgBr2 switch from white to
yellow -brown. The height of the color bar is proportional to the average
concentration of arsenic in
Reaction equation:
AsO43- + 2I--+ 4H+ = AsO22- + I2 + 2H2O
AsO22- + Zn + 14H+ = 2AsH3 + Zn2+ + H2O
AsH3+ 3HgBr2 = As(HgBr2)3 +3HCl
7. Process of analysis
Obtaining a precise amount of sample to be analyzed (V = 50ml) in 100ml
volumetric flask. Then add 25ml, respectively, and 5 drops of 1:2 HCl to remove
the entire KI As (V) to As (III). Let stand about 15 minutes. The amount of
liberated I2 makes the solution is yellow. Give 4-5 drops of saturated SnCl2 into the
bottle and shake to remove the form I- I2. HgBr2 soaked shredded paper size 3x150
mm was put into a small glass tube rubber buttons. Next soaked paper wrapped
Pb(CH3COO)2 in the top of the bottle. 3 grams of zinc particles in, and seal the
paper. Insert the glass tube containing impregnated paper into the jar HgBr2. AsH3
gas generated by the reaction of arsenite with hydrogen produced will draw up new,
impregnated paper HgBr2 move from white to yellow -brown. To react for 60
minutes then take out HgBr2 impregnated paper about color measurement height.
The amount of arsenic in the sample will be proportional to the height h.
25
Table 2.3: The standard curve of arsenic

C(ppb)
100
300
500
700
900
1000
h(mm)
6.75
16.4
28.1
37.5
48.1
52.4
60
y = 0.0513x + 1.6342
R = 0.9991
height (mm)
50
40
30
20
10
0
0
200
400
600
800
1000
1200
C(ppb)
Figure 2.2: Calibration curve of As
2.6.
Method of calculating the adsorption capacity of the material
2.6.1. Investigation of ion adsorption capacity[1][7]

Model calculations for the adsorption technique, commonly used is
Langmuir or Freundlich equation. Langmuir proposed his theory by making
following assumption:
1. Fixed number of vacant or adsorption sites are available on the
surface of solid [6].
2. All the vacant sites are of equal size and shape on the surface of
adsorbent [6].
26
3. Each site can hold maximum of one gaseous molecule and a constant
amount of heat energy is released during this process [6].
4. Dynamic equilibrium exists between adsorbed gaseous molecules and
the free gaseous molecules [6].
Where A (g) is unadsorbed gaseous molecule, B(s) is unoccupied metal

surface and AB is Adsorbed gaseous molecule [6].
5. Adsorption is monolayer or unilayer [6].
Langmuir adsorption theory is described by a equation:
.
Where:
: the amount of adsorption in units of moles adsorbate per mass
adsorbant and the maximal adsorption (mg/g)
C : the solution concentration at equilibrium
b: Langmuir equation coefficients (determined from experiments)
27
To determine the constants in the Langmuir equation, we can write the

equation in the form of:
Line performing C / m depends on C is a line with slope 1 / m and cutting

vertical axis at 1 / bm.
Thus:
2.6.2. Investigation of adsorption equilibrium time

Arsen: Weighing 6 AC samples, each sample 0.5 g, into a 250 ml
Erlenmeyer flask. Add 50 ml As solution 1ppm. Bring it on the machine,
shaking during continuous turn: 1h, 2h, 3h, 4h, 5h, 6h. After that take part in
the solution and analyze the remaining amount of As. From the obtained
results, we determined the time to reach equilibrium adsorption of As of
materials.
Ammonium:
Preparing 8 samples of each material, each sample weigh of
0.5 g, into an 250 ml Erlenmeyer flask. Add 50 ml of 5mg/l ammonium
28
solution and shaking continuously on the machine. Just after 30 minutes,

taking 1 sample analyzed the remaining amount of ammonium.
2.6.3. Determination of the maximal adsorption
Arsenic: Preparing 7 samples of each material, each sample weigh of 0.5 g

into a 250 ml Erlenmeyer flask. Add 100 ml arsenic solution with
concentrations of 10, 20, 30, 40, 70, 100, 150 mg/l. The mixture was shaking
for 4 hours. Then extract the solution and dilute so that the concentration of
the final As solution was approximately 1ppm and determine arsenic
remaining amount.
Ammonium: Preparing 8 samples of each material, each sample weigh of 0.5

g into a 250 ml Erlenmeyer flask. Adding 100 ml ammonium solution with
concentrations of 5, 10, 20, 30, 40, 70,80, 100 mg / l. Shaking the mixture
for 2 hours. Then extracting the solution and diluting so that the remaining
ammonium amount of approximately 5 ppm and determining remaining
amount.
29
Chapter 3. Results and Discussion

3.1.
Determination of KMnO4 consumption of activated carbon

The average result of three parallel experiments is showed in table 3.1.
Table 3.1: Consumption of KMnO4 for oxidation of activated carbon
Total initial amount of
Exceed amount of
Consumed amount of
KMnO4 (mmol/g)
KMnO4 (mmol/g)
KMnO4 (mmol/g)
2.265
0.735
Based on the experimental result above, every one gram activated carbon
required 0.735 mmol of KMnO4 to reduce almost reductive groups, which have
oxidation reduction potential lower than that of KMnO4 (about +1.54 V). In acidic
condition, MnO4- reduced into Mn2+, therefore, 1 g activated carbon has received
the sum of electrons in this reaction as follow:
Total electrons exchanged = 0.735 x 5 x 6.023.1023 = 22.135.1023.
3.2.
Preliminary determination of total acid center on activated
carbons surface
The total number of acid center on the surface of oxidized activated carbon
was determined by the neutralizing titration method with NaOH solution. Because
NaOH is a strong alkali, it can react with almost acid functional groups. Therefore,
the result is the total number of acid center on the surface of oxidized activated
carbon. The data of titration curve is in the below table:
30
Table 3.2: pH of original and oxidized activated carbon with corresponding

volume of NaOH 0.01M
Oxidized AC
Original AC
V (mL)
pH
V (mL)
pH
5.67
3.85
2.5
6.58
6.57
6.88
10
9.75
10
7.14
15
10.27
15
7.28
20
10.53
17.5
7.42
25
10.71
20
7.47
30
10.83
25
7.71
35
10.85
30
7.75
50
10.95
32.5
7.85
60
11.03
35
7.95
70
11.11
37.5
8.03
80
11.21
40
8.13
90
11.28
42.5
8.2
100
11.33
45
8.34
47.5
8.45
52.5
8.89
60
9.29
65
9.56
70
9.65
75
9.71
80
9.8
85
9.93
90
10.01
95
10.09
100
10.13
105
10.17
110
10.24
120
10.38
31
From this table we have the graph:

12
10
pH
8
6
oxidized AC
unoxidized
4
2
0
0
50
Volume(ml)
100
150
Figure 3.1: Titration curve of AC and denatured AC

According to the titrating result, it can be that the titrating curve of original
AC has a big jump from 0 to 10 ml, after 40 ml, the pH of solution is nearly
unchanged. It proves that all acid centers, even weak acids having pKa>10 were
neutralized. The total mol of acid and total number of acid centers can be
calculated. Applying the formula (*), the number of acid centers in 1g of original
activated carbon is 2.4 x 1020 (center/g). With oxidized activated carbon (material
AC-1), the titrating curve has 3 curling ranges corresponding with 3 general
intensity levels of acid groups that were created after oxidizing the activated carbon.
These ranges are from 0.0 to about 20 ml of NaOH; from 30 ml to about 65 ml and
from 65 ml to 120 ml of 0.01 M NaOH solution. However, after 100 ml of 0.01M
NaOH solution, the pH value of solution is nearly unchanged. It proves that all acid
centers, even weak acids having pKa>10 were neutralized. The number of acid
centers in 1g of oxidized activated carbon is 6.1020 (center/g) calculated according
to formula (*).
32
3.3.
Investigation of Arsenic adsorption capacity of the material
3.3.1. Investigation of Arsenic adsorption equilibrium time

Because of the similar characteristic of materials, in this part, only one
material was chosen to examine the the maximal adsorption equilibrium time As of
material. It was AC-2(B) material.
We have the result table below:
Table 3.3: The data of arsenic adsorption equilibrium time of material AC2(B)
Sample
M1
M2
M3
M4
M5
Time
1h
2h
3h
4h
5h
h(mm)
14
12.2
11.4
10.2
7.2
CAs excess (ppm)
4.272732
4.376979
4.423311
4.492809
4.666554
4.7
C adsop
4.6
4.5
4.4
4.3
4.2
0
t(h)
Figure 3.2: The Arsenic adsorption equilibrium time
Examining similarly other materials gave the result that the maximal
adsorption equilibrium time of materials is from 4 to 5 hours. Therefore, in other
similar experiments, As was adsorbed in 5 hours continuously.
33
3.3.2. Determination of the maximal arsenic adsorption capacity

3.3.2.1. Material AC-1
The examining results of 7 AC-1 samples with the arsenate solution with
concentration from 5ppm, 10ppm, 20ppm, 30ppm, 40ppm, 60ppm, 70ppm are
shown in the below table:
Table 3.4: The examination data of material AC-1
H(mm)
Cf(ppm)
Q(mg/g)
Cf/Q
11.3
1.42724421
0.71455116
1.99739962
10
11.6
2.941361
1.4117278
2.08351851
20
12.3
6.28812741
2.74237452
2.29294991
30
14.6
9.52521718
4.09495656
2.32608503
40
10.1
12.5349903
5.49300193
2.28199271
60
18
23.9732143
7.20535714
3.32713755
70
23.1
31.3573842
7.72852317
4.05735785
Cf/Q
Co(ppm)
7
6
5
4
3
2
1
0
y = 0.1237x + 1.4389
R = 0.9699
10
15
20
25
30
35
40
45
Cf
Figure 3.3: The Langmuir adsorption isotherm of AC-1
From the graph, we can determine the maximal arsenic adsorption of
material AC-1:
Qmax = 1/0.1237 =8.084 mg/g or 0.058mmol/g
34
This result shows that the oxidized activated carbon has ability of adsorbing
arsenic in form of ion AsO43- was not appropriate for its surface. Although the
adsorption ability is not high, adsorption capacity is quite low, there is a great
improvement in comparing with the un-oxidized activated carbon. This allows to
predict that: it is possible to modify the surface of activated carbon by oxidizing
factor to change the hydrophobic surface of Tra Bac activated carbon in order to
change the structure and adsorption ability, specially arsenic adsorption ability.
3.3.2.2. Material AC-2
The examining results of 7 AC-2 samples with the arsenate solution with
concentration from 10ppm, 30ppm, 50ppm, 70ppm,100ppm,120ppm, 150ppm are
Table 3.5: The examination data of material AC-2
Co
H(mm)
Cf(ppm)
Q(mg/g)
Cf/Q
10
0.493726
1.901255
0.259684
30
12
2.038127
5.592375
0.364448
50
19
3.389479
9.322104
0.363596
70
28.9
5.300676
12.93986
0.409639
100
13.2
11.34894
17.73021
0.64009
120
17.2
15.20994
20.95801
0.725734
150
30
27.56515
24.48697
1.125707
1.2
1
Cf/Q
0.8
0.6
y = 0.0312x + 0.2639
R = 0.9948
0.4
0.2
0
0
10
15
20
25
30
Cf
Figure 3.4: The Langmuir adsorption isotherm of AC-2
35
From the graph, we can determine the maximal arsenic adsorption of

material AC-2:
Qmax = 1/0.0312 =32.05 mg/g or 0.23mmol/g
The results show that arsenic adsorption ability in form of AsO43- of AC-2
material is 4 times higher than AC-1 and much higher than AC-0. It proves that
adding MnO2, Fe2O3, Al2O3 to the surface of activated carbon after modifying
increases arsenic adsorption ability of activated carbon. We can see that there are
many other oxides and compounds that can be added to the activated carbons
surface to change the structure and adsorption ability of activated carbon. It can be
applied in field of processing hazardous materials in water such as AsO43- .
3.3.2.3. Material AC-2(B)
The examining results of 9 AC-2(B) samples with the arsenate solution with
concentration from 10ppm, 30ppm, 50ppm, 70ppm, 80ppm, 100ppm, 120ppm,
150ppm, 170ppm are shown in the below table:
Table 3.6: The examination data of material AC-2(B)
Co
H(mm)
Cf(ppm)
Q(mg/g)
Cf/Q
10
8.5
1.021839
1.795632
0.569069
30
14.85
3.882481
5.223504
0.743271
50
24.6
6.70584
8.658832
0.774451
70
35.5
9.86221
12.02756
0.819968
80
42
11.74445
13.65111
0.860329
100
11.2
14.12765
17.17447
0.822596
120
14.8
19.34001
20.132
0.96066
150
20
26.86897
24.62621
1.091072
36
170
27
37.0041
26.59918
1.391175
1.6
1.4
1.2
Cf/Q
y = 0.02x + 0.6027
R = 0.9579
0.8
0.6
0.4
0.2
0
0
10
15
20
25
30
35
40
Cf
Figure 3.5: The Langmuir adsorption isotherm of AC-2(B)
From the graph, we can determine the maximal Arsenic adsorption of
material AC-2(B):
Qmax = 1/0.02 =50 mg/g or 0.359 mmol/g
3.3.2.4. Material AC-2(A)
The examining results of 7 AC-2(A) samples with the arsenate solution with
concentration from 10ppm, 20ppm, 50ppm, 60ppm, 70ppm, 80ppm, 100 ppm are
Table 3.7: The examination data of material AC-2(A)
Co
Cf
Cf/Q
10
7.3
0.565396
1.886921
0.299639
20
15.3
1.337597
3.732481
0.358367
50
19.8
3.543919
9.291216
0.381427
60
25.1
4.567085
11.08658
0.411947
70
30.4
5.590251
12.88195
0.43396
80
39.5
7.347008
14.5306
0.505623
37
100
17.3
15.30647
16.93871
0.903638
Cf/Q
0.8
0.6
0.4
y = 0.0401x + 0.2517
R = 0.963
0.2
0
0
10
12
14
16
18
Cf
Figure 3.6: The Langmuir adsorption isotherm of AC-2(A)
From the graph, we can determine the maximal Arsenic adsorption of
material AC-2(A):
Qmax = 1/0.0401 = 24.937 mg/g or 0.179 mmol/g
Through examining the Arsenic adsorption capacity in form of AsO43- of
material, it can be seen that the As adsorption ability of material AC-2(B) is 6 times
higher than material AC-1; 1.56 times higher than material AC-2 and 2 times higher
than material AC-2(A). It show that modifying to have alkaline form of activated
carbon improves the As adsorption ability in form of ion AsO43-.
3.4.
Investigation of ammonium adsorption capacity of the material
3.4.1. Investigation of ammonium adsorption equilibrium time

The examining results show that ammonium adsorption capacities of
material AC-1 and AC-2 are quite low (hardly adsorbed). It allows predict that: the
oxidation of the activated carbons surface does not improve the ammonium
adsorption ability of materials. Therefore, I continues examining material AC-2(A)
and AC-2(B).
38
Because of the similar characteristic of materials, in this part, only one

material was chosen to examine the the maximal Ammonium adsorption
equilibrium time of material. It was AC-2(B) material.
We have the table:
Table 3.8: The data of ammonium adsorption equilibrium time of material
AC-2(B)
t(h)
Abs
Cf
Chp
0.5
0.903
3.42640693
1.57359307
0.901
3.41558442
1.58441558
0.837
3.06926407
1.93073593
2.5
0.833
3.04761905
1.95238095
0.822
2.98809524
2.01190476
3.5
0.823
2.99350649
2.00649351
2.5
C ads (ppm)
2
1.5
1
0.5
0
3
t (h)
Figure 3.7: The Ammonium adsorption equilibrium time

Examining similarly other materials gave the result that the maximal
adsorption equilibrium time of materials is from 1.5 to 2 hours. Therefore, in other
similar experiments, As was adsorbed in 2 hours continuously.
3.4.2. Determination of maximal ammonium adsorption of material AC2(B)
39
3.4.2.1. Material AC-2(B)

The examining results of 8 AC-2(B) samples with the ammonium solution
with concentration from 5ppm, 10ppm, 20ppm, 30ppm, 50ppm, 70ppm, 90ppm,
100ppm are shown in the below table:
Table 3.9: Langmuir examining results of material AC-2(B)
Co
Abs
Cf
Cf/Q
0.678
2.208874
0.279113
7.91392
10
0.751
5.207792
0.479221
10.86721
20
0.689
11.34199
0.865801
13.1
30
0.608
18.30087
1.169913
15.64292
50
0.899
34.04762
1.595238
21.34328
70
1.203
50.49784
1.950216
25.89345
90
0.763
66.72078
2.327922
28.66109
100
0.827
76.46104
2.353896
32.48276
50
70
35
y = 0.2959x + 9.455
R = 0.9731
30
Cf/Q
25
20
15
10
5
0
0
10
20
30
40
60
80
Cf(ppm)
Figure 3.8: The Langmuir adsorption isotherm of AC-2(B)

From the graph, we can determine the maximal Ammonium adsorption of
material AC-2(B):
Qmax = 1/0,2986 =3.453 mg/g or 0.191 mmol/g
40
3.4.2.2. Material AC-2(A)

The examining results of 6 AC-2(A) samples with the ammonium solution
with concentration from 5ppm, 10ppm, 15ppm, 20ppm, 30ppm, 40ppm are shown
in the below table:
Table 3.10: Langmuir examining results of material AC-2(A)
C
Cf
Cf/q
0.835
3.05844156
0.01941558
157.525084
10
0.956
6.18867244
0.03811328
162.375769
15
0.619
9.44805195
0.05551948
170.175439
20
0.74
12.7218615
0.07278139
174.795539
30
0.987
18.8636364
0.11136364
183.146736
40
0.785
28.0952381
0.11904762
230
250
y = 2.7226x + 143.96
R = 0.9033
200
150
100
50
0
0
10
15
20
25
30
Figure 3.9: The Langmuir isotherm of AC-2(A)

From the graph, we can determine the maximal Ammonium adsorption of
material AC-2(A):
Qmax = 1/2.7226 =0.36729 mg/g or 0.0204 mmol/g
41
Through examining the ammonium adsorption capacity in form of NH4+ of

materials AC-1, AC-2, AC-2(A) and AC-2(B), it can be seen that the ammonium
adsorption ability of AC-2(B) is the best (Qmax = 3,453 mg/g) while material AC-1
and AC-2 adsorb ammonium hardly. The reason may be that the surface of material
AC-2(B) has alkaline form that increases the ammonium adsorption ability of AC2(B). The result is that the maximal adsorption capacity of AC-2(B) is 10 times
higher than AC-2.
The results show that materials AC-1, AC-2, AC-2(B) and AC-2(A) can
adsorb anion AsO43- better than cation NH4+. It can be an important advantage of
modified activated carbon and open a new direction for researching using activated
carbon as adsorbent for small size particles which other methods cannot adsorb.
42
CONCLUSION
In this reseach, I focus on the modification of the activated carbons surface
by using strong oxidizers and adding Mn(IV), Fe(III) and Al to the surface of
activated carbon after modifying in order to create the materials having stronger
adsorpting center. The obtaining results are:
1. In my initiating investigation the total electron exchanged and total acid
groups on the oxidized activated carbon were determined. The number of
electrons exchanged is 2.2131024 electrons per 1.00 gram and the total
number of acid center is about 61020 centers per 1.00 gram.
2. We have carried out the oxidized reduction surface of activated carbon by
KMnO4 solution in acidic H2SO4 to modify the reduction surface of
activated carbon into the oxidized surface, transforming from a hydrophobic
surface to hydrophilic surface (materials AC -1)
3. We have conducted a study by adding MnO2, Fe2O3, Al2O3 on the surface of
activated carbon after oxidizing. We have created a new hybrid material
(AC-2 material).
4. Modifying AC-2 surface by NaOH solution to gain a material which has
alkaline surface (material AC-2(B)) and by H2SO4 solution to gain a material
which has acidic (material AC-2(A)).
5. Carried out examining, determining that the adsorption capacity for arsenic
of materials AC-1, AC-2, AC-2(B) and AC-2(A) are 8.084mg/g; 32.05
mg/g; 50 mg/g; 24.937 mg/g respectively in the normal condition. The
maximal equilibrium time is 5h. Determining that the adsorption capacity for
ammonium of materials AC-2(A), AC-2(B) are 0.36729 mg/g; 3.453mg/g
respectively in the normal conditions, the maximal equilibrium time is 2h.
The results show that modified activated carbon has better adsorption ability
for the toxic compounds in form of anion in comparing with cation.
43
REFERENCES
[1] V Ngc Ban(2007), Gio trnh thc tp Ha l, Nh xut bn i hc Quc
gia H Ni.
[2] F. Julien, M. Baudu and M. Mazet (1998), Relationship between chemical and
physical properties of activated carbon, Wat. Res, 32(11), pp. 3414-3424.
[3] Roop Chand Bansal, MeenakshiGoyal (2005), Activated Carbon Adsorption,
Taylor & Francis Group, LLC.
[4] S.
Biniak, G.Szymaki, J. Siedlewski, A. Swiatkowski (1997), The
characterization of activated carbons with oxygen and nitrogen surface group,

Carbon, 35(12), pp. 1799-1810.
[5] Shaobin Wang, Z.H.Zhu, Anthony Coomes, F. Haghseresht,G.Q.Lu (2004),
The physical and surface chemical characteristics of activated carbons and the
adsorption of methylene blue from wastewater, Journal of Colloid and Interface
Science.
[6] http://en.wikipedia.org/wiki/Activated_carbon
[7] http://www.chemistrylearning.com/langmuir-adsorption-isotherm/
44

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VIETNAM NATIONAL UNIVERSITY, HA NOI

VNU UNIVERSITY OF SCIENCE

OXIDATIVE DENATURATION OF ACTIVATED CARBON SURFACE

Hanoi, June 2015

Activated Carbon ........................................................................................... 7

Porous Structure of Activated Carbon Surface ............................................ 9

Chemical Structure of Activated Carbon Surface ...................................... 12

Carbon-Oxygen Surface Groups...........................................................13

Characterization of Carbon-Oxygen Surface Groups ...........................14

Applications of Activated Carbons ............................................................ 16

Experiments and methods .............................................................. 18

Research objective ....................................................................................... 18

Equipment and chemical ............................................................................. 18

Chemical subtance ................................................................................19

Method of examining features of denatured activated carbon .................... 21

Determination of KMnO4 consumption and total electrons exchanged

Determination of acid groups in activated carbon and oxidized

activated carbon ..................................................................................................21

Method for determination of ions in solution .............................................. 22

Determination of ammonium concentration .........................................22

Determination of Arsenic concentration ...............................................24

Method of calculating the adsorption capacity of the material ................... 26

Investigation of ion adsorption capacity ...............................................26

Investigation of adsorption equilibrium time .......................................28

Determination of the maximal adsorption ............................................29

Results and Discussion ....................................................................30

Determination of KMnO4 consumption of activated carbon ....................... 30

Preliminary determination of total acid center on activated carbons surface30

Investigation of Arsenic adsorption capacity of the material ...................... 33

Investigation of Arsenic adsorption equilibrium time ..........................33

Determination of the maximal arsenic adsorption capacity .................34

Material AC-1 ................................................................................34

Material AC-2 ................................................................................35

Material AC-2(B) ...........................................................................36

Material AC-2(A) ...........................................................................37

Investigation of ammonium adsorption capacity of the material ................ 38

Investigation of ammonium adsorption equilibrium time ....................38

Determination of maximal ammonium adsorption of material AC2(B)

Material AC-2(B) ...........................................................................40

Material AC-2(A) ...........................................................................41

Activated carbon, also called activated charcoal, activated coal, carbon

Porous Structure of Activated Carbon Surface [3]

a strongcross-linking between them have a well-developed porous structure. They

development of a micro-porous structure. In the latter phase of the reaction, the

Mesopores, also called transitional pores, have effective dimensions in the 2

micropore volume and, therefore, determine to a considerable extent the adsorption

Chemical Structure of Activated Carbon Surface [3]

1.3.1. Carbon-Oxygen Surface Groups

spectroscopy, and radiotracer studies will contribute significantly to a more precise

Figure 1.2: The reactions of activated carbons with oxygen gas

Figure 1.4: Model of a fragment of an oxidized activated carbon surface.

Applications of Activated Carbons [3]

Chapter 2. Experiments and methods

H2SO4 at the difference concentration of acid and KMnO4 at room temperature in

Equipment and chemical

TraBac Joint Stock Company, size

Chinese, 0.025M, PA.

Chinese, 0.1M, PA.

Method of examining features of denatured activated carbon

2.4.1. Determination of KMnO4 consumption and total electrons exchanged

V volume of NaOH solution used to neutralize (ml)

Method for determination of ions in solution